JPH0876314A - Silver halide photographic sensitive material and its processing method - Google Patents

Abstract

PURPOSE: To provide the silver halide photographic sensitive material capable of forming a negative image high in contrast. CONSTITUTION: The silver halide photographic sensitive material uses a compound represented by the formula in which Z<1> is a nonmetallic atomic group necessary to form a 5- or 6-membered ring; X<1> is an N atom or a CR<12> group; R<1> is an alkyl group or the like; each of R<11> and R<12> is an H atom or the like; m<1> is 0 or an integer of <= a maximum substitutable number on the ring; Y<1> is a counter ion; and the total C number of groups substituted on the ring (including R<1> ) is 15-40.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material and a method for forming a high-contrast image using the same, and more particularly to a silver halide photographic light-sensitive material with controlled gradation.

[0002]

2. Description of the Related Art Halftone dot images (doti
mage) for continuous tone reproduction or line drawing reproduction
In order to be successful, there is a need for an imaging system that exhibits ultrahigh contrast photographic properties. Conventionally, a special developer called a lith developer has been used for this purpose. The lith developer contains only hydroquinone as a developing agent, and a sulfite salt used as a preservative is used in the form of an adduct with formaldehyde so as not to impair the infectious developability, and the concentration of free sulfite ion is extremely low. (Usually 0.1 mol / liter or less) and high pH (substantially pH 1
1) or more), the desired performance cannot be obtained. Therefore, the lith developer has a serious drawback that it is extremely susceptible to air oxidation and cannot be stored for more than 3 days. Therefore, when the processing stability is emphasized and the processing is carried out with a general black and white developing solution, the stability of the developing solution is remarkably improved. It had a problem that it was inferior to the case. Further, U.S. Pat. No. 2,419,975 describes that a certain kind of hydrazine compound is added to a silver halide emulsion to obtain a hard negative image, which is specifically shown in this patent specification. In order to obtain a super-high contrast (γ ≧ 10) negative image using the hydrazine compound described above, a developer having a high pH of 12.8 must be used. But,
A strong alkaline developer having a pH close to 13 is easily oxidized by air and is unstable, and cannot withstand long-term storage and use. Of course, if the content of sulfite ion is increased, the storage stability will be improved, but in order to sufficiently improve the stability of such a high pH developer, it is necessary to add a large amount of sulfite, resulting in contamination of the processing solution. In addition to the above, there is a serious problem that the image becomes harder. Therefore, there has been a demand for an image forming system which does not have the above-mentioned drawbacks and which has an ultrahigh contrast and has a good storability of the processing liquid.

Japanese Unexamined Patent Application Publication No. Hei 5-
No. 53231, JP-A-6-102633 and the like disclose mono- and bisonium salt compounds. However, these known compounds do not show a sufficient contrast-enhancing effect and cannot be said to have sufficient halftone dot quality. Further, there is a problem that these known compounds easily diffuse and are eluted into the processing solution to cause contamination of the processing solution.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material capable of obtaining a photographic characteristic of a hard negative tone using a stable developing solution and an image forming method using the same. Is to provide.

[0005]

The object of the present invention has been achieved by a silver halide photographic light-sensitive material characterized by containing a compound represented by the following general formula (N-1). General formula (N-1)

[0006]

[Chemical 3]

[0007] In the formula, Z ¹ is N, represents a non-metallic atomic group necessary for forming a nitrogen-containing aromatic heterocyclic ring of 5 or 6 membered jointly with X ^1, X ¹ represents N or CR ¹² . Here, R ¹² has the same meaning as R ¹¹ . R ¹ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. R ¹¹ 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. m ¹ is 0 or an integer equal to or less than the maximum substitutable number in the ring. When m ¹ is 2 or more, each R ¹¹ may be the same or different, and each R ¹¹ may be bonded to form a ring. Further, two radicals free of one arbitrary hydrogen atom from the formula (N-1) may be bonded to each other to form a bis type structure. Y ¹ is a counter ion for charge balance, and n ¹ is a number required for charge balance. The total number of carbon atoms contained in the substituent substituting the 5- or 6-membered nitrogen-containing aromatic heterocycle completed by Z ¹ and the carbon number contained in R ¹ is 15 to 40.

Next, the general formula (N-1) will be described in detail.
Z ¹ represents a nonmetal atomic group necessary for forming a 5- or 6-membered nitrogen-containing aromatic heterocycle in cooperation with N and X ^1.
1 represents N or CR ¹² . Here, R ¹² has the same meaning as R ¹¹ . The 5-membered nitrogen-containing heterocycle formed by Z ¹ , N and X ¹ is, for example, pyrazole, imidazole, oxazole, thiazole, triazole or tetrazole. The group in which R ¹¹ or R ¹² is bonded to form a condensed aromatic ring is, for example, indazole, benzimidazole, benzoxazole, benzothiazole, benzotriazole or benzisoxazole. The 5-membered nitrogen-containing aromatic heterocycle completed by Z ¹ is preferably pyrazole, imidazole, oxazole, benzimidazole or benzothiazole, more preferably imidazole, oxazole or benzothiazole, most preferably benzothiazole. The 6-membered nitrogen-containing heterocycle formed by Z ¹ , N and X ¹ is, for example, pyridine, pyrazine, pyrimidine, pyridazine or triazine.
The group in which R ¹¹ or R ¹² is bonded to form a condensed ring is, for example, quinoline, isoquinoline, naphthyridine, phthalazine, quinoxaline, quinzolin, synonine, pteridine, purine, acridine, phenanthridine, phenazine, phenanthroline. . Completed with Z ¹ 6
As the member-containing nitrogen-containing aromatic heterocycle, pyridine, quinoline, isoquinoline and phenanthridine are preferable, pyridine, quinoline and isoquinoline are more preferable, and pyridine is most preferable.

R ¹ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. These are alkyl groups, alkenyl groups, alkynyl groups, hydroxyl groups, mercapto groups, nitro groups, carboxyl groups,
Cyano group, halogen atom, aryl group, heterocyclic group, mercapto-substituted heterocyclic group, alkoxy group, aryloxy group, acylamino group, thioamide group, alkylamino group, anilino group, ureido group, thioureido group, sulfamoylamino group , An alkylthio group, an arylthio group,
Alkoxycarbonylamino group, sulfonamide group, carbamoyl group, thiocarbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyl group, silyloxy group, aryloxycarbonyl Amino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group, aryloxycarbonyl group,
It may be further substituted with a substituent consisting of an acyl group, a thiocarbonyl group and a combination thereof.

An example of R ¹ will be shown in more detail. The alkyl group is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, and examples thereof include methyl, ethyl, propyl, isopropyl, allyl, propargyl, octyl, decyl, dodecyl, Benzyl, 2-
Methoxyethyl, butoxycarbonylmethyl, phenylcarbamoylmethyl.

The alkenyl group has 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms, and examples thereof include vinyl and 2-styryl. The alkynyl group has 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms, and examples thereof include ethynyl and phenylethynyl.

The aryl group is an aryl group having 6 to 24 carbon atoms, preferably 6 to 12 carbon atoms, such as phenyl.
Naphthyl and p-methoxyphenyl. The heterocyclic group is a 5-membered or 6-membered saturated or unsaturated heterocycle containing at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, and the number of heteroatoms constituting the ring. And the number of kinds of elements may be one or more, for example,
2-furyl, 2-thienyl and 4-pyridyl.

R ¹ is preferably an alkyl group, an alkenyl group or an alkynyl group, more preferably an alkyl group or an alkenyl group, and most preferably an alkyl group.

R ¹¹ and R ¹² represent 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 at the carbon atom of R ¹¹ and R ¹² , 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, in which an oxygen atom is bonded, a hydroxy group, an alkoxy group, an aryloxy group, Heterocyclic oxy group, acyloxy group, carbamoyloxy group, sulfonyloxy group,
As a bond with a nitrogen atom, an acylamino group, amino group, alkylamino group, arylamino group, heterocyclic amino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group , An imide group, a heterocyclic group, an alkylthio group as a sulfur atom,
Arylthio group, heterocyclic thio group, sulfamoyl group,
Examples thereof include an alkoxysulfonyl group, an aryloxysulfonyl group, a sulfonyl group, a sulfo group, and a sulfinyl group. These may be further substituted with the groups described as the substituents for R ¹ .

The R ¹¹ and R ¹² will be described in more detail. The halogen atom is, for example, a fluorine atom, a chlorine atom or a bromine atom. 1 to 3 carbon atoms as an alkyl group
0, preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, for example, methyl, ethyl, isopropyl, t-butyl, 1-butylpentyl, benzyl,
3-hexanoyloxypropyl and octadecanoylaminomethyl. Alkenyl group has 2 to 1 carbon atoms
6, such as vinyl, 1-propenyl, 1-hexenyl, styryl and the like. The alkynyl group has 2 to 16 carbon atoms, and examples thereof include ethynyl, 1-butynyl, 1-dodecenyl, phenylethynyl and the like. The aryl group is an aryl group having 6 to 24 carbon atoms, and examples thereof include phenyl, naphthyl and p-methoxyphenyl.

The carbamoyl group has 1 to 25 carbon atoms, and includes, for example, carbamoyl, N-ethylcarbamoyl, N, N-diethylcarbamoyl, N-octylcarbamoyl, N-dodecylcarbamoyl, N-phenylcarbamoyl and N- (3 -Phenoxypropyl) carbamoyl.

The alkoxycarbonyl group has 2 carbon atoms.
~ 18, for example, methoxycarbonyl, benzyloxycarbonyl. The aryloxycarbonyl group has 7 to 18 carbon atoms and is, for example, phenoxycarbonyl. The acyl group has 1 to 18 carbon atoms, and examples thereof include 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 heteroatoms constituting the ring and the number of kinds of elements may be one or more, for example, 2-furyl, 2-thienyl,
2-pyridyl and 2-imidazolyl.

