JPH08166652A - Silver halide photographic sensitive material and method for forming high-contrast image - Google Patents

Abstract

PURPOSE: To obtain a good high-contrast image by incorporating a specified hydrazine compound in an emulsion layer or a hydrophilic colloidal layer even in the case of using a developing solution containing any of dihydroxybenzenes and reductons as a developing agent or not. CONSTITUTION: At least one of the emulsion layers and other hydrophilic colloidal layer contains at least one of the hydrazine compounds represented by the formula in which R1 is an H atom or an aliphatic group or the like; R2 is an H atom or a blocking group; both of A1 and A2 are H atoms or one of them is an H atom and the other is a sulfonyl or acyl group or the like; E is a carbonyl or sulfonyl group or the like G1 is a divalent aliphatic or aromatic group or the like; G2 is a divalent aromatic or unsaturated heterocyclic group; L is a divalent bonding group; R3 <+> is an N-containing 6-membered optionally substituted aromatic quaternary base baser than -0.6V in reduction potential; and X is an anion optionally forming an intramolecular salt.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a photolithography plate for printing of graphic arts in a development processing method using any of alkaline developers having different compositions containing dihydroxybenzenes or reductones as main developing agents. The present invention relates to a silver halide photographic light-sensitive material which is useful in a process and which gives an extremely hard negative image, and a high-contrast image forming method using the same.

[0002]

2. Description of the Related Art In the photolithography process for printing of graphic arts, since it is required to form a sharp halftone dot image or a line image, a hard image forming system exhibiting a photographic characteristic of gamma of 10 or more is required. An image forming system capable of obtaining such a hard photographic characteristic is disclosed in Japanese Patent Application Laid-Open No. 56-106244 and U.S. Pat. No. 4,16.
No. 8,977, No. 4,224,401, No. 4,2
41,164, 4,269,929, and 4,
311,781, 4,650,746, 4,686,167, 4,927,734 and the like disclosed in silver halide photographic light-sensitive materials as a so-called contrast adjusting agent. Prepared so as to obtain a desired photographic light-sensitive material by containing a hydrazine compound and further using silver halide grains that effectively exhibit the high contrast property of the hydrazine compound, or by appropriately combining a nucleation accelerator and other photographic additives. However, it is possible to obtain a high-contrast photographic image by processing with a developer containing hydroquinone, which can be rapidly processed, as a developing agent.

However, the system using the hydrazine compound as described above generally has a drawback that it must be developed at a high pH value, and such a strongly alkaline developer does not undergo air oxidation. It is easy to receive, it is inconvenient for long-term storage because the development characteristics change,
It was not preferable due to corrosion of the developing device, work safety problems, and waste liquid problems.

In order to avoid the problem that these developers are strongly alkaline, a silver halide capable of obtaining a hard photographic image with a developer having a low pH value of 11.0 or less. Photosensitive material is European Patent No. 25
No. 3,665, No. 333,435, No. 345,0
25, 356,898, U.S. Pat. No. 4,98.
No. 8,604, No. 4,994,365, No. 5,0
41,355, JP-A-63-223744, JP-A-63-234244, JP-A-63-234245, JP-A-63-234246, JP-A-2-7705.
No. 7, gazette 2-220042, gazette 2-2219.
No. 53, No. 4-19646, No. 4-5114
No. 3, gazette 4-67140, gazette 4-67141.
No. 4,98,239 and No. 4-106542.
It is disclosed in Japanese Patent Laid-Open Publication No. 4-178644 and the like.

However, the contrast-increasing activity of the contrast-increasing agents used for these sharply fluctuates when the pH of the developing solution is 11.0 or less with respect to changes in the pH due to processing fatigue of the developing solution or air oxidation. It had a drawback that stable and good halftone dot quality could not be obtained.

On the other hand, the harmfulness of hydroquinone has become a problem as a problem due to environmental pollution in recent years, and a high contrast image forming method using a developing solution which does not use hydroquinone is desired. As a system that does not use hydroquinones that can form a high contrast image that can be used in the photolithography process of Graphic Arts as a main developing agent,
JP-A-4-32838 and JP-A-4-128742.
JP-A-5-88306 and JP-A-5-2102, a method of forming a high contrast image using a developer containing four components of reductones, aminophenols, quaternary ammonium salt compounds and specific indazole compounds.
A method using an ascorbic acid-based developer having a pH of 12.0 or more according to JP-A No. 20-52, US Pat. No. 5,264,323.
And a method using an ascorbic acid type developing solution as a developing solution in a silver halide light-sensitive material containing a hydrazine compound according to JP-A-5-23737.
No. 10, gazette No. 5-53231, gazette No. 5-2737.
No. 08, a method of using a developer containing a specific quaternary salt in a silver halide light-sensitive material and using ascorbic acid as a developing agent, and a reduction potential in a silver halide photographic light-sensitive material according to JP-A-6-43602. There is known a method in which a negative organic compound is present and development processing is performed with an alkaline developer containing an aminophenol-based developing agent and reductones.

However, in the method in which these reductones such as ascorbic acid are used as a developing agent, the photographic performance is unstable because of the high pH, and the developing solution is unstable when the developing treatment is carried out by an automatic processor, and the developer is constantly produced. There is a problem that stable photographic performance cannot be obtained.

Furthermore, in recent years, a high-contrast image forming method using a developer containing an eco-friendly reductone as a developing agent as described above has been disclosed, but the same silver halide photographic light-sensitive material is used and dihydroxybenzene is used. No method has been known for obtaining a good and high-contrast image with both a developing solution containing a system compound as a developing agent and a developing solution containing a reductone as a developing agent.

[0009]

SUMMARY OF THE INVENTION Therefore, the first object of the present invention is to obtain a high contrast both by using a developing solution containing dihydroxybenzenes as a developing agent and by using a developing solution containing reductones as a developing agent. The present invention is to provide a silver halide photographic light-sensitive material capable of obtaining a good image.

A second object of the present invention is to develop either an alkaline developing solution containing dihydroxybenzenes as a main developing agent or an alkaline developing solution containing reductones as a main developing agent using the above silver halide light-sensitive material. It is also an object of the present invention to provide a high-contrast image forming method capable of obtaining a high-contrast and good image even in a liquid development processing method.

[0011]

The above object of the present invention is to provide a negative-working silver halide photographic light-sensitive material having at least one negative-working silver halide emulsion layer on a support and, if necessary, another hydrophilic colloid layer. In the material, at least one of the hydrazine compounds represented by the general formula (I) is contained in at least one of the emulsion layer and the other hydrophilic colloid layer, and a silver halide photographic light-sensitive material characterized by being alkaline It was achieved by developing with a developer.

[0012]

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(In the formula, R ₁ represents a hydrogen atom, an optionally substituted aliphatic group, an optionally substituted aromatic group or an optionally substituted heterocyclic group. R ₂ is a hydrogen atom. Or a block group, A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is a sulfonyl group, an acyl group or an oxalyl group, and E is a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group, or oxalyl. Represents a group or an iminomethylene group, G ₁ represents a divalent optionally substituted aliphatic group, an optionally substituted aromatic group or an optionally substituted heterocyclic group, and G ₂ represents 2
Represents a valent aromatic group which may be substituted or an unsaturated heterocyclic group which may be substituted. L is a divalent linking group. R ₃ ⁺ represents a nitrogen-containing 6-membered aromatic quaternary base whose reduction potential is less than -0.6 V, and may be further substituted with a substituent. As the substituent which may be substituted, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group,
Alkoxy group, substituted amino group, acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, ester group, sulfonate ester group, aryl group, alkylthio group, arylthio group, carboxyalkyl group , A sulfoxyalkyl group, an acyl group, a substituted sulfonyl group, a sulfinyl group, a hydroxy group, a cyano group, a sulfoxyl group, a carboxyl group, and a halogen atom. These substituents may be further substituted and may be connected to each other to form an aliphatic ring, aromatic ring or hetero ring. X ⁻ is a counter anion and may form an inner salt. )

Next, the hydrazine compound represented by the general formula (I) used in the present invention will be described in detail.