The alkoxy group has 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms and is, for example, methoxy, 2
-Methoxyethoxy and 2-methanesulfonylethoxy. The aryloxy group has 6 to 24 carbon atoms and includes, for example, phenoxy, p-methoxyphenoxy, 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,
It is 2-pyridyloxy. The acyloxy group has 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms, and examples thereof include acetoxy, benzoyloxy and 4-hydroxybutanoyloxy. The carbamoyloxy group has 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms, and examples thereof include N, N-dimethylcarbamoyloxy, N-hexylcarbamoyloxy and N-phenylcarbamoyloxy. The sulfonyloxy group has 1 to 1 carbon atoms
And 6 are, for example, methanesulfonyloxy and benzenesulfonyloxy.

The acylamino group has 1 to 30 carbon atoms,
Preferred are those having 1 to 20 carbon atoms such as acetamide, hexanoamide, and phenoxyacetamide.
The alkylamino group has 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms, and examples thereof include N, N-dimethylamino and N- (2-hydroxyethyl) amino. The arylamino group has 6 to 24 carbon atoms and is, for example, anilino or 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 30 carbon atoms, preferably 1 to 20 carbon atoms, and examples thereof include ureido, methylureido, 3-phenoxypropylureido, N, N-.
They are diethyl ureido and 2-methanesulfonamidoethyl ureido.

The sulfamoylamino group has 0 carbon atoms.
To 16, preferably 0 to 10 carbon atoms, such as methylsulfamoylamino and 2-methoxyethylsulfamoylamino. The alkoxycarbonylamino group has 2 to 16 carbon atoms, preferably 2 to 10 carbon atoms, and is, for example, methoxycarbonylamino group. The aryloxycarbonylamino group has 7 to 24 carbon atoms, for example, phenoxycarbonylamino, 2,6-
It is dimethoxyphenoxycarbonylamino.

The sulfonamide group has 1 to 3 carbon atoms.
0, preferably having 1 to 25 carbon atoms, such as methanesulfonamide, p-toluenesulfonamide, and 2-butoxy-5-t-octylphenylsulfonamide.

The imide group has 4 to 16 carbon atoms, and examples thereof include N-succinimide and N-phthalimide. The heterocyclic group linked by a ring nitrogen atom is a 5- to 6-membered heterocycle consisting of at least one kind of carbon atom, oxygen atom or sulfur atom and a nitrogen atom, and examples thereof include pyrrolidino, morpholino and imidazolino.

The alkylthio group has 1 to 3 carbon atoms.
0, preferably those having 1 to 20 carbon atoms, such as methylthio, 2-phenoxyethylthio, 2-propionyloxyethylthio, and 2-dodecanoyloxyethylthio. The arylthio group has 6 to 24 carbon atoms, and examples thereof include phenylthio and 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
6, preferably those having 0 to 10 carbon atoms, such as sulfamoyl, methylsulfamoyl and phenylsulfamoyl. The alkoxysulfonyl group has 1 to 1 carbon atoms.
16, preferably those having 1 to 10 carbon atoms, such as methoxysulfonyl. The aryloxysulfonyl group has 6 to 24 carbon atoms, preferably 6 to 12 carbon atoms, and is, for example, phenoxysulfonyl. The sulfonyl group has 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms.
And examples thereof include methanesulfonyl and benzenesulfonyl. The sulfinyl group has 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms, and examples thereof include methanesulfinyl and benzenesulfinyl.

R ¹¹ and R ¹² are preferably an alkyl group, an aryl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, a cyano group, an alkoxy group, an aryloxy group, a carbamoyloxy group, an acylamino group, Ureido group, sulfamoylamino group, alkoxycarbonylamino group, sulfonamide group, sulfamoyl group, sulfonyl group, alkylthio group, and more preferably alkyl group, aryl group, carbamoyl group, acylamino group, ureido group, sulfonamide group. , A sulfamoyl group, most preferably an alkyl group, an aryl group, a carbamoyl group, and a sulfamoyl group.

Y ¹ is a counter ion for charge balance, and is an anion or a cation when it has two or more anionic groups in the molecule. Examples of the anion include chlorine ion, bromine ion, iodine ion, p-toluenesulfonate ion, sulfate ion, perchlorate ion, trifluoromethanesulfonate ion, boron tetrafluoride ion, phosphorus hexafluoride ion and the like. Examples of the cation include sodium ion, potassium ion, lithium ion, calcium ion, ammonium ion, tetrabutylammonium ion, and triethylammonium ion. n ¹ is a number required for charge balance, and is 0 when forming an intramolecular salt.

When two R ¹¹ 's combine to form a ring when m ¹ is 2 or more, examples thereof include a 5- to 7-membered aromatic ring and non-aromatic ring, a carbocycle and a heterocycle.

The total number of carbon atoms contained in the substituent substituting on the 5- or 6-membered nitrogen-containing aromatic heterocycle completed by Z ¹ and the carbon number contained in R ¹ is 15 to 40, preferably Is 18 to 30.

The compound represented by (N-1) of the present invention preferably has a ballast group for reducing the diffusivity in order to add it to a specific layer of the silver halide light-sensitive material. The ballast group is preferably one having a total carbon atom number of 8 or more and used in a silver halide photographic coupler.

From the formula (N-1), two radicals free of one arbitrary hydrogen atom are combined to form a bis type structure, preferably the following general formulas (N-2) and (N-
3). General formula (N-2)

[0032]

[Chemical 4]

In the formula, Z ²¹ and Z ²² are Z in formula (N-1).
¹ , ¹ , X ²¹ and X ²² are X ¹ , R ²¹ and R ²² are R ¹¹ , and Y ²
Is synonymous with Y ¹ , m ²¹ and m ²² are synonymous with m ¹ , and n ² is synonymous with n ¹ . R ² is a divalent linking group in which a hydrogen atom is removed from R ¹ (alkylene group, alkenylene group, alkynylene group, arylene group, divalent heterocyclic group and their -O-, -S
-, - NH -, - CO -, - it is the concatenation alone or in comprising a combination groups such) - SO _2. These preferred ones are also the same as in formula (N-1).

The alkylene group for R ² is, for example, ethylene, trimethylene, pentamethylene, octamethylene, propylene, 2-butene-1,4-yl, 2-butyn-1,4-yl or 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. R ² is preferably an alkylene group or an alkenylene group, more preferably an alkylene group.

The total number of carbon atoms contained in the substituent substituting the 5- or 6-membered nitrogen-containing aromatic heterocycle completed by Z ²¹ and Z ²² and the carbon number contained in R ² is 15 to Four
It is 0, preferably 18-30. General formula (N-3)

[0036]

[Chemical 5]

In the formula, Z ³¹ and Z ³² are Z in formula (N-1).
¹ , X ³¹ and X ³² are X ¹ , R ^3a and R ^3b are R ¹ ,
R ³¹ and R ³² are R ¹¹ , Y ³ is Y ¹ , and m ³¹ and m ³² are m ^1.
And n ³ is synonymous with n ¹ . R ³³ is a divalent linking group having a hydrogen atom removed from R ¹¹ . These preferred ones are also the same as in formula (N-1).

The total number of carbon atoms contained in the substituent substituting the 5- or 6-membered nitrogen-containing aromatic heterocycle completed by Z ³¹ and Z ³² and the carbon number contained in R ³³ is 15 to Four
It is 0, preferably 18-30.

Of the compounds of the present invention represented by the general formula (N-1), the following general formulas (N-4) to (N-6) are preferable.
It is represented by. General formula (N-4)

[0040]

[Chemical 6]

In the formula, R ⁴ , R ⁴¹ , m ⁴ , Y ⁴ and n ⁴ have the same meanings as R ¹ , R ¹¹ , m ¹ , Y ¹ and n ^{1 of} formula (N-1), respectively. These preferred ones are also the same as in formula (N-1). General formula (N-5)

[0042]

[Chemical 7]

In the formula, R ⁵ , R ⁵¹ , R ⁵² , m ⁵¹ , m ⁵² , Y
⁵ , n ⁵ are R ² , R ²¹ , R ²² and R ^{22 of} the formula (N-2), respectively.
It has the same meaning as m ²¹ , m ²² , Y ² and n ² . These preferred ones are also the same as in formula (N-2). General formula (N-6)

[0044]

Embedded image

In the formula, R ^6a , R ^6b , R ⁶¹ , R ⁶² , m ⁶¹ , m
⁶² , R ⁶³ , Y ⁶ and n ⁶ are each R ^{3a of} the formula (N-3),
It has the same ^meaning as R ^3b , R ³¹ , R ³² , m ³¹ , m ³² , R ³³ , Y ³ and n ³ . These preferable ones are also the same as those in formula (N-3).

Specific examples of the compound represented by formula (N-1) according to the present invention are shown below, but the invention is not limited thereto.

[0047]

[Chemical 9]

[0048]

[Chemical 10]

[0049]

[Chemical 11]

[0050]

[Chemical 12]

[0051]

[Chemical 13]

[0052]

Embedded image

[0053]

[Chemical 15]

The compound represented by the general formula (N-1) of the present invention was synthesized according to the following synthetic method of a typical compound.

Synthesis Example: Synthesis of Exemplified Compound 2 A mixed solution of 4-phenylpyridine (15.5 g), 1-bromododecane (26.1 g) and ethanol (200 ml) was heated under reflux for 5 hours. The reaction solution was cooled and then poured into ethyl acetate, and the precipitated crystals were collected by filtration. The obtained crystals are 2-
Recrystallized and purified with propanol to obtain the desired product (33.1 g)
I got The chemical structure was confirmed by nmr spectrum and ir spectrum.

Synthesis Example: Synthesis of Exemplified Compound 26 A mixed solution of 4- (1-butylpentyl) pyridine (22.6 g), 1,10-dichlorodecane (10.6 g) and butanol (150 ml) was heated under reflux for 6 hours. did. After cooling the reaction solution, it was poured into ethyl acetate and the precipitated crystals were collected by filtration.
The obtained crystals were recrystallized and purified with 2-propanol to obtain the desired product (19.5 g). The chemical structure was confirmed by nmr spectrum and ir spectrum.

When the compound represented by the general formula (N-1) of the present invention is added to the silver halide light-sensitive material, it is contained in the silver halide emulsion layer or other hydrophilic colloid layer. The time of addition may be any step, but it is preferably added immediately before coating. The addition amount of the compound of the present invention varies depending on the composition and particle size of silver halide grains and the type of compound used, but it is 1 × 10 5 per mol of silver halide.
The range from ^-6 mol to 1 x 10 ^-1 mol is suitable, and 1 x 1
The range of 0 ^-4 mol to 5 × 10 ^-2 mol is preferable, and 1 × 1
A range of 0 ^-3 mol to 1 × 10 ^-2 mol is particularly preferable.

Next, the developing solution used in the present invention will be described. The developer used in the development processing of the light-sensitive material according to the present invention may contain an additive which is usually used (for example, a developing agent, an alkaline agent, a pH buffering agent, a preservative and a chelating agent). Any known method can be used for the development processing of the present invention, and a known development processing solution can be used.

The main developing agent of the developing solution preferably used in the present invention is a compound represented by the general formula (N-11). General formula (N-11)

[0060]

Embedded image

In the formula, R ⁷¹ and R ⁷² each represent a hydroxy group, an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group or an alkylthio group. P and Q represent a hydroxy group, a carboxyl group, an alkoxy group, a hydroxyalkyl group, a carboxyalkyl group, a sulfo group, a sulfoalkyl group, an amino group, an aminoalkyl group, an alkyl group or an aryl group, or P and Q are It represents an atomic group which is bonded to each other to form a 5- to 7-membered ring with two vinyl carbon atoms substituted by R ⁷¹ and R ⁷² and a carbon atom substituted by Y. Y represents = O or = N-R ^73,. R ⁷³ represents a hydrogen atom, a hydroxyl group, an alkyl group, an acyl group, a hydroxyalkyl group, a sulfoalkyl group or a carboxyalkyl group. The developer of the present invention may contain an auxiliary developing agent, among which a p-aminophenol type developing agent and / or
It preferably contains a 1-phenyl-3-pyrazolidone-based auxiliary developing agent.

The formula (N-1) which is the developing agent of the present invention is used.
The compound 1) will be described in detail. General formula (N-1
In 1), R ⁷¹ and R ⁷² are respectively a hydroxy group and an amino group (as a substituent, an alkyl group having 1 to 10 carbon atoms,
For example, those having a methyl group, an ethyl group, an n-butyl group, a hydroxyethyl group or the like as a substituent are included. ), Acylamino group (acetylamino group, benzoylamino group, etc.), alkylsulfonylamino group (methanesulfonylamino group, etc.), arylsulfonylamino group (benzenesulfonylamino group, p-toluenesulfonylamino group, etc.), alkoxycarbonylamino group (Methoxycarbonylamino group, etc.), mercapto group, alkylthio group (methylthio group, ethylthio group, etc.).
Preferred examples of R ⁷¹ and R ⁷² 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 P and Q are bonded to each other, together with the two vinyl carbon atoms substituted by R ⁷¹ and R ⁷² and the carbon atom substituted by Y, It represents an atomic group necessary for forming a 7-membered ring. Specific examples of the ring structure include -O-, -C ( ^R74 ) ( ^R75 ).
-, -C ( ^R76 ) =, -C (= O)-, -N ( ^R77 )
It is configured by combining − and −N =. However, R ⁷⁴ ,
R ⁷⁵ , R ⁷⁶ , and R ⁷⁷ are each a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted (a hydroxy group, a carboxy group, a sulfo group can be mentioned as the substituent), a hydroxy group or a carboxy group. Represent 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, azacyclohexenone ring,
The uracil ring can be mentioned.

Y is a group composed of ═O or ═N—R ⁷³ . Here, R ⁷³ 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), carboxy. Represents an alkyl group (eg carboxymethyl, carboxyethyl). Specific examples of the compound represented by formula (N-11) are shown below, but the invention is not limited thereto.

[0066]

[Chemical 17]

[0067]

[Chemical 18]

[0068]

[Chemical 19]

[0069]

Embedded image

[0070]

[Chemical 21]

[0071]

[Chemical formula 22]

Among these, ascorbic acid or erythorbic acid (diastereomer of ascorbic acid) is preferable. The general range of the amount of the compound of the general formula (N-11) used is 5 × per liter of the developing solution.
10 ⁻³ mol to 1 mol, particularly preferably 10 ⁻² mol to 0.
It is 5 mol.

The developer of the present invention preferably contains an auxiliary developing agent.

As auxiliary developing agents, dihydroxybenzenes (eg, hydroquinone, chlorohydroquinone,
Bromohydroquinone, isopropylhydroquinone,
Methylhydroquinone, 2,3-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,5-dimethylhydroquinone, potassium hydroquinone monosulfonate, sodium hydroquinone monosulfonate, catechol, pyrazole, etc., 3-pyrazolidones (for example, 1 -Phenyl-3-pyrazolidone, 1-phenyl-
4-methyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-phenyl-4-ethyl-
3-pyrazolidone, 1-phenyl-4,4-dimethyl-
3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-
4,4-dihydroxymethyl-3-pyrazolidone, 1,
5-diphenyl-3-pyrazolidone, 1-p-tolyl-
3-pyrazolidone, 1-phenyl-2-acetyl-4,
4-dimethyl-3-pyrazolidone, 1-p-hydroxyphenyl-4,4-dimethyl-3-pyrazolidone, 1-
(2-Benzothiazolyl) -3-pyrazolidone, 3-acetoxy-1-phenyl-3-pyrazolidone, etc.), 3
-Aminopyrazolines (for example, 1- (p-hydroxyphenyl) -3-aminopyrazolidone, 1- (p-methylaminophenyl) -3-aminopyrazoline, 1- (p
-Amino-m-methylphenyl) -3-aminopyrazoline and the like) and phenylenediamines (for example, 4-amino-N, N-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline, 4 -Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-
β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, etc.) can be added.

Furthermore, even when aminophenols are used as an auxiliary developing agent, a high contrast image can be obtained.
As aminophenol developing agents, 4-aminophenol, 4-amino-3-methylphenol, 4- (N-
Methyl) aminophenol, 2,4-diaminophenol, N- (4-hydroxyphenyl) glycine, N-
(2'-hydroxyethyl) -2-aminophenol,
Examples thereof include 2-hydroxymethyl-4-aminophenol, 2-hydroxymethyl-4- (N-methyl) aminophenol, and hydrochlorides and sulfates of these compounds.

The amount of these auxiliary developing agents used is generally in the range of 5 × 10 ^-3 mol to 1 mol, preferably 10 ^-2 mol to 0.5 mol, per liter of the developing solution.

The developer of the present invention preferably contains a preservative and an alkali in addition to the above essential components. Sulfite can be used as a preservative. Examples of sulfites include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium bisulfite, and potassium metabisulfite. The addition amount of these sulfites is preferably 0.5 mol or less per liter of the developing solution.

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. As additives used other than the above, development inhibitors such as sodium bromide and potassium bromide; organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide; alkanolamines such as diethanolamine and triethanolamine, Development accelerators such as imidazole and its derivatives; mercapto compounds, indazole compounds, benzotriazole compounds, benzimidazole compounds as antifoggants or black pep
per) inhibitor may be included. Specifically, 5-nitroindazole, 5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-
Nitroindazole, 3-methyl-5-nitroindazole, 5-nitrobenzimidazole, 2-isopropyl-5-nitrobenzimidazole, 5-nitrobenztriazole, 4-[(2-mercapto-1,3,4-
Thiadiazol-2-yl) thio] butanesulfonate sodium, 5-amino-1,3,4-thiadiazole-
2-thiol, methylbenzotriazole, 5-methylbenzotriazole, 2-mercaptobenzotriazole and the like can be mentioned. The amount of these antifoggants is usually 0.01 to 10 mmol, and more preferably 0.05 to 2 mmol, per liter of the developing solution.

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

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

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

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

The developer used in the present invention contains a carbonate as a buffer, boric acid described in JP-A-62-186259, sugars (eg saccharose) described in JP-A-60-93433, and oximes. (Eg acetoxime),
Phenols (for example, 5-sulfosalicylic acid), tertiary phosphate (for example, sodium salt, potassium salt), aluminic acid (for example, sodium salt) and the like are used, and carbonate and borate are preferably used. The pH of the developer is 9.5
.About.11.5 is preferable, and particularly preferably 9.5 to 11.
The range is 0. Development temperature and time are interrelated and are determined in relation to the total processing time, but generally the development temperature is from about 20 ° C to about 50 ° C, preferably from 25 to 45 ° C.
C., development time 5 seconds to 2 minutes, preferably 7 seconds to 1 minute 3
0 seconds. When processing 1 square meter of a silver halide black and white photographic light-sensitive material, the replenisher amount of the developing solution is 500 ml or less, preferably 400 ml or less. It is preferable to concentrate the treatment liquid and dilute it at the time of use for the purpose of transportation cost of the treatment liquid, packaging material cost, space saving and the like. In order to concentrate the developer, it is effective to potassium salt the salt component contained in the developer.