Examples of the optionally substituted aliphatic group represented by R ₁ in the general formula (I) include linear, branched or cyclic alkyl groups, alkenyl groups and alkynyl groups, and substituents suitable for these. (For example, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, heterocyclic onium group, amino group, ammonium group, acylamino group, carbamoyl group, sulfonamide group, sulfamoyl group, ureido group, alkoxy group, aryloxy Group, heterocyclic oxy group, hydroxyl group, alkoxycarbonylamino group, alkylthio group, arylthio group, heterocyclic thio group, sulfonyl group, sulfinyl group,
Examples thereof include a halogen atom, a cyano group, a sulfoxyl group, a carboxyl group, an acyloxy group, an acyl group, an acyloxycarbonyl group, a nitro group, a thioacyl group, a thioacylamino group and a thioureido group.

The optionally substituted aromatic group represented by R ₁ in the general formula (I) is an aryl group such as a monocyclic ring (eg, phenyl) or a condensed ring (eg, naphthyl) and the like. A substituent such as an alkyl group,
Examples thereof include groups having an alkenyl group, an aryl group, a heterocyclic group and the like described as the substituents of the above-mentioned aliphatic groups).

The optionally substituted heterocyclic group represented by R ₁ in the general formula (I) is a 3- to 10-membered ring containing at least one of N, O or S atoms, and Include those having a suitable substituent (for example, a group described as a substituent of the above-mentioned aliphatic group such as an alkyl group, an alkenyl group, an aryl group, and a heterocyclic group). A ring (for example, pyrrole, thiophene, furan, imidazole, oxazole, thiazole, isoxazole, isothiazole, oxadiazole, thiadiazole, triazole, pyrroline,
Imidazoline, pyrrolidine, imidazolidine, tetrazole, etc.), 6-membered ring (eg, pyridine, pyrazine, pyrimidine, pyridazine, triazine, piperidine, piperazine, morpholine, pyran, dithiine, etc.) and condensed rings of these with an appropriate ring (eg, benzo) Oxazole, benzothiazole, benzimidazole, indole, quinoline, isoquinoline, quinoxaline, quinazoline, carbazole, acridine, benzothiophene, phenoxazine, phenothiazine, indoline, etc.) or onium salts of these heterocycles.

In the general formula (I), A ₁ and A ₂ are
A hydrogen atom, an alkylsulfonyl group having 20 or less carbon atoms and an arylsulfonyl group (preferably a phenylsulfonyl group or a phenylsulfonyl group substituted such that the sum of Hammett's substitution constants is −0.5 or more); and 2 carbon atoms.
An acyl group of 0 or less (preferably a benzoyl group or a benzoyl group substituted such that the sum of Hammett's substituent constants is −0.5 or more) and a linear, branched or cyclic unsubstituted aliphatic acyl group, and Substituted aliphatic acyl group (as a substituent, for example, a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group,
Sulfonic acid groups, etc.). A ₁ and A
Most preferably, both ₂ are hydrogen atoms.

In the general formula (I), E represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group or an iminomethylene group, and the E is most preferably a carbonyl group.

In formula (I), R ₂ is a hydrogen atom or an alkyl group which may be substituted as a blocking group (for example, methyl, ethyl, benzyl, methoxymethyl, trifluoromethyl, phenoxymethyl, 4-methoxybenzene). Sulfonylmethyl, 1-pyridiniomethyl, hydroxymethyl, methylthiomethyl, phenylthiomethyl, etc.), an optionally substituted aryl group (eg, phenyl, hydroxymethylphenyl, chlorophenyl, etc.), an optionally substituted heterocyclic group (eg, Pyridyl, thienyl, furyl, etc.), -COOR ₄ , -CON
The group (R ₅ ) R ₆ is preferred. R ₄ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ₅ and R ₆ represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group,
Heterocyclic group, hydroxyl group, alkoxy group, alkenyloxy group, alkynyloxy group, aryloxy group,
It represents a heterocyclic oxy group or an amino group.

In the general formula (I), 2 represented by G ₁
Examples of the valent aliphatic group which may be substituted include linear, branched or cyclic alkylene groups having 1 to 20 carbon atoms, alkenylene groups having 2 to 20 carbon atoms, alkynylene groups and substituents suitable for these (eg, Examples thereof include those having an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, and the like, which are described as the substituents for R ₁ described above.

In the general formula (I), 2 represented by G ₁
As the valent aromatic group which may be substituted, an arylene group such as a monocyclic ring (for example, phenylene or the like) or a condensed ring (for example, naphthylene, etc.) and a substituent suitable for these (for example, an alkyl group, an alkenyl group, an aryl group, Examples thereof include those having a group such as a heterocyclic group described above as the substituent for R ₁ .

In the general formula (I), 2 represented by G ₁
As the valent optionally substituted heterocyclic group, N,
O, S, 3 to 10-membered ones, and these suitable substituent (for example, an alkyl group of rings containing at least one atom selected from Se, alkenyl group, aryl group, and heterocyclic group substituents of the aforementioned R ₁ And the like, but specifically include a 5-membered ring (eg, pyrrole, thiophene, furan, imidazole, oxazole, thiazole, selenazole, isoxazole, isothiazole, oxadiazole, thiadiazole). , Triazole, pyrroline, imidazoline, pyrrolidine, imidazolidine, tetrazole, etc.), 6-membered ring (for example, pyridine, pyrazine, pyrimidine, pyridazine, triazine, piperidine, piperazine, morpholine, pyran, dithiine) and their suitable ring Fused rings (eg benzoxazo Le, benzothiazole, benzimidazole, indole, quinoline, isoquinoline, quinoxaline, quinazoline, carbazole, acridine, benzothiophene, phenoxazine, phenothiazine, those indoline, etc.) preferred.

In the general formula (I), ₂ represented by G 2
Examples of the optionally substituted aromatic group include arylene groups such as a monocyclic ring (eg, phenylene) and a condensed ring (eg, naphthylene). In the general formula (I), the divalent optionally substituted unsaturated heterocyclic group represented by G ₂ is a heterocyclic group containing at least one atom selected from N, O, S and Se. (For example, thiophene, furan, benzothiophene, pyran, pyridine, quinoline, pyrazine, pyrimidine, pyridazine, cinnoline, quinazoline, benzothiazole, etc.) can be mentioned.

In the general formula (I), the group capable of substituting the aromatic group or unsaturated heterocyclic group represented by G ₂ is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group (preferably Is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group), an aryl group (eg, a phenyl group), an alkoxy group (preferably having an alkyl moiety having 1 to 20 carbon atoms), alkenyloxy. Group (eg allyloxy, butenyloxy etc.), alkynyloxy group (eg propargyloxy, butynyloxy etc.), aryloxy group (eg phenoxy etc.), acyloxy group (eg acetyloxy, propionyloxy, benzoyloxy etc.), acylamino group (eg acetyl) Amino, propionylamino, butanoylami , Octanoylamino, benzoylamino, etc.), a sulfonylamino group (e.g., methylsulfonylamino, ethylsulfonylamino,
Butylsulfonylamino, hexylsulfonylamino,
Octylsulfonylamino, phenylsulfonylamino, etc.), ureido groups (eg methylureido, ethylureido, propylureido, butylureido, hexylureido, cyclohexylureido, octylureido,
Dodecyl ureido, octadecyl ureido, phenyl ureido, naphthyl ureido, etc.), hydrazinocarbonylamino group (for example, methylhydrazinocarbonylamino,
Ethylhydrazinocarbonylamino, dimethylhydrazinocarbonylamino, diphenylhydrazinocarbonylamino, phenylhydrazinocarbonylamino, phenylmethylhydrazinocarbonylamino, etc.), alkylamino groups (eg methylamino, ethylamino, butylamino, octylamino, Dodecylamino etc.), dialkylamino groups (eg dimethylamino, diethylamino,
Dibutylamino, methyloctylamino, etc.), amino group, hydroxyl group, halogen atom, alkylthio group (preferably one having 1 to 20 carbon atoms in the alkyl moiety),
Alkenylthio groups (eg allylthio, butenylthio etc.), mercapto groups, sulfo groups, carboxyl groups, thioureido groups (eg methylthioureido, ethylthioureido, butylthioureido, cyclohexylthioureido, octylthioureido, dodecylthioureido,
Phenylthioureido etc.), cyano group, sulfonyl group (eg methanesulfonyl etc.), sulfamoyl group (eg methylsulfamoyl, ethylsulfamoyl, butylsulfamoyl, phenylsulfamoyl etc.), carbamoyl group (eg methylcarbamoyl) , Ethylcarbamoyl, butylcarbamoyl, octylcarbamoyl, phenylcarbamoyl and the like).

In the general formula (I), the divalent linking group represented by L is not particularly limited, but typical examples thereof include linear, branched or cyclic C1 to C20. An alkylene group, an alkenylene group and an alkynylene group having 2 to 20 carbon atoms, an arylene group such as a monocyclic ring (eg phenylene) or a condensed ring (eg naphthylene), a heterocyclic group (eg pyrrole, pyridine, benzoxazole, etc.) G ₁ Group described as the divalent heterocyclic group) and a group represented by the general formula (III).

[0027]

[Chemical 4]

(Wherein Y ₁ , Y ₂ and Y ₃ are each a methylene group, l, n and p are each an integer of 0 to 10, and l + n + p is an integer of 1 to 10).
Q represents a carbonyl group, a sulfonyl group, a sulfinyl group, a phosphonyl group, an ester group, a thioester group, an aminocarbonyl group, an aminosulfonyl group or the like, and m is 0 or 1. G ₃ is a divalent linking group, specifically, an arylene group such as a monocyclic ring (eg, phenylene) or a condensed ring (eg, naphthylene), a heterocyclic group (eg, pyrrole,
Examples thereof include the groups described as the divalent heterocyclic group of G ₁ such as pyridine and benzoxazole. )

The divalent linking group represented by L may be further substituted with a substituent, and the substituent which may be substituted is, for example, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, etc. The groups described as the substituent of _{1 and} the like can be mentioned.

The nitrogen-containing six-membered aromatic quaternary base represented by R ₃ ⁺ in the general formula (I) and having a reduction potential of less than -0.6 V is at least one nitrogen atom. One or more of the nitrogen atoms of a member ring (eg pyridine, pyrimidine, 1,3,5-triazine etc.) or a further condensed ring (eg quinoline, isoquinoline, quinoxaline, oxazolopyridine etc.) is quaternized, The reduction potential of the quaternary salt portion is less than -0.6 V. These nitrogen-containing 6-membered aromatic quaternary bases may be further substituted with a substituent. The substituent which may be substituted is a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group (preferably an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group), aralkyl Groups (eg benzyl, phenethyl, phenylpropyl, phenylhexyl etc.), alkoxy groups (eg methoxy, ethoxy, propyloxy, hexyloxy, allyloxy etc.), substituted amino groups (eg methylamino,
Ethylamino, hexylamino, dimethylamino, diethylamino, allylamino, methylhexylamino, methylphenylamino, etc.), an acylamino group (eg, acetylamino, propionylamino, benzoylamino,
N-methylacetylamino etc.), sulfonylamino group (eg methylsulfonylamino, ethylsulfonylamino, hexylsulfonylamino, phenylsulfonylamino, toluenesulfonylamino etc.), ureido group (eg methylureido, ethylureido, propylureido, hexylureido) , Dodecylureido, phenylureido, methylphenylureido, etc.), urethane groups (eg, methylurethane, ethylurethane, butylurethane, octiuurethane, phenylurethane, etc.), aryloxy groups (eg, phenoxy, naphthoxy, etc.), sulfamoyl groups (eg, Methylsulfamoyl, ethylsulfamoyl, propylsulfamoyl, hexylsulfamoyl, diethylsulfamoyl, phenylsulfamoyl, etc.), cal Sulfamoyl group (e.g. methylcarbamoyl, ethylcarbamoyl, propylcarbamoyl,
Hexylcarbamoyl, cyclohexylcarbamoyl,
Hydroxyethylcarbamoyl, dimethylcarbamoyl, phenylcarbamoyl, etc.), ester group (eg, methoxycarbonyl, ethoxycarbonyl, propyloxycarbonyl, hexyloxycarbonyl, dodecyloxycarbonyl, cyclohexyloxycarbonyl, allyloxycarbonyl, phenoxycarbonyl, etc.), sulfonate ester Groups (eg methoxysulfonyl, ethoxysulfonyl, propyloxysulfonyl, octyloxysulfonyl, phenoxysulfonyl etc.), aryl groups (eg phenyl, tolyl, naphthyl, anthranyl etc.), alkylthio groups (eg methylthio, ethylthio, propylthio, cyclohexylthio, allylthio) Etc.), arylthio groups (eg phenylthio, tolylthio, naphthylthio, etc.) Carboxyalkyl groups (e.g., carboxyethyl, carboxybutyl, etc.), sulfoxide group (e.g. sulfo propyl, sulfoxide butyl), an acyl group (e.g. acetyl, propionyl,
Hexanoyl, acryloyl, benzoyl etc.), substituted sulfonyl group (eg methylsulfonyl, ethylsulfonyl, hexylsulfonyl, dodecylsulfonyl, cyclohexylsulfonyl, phenylsulfonyl etc.), sulfinyl group (eg methylsulfinyl, ethylsulfinyl, nonylsulfinyl, phenylsulfinyl etc.) , A hydroxy group, a cyano group, a carboxyl group, a sulfoxyl group, a halogen atom and the like. These substituents may be further substituted with a substituent. Further, the substituents may be linked to each other to form a ring, an aromatic ring or a heterocycle.

As the counter anion represented by X ⁻ in the general formula (I), a halide ion (for example, Cl ⁻ ,
Br ⁻ , I ^−, etc.), sulfate ion, alkyl sulfonate ion (eg, methane sulfonate ion, ethane sulfonate ion, dodecyl sulfonate ion, etc.), allyl sulfonate ion (benzene sulfonate ion, toluene sulfonate ion, naphthalene) Sulfonate ion etc.), carboxylate ion (eg acetate ion, trifluoroacetate ion, parachlorobenzoate ion, oxalate ion etc.), nitrate ion, phosphate ion, BF ₄ ⁻ , ClO ₄ ^{− and the} like. Preferable are halide ion and paratoluenesulfonate ion.