The fixing solution used in the fixing step 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. Particularly preferably, it is 0.2 to 1.5 mol / liter. If desired, the fixer may include a hardening agent (eg, water-soluble aluminum compound), preservative (eg, sulfite, bisulfite), pH buffer (eg, acetic acid), pH adjuster (eg, ammonia, sulfuric acid). ), A chelating agent, a surfactant, a wetting agent, and a fixing accelerator. Examples of the surfactant include anionic surfactants such as sulfates and sulfonates, polyethylene 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 fixing accelerators include JP-B-45-35754 and JP-A-58-122535.
No. 58-122536, thiourea derivatives, alcohol having triple bond in the molecule, US Pat.
A thioether compound described in JP-A-126459, JP-A-4-
The mesoionic compounds described in JP-A No. 229860 and the like may be mentioned, and the compounds described in JP-A-2-44355 may be used. Examples of the pH buffering agent include organic acids such as acetic acid, malic acid, succinic acid, tartaric acid, citric acid, oxalic acid, maleic acid, glycolic acid, and adipic acid, and inorganic acids such as boric acid, phosphate, and sulfite. A buffer can be used. Acetic acid, tartaric acid, and sulfite are preferably used. Here, the pH buffer is used for the purpose of preventing the pH of the fixing agent from rising due to the carry-in of the developer, and 0.01 to 1.
The amount used is 0 mol / liter, more preferably about 0.02 to 0.6 mol / liter. The pH of the fixer is 4.0 to 6.
5 is preferable, and the range of 4.5 to 6.0 is particularly preferable. Further, as a dye elution accelerator, JP-A-64-47
The compounds described in No. 39 can also be used.

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

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

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

In the present invention, a hydrazine derivative may be contained in the emulsion layer or other hydrophilic colloid layer of the light-sensitive material. The hydrazine derivative used in the present invention is preferably a compound represented by the following general formula (N-21). General formula (N-21)

[0089]

[Chemical formula 23]

In the formula, R ⁸¹ represents an aliphatic group or an aromatic group, and R ⁸² represents a hydrogen atom, an alkyl group, an aryl group, an unsaturated heterocyclic group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group. G ⁸¹ is a —CO— group,
-SO ₂ - group, -SO- group,

[0091]

[Chemical formula 24]

Represents a --CO--CO-- group, a thiocarbonyl group, or an iminomethylene group, wherein A ⁸¹ and A ⁸² 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 ⁸³ is selected from the same range as the groups defined in R ^82, may be different from R ^82.

In the general formula (N-21), the aliphatic group represented by R ⁸¹ preferably has 1 to 30 carbon atoms, and particularly preferably has 1 to 20 carbon atoms and is a linear, branched or cyclic alkyl group. Is. Here, the branched alkyl group may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Moreover, this alkyl group may have a substituent. General formula (N-2
In 1), the aromatic group represented by R ⁸¹ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group. For example, benzene ring, naphthalene ring, pyridine ring, pyrimidine ring,
There are an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, a benzothiazole ring and the like, and among them, those containing a benzene ring are preferable. Particularly preferred as R ⁸¹ is an aryl group. The aliphatic group or aromatic group of R ⁸¹ may be substituted, and typical examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group-containing group, a pyridinium group, a hydroxy group, Alkoxy group, aryloxy group, acyloxy group, alkyl or aryl sulfonyloxy group, amino group, carbonamide group, sulfonamide group, ureido group, thioureido group, semicarbazide group, thiosemicarbazide group, urethane group, group having a hydrazine structure, 4 Group having a primary ammonium structure, alkyl or arylthio group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group, carboxyl group, sulfo group, acyl group,
Alkoxy or aryloxycarbonyl group, carbamoyl group, sulfamoyl group, halogen atom, cyano group,
Examples thereof include a phosphoric acid amide group, a diacylamino group, an imide group, a group having an acylurea structure, a group containing a selenium atom or a tellurium atom, and a group having a tertiary sulfonium structure or a quaternary sulfonium structure. Chain, branched or cyclic alkyl group (preferably having 1 carbon atom)
To 20), an aralkyl group (preferably a monocyclic or bicyclic alkyl group having 1 to 3 carbon atoms), an alkoxy group (preferably having 1 to 20 carbon atoms), a substituted amino group (preferably Amino group substituted with alkyl group having 1 to 20 carbon atoms, acylamino group (preferably having 2 carbon atoms)
To 30), sulfonamide group (preferably having 1 to 30 carbon atoms), ureido group (preferably having 1 to 30 carbon atoms), phosphoric acid amide group (preferably having 1 to 30 carbon atoms) Stuff).

In the general formula (N-21), the alkyl group represented by R ⁸² is preferably an alkyl group having 1 to 4 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group, For example, it contains a benzene ring. The unsaturated heterocyclic group is a compound having a 5- or 6-membered ring containing at least one nitrogen, oxygen, and sulfur atom, for example, imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, pyridyl group, pyridinium group,
Examples include quinolinium group and quinolinyl group. A pyridyl group or a pyridinium group is particularly preferable. The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms,
The aryloxy group is preferably a monocyclic one, and the amino group is preferably an unsubstituted amino group, and an alkylamino group having 1 to 10 carbon atoms or an arylamino group. R ⁸² may be substituted, and as the preferable substituent, those exemplified as the substituent of R ⁸¹ are applicable. Of the groups represented by R ⁸² , preferred is a hydrogen atom, an alkyl group (eg, methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfone) when G ⁸¹ is a —CO— group. Amidopropyl group, phenylsulfonylmethyl group etc.), aralkyl group (eg o-hydroxybenzyl group etc.), aryl group (eg phenyl group,
3,5-dichlorophenyl group, o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, 2-
(E.g., a hydroxymethylphenyl group) and the like, and a hydrogen atom and a trifluoromethyl group are particularly preferable. When G ⁸¹ is a —SO ₂ — group, R ⁸² is an alkyl group (eg,
A methyl group etc.), an aralkyl group (eg o-hydroxybenzyl group etc.), an aryl group (eg phenyl group etc.) or a substituted amino group (eg dimethylamino group etc.) are preferable. When G ⁸¹ is a -COCO- group, an alkoxy group, an aryloxy group and an amino group are preferable. As G ^{81 in the} general formula (N-21), —CO— group,
A COCO- group is preferred, and a -CO- group is most preferred.
R ⁸² also splits the G ⁸¹ -R ⁸² portion from the rest of the molecule,
It may be one that causes a cyclization reaction to form a cyclic structure containing atoms of the —G ⁸¹ and —R ⁸² moieties, and examples thereof include those described in JP-A-63-29751. There are things.

A ⁸¹ and A ⁸² 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-).
Phenylsulfonyl group substituted to be 0.5 or more), acyl group having 20 or less carbon atoms (preferably benzoyl group, or substituted so that the sum of Hammett's substituent constants is -0.5 or more) A benzoyl group, or a linear, branched, or cyclic unsubstituted or substituted aliphatic acyl group (as the substituent, for example, a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group, a sulfonic acid group Can be mentioned)). A ⁸¹ , A ⁸²
Is most preferably a hydrogen atom.

The substituents of R ⁸¹ and R ⁸² in formula (N-21) may be further substituted, and a preferable example is R
Those exemplified as the substituent of ⁸¹ can be mentioned. Further, the substituent, the substituent of the substituent, the substituent of the substituent of the substituent, ..., may be multiply substituted,
Preferred examples are also those exemplified as the substituents of R ⁸¹ .

R ⁸¹ or R ⁸² of the general formula (N-21) may have a ballast group or a polymer incorporated therein which is commonly used in a non-moving photographic additive such as a coupler. The ballast group has 8 or more carbon atoms,
It is a group relatively inert to photographic properties, and can be selected from, for example, an alkyl group, an aralkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group and the like. Examples of the polymer include those described in JP-A No. 1-100530.

R ⁸¹ or R ^{82 in the} general formula (N-21) may have a group incorporated therein to enhance adsorption to the surface of the silver halide grain. Examples of the adsorptive group include alkylthio groups, arylthio groups, thiourea groups, heterocyclic thioamide groups, mercaptoheterocyclic groups, and triazole groups.
9,347, JP-A-59-195233, 59-59.
No. 200231, No. 59-201045, No. 59-2
No. 01046, No. 59-201047, No. 59-20
No. 1048, No. 59-201049, and JP-A-61-1.
70733, 61-270744, 62-94.
No. 8, No. 63-234244, No. 63-234245.
And the groups described in JP-A No. 63-234246.

Particularly preferred hydrazine derivative in the present invention is that R ⁸¹ is a ballast group through a sulfonamide group, an acylamino group or a ureido group, a group which promotes adsorption to the surface of silver halide grains, a group having a quaternary ammonium structure, Or a phenyl group having an alkylthio group, G ⁸¹ is a -CO- group, R ⁸² is a hydrogen atom, a substituted alkyl group or a substituted aryl group (the substituent is an electron-withdrawing group or a hydroxymethyl group at the 2-position). Is preferred)
Is a hydrazine derivative. Note that any combination of the above R ⁸¹ and R ⁸² options is possible and preferable.

Specific examples of the compound represented by formula (N-21) are shown below. However, the present invention is not limited to the following compounds.