X ⁻ may be contained in the above R ₃ ⁺ to form an intramolecular ion. Specifically, it is a case where the substituent of R ₃ ⁺ is a carboxyl group, a sulfoxyl group, a carboxyalkyl group, a sulfoxyalkyl group, or the like. The value of the reduction potential Ered used here is a nitrogen-containing hexagonal compound having a reduction potential represented by the general formula (IV), which is a precursor of the hydrazine compound represented by the general formula (I), lower than -0.6 V. A carbonyl compound containing a membered-ring aromatic quaternary base means a potential at which a carbonyl compound undergoes electron injection at a cathode and is reduced in voltammetry.

[0033]

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(In the general formula (IV), R ₁ , R ₃ ⁺ , L
And X ⁻ are the same as R ₁ , R ₃ ⁺ , L and X ⁻ in formula (I). )

The value of the reduction potential Ered can be accurately measured by voltammetry. That is, dyes or pyridinium salt derivatives 1 × 10 ⁻³ M to 1 × 10 ⁻⁴ M voltammograms were measured in acetonitrile containing 0.1 M tetra-n-butylammonium perchlorate as a supporting electrolyte. It was determined as the half-wave potential obtained from the above. Platinum was used as a working electrode and a saturated calomel electrode (SCE) was used as a reference electrode, and the measurement was performed at 25 ° C.
More specifically, U.S. Pat. No. 3,501,307 and P. Delahay, New Instrumental Methods in Electrochemistry (New I).
nstrumental Methods in Ele
ctrochemistry ((Interscience Publishers) (Interscience P
Publishers), 1954) and the like.

Next, specific examples of the hydrazine compound represented by the general formula (I) are shown below, but the present invention is not limited thereto.

[0037]

[Chemical 6]

[0038]

[Chemical 7]

[0039]

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[0040]

[Chemical 9]

[0041]

[Chemical 10]

[0042]

[Chemical 11]

[0043]

[Chemical 12]

[0044]

[Chemical 13]

[0045]

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[0046]

[Chemical 15]

[0047]

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[0048]

[Chemical 17]

The hydrazine compound represented by the general formula (I) used in the present invention is a Schiff base compound, for example, a carbonyl compound represented by the following general formula (IV) and a general formula (V) below. It can be easily synthesized by a dehydration condensation reaction with an amine compound according to the synthetic reaction of the general formula (I).

[0050]

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[0051] R ₁ in the general formula ^{_{(IV), R 3 +,}} L and X ^- is, R ₁ in the general formula ^{_{(I), R 3 +,}} L and X ^- is the same as.

[0052]

[Chemical 19]

In the general formula (V), R ₂ , G ₁ , G ₂ ,
A ₁ , A ₂ and E are R ₂ , G in the general formula (I).
_{The same as 1} , G ₂ , A ₁ , A ₂ and E.

[0054]

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To synthesize a Schiff base hydrazine compound of the general formula (I) from the carbonyl compound of the general formula (IV) and the amine compound of the general formula (V), the above-mentioned general formula ( Although it can be easily synthesized according to the synthetic reaction of I), detailed synthetic conditions are described in, for example, "Organic Chemistry Handbook" edited by the Society of Synthetic Organic Chemistry, page 370 (Gihodo, 1968), Chemical Society of Japan, "New Experimental Chemistry Lecture, v.
ol. 14 "1410 (Maruzen, 1978), M.M.
M. Sprung, Chem, Rev, 26, 297.
(1940), R.A. N. Layer, Chem, Re
v, 63, 489 (1963) and the like, and can be synthesized.

The carbonyl compound represented by the general formula (IV) is a nitrogen-containing 6-membered ring aromatic quaternary salt compound. For example, a quaternary compound of a nitrogen-containing 6-membered aromatic compound and a carbonyl compound having a halogen atom. It can be easily synthesized by a chemical reaction. Specific synthetic methods include, for example, “Oitagaku Kagaku”, Vol. 16 (III), pages 7 and 129 (1959, Asakura Shoten), supervised by M. Otake. Grob, E .; Ren
Report by Helk. Chim. Acta 37 , 1
672 (1954); E. FIG. Lyle, E .; F. Pe
rlowski, H .; J. Troscaniec,
G. G. Lyle, J. J. Org. Chem. 2
0 , 1761 (1955); R. Lamborg,
R. M. Burton, N.M. O. Kaplan, J. Am. Am. Chem. Soc. 79 , 6173 (1
957); Ciusa, A .; Report by Buccelli, Gazzetta Chimia Italian
a 88 , 393 (1958) and the like. The amine compound represented by the general formula (V) can be synthesized, for example, by the following synthetic reaction.

[0057]

[Chemical 21]

Regarding the synthetic reaction of the amine compound represented by the general formula (V), the nitro compound as a starting material can be purchased as a commercially available reagent or an industrial chemical. Regarding the method of synthesizing the amine compound which is another starting material,
For example, JP-A-5-93977 and JP-A-5-17328.
No. 1, gazette No. 5-204075, gazette No. 5-2161
It can be easily synthesized by referring to the method for synthesizing an amine compound described in Japanese Patent Publication No. 51, etc.

Next, a specific method for synthesizing a typical compound represented by formula (I) used in the present invention will be described. The specific example compound H-1 can be synthesized according to the following synthetic scheme (1).

[0060]

[Chemical formula 22]

1.58 g of pyridine and 2.32 g of p- (chloromethyl) benzaldehyde were dissolved in 35 ml of 1,4-dioxane, and the mixture was heated under reflux for 15 hours.
Crystals precipitated during the reaction were filtered to give compound ( 1 ) at 2.0
7 g was obtained. 11.90 g of m-nitrobenzenesulfonyl chloride was dissolved in 300 ml of a tetrahydrofuran solution in which 7.60 g of 2- (p-aminophenyl) formylhydrazine ( 2 ) and 4.20 g of pyridine were dissolved at 10 ° C or lower for 35 minutes. 150 ml of a tetrahydrofuran solution was added dropwise. Then, the mixture was reacted at room temperature for 3 hours, concentrated, treated with water, and extracted with ethyl acetate.
The crude product obtained by concentrating the extract was recrystallized from 400 ml of a mixed solvent of ethanol: methanol = 1: 1 to obtain 10.20 g of compound ( 3 ). 1 in tetrahydrofuran
The compound ( 3 ) was subjected to 10% atmospheric pressure at room temperature using 0% Pd / C.
After catalytic reduction for a period of time, after the reaction, the mixture was filtered and concentrated to obtain 9.20 g of a pale yellow paste compound ( 4 ). Compound ( 1 )
0.70 g and 0.92 g of compound ( 4 ) were dissolved in 30 ml of absolute ethanol, and the mixture was heated at 80 ° C. for 15 hours for reaction. After the reaction, the mixture was concentrated and purified by alumina column chromatography (eluent: methanol) to obtain 1.11 g (yield 71%) of compound H-1. The structure of compound H-1 was confirmed by NMR, IR, and MS.

Specific example compound H-5 can be synthesized according to the following synthetic scheme (2).

[0063]

[Chemical formula 23]

Nicotinamide (1.22 g) and p- (chloromethyl) benzaldehyde (1.55 g) were dissolved in 1,4-dioxane (30 ml) and the mixture was heated under reflux for 15 hours. Crystals precipitated during the reaction were filtered to obtain 1.72 g of compound ( 5 ). 7.60 g of 2- (p-aminophenyl) formylhydrazine ( 2 ) and 4.20 g of pyridine
In 300 ml of a tetrahydrofuran solution in which is dissolved 1
150 ml of a tetrahydrofuran solution in which 11.90 g of p-nitrobenzenesulfonyl chloride was dissolved was added dropwise over 35 minutes at 0 ° C or lower. Then, the mixture was reacted at room temperature for 3 hours, concentrated, treated with water, and extracted with ethyl acetate. The crude product obtained by concentrating the extract was recrystallized from 400 ml of a mixed solvent of ethanol: methanol = 1: 1 to obtain 10.03 g of compound ( 6 ). The compound ( 6 ) was subjected to catalytic reduction in normal temperature and room temperature for 10 hours using 10% Pd / C in tetrahydrofuran, filtered after reaction, and concentrated to give 9.01 g of a pale yellow paste-like compound ( 7 ). Obtained. 0.83 g of the compound ( 5 ) and 0.92 g of the compound ( 7 ) were dissolved in 50 ml of absolute ethanol, and the mixture was heated under reflux for 15 hours. After the reaction, the mixture was concentrated and purified by alumina column chromatography (eluent: methanol) to give compound H-5.
Was obtained (0.98 g, yield 58%). The structure of compound H-5 was confirmed by NMR, IR, and MS.

Specific example compound H-9 can be synthesized according to the following synthetic scheme (3).

[0066]

[Chemical formula 24]

Isoquinoline (1.94 g) and p- (chloromethyl) benzaldehyde (2.32 g) were dissolved in 1,4-dioxane (30 ml) and heated under reflux for 15 hours. The crystals precipitated during the reaction were filtered to obtain 3.12 g of compound ( 8 ). 2,6-dimethylnitrobenzene 3
Dissolve 0.00 g in 100 ml of dichloromethane,
While keeping the temperature below 0 ° C, 47.00 g of chlorosulfuric acid was added dropwise over 2 hours. After heating under reflux for 3 hours, ice water was added after the reaction, and the mixture was extracted with chloroform. The chloroform layer was separated, dried and concentrated to give crude crystals. The crude crystals were washed with n-hexane to obtain 31.02 g of white crystalline compound ( 9 ). Two
-(P-Aminophenyl) formylhydrazine 18.8
Compound ( 9 ) 3 was added to 300 ml of tetrahydrofuran in which 0 g and 13.70 g of triethylamine were dissolved under ice cooling.
Tetrahydrofuran solution 200 m in which 1.00 g was dissolved
1 was added dropwise over 2 hours. After further reacting at room temperature for 2 hours, the mixture was concentrated under reduced pressure and treated with 300 ml of water, and the precipitated crystals were separated by filtration to obtain crude crystals. Ethanol 300m
Recrystallization with l gave 29.08 g of compound ( 10 ). Compound ( 10 ) was catalytically reduced in tetrahydrofuran at room temperature under normal pressure for 25 hours using 10% Pd / C, and after reaction,
It was filtered off and concentrated to obtain 25.11 g of compound ( 11 ).
0.85 g of compound ( 8 ) and 1.00 of compound ( 11 )
g was dissolved in 50 ml of absolute ethanol, and the mixture was heated under reflux for 15 hours. After the reaction, the mixture was concentrated and purified by alumina column chromatography (eluent: methanol / acetonitrile) to give 0.95 g of compound H-9 (yield 53
%)Obtained. The structure of compound H-9 was confirmed by NMR, IR, and MS.

Specific example compound H-28 can be synthesized according to the following synthetic scheme (4).

[0069]

[Chemical 25]

Compound ( 12 ) 2.00 was prepared by the synthetic method described on page 19 of JP-A-4-194923.
g was obtained. Compound ( 1 ) synthesized in Synthesis Scheme ( 1 )
0.70 g and 1.46 g of the compound ( 12 ) were dissolved in 50 ml of absolute ethanol, and the mixture was heated under reflux for 18 hours. After the reaction, the mixture was concentrated and purified by alumina column chromatography (eluent: methanol / acetonitrile),
1.01 g (yield 48%) of compound H-28 was obtained. The structure of compound H-28 was confirmed by NMR, IR, and MS.

The silver halide photographic light-sensitive material of the present invention contains at least one kind of hydrazine compound represented by the general formula (I), and the general formula (I) contained in the photographic light-sensitive material. The amount of the hydrazine compound represented by is 1 per mol of silver halide contained in the photographic light-sensitive material.
It is preferably from 10 ^-7 mol to 1 10 ^-1 mol. Particularly, it is preferably in the range of 5 × 10 ⁻⁴ mol to 3 × 10 ⁻² mol.

The hydrazine compound represented by the general formula (I) is a suitable water-miscible organic solvent such as alcohols (eg methanol, ethanol, propanol, fluorinated alcohol), ketones (eg acetone, methyl ethyl ketone etc.). , Dimethylformamide, dimethylsulfoxide, methylcellosolve, etc. Further, by a well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. It is also possible to create and use things. Alternatively, the hydrazine compound 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.

In order to incorporate the hydrazine compound represented by the general formula (I) into the silver halide photographic light-sensitive material of the present invention, it is preferable to incorporate it into the hydrophilic colloid layer in the light-sensitive material, particularly preferably halogenated. It may be contained in the silver emulsion layer and / or the hydrophilic colloid layer adjacent to the silver halide emulsion layer.

The hydrazine compound represented by the general formula (I) may be added to the silver halide photographic light-sensitive material at any time during the process for producing the silver halide photographic light-sensitive material. For example, when it is added to a silver halide emulsion, it can be added at any time from the start of chemical ripening to before coating, but it is preferably added at any time from the end of chemical ripening to just before coating. .

Next, the silver halide photographic light-sensitive material of the present invention will be described. The silver halide photographic light-sensitive material of the present invention has at least one emulsion layer composed of a silver halide emulsion. There is no particular limitation on the halogen composition of the silver halide emulsion used, and any composition such as silver chloride, silver chlorobromide, silver iodobromide, silver iodobromochloride can be used. The content of silver iodide is 5 mol% or less, preferably 3 mol% or less.

The silver halide grains used in the present invention are
It is possible to have a relatively wide particle size distribution, but it is preferable to have a narrow particle size distribution, especially 9% of all particles.
A monodisperse emulsion in which the grain size accounting for 0% is within ± 40% of the average grain size is preferable.

The silver halide grains used in the present invention are
The average particle size is preferably 0.7 μm or less, particularly 0.4 μm
The following are preferred. Further, silver halide grains having a regular crystal form such as a cube and an octahedron are spherical,
It may have an irregular crystal shape such as a plate shape or a clam shape.

The silver halide crystal used in the present invention is
The inside and the surface layer may be formed of uniform layers or different layers. The silver halide grains used in the present invention can be prepared by any known method.
That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a reaction mode of a soluble silver salt and a soluble halogen salt, any one of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof and the like is used. May be. As one of the simultaneous mixing methods, a method of keeping the silver ion concentration (pAg) in the liquid phase where silver halide is produced constant, that is, a pAg controlled double jet method (CDJ method) is used. When used, monodispersed silver halide grains having a uniform crystal form and a substantially uniform grain size can be obtained. Further, grains can be formed by using a silver halide solvent such as ammonia, thioether, or tetra-substituted thiourea.