[0101]

[Chemical 25]

[0102]

[Chemical formula 26]

[0103]

[Chemical 27]

[0104]

[Chemical 28]

[0105]

[Chemical 29]

[0106]

[Chemical 30]

[0107]

[Chemical 31]

[0108]

[Chemical 32]

[0109]

[Chemical 33]

[0110]

Embedded image

[0111]

Embedded image

As the hydrazine derivative used in the present invention, in addition to the above, RESEARCH DISCLOSURE Item 2
3516 (November 1983, p. 346) and references cited therein, as well as U.S. Pat. No. 4,080,20.
No. 7, No. 4,269,929, No. 4,276,364
Nos. 4,278,748, 4,385,108
Issue No. 4,459,347 Issue No. 4,478,928
Nos. 4,560,638 and 4,686,167
No. 4,912,016, 4,988,604
Issue No. 4,994,365 Issue 5,041,355
No. 5,104,769, British Patent No. 2,011,
391B, European Patent Nos. 217,310 and 301,
799, 356, 898, JP-A-60-1797.
34, 61-170733, 61-27074.
No. 4, No. 62-178246, No. 62-270948.
No. 63, No. 63-29751, No. 63-32538, No. 63-104047, No. 63-121838, No. 6
3-129337, 63-223744, 63
-234244, 63-234245, 63-
234246, 63-294552, 63-3
06438, 64-10233 and JP-A-1-90.
No. 439, No. 1-100530, No. 1-105941
No. 1, No. 1-105943, No. 1-276128, No. 1-280747, No. 1-283548, No. 1-2.
83549, 1-285940, 2-2541.
No. 2, No. 2-77057, No. 2-139538, No. 2
-196234, 2-196235, 2-19
No. 8440, No. 2-198441, No. 2-19844
No. 2, No. 2-220042, No. 2-221953,
2-221954, 2-285342, 2-
285343, 2-289843, 2-302
No. 750, No. 2-304550, No. 3-37642
No. 3, No. 3-54549, No. 3-125134, No. 3
-184039, 3-240036, 3-24
No. 0037, No. 3-259240, No. 3-28003
No. 8, No. 3-228536, No. 4-51143, No. 4-56842, No. 4-84134, No. 2-230.
No. 233, No. 4-96053, No. 4-21654,
No. 5-45761, No. 5-45762, No. 5-45
No. 763, No. 5-45764, No. 5-45765,
What was described in Japanese Patent Application No. 5-94925 can be used.

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

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

The silver halide emulsion used in the present invention may have a composition of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver iodochlorobromide and the like. As a method for preparing the silver halide emulsion used in the present invention, various methods known in the field of silver halide photographic light-sensitive materials are used. For example, P. Glafkides "Chimie et Physique Photographique" (Paul Mantel, 1967), GF Duffinu "GFDuffinu" Photographic E, chemistry
mulsion Chemistry) (The F)
Ocal Press), 1966) by VL Zemlikman et al., "Making and.
Coating Photographic Emulsion (Ma
kig and Coating Photographic Emulsion) "(Published by The Focal Press, 1964)
And the like. The emulsion of the present invention is preferably a monodisperse emulsion and has a coefficient of variation of 2
It is 0% or less, particularly preferably 15% or less. Here, the coefficient of variation is {(standard deviation of particle size) / (average particle size)} × 1
It is a numerical value represented by 00.

The average grain size of grains in the monodisperse silver halide emulsion is 0.5 μm or less, and particularly preferably 0.
It is 1 μm to 0.4 μm. As a method for reacting the water-soluble silver salt (silver nitrate aqueous solution) with the water-soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. As one type of simultaneous mixing method, a method of keeping pAg constant in a liquid phase in which silver halide is produced, that is, a control double jet method can be used. Further, it is preferable to form grains using a so-called silver halide emulsion such as ammonia, thioether, substituted thiourea. Substituted thiourea compounds are more preferred, and JP-A-53-82408 and JP-A-55-77737 are preferred.
No. etc. A preferred thiourea compound is tetramethylthiourea, 1,3-dimethyl-2-imidazolidinethione. In the control double jet method and the grain forming method using a silver halide solvent,
It is easy to prepare a silver halide emulsion having a regular crystal form and a narrow grain size distribution, and it is a useful means for preparing the emulsion used in the present invention. The monodisperse emulsion preferably has a regular crystal form such as a cube, an octahedron and a tetradecahedron, and a cube is particularly preferable. The silver halide grains may have a uniform phase in the inside and the surface layer, or may have different phases.

In the present invention, a silver halide emulsion particularly suitable as a light-sensitive material for line drawing and halftone dot formation is silver 1
It is an emulsion produced in the presence of 10 ⁻⁸ to 10 ⁻⁵ mol of iridium salt or its complex salt per mol. In the present invention, a silver halide emulsion which is particularly suitable as a reversal light-sensitive material is a silver halide containing 90 mol% or more, and more preferably 95% mol or more of silver chloride.
It is 0 mol% silver chlorobromide or silver chloroiodobromide. If the proportion of silver bromide or silver iodide is increased, the safety of safelight in a bright room is deteriorated or γ is decreased, which is not preferable.

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

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

As the selenium sensitizer used in the present invention, known selenium compounds can be used. That is, it is usually carried out by adding an unstable and / or unstable selenium compound and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain period of time. Unstable selenium compounds are disclosed in JP-B-44-15748 and JP-B-43-1.
3489, JP-A-4-25832, and 4-1092.
No. 40, No. 4-324855, etc. can be used. It is particularly preferable to use the compounds represented by the general formulas (VIII) and (IX) in JP-A-4-324855.

The tellurium sensitizer used in the present invention is a compound that forms silver telluride, which is presumed to be a sensitizing nucleus, on the surface or inside of the silver halide grain. Regarding the rate of silver telluride formation in a silver halide emulsion, Japanese Patent Application No. 4-
It can be tested by the method described in 146739.
Specifically, US Pat. Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211 and 1,121,496.
No. 1, No. 1,295,462, No. 1,396,69
6, Canadian Patent No. 800,958, Japanese Patent Laid-Open No. 4-20
No. 4640, No. 4-271341, No. 4-33304
No. 3, No. 4-129787, J. Chem. Soc. Chem. Commu
n., 635 (1980), ibid. 1102 (1979), ibid. 645 (1979), J. Chem. Soc. Perkin.Trans., 1,
2191 (1980), edited by S. Patai, The Chemistry of
OrganicSerenium and Tellurium Compounds.Voll (1
986) and Vo12 (1987) can be used. The compounds represented by formulas (II), (III) and (IV) in JP-A-4-146739 are particularly preferable.

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

Examples of the noble metal sensitizer used in the present invention include gold, platinum and palladium, with gold sensitization being particularly preferred. Specific examples of the gold sensitizer for use in the present invention include chloroauric acid, potassium chlorate, potassium Orichi isothiocyanate, include such gold sulfide, a 10 ^-7 to 10 ^-2 mol per mol of silver halide 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 or the like may coexist in the process of forming silver halide grains or in the process of physical ripening. Reduction sensitization can be used in the present invention. As the reduction sensitizer, stannous salt, amines, formamidinesulfinic acid, silane compound and the like can be used. A thiosulfonic acid compound may be added to the silver halide emulsion of the present invention by the method shown in EP 293,917. The silver halide emulsion in the light-sensitive material used in the present invention may be one kind or two or more kinds (for example, those having different average grain sizes, different halogen compositions, different crystal habits, chemically sensitized ones). (Under different conditions) may be used together.

The silver halide photographic light-sensitive material of the present invention may contain a rhodium compound in order to achieve high contrast and low fog. As the rhodium compound used in the present invention, a water-soluble rhodium compound can be used. For example, a rhodium (III) halide compound, or a rhodium complex salt having a halogen, amines, oxalate, etc. as a ligand, for example, hexachlororhodium (I
II) Complex salt, hexabromorhodium (III) complex salt, hexaamminerhodium (III) complex salt, trizalatrodium (III)
Complex salts and the like can be mentioned. These rhodium compounds are used by dissolving them in water or a suitable solvent, and they are generally used for stabilizing the solution of the rhodium compound, that is, an aqueous solution of hydrogen halide (for example, hydrochloric acid,
A method of adding bromic acid, hydrofluoric acid, etc.) or an alkali halide (eg, KCl, NaCl, KBr, NaBr, etc.) can be used. Instead of using water-soluble rhodium, it is also possible to add and dissolve another silver halide grain which has been previously doped with rhodium when preparing the silver halide.

The total addition amount of the rhodium compound is 1 × 10 ^{-8 to} 5 × 1 per mol of the finally formed silver halide.
0 ^-6 mol is suitable, and preferably 5 x 10 ^-8 to 1 x 1
It is 0 ^-6 mol. The addition of these compounds can be appropriately carried out at the time of producing silver halide emulsion grains and at each stage before coating the emulsion, but it is particularly preferable to add them at the time of emulsion formation and to be incorporated in the silver halide grains. preferable.

The silver halide photographic light-sensitive material of the present invention may contain an iridium compound in order to achieve high sensitivity and high contrast. As the iridium compound used in the present invention, various compounds can be used, and examples thereof include hexachloroiridium, hexaammineiridium, trioxalatoiridium, hexacyanoiridium and the like. These iridium compounds are used by dissolving them in water or a suitable solvent, and a method that is generally performed to stabilize the solution of the iridium compound,
That is, a method of adding an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid, etc.) or an alkali halide (for example, KCl, NaCl, KBr, NaBr, etc.) can be used. Instead of using water-soluble iridium, it is also possible to add and dissolve another silver halide grain which has been previously doped with iridium when preparing the silver halide.

The total amount of the iridium compound added is 1 × 10 ^{-8 to} 5 × per mol of the finally formed silver halide.
10 ⁻⁶ mol is suitable, and preferably 1 × 10 ⁻⁸ to 1 ×.
It is 10 ^-6 mol. The addition of these compounds can be appropriately carried out at the time of producing silver halide emulsion grains and at each stage before coating the emulsion, but it is particularly preferable to add them at the time of emulsion formation and to be incorporated in the silver halide grains. preferable.