The control double jet method and the grain forming method using a silver halide solvent make it easy to form a silver halide emulsion having a regular crystal form and a narrow grain size distribution. It is an effective means to make.

The silver halide emulsion used in the present invention includes a cadmium salt, an iridium salt, a rhodium salt, a rhenium salt or a ruthenium salt in order to increase the contrast of the silver halide emulsion in the process of silver halide grain formation or physical ripening. And these complex salts and the like may coexist.

Emulsions usually remove soluble salts after the formation of precipitates or after physical ripening.
The noodle washing method performed by gelatinizing gelatin may be used, and inorganic salts composed of polyvalent anions (eg sodium sulfate, magnesium sulfate, etc.), anionic surfactants, anionic polymers (eg polystyrene sulfonic acid, β -Naphthalenesulfonic acid formalin condensate, aromatic sulfonic acid formalin condensate, etc.) or a gelatin derivative (eg, aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.) for precipitation (flocculation) ) May be used.

The silver halide emulsion used in the present invention is
It may or may not be chemically sensitized. As the chemical sensitization method, known methods such as a sulfur sensitization method, a reduction sensitization method, a noble metal sensitization method, a selenium sensitization method and a tellurium sensitization method can be used, and they can be used alone or in combination. To be

As the sulfur sensitizer, various sulfur compounds, such as thiosulfates, thioureas, thiazoles and rhodanins, can be used in addition to the sulfur compounds contained in gelatin. Specific examples are US Pat. No. 1,574,
No. 944, No. 2,278,947, No. 2,41
0,689, 2,728,668, 3,5
No. 01,313 and No. 3,656,955.

As the reduction sensitizer, stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used. Specific examples thereof are described in US Pat.
No. 487,850, No. 2,518,698, No. 2,983,609, No. 2,983,610, No. 2,694,637 and the like.

Among the noble metal sensitization methods, the gold sensitization method is a typical one and uses a gold compound, mainly a gold complex salt. A noble metal other than gold, for example, a complex salt of platinum, palladium, iridium or the like may be contained. Specific examples are U.S. Pat. No. 2,448,060 and British Patent 618,061.
No. etc.

In the selenium sensitization method, an inorganic selenium compound or an organic selenium compound can be used as a selenium sensitizer, and specific examples thereof are US Pat. No. 1,574,94.
No. 4, No. 1,602,592, No. 1,623,4
No. 99, No. 3,297,446, No. 3,297,
No. 447, No. 3,320,069, No. 3,40
No. 8,196, No. 3,408,197, No. 3,4
42,653, 3,420,670, 3,
591,385, Japanese Patent Publication Nos. 52-34491, 52-34492, 53-295, and 5
7-22090, JP-A-59-180536, JP-A-59-185330, and JP-A-59-18133.
7 gazette, the same 59-187338 gazette, the same 59-19.
No. 2241, No. 60-150046, No. 60
-151637 gazette, the same 61-246738 gazette,
It is described in JP-A-5-11385.

Regarding the tellurium sensitization method and the tellurium sensitizer, US Pat. Nos. 1,623,499 and 3,320 are cited.
069, 3,772,031 and 3,53
1,289, 3,655,394, British Patents 235,211, 1,121,496, 1,295,462, Canadian Patent 800,958.
No. 5, JP-A-5-11386, JP-A-5-11387, JP-A-5-11388, JP-A-5-11390, JP-A-5-11392, JP-A-5-11393, and JP-A-5-19395. It is described in JP-A-5-45768, JP-A-5-45769 and JP-A-5-45772.

The silver halide emulsion used in the present invention is:
It may be spectrally sensitized with a sensitizing dye in order to impart photosensitivity to a desired photosensitive wavelength range. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, oxonol dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. Any of the nuclei normally used for cyanine dyes as the basic heterocyclic nuclei of dyes can be applied.

That is, a pyrroline nucleus, an oxazole nucleus,
Oxazoline nucleus, thiazole nucleus, thiazoline nucleus, pyrrole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, indole nucleus, benzoxazole nucleus, benzothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. can be applied. .

These sensitizing dyes may be used alone, or may be used in combination for the purpose of providing spectral sensitivity according to the purpose or for the purpose of supersensitization. Supersensitization can also be performed by adding a dye that does not have a spectral sensitizing effect itself or a substance that does not substantially absorb visible light together with the sensitizing dye. Here, the sensitizing dye may be added at any stage of coating the silver halide emulsion.
For example, it is added during the formation of silver halide sulfuric acid, during physical ripening, during chemical ripening, and in the coating solution of the emulsion prepared for coating. The preferred amount of the sensitizing dye used in the present invention is 1 × 10 ⁻⁶ mol to 1 × per mol of silver.
It is in the range of 10 ^-1 mol, particularly preferably in the range of 5 × 10 ^-5 mol to 1 × 10 ^-2 mol.

The binder contained in the silver halide emulsion layer used in the present invention is 250 per mol of silver halide.
It is preferable not to exceed g. Gelatin is most preferable as the binder, but a hydrophilic colloid other than gelatin can be used. For example, albumin, casein, graft polymers of gelatin and other polymers, hydrophilic polymers such as polyvinyl alcohol and polyacrylamide, etc. can be used.

The silver halide emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. it can. That is, an emulsion stabilizer (eg 6-hydroxy-4-methyl-1,
Hydroxytetrazaindene compounds such as 3,3a, 7-tetrazaindene), antifoggants (for example, azoles, mercaptotriazines, thiocarbonyl compounds such as oxazolinethione, azaindenes, benzenethiosulfonic acid, benzenesulfinine) Acid, benzene sulfonic acid amide, etc.), various surfactants (eg, cationic, anionic, nonionic, amphoteric surfactants, etc.), spreading agents (saponin, etc.), gelatin plasticizers (copolymers of acrylic acid ester) Etc.), a photographic property improving agent (for example, development acceleration, contrast enhancement, etc.).

The silver halide photographic light-sensitive material of the present invention is formed by coating at least one hydrophilic colloid layer containing a silver halide emulsion on a support, but other non-photosensitive hydrophilic colloids. Layers such as a protective layer, an intermediate layer, an antihalation layer, and a filter layer may be provided by coating.

The photographic emulsion layer or other hydrophilic colloid layer of the silver halide photographic light-sensitive material of the present invention contains, as a nucleation promoting compound, at least one of amine compounds, hydrazine compounds and quaternary onium salt compounds. can do. Specific examples of the nucleation promoting compound include JP-A-53
-77616, 53-137133, 54-37732, 60-14959.
No. 60-140340, No. 2-8833, No. 4-438, No. 4-5652, No. 4
-5653, 4-6548, 4-11
No. 4150, No. 4-212144, No. 4-1.
Amine compounds described in JP-A-22926, JP-A-2-170155, JP-A-5-93977,
Amine compounds as "inclusion boosters" described in U.S. Pat.
No. 51143, No. 5-127286, No. 5-
No. 134337, No. 5-134357, No. 5
Examples thereof include amine compounds, hydrazine compounds and quaternary onium salt compounds described in JP-A-197057, JP-A-5-232616 and the like, and any of these compounds is contained in the silver halide photographic light-sensitive material of the present invention. It can be contained and used.

The silver halide photographic light-sensitive material of the present invention can contain a polyalkylene oxide derivative. Examples of the polyalkylene oxide derivative used in the present invention include polyalkylenes such as polyethylene oxide and polypropylene oxide, and polyalkylene oxides such as polyethylene oxide and polypropylene oxide and water, aliphatic alcohols, phenols, glycols, fatty acids, and organic compounds. Addition polymerization product of one compound selected from the group of amines, condensate of polyalkylene oxide and one compound selected from the above compound group, or various alkylene oxides (for example, ethylene oxide and propylene oxide). )
Mutual block copolymers and the like. The polyalkylene oxide derivative used in the present invention has a number average molecular weight of 500 to 20,000.

The photographic emulsion layer or other hydrophilic colloid layer of the silver halide photographic light-sensitive material of the present invention may contain an inorganic or organic hardener. As hardeners, chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glyoxal, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.),
Active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, mucochloric acid, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, etc.), epoxy and aziridine type hard films Agents and the like can be used.

In the photographic emulsion layer or other hydrophilic colloid layer of the silver halide photographic light-sensitive material of the present invention, various photographic additives, antistatic agents, coating aids, slip improvers, matting agents and photographic light-sensitive agents are further added. For the purpose of improving the dimensional stability of the material, water-insoluble or sparingly soluble polymer latex (a homo- or copolymer of alkyl acrylate, alkyl methacrylate, acrylic acid, glycidyl acrylate, etc.) etc. is used within a range not impairing the effect of the present invention. Can be used.

The support of the silver halide photographic light-sensitive material of the present invention includes cellulose triacetate, cellulose diacetate, nitrocellulose, polystyrene, polyethylene terephthalate, paper, synthetic paper, or a combination thereof (for example, paper or film). A well-known support such as a glass plate having both surfaces or one surface coated with polyolefin) or a glass plate can be used. A polyethylene terephthalate film is particularly preferably used.
These supports may be subjected to corona treatment by a known method, and if necessary, may be subjected to undercoating treatment by a known method. Further, a waterproof layer containing a polyvinylidene chloride-based polymer may be provided in order to improve so-called dimensional stability, which changes in dimension due to changes in temperature and humidity.

Next, the alkaline photographic developing solution containing dihydroxybenzenes as the main developing agent and the alkaline developing solution containing reductones as the main developing agent will be described. As the alkaline developing solution containing dihydroxybenzenes as a main developing agent used in the present invention, a rapid access type developing solution which is widely used at present can be used.

The dihydroxybenzenes used as the main developing agent are not particularly limited, but for example, hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2, Examples thereof include 3-dibromohydroquinone, 2,5-dimethylhydroquinone, potassium hydroquinone monosulfonate, sodium hydroquinone monosulfonate, catechol, and pyrazole, with hydroquinone being particularly preferable. The amount of the main developing agent added is 1 g to 200 g, especially 5 g per liter of the developing solution.
It is preferably used in the range of 50 to 50 g.

In the alkaline developing solution containing dihydroxybenzenes as a main developing agent used in the present invention, 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone, 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.) or aminophenols (eg p-aminophenol, 3-methyl-p-aminophenol, N-methyl-)
p-aminophenol, 2,4-diaminophenol,
N- (4-hydroxyphenyl) glycine, N- (β-
(Hydroxyethyl) -2-aminophenol, 2-hydroxymethyl-p-aminophenol, 2-hydroxymethyl-N-methyl-p-aminophenol, etc.),
Hydrochlorides, sulfates and the like of these compounds can be added and used. Two or more kinds of these auxiliary developing agents may be mixed and used. N-methyl-p-aminophenol is particularly preferable as the auxiliary developing agent. The amount of these auxiliary developing agents added is 0.2 per liter of developing solution.
g to 20 g, preferably O. It is 5 to 10 g.

The alkaline developing solution containing dihydroxybenzenes as the main developing agent used in the present invention preferably contains a preservative in addition to the above essential components. Sulfite can be used as a preservative. As sulfite,
Sodium sulfite, potassium sulfite, lithium sulfite,
Examples include ammonium sulfite, sodium bisulfite, potassium bisulfite, and potassium metabisulfite. The addition amount of these sulfites is preferably 0.3 to 2.5 mol per liter of the developing solution.

Next, the alkaline developer containing the reductone as the main developing agent used in the present invention will be described. The reductones used as the main developing agent in the alkaline developer of the present invention include endiol type (Enddiol),
Enaminol type (Enaminel), enediamine type (Endamine), thiol enol type (Thi
ol-Enol) and enamine thiol type (Ena
Mine-Thiol) is generally known as a compound. Examples of these compounds are described in US Pat. No. 2,688,5
No. 49, JP-A-62-237443 and the like. Methods for synthesizing these reductones are well known, and are described in detail, for example, in "The Chemistry of Reductones" by Yuji Nomura and Hirohisa Omura (1969, Uchida Lao Tsukuba Shinsha).

Of these, reductones which are particularly preferred for use in the present invention are compounds represented by the following general formula (II).

[0105]

[Chemical formula 26]

In the formula, Z is a hydrogen atom or a hydroxyl group,
d is an integer from 0 to 3.

Next, specific examples of the reductones used in the present invention will be given, but the present invention is not limited to these specific examples.

[0108]

[Chemical 27]

[0109]

[Chemical 28]

[0110]

[Chemical 29]

The reductones used as the main developing agent in the alkaline developer of the present invention can be used in the form of alkali metal salts such as lithium salt, sodium salt and potassium salt. The amount of these reductones added is preferably in the range of 1 to 200 g, particularly 10 to 100 g per liter of the developing solution.

In the alkaline developer containing reductone as a main developing agent used in the present invention, dihydroxybenzenes (eg, hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, etc.) as auxiliary developing agents can be used in addition to the above-mentioned main developing agents. , 2,3-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,5-dimethylhydroquinone, potassium hydroquinone monosulfonate, sodium hydroquinone monosulfonate, catechol, pyrazole, etc.), 3-pyrazolidones (eg 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-aminopyrazoline, 1- (p-methylaminophenyl) -3-)
Aminopyrazoline, 1- (p-amino-m-methylphenyl) -3-aminopyrazoline, etc.), 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.) and aminophenols (eg p-aminophenol, 3-methyl-p-aminophenol, N-methyl-p-aminophenol,
2,4-diaminophenol, N- (4-hydroxyphenyl) glycine, N- (β-hydroxyethyl) -2
-Aminophenol, 2-hydroxymethyl-p-aminophenol, 2-hydroxymethyl-N-methyl-p
-Aminophenol, etc.), and hydrochlorides or sulfates of these compounds can be added and used. Two or more kinds of these auxiliary developing agents may be mixed and used.

The amount of these auxiliary developing agents added is 0.2 g to 20 g, preferably 0. 5
It is from g to 10 g.

The alkaline developer containing a reductone as a main developing agent used in the present invention preferably contains a preservative 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.

The alkaline agent used in the alkaline developing solution containing dihydroxybenzenes as a main developing agent and the alkaline developing solution containing reductones as a main developing agent used in the present invention includes an ordinary water-soluble inorganic alkali metal salt (for example, water). Lithium oxide, sodium hydroxide, potassium hydroxide,
Sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, potassium triphosphate, etc.), organic amine compounds (eg butylamine, diethylamine, triethylamine, ethanolamine, dimethylethanolamine, triethanolamine, ethylenediamine, pyridine, etc.) Can be used.