The silver halide grains used in the present invention include
It may contain metal atoms such as iron, cobalt, nickel, ruthenium, palladium, platinum, gold, thallium, copper, lead and osmium. The metal is preferably 1 × 10 ⁻⁹ to 1 × 10 ⁻⁴ mol per mol of silver halide. Further, in order to contain the above metal, a metal salt in the form of a single salt, a double salt or a complex salt can be added and added at the time of preparation of particles.

The silver halide grains used in the silver halide photographic light-sensitive material of the present invention may contain at least one metal selected from rhenium, ruthenium and osmium. This content is 1 × 10 ⁻⁹ to 1 mol of silver.
The range of 1 × 10 ^-5 mol is preferable, and further 1 × 10 ^-8
The range of ^x1x10-6 is preferable. Two or more of these metals may be used in combination. These metals can be uniformly contained in the silver halide grains, and are disclosed in JP-A-63-29.
No. 603, JP-A Nos. 2-306236 and 3-1675.
No. 45, No. 4-76534, Japanese Patent Application No. 4-68305
No. 4,258,187, etc., it is also possible to have a distribution in the particles to contain them. Rhenium, ruthenium and osmium are disclosed in JP-A-63-2042.
No. 2, Unexamined Japanese Patent Publication No. 1-285941, No. 2-20852,
It is added in the form of a water-soluble complex salt described in JP-A-2-20855. Particularly preferred are hexacoordinated complexes represented by the following formulas. [ML ₆ ] _-n where M
Represents Ru, Re, or Os, and n is 0, 1, 2,
Represents 3 or 4. In this case, the counterion has no significance and ammonium or alkali metal ions are used. Further, preferred ligands include halide ligands, cyanide ligands, cyan oxide ligands, nitrosyl ligands, thionitrosyl ligands and the like. Examples of specific complexes used in the present invention are shown below, but the present invention is not limited thereto.

[ReCl ₆ ] ^-3 [ReBr ₆ ] ^-3 [ReCl ₅ (NO)] ^-2 [Re (NS) Br ₅ ] ^-2 [Re (NO) (CN) ₅ ] ^-2 [Re (O ) ₂ (NO) ₄ ] ^-3 [RuCl ₆ ] ^-3 [RuCl ₄ (H ₂ O) ₂ ] ^-1 [RuCl ₅ (NO)] ^-2 [RuBr ₅ (NS)] ^-2 [Ru (CN) _6] ^-4 [Ru (CO) ₃ Cl _3] ^-2 [Ru (CO) Cl _5] ^-2 [Ru (CO) Br _5] ^-2 [OsCl _6] ^-3 [OsCl ₅ (NO)] ^-2 [Os (NO) (CN) ₅ ] ^-2 [Os (NS) Br ₅ ] ^-2 [Os (CN) ₆ ] ^-4 [Os (O) ₂ (CN) ₄ ] ^-4

The addition of these compounds can be appropriately carried out at the time of producing silver halide emulsion grains and at each stage before coating the emulsion.
It is preferably incorporated into silver halide grains. In order to add these compounds to the silver halide grains by adding them during grain formation of silver halide, a powder of a metal complex or an aqueous solution dissolved with NaCl or KCl is used to form a water-soluble salt or a water-soluble salt during grain formation. Method in which it is added to the basic halide solution, or when a silver salt and a halide solution are simultaneously mixed, and added as a third solution to prepare silver halide grains by a three-liquid simultaneous mixing method, or grain formation There is a method in which a necessary amount of an aqueous solution of a metal complex is charged into a reaction vessel. Especially powder or NaCl, KCl
A method in which an aqueous solution dissolved together with is added to the water-soluble halide solution is preferable. To add to the surface of the particles, a necessary amount of an aqueous solution of the metal complex can be added to the reaction solution immediately after the particles are formed, during or after physical ripening, or during chemical ripening. The silver halide grain in the present invention may be doped with another heavy metal salt. In particular, K ₄ [Fe (C
Doping with Fe salts, such as N) ₆ ], is advantageous. Further, in the present invention, other metals included in Group VIII, namely, cobalt, nickel, iridium, palladium,
You may use platinum etc. together. In particular, the combined use with iridium salts such as iridium chloride and ammonium hexachloroiridium (III) is advantageous because a high-sensitivity and high-contrast emulsion can be obtained.

A spectral sensitizing dye selected according to the exposure wavelength can be added to the silver halide emulsion layer used in the present invention. 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. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance that does not substantially absorb visible light and exhibits supersensitization may be included in the emulsion. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosure (Research Disclosure).
Disclosure) 176, 17643 (published December 1978), page 23, IV, paragraph J. The content of the sensitizing dye of the present invention depends on the grain size of the silver halide emulsion, the halogen composition, the method and degree of chemical sensitization, the relationship between the layer containing the compound and the silver halide emulsion, the type of antifoggant compound, and the like. It is desirable to select the optimum amount accordingly, and the test method for the selection is well known to those skilled in the art.
Usually, it is preferably used in the range of 10 ^-7 to 1 × 10 ^-2 mol, particularly 10 ^-6 to 5 × 10 ^-3 mol per mol of silver halide.

Gelatin is advantageously used as a binder for the protective colloid of the photographic emulsion or the other hydrophilic colloid layer of the emulsion layer, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol. , Polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone,
Various synthetic hydrophilic polymer substances such as single or copolymers of polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole and the like can be used. As the gelatin, acid-treated gelatin may be used in addition to lime-treated gelatin, and gelatin hydrolyzate and gelatin enzyme-decomposed product may also be used.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process of the light-sensitive material, during storage or during photographic processing or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitrobenzotriazoles, Etc .; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,
3,3a, 7) Tetrazaindenes), pentaazaindenes, etc .; Hydroquinone and its derivatives; Disulfides such as thioctic acid; Antifoggants such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. Alternatively, many compounds known as stabilizers can be added. Among these, preferred are benzotriazoles (eg, 5
-Methyl-benzotriazole) and nitroindazoles (eg 5-nitroindazole). Also,
These compounds may be contained in the treatment liquid.

The light-sensitive material of the present invention may contain an organic desensitizer. Preferred organic desensitizers have at least one water-soluble group or alkali-labile group. These preferred organic desensitizers are exemplified in US Pat. No. 4,908,293. When an organic desensitizer is used, 1.0 × 10 ^{−8 to} 1.0 × 10 ⁻⁴ mol / m ² , preferably 1.0 × 10 ^{−7 to} 1.0 × 10 ^{− in the} silver halide emulsion layer. ^It is suitable that ⁵ mol / m ^{2 is} present.

The light-sensitive material of the present invention may contain a development accelerator. Suitable development accelerators or nucleation-infectious development accelerators for use in the present invention are disclosed in JP-A-53-77616.
No. 54, No. 54-37732, No. 53-137, 133.
No. 60, No. 60-140, No. 340, No. 60-14959.
No., etc. In addition to the compounds, various compounds containing N or S atoms are effective.

Although the optimum addition amount of these accelerators varies depending on the kind of the compound, 1.0 × 10 ^{−3 to} 0.5 g / m ² ,
It is preferably used in the range of 5.0 × 10 ^{−3 to} 0.1 g / m ² . These promoters are suitable solvents (H
₂ O) dissolved in alcohols such as methanol and ethanol, acetone, dimethylformamide, methylcellosolve, etc.) and added to the coating solution. You may use these additives together in multiple types.

The emulsion layer of the present invention or the other hydrophilic colloid layer may contain a dye as a filter dye or for various purposes such as prevention of irradiation. As a filter dye, a dye for further reducing photographic sensitivity, preferably an ultraviolet absorber having a spectral absorption maximum in the intrinsic sensitivity region of silver halide, and safety against safelight light when handled as a light-sensitive material A dye having substantial light absorption mainly in the region of 310 nm to 600 nm is used to enhance the light emission. These dyes are added to the emulsion layer according to the purpose, or added together with a mordant to the upper part of the silver halide emulsion layer, that is, to the non-photosensitive hydrophilic colloid layer farther from the silver halide emulsion layer with respect to the support. It is preferable to fix it before use. It depends on the molar absorption coefficient of the dye, but usually 10 ^-3 g / m ^{2 -1}
It is added in the range of g / m ² . Preferably 10 mg to 500
It is mg / m ² . The above dye can be added to the coating solution after being dissolved or dispersed in an appropriate solvent [eg, water, alcohol (eg, methanol, ethanol, propanol, etc.), acetone, methyl cellosolve, etc., or a mixed solvent thereof]. These dyes can be used in combination of two or more kinds. Specific examples of these dyes are described in US Pat. No. 4,908,293. Other,
US Pat. Nos. 3,533,794 and 3,314,794
No. 3,352,681, JP-A-46-2784
U.S. Pat. Nos. 3,705,805 and 3,707,3.
No. 75, No. 4,045,229, No. 3,700,45
5, 3,499,762, West German patent application publication 1,
The ultraviolet absorbing dyes described in 547, 863, etc. are also used. In addition, pyrazolone oxonol dyes described in US Pat. No. 2,274,782, US Pat.
956,879, diarylazo dyes, US Pat. Nos. 3,423,207 and 3,384,487, styryl dyes and butadienyl dyes, and US Pat. No. 2,527,583. Merocyanine dyes, US Pat. Nos. 3,486,897 and 3,652,284
No. 3,718,472, merocyanine dyes and oxonol dyes, and US Pat. No. 3,976,661.
No. 584,609, No. 1,177,429, JP-A Nos. 48-85130, 49-99620, and 49-
114420, US Pat. Nos. 2,533,472, 3,148,187, and 3,177,078,
No. 3,247,127, No. 3,540,887
No. 3,575,704, No. 3,653,90
The dye described in No. 5 can also be used.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers. For example, chromium salts (chromium yoban, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldeside, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane). Etc.), active vinyl compounds (1, 3,
5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc., active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid) , Mucophenoxycyclo acid, etc.), an epoxy compound (tetramethylene glycol diglycidyl ether, etc.), an isocyanate compound (hexamethylene diisocyanate, etc.), etc. can be used alone or in combination. Also, JP-A-56-66841
U.S. Pat. No. 1,322,971 and U.S. Pat. No. 3,67
The polymer hardeners described in No. 1,256 can also be used.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced according to the present invention has a coating aid, an antistatic agent, an improvement in slipperiness, an emulsion dispersion, an adhesion prevention and an improvement in photographic characteristics (for example, development acceleration). , Contrast enhancement, sensitization), and various other surfactants may be included. For example, saponin (steroidal), alkylene oxide derivative (eg polyethylene glycol, polyethylene glycol /
Polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, silicone polyethylene oxide adducts), glycidol derivatives ( Non-ionic surfactants such as alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkyls Naphthalene sulfonate, alkyl sulfates, alkyl phosphates, N-acyl-N-alk Such as taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc., such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc. Anionic surfactants containing acidic groups; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric acids or phosphoric acid esters, alkylbetaines, amine oxides; alkylamine hydrochloric acid, aliphatic or aromatic primary surfactants. Quaternary ammonium salts, pyridinium,
Heterocyclic quaternary ammonium salts such as imidazolium,
And cationic surfactants such as phosphonium or sulfonium salts containing aliphatic or heterocyclic rings can be used. Particularly, the surfactant preferably used in the present invention has a molecular weight of 60 described in JP-B-58-9412.
It is 0 or more polyalkylene oxides. Also, a polymer latex such as a polyalkyl acrylate may be incorporated for dimensional stability.

The present invention may include a conductive metal oxide. The conductive metal oxides are crystalline metal oxide particles, but generally include those containing oxygen vacancies and those containing a small amount of different atoms forming donors with respect to the metal oxide used. It is particularly preferable because it has high conductivity, and the latter is particularly preferable because it does not cause fog in the silver halide emulsion. Examples of metal oxides include ZnO, TiO ₂ ,
SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , Mg
O, BaO, MoO ₃ , V ₂ O _{5 and the} like or composite oxides thereof are preferable, and ZnO, TiO ₂ and SnO ₂ are particularly preferable. Examples of containing different kinds of atoms include, for example, addition of Al, In, etc. to ZnO, Sb to SnO ₂ ,
It is effective to add Nb, a halogen element or the like, or add Nb, Ta or the like to TiO ₂ .

The addition amount of these hetero atoms is preferably in the range of 0.01 mol% to 30 mol%, particularly 0.1 mol% to
A range of 10 mol% is preferable. The metal oxide fine particles of the present invention have conductivity, and their volume resistivity is 10 ⁷ Ω-c.
It is preferably m or less, particularly 10 ⁵ Ω-cm or less.
Regarding these oxides, JP-A-56-143431
No. 56-120519 and No. 58-62647. Furthermore, as described in JP-B-59-6235, a conductive layer material obtained by adhering the above-mentioned metal oxide to other crystalline metal oxide particles or fibrous material (for example, titanium oxide) may be used. . The particle size that can be used is preferably 10 μm or less, but when it is 2 μm or less, stability after dispersion is good and it is easy to use. Further, in order to make the light scattering property as small as possible, it is very preferable to use the conductive particles of 0.5 μm or less because a transparent photosensitive material can be formed. When the conductive material is needle-shaped or fibrous, the length is preferably 30 μm or less and the diameter is 2 μm or less, and particularly preferably, the length is 25 μm or less and 0.5 μm or less. Is 3 or more. In the present invention, these conductive metal oxides are preferably added to the antihalation layer, back layer and undercoat layer.

There are no particular restrictions on the various additives and the like used in the light-sensitive material of the present invention, and for example, those described in the following relevant parts can be preferably used. Item This section 1) Spectral sensitizing dye JP-A-2-12236, page 8, lower left column, line 13 to same, lower right column, line 4, and JP-A-2-103536, page 16, lower right column, line 3 See page 17, lower left column, line 20, and further JP-A Nos. 1-112235, 2-48653, 2-105135, 2-124560, 3-7928, and 3-67242. No. 5-11389, Japanese Patent Application No. 3-41 1064, and No. 4-354748, the spectral sensitizing dyes. 2) Nucleation accelerator A compound represented by the general formula (I), (II), (III), (IV), (V) or (VI) described in Japanese Patent Application No. 4-237366. JP-A-2-103536, page 9, right upper column, line 13 to page 16, upper left column, line 10 of the general formulas (II-m) to (II-p) and compounds II-1 to II-22. , Compounds described in JP-A-1-179939. 3) Surfactant, antistatic JP-A-2-12236, page 9, upper right column, line 7 to agent, same as lower right column, line 7 and JP-A-2-18542, page 2, lower left column, line 13 to same Page 4, lower right column 18, line 18. 4) Antifoggants and Stabilizers JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5 Furthermore, the thiosulfinic acid compounds described in JP-A-1-237538. 5) Polymer latex JP-A-2-103536, page 18, lower left column, lines 12 to 20. 6) Compounds having an acid group JP-A-2-103536, page 8, lower right column, line 5 to page 19, upper left column, line 1 and page 2-55349, page 8 lower right column, line 13 To page 11, upper left column, line 8. 7) Matting agent, slipping agent, possible JP-A-2-103536, page 19, upper left column, line 15 Plasticizer to page 19, upper right column, line 15 8) Hardeners, JP-A-2-103536, page 18, upper right column, lines 5 to 17; 9) Dyes, JP-A-2-103536, page 17, lower right column, lines 1 to 18; JP-A-2-39042, page 4, upper right column, line 1 to page 6, upper right column, line 5. Furthermore, the solid dyes described in JP-A-2-294638 and JP-A-5-11382. 10) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 20. 11) Anti-black spot agent Compounds described in U.S. Pat. No. 4,956,257 and JP-A-1-118832. 12) Redox compounds Compounds represented by formula (I) in JP-A No. 2-301743 (particularly compound examples 1 to 50), and general formula (R in pages 3 to 20 of JP-A No. 3-174143) -1), (R-2), (R-3), compound examples 1 to 75, and compounds described in Japanese Patent Application No. 3-69466 and Japanese Patent Application Laid-Open No. 4-278939. 13) Monomethine compounds Compounds of general formula (II) described in JP-A-2-287532 (particularly compounds II-1 to II-26). 14) Dihydroxybenzene Compounds described in JP-A-3-39948, page 11, upper left column to category 12, page 12 lower left column, and European Patent No. 452,772A.

[0145]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

Example 1 <Preparation of silver halide photographic light-sensitive material> Emulsion preparation Emulsion A was prepared by the following method. [Emulsion A] Aqueous silver nitrate solution, potassium bromide, sodium chloride and K ₃ corresponding to 3.5 × 10 ^-7 mol per mol of silver
IrCl ₆ and K ₂ Rh (H ₂ O) Cl ₅ equivalent to 2.0 × 10 ⁻⁷ mol
Halogen salt aqueous solution containing sodium chloride, 1,3-
The mixture was added to a gelatin aqueous solution containing dimethyl-2-imidazolidinethione by a double jet method with stirring to prepare silver chlorobromide grains having an average grain size of 0.25 μm and a silver chloride content of 70 mol%.

Then, after washing with water by the flocculation method according to a conventional method, 40 g of gelatin was added per 1 mol of silver, and further 7 mg of sodium benzenethiosulfonate and 2 mg of benzenesulfinic acid were added per 1 mol of silver.
Adjusted to H6.0 and pAg7.5, 2mg per mol of silver
6 of sodium thiosulfate and 4 mg of chloroauric acid
Chemical sensitization was performed so that the optimum sensitivity was obtained at 0 ° C. Then, 4-hydroxy-6-methyl-1,3,3 as a stabilizer
150 mg of a, 7-tetrazaindene was added, and further 100 mg of proxel was added as a preservative. The obtained grains each have an average grain size of 0.25 μm and a silver chloride content of 7
It was 0 mol% of silver chlorobromide cubic grains. (Variation coefficient 1
0%)

Preparation of Coating Sample On a polyethylene terephthalate film support having a moistureproof layer undercoat containing vinylidene chloride, from the support side,
Samples 101 to 120 were prepared by sequentially coating so as to have a layer structure of a UL layer, an EM layer, a PC layer, and an OC layer. The preparation method and coating amount of each layer are shown below.

(UL layer) To a gelatin aqueous solution, a dispersion of 30 wt% of polyethyl acrylate with respect to gelatin was added and coated so as to have gelatin of 0.5 g / m ² .

[0150] in (EM layer) above emulsions 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), further 3 × 10 ^-4 mol of mercapto compound represented by the following (a), 4 × 10 ^-4 mol of mercapto compound represented by (b), and 4 × 10 ^-4 mol of (c) per 1 mol of silver The triazine compound, 2 × 10 ⁻³ mol of 5-chloro-8-hydroxyquinoline was added. Further, the onium salt compound of the present invention and the following comparative compound were added as shown in Table 1. Furthermore, hydroquinone 100 mg, N-oleyl-
N-Methyltaurine sodium salt was added so as to be coated at 30 mg / m ² . Subsequently (d) 200mg / m ² of water-soluble latex represented by the dispersion was 400 mg / m ² of polyethyl acrylate, an average particle diameter of the colloidal silica 200 mg / m ² of 0.02 [mu] m, as further hardeners 1 200 mg / m ² of 3-divinylsulfonyl-2-propanol was added. The pH of the solution was adjusted to 5.65 with acetic acid. They were coated such that the coated silver amount was 3.5 / m ² .