The developer used in the present invention contains an amine compound for the purpose of increasing sensitivity, increasing contrast or promoting development.
At least one or more of a hydrazine compound and a quaternary onium salt compound can be contained. As a specific example,
JP-A-53-77616 and JP-A-53-137133.
No. 54-37732 and No. 60-1495.
No. 9, JP-A No. 60-140340, and JP-A No. 2-8.
833, 2-170155, 4-43.
No. 8, No. 4-5652, No. 4-5653, No. 4-6548, No. 4-114150, No. 4-212144, No. 4-122926, No. 5-93977. Publication, US Pat. No. 4,97
Amine compounds described in Japanese Patent No. 5,354, European Patent No. 518,352A1 and the like, JP-A-4-511143.
JP-A-5-127286 and JP-A-5-13433.
No. 7, JP-A No. 5-134357, and No. 5- 1970.
The amine compound, the hydrazine compound, the quaternary onium salt compound, etc. which are described in JP-A-57-52, JP-A-5-232616, etc. can be mentioned.

The alkaline developing solution containing dihydroxybenzenes as a main developing agent and the alkaline developing solution containing reductones as a main developing agent used in the present invention may optionally contain a water-soluble acid (for example, Acetic acid, boric acid, etc., pH buffering agent (eg, sodium phosphate tribasic, sodium carbonate, potassium carbonate, sodium metaborate,
Lithium tetraborate, etc.), inorganic fogging inhibitor (eg, sodium bromide, potassium bromide, etc.), organic fog inhibitor (eg, 1-phenyl-5-mercaptotetrazole, 5-nitroindazole, etc.), organic solvent ( For example,
Ethylene glycol, diethylene glycol, methyl cellosolve, etc.), toning agents, surfactants, antifoaming agents, water softeners, etc. can be used within the range that the effects of the present invention are not impaired.

The developing processing temperature of the alkaline developing solution containing dihydroxybenzenes as a main developing agent and the alkaline developing solution containing reductones as a main developing agent used in the present invention is selected from the range of 18 to 50 degrees Celsius. , And more preferably in the range of 20 to 40 degrees Celsius. The processing time varies depending on the developing temperature and the processing conditions, but is 10
It is preferably 15 seconds to 5 minutes between seconds and 10 minutes.

The silver halide photographic light-sensitive material of the present invention undergoes (stopping), fixing, washing with water and drying after imagewise exposure even if it is developed with an alkaline developer having a different main developing agent used in the present invention. Through the steps, it is possible to obtain a high contrast image with high sensitivity and similar photographic performance.

The silver halide photographic light-sensitive material developed by the high contrast image forming method of the present invention may be optionally treated with an acidic solution so that the development does not proceed further. It is not always used when automatically conveyed and directly fixed as in the case of using an automatic development processor. As the acidic stop solution, a dilute acetic acid solution, a solution of isomeric potassium bisulfite, or an acidic solution of chrome alum can be used, and sodium sulfate that suppresses swelling of the gelatin film can also be added. The treatment conditions in the stop bath are selected from the range of 10 to 50 degrees Celsius and the range of several seconds to several minutes.

As the fixing solution used in the high contrast image forming method of the present invention, those having a generally used formulation can be used. For example, “Basics of Photographic Engineering” edited by the Photographic Society of Japan
Silver salt photograph edition ”, pp. 330 onward (Corona Publishing Co., Ltd., 1979),
Akira Sasai, "Chemistry of Photography", page 320 and beyond (1982, Photo Industry Publishing Co., Ltd.) and "SPS Handbook of Photographic Science and Engineering" (SPSE HANDBOOK)
OF PHOTOGRAPHY SCIENCE
AND ENGINEERING "Thomas (WT
HOMAS, Jr. ), Published by John Wiley & Sons (1)
973) page 528 and the like. As the fixer main agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixers can be used. Further, as fixing aids, acid agents (eg, acetic acid, citric acid, etc.), preservatives (eg, sodium sulfite, etc.), buffering agents (eg, boric acid, etc.) and hardening agents (eg, potassium alum, alum, sulfuric acid). Aluminum etc.)
Etc. can be used. The fixing temperature and time are the same as in the case of development.

The washing water used in the high-contrast image forming method of the present invention includes antifungal agents (for example, compounds described in "Chemistry of Antibacterial and Antifungal" by Horiguchi), washing accelerators (for example, sulfite). Chelating agents, surfactants (eg anionic,
(Nonionic, cationic, amphoteric, etc.) may be contained. Washing with water is carried out in order to almost completely remove the silver salt dissolved by the fixing and the dye in the film, and the washing is performed at about 20 ° C to 5 ° C.
It is preferably carried out at 0 ° C. for 10 seconds to 5 minutes.

Drying in the high-contrast image forming method of the present invention is preferably carried out in the range of room temperature to 80 ° C. The drying time is appropriately changed depending on the drying conditions, but is usually about 5 seconds to half a day. The developing-fixing-washing-drying process steps are:
It is convenient to use a roller-conveying type automatic development processor capable of continuously performing this, and it is a method generally used in the art as an effective means. Regarding the automatic processor, U.S. Pat. Nos. 3,025,779 and 3,54
5,971 and the like.

[0124]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

Example 1 A silver nitrate aqueous solution and silver were added to a gelatin aqueous solution kept at 40 ° C.
1.5 x 10 per mole^-7Molar rhodium hexachloride (II
I) Potassium bromide and sodium chloride containing sodium
Mixed aqueous solution (molar ratio Br: Cl = 30: 70)
Keep pAg 7.2 while simultaneously applying for 75 minutes.
To obtain a cubic crystal monodisperse with an average particle size of 0.18 μm
Of silver chlorobromide emulsion (70 mol% of AgCl) was prepared.
Was. After removing soluble salts by a conventional method, silver halide
2.5 x 10 per mole^-FiveMolar sodium thiosulfate
And 1.6 × 10^-FiveMolar chloroauric acid trihydrate (HAuC
l _Four ・ 3H₂ O) is added and chemistry is performed at 50.0 ° C for 100 minutes.
Aged 80 g per mol of silver halide in this emulsion
Contains gelatin. The emulsion prepared in this way
1 x 10 per mol of silver halide^-3Molar iodide
Lium and 1.2x10^-2Mole of 6-hydroxy-4
-Methyl-1,3,3a, 7-tetrazaindene was added
did. This emulsion was subdivided into 6 parts, each of which is shown in Table 1.
Added specific example compounds of general formula (I) and comparative compounds
After that, polyethylene terfev coated with a subbing layer in advance
100 cm on the Talate (PET) base² 40m
It was applied so that the amount of silver was g. This emulsion layer as a hardener
And gelatin containing formalin and dimethylolurea
Protect with a protective layer and attach the film of sample Nos. 1 to 6
It was made.

[0126]

Embedded image

[0127]

[Table 1]

The film sample produced as described above was exposed for 5 seconds using a LB-200 filter with a tungsten light source of 2666K through a step wedge having a step of 0.15, and then a developing solution 1 and a developing solution having the following formulations were prepared. 2. Using developer 3 respectively, development processing was carried out at 35 ° C. for 30 seconds, stopping, fixing, washing with water and drying.

Formulation of Developer 1 Anhydrous sodium sulfite 70.0 g Hydroquinone 30.0 g N-Methylparaaminophenol 1/2 sulfate 2.5 g Anhydrous sodium carbonate 40.0 g Sodium hydroxide 12.0 g Odor Potassium iodide 1.0 g 5-methylbenzotriazole 0.4 g 5-nitroindazole 0.04 g Water was added to make the total volume 1.0 liter, and the pH was adjusted to 10.8.

Formulation of Developer 2 N-methylparaaminophenol.1 / 