[0151]

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[0152]

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(PC layer) A dispersion of 50 wt% ethyl acrylate in gelatin aqueous solution, and
Sodium ethyl sulfonate was added at 5 mg / m ² , 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 40 having an average particle size of about 3.5 μm
mg / m ² , methanol silica 0.1 g / m ² , polyacrylamide 100 mg / m ² , silicone oil 20 mg / m ^2, and a fluorosurfactant 5 mg / m ^{2 represented by the following} structural formula (e) as a coating aid. 100 mg / m ² of sodium dodecylbenzene sulfonate was applied.

[0155]

[Chemical 38]

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

[0157]

[Chemical Formula 39]

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

[0159]

[Chemical 40]

[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

<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 light emission time of 10 ⁻⁵ se through a step wedge.
After being exposed to the xenon flash light of c, and developed using the developers A and B having the following compositions at 35 ° C. for 30 seconds, fixing, washing with water and drying were performed. A fixing solution having the following composition was used as the fixing solution.

Developer A (Invention) Sodium hydroxide 10.0 g Diethylenetriamine-pentaacetic acid 1.5 g Potassium carbonate 15.0 g Potassium bromide 3.0 g 5-Methylbenzotriazole 0.10 g 1-Phenyl-5-mercaptotetrazole 0.02 g potassium sulfite 10.0 g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 0.40 g sodium erythorbate 30.0 g potassium hydroxide is added and water is added to make 1 liter p
Adjust H to 10.5.

Developer B Sodium hydroxide 10.0 g Diethylenetriamine-pentaacetic acid 1.5 g Potassium carbonate 15.0 g Potassium bromide 3.0 g 5-Methylbenzotriazole 0.10 g 1-Phenyl-5-mercaptotetrazole 0.02 g Sulfurous acid Potassium 10.0 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 0.40 g Hydroquinone 15.3 g Potassium hydroxide is added and water is added to make 1 liter p.
Adjust H to 10.5.

Fixing solution Ammonium thiosulfate 359.1 ml Ethylenediaminetetraacetic acid 2Na dihydrate 2.26 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 sulphate 25.3 g pH (adjusted with sulfuric acid or sodium hydroxide) 4.85 Add water 1 liter (2) Evaluation of image contrast As an index (gamma) indicating the image contrast, the characteristic curve From the point of fog + concentration 0.3, fog + concentration 3.
The point of 0 was connected by a straight line, and the slope of this straight line was expressed as a gamma value. That is, gamma = (3.0-0.3) / [l
og (exposure amount that gives a density of 3.0)-(exposure amount that gives a density of 0.3)], and the larger the gamma value, the harder the photographic characteristics. (3) Evaluation of halftone dot quality (DQ) The halftone dots of the light-sensitive material exposed through the contact screen were observed with a magnifying glass, and the sharpness and smoothness were evaluated on a 5-point scale.
"5" represents the best level for both sharpness and smoothness, and "1" represents the lowest level. When the level is "3" or more, the sharpness and smoothness of the on / off portion of the image when the scanner is actually exposed is practically acceptable. (4) Evaluation of sensitivity The sensitivity was shown by the relative value of the reciprocal of the exposure amount giving a density of 1.5. The sensitivity of the sample No. 4 was set to 100.

The above results are shown in Table 1.

[0166]

[Table 1]

<Results> The compound of the present invention has a high contrast-increasing effect with respect to the onium compound of Comparative Example. When the developer A is used, the use of the onium compound of the present invention causes a higher specific contrast-increasing action. Also, a sample having good sensitivity and high halftone dot quality was obtained. Example 2 1 mmol / Agmol of the following hydrazine derivative was added to the EM layer.
A sample similar to that of Example 1 was prepared except that it was contained, and the same photographic performance evaluation was performed.

[0168]

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The same effect as in Example 1 was obtained. Example 3 <Preparation of silver halide photographic light-sensitive material> Emulsion preparation Emulsion B was prepared by the following method. [Emulsion C] An aqueous solution of silver nitrate and an aqueous solution of sodium chloride were simultaneously mixed in an aqueous gelatin solution kept at 40 ° C. in the presence of 5.0 × 10 ^-6 mol of NH ₄ RhCl ₆ per 1 mol of silver, which was well known in the art. After removing the soluble salt by the method described above, gelatin was added, and 2-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added as a stabilizer without chemical ripening. This emulsion has an average grain size of 0.2
It was a monodisperse emulsion having a cubic crystal shape of μ.

Preparation of Coating Sample On a polyethylene terephthalate film support having a moistureproof layer undercoat containing vinylidene chloride, from the support side,
Samples 301 to 324 were prepared by sequentially coating so as to have a layer structure of an EM layer and a PC layer. The preparation method and coating amount of each layer are shown below. [EM Layer] To this emulsion B, as shown in Table 2, the onium salt compound of the present invention and the comparative compound were added. Then,
2.0 × 10 ⁻³ mol of the hydrazine derivative shown in Table 2 was added per mol of silver.

Further, polyethyl acrylate latex was added in a solid content of 30 wt% with respect to gelatin, 1,3-di-vinylsulfonyl-2-propanol was added as a hardening agent, and 3.8 g / m 2 was added on the polyester support. ^It was applied so that the Ag amount was ² . The gelatin was 1.8 g / m ² . [PC Layer] Gelatin 1.5 g / m ^2, was coated with a layer of polymethyl methacrylate 0.3 g / m ² of particle size 2.5 [mu].

The base used in this example has a back layer and a back protective layer having the following compositions. Here, the swelling ratio on the back side is 110%. (Back layer formulation) Gelatin 170 mg / m ² Sodium dodecylbenzenesulfonate 32 mg / m ² Dihexyl-α-sulfosuccinate sodium 35 mg / m ² (Back protective layer formulation) Gelatin 2.7 g Silicon dioxide matting agent (average particle size 3 .5 μm) 26 mg / m ² dihexyl-α-sulfosuccinate sodium 20 mg / m ² sodium dodecylbenzenesulfonate 67 mg / m ²

[0173]

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[0174]

[Chemical 43]

Ethyl acrylate latex (average particle size 0.05 μm) 260 mg / m ² 1,3-divinylsulfonyl-2-propanol 149 mg / m ²

<Evaluation of Photographic Performance> (1) Exposure and Development Treatment The obtained sample was exposed through a step wedge with a bright room printer P-627FM manufactured by Dainippon Screen Co., Ltd. Automatic processor FG710NH
Was developed at 38 ° C. for 20 seconds with the developer A described in Example 1, fixed with the fixer described in Example 1, washed with water and dried. (2) Evaluation of Image Contrast The same procedure as in Example 1 was performed.

(3) Evaluation of Image Quality of Extracted Characters When the image quality of extracted characters is 5, it means that 50% of the halftone dot area is 50% of the halftone dot area on the return sensitive material using the original as shown in FIG. The image quality is such that a character with a width of 30 μm is reproduced when the appropriate exposure is performed, and it is a very good extracted character image quality.
On the other hand, a blank character image quality of 1 is an image quality that cannot be said to be an image quality in which only characters having a width of 150 μm or more can be reproduced when exposure is performed with the appropriateness as described above. 5
A sensory evaluation ranked between 4 and 1 between 4 and 2. A level of 3 or more is a practical level.

The results are shown in Table 2.

[0179]

[Table 2]

<Results> When the compound of the present invention was used, a sample having a super-high contrast and a good image quality of extracted characters was obtained.

[Brief description of drawings]

FIG. 1 shows a configuration at the time of exposure when a blank character image is formed by stacking back, and each reference numeral indicates the following. (A) Transparent or semi-transparent embedment base (b) Line drawing original (black part shows line drawing) (c) Transparent or semi-transparent embedding base (d) Halftone dot manuscript (black part is halftone dot) (E) Photosensitive material for flipping back (note that the shaded area indicates the photosensitive layer)

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material comprising a compound represented by the following general formula (N-1). General formula (N-1): Wherein, Z ¹ is N, represents a non-metallic atomic group necessary for forming a nitrogen-containing aromatic heterocyclic ring of 5 or 6 membered jointly with X ^1, X ¹ represents N or CR ^12. Where R ¹² is R
Synonymous with ¹¹ . R ¹ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. R ¹¹
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.
m ¹ is 0 or an integer equal to or less than the maximum substitutable number in the ring. When m ¹ is 2 or more, each R ¹¹ may be the same or different, and each R ¹¹ may be bonded to form a ring. Further, two radicals free of one arbitrary hydrogen atom from the formula (N-1) may be bonded to each other to form a bis type structure. Y ¹ is a counter ion for charge balance, and n ¹
Is the number required for charge balance. Completed with Z ¹ 5
The total number of carbon atoms contained in the substituent substituting on the 6-membered or 6-membered nitrogen-containing aromatic heterocycle and the carbon number contained in R ¹ is from 15 to 40. 2. A silver halide photographic light-sensitive material according to claim 1, which is imagewise exposed and then treated with a developer containing a developing agent represented by the following general formula (N-11). Processing method of silver photographic light-sensitive material. General formula (N-11): In the formula, R ⁷¹ and R ⁷² are each a hydroxy group, an amino group,
It represents an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group or an alkylthio group. P, Q
Is a hydroxy group, a carboxyl group, an alkoxy group, a hydroxyalkyl group, a carboxyalkyl group, a sulfo group,
It represents a sulfoalkyl group, an amino group, an aminoalkyl group, an alkyl group or an aryl group, or P and Q are bonded to each other and two vinyl carbon atoms substituted by R ⁷¹ and R ⁷² are substituted by Y. Represents an atomic group forming a 5- to 7-membered ring together with the carbon atom. Y is = O, or = N-R ⁷³
Represents R ⁷³ represents a hydrogen atom, a hydroxyl group, an alkyl group, an acyl group, a hydroxyalkyl group, a sulfoalkyl group or a carboxyalkyl group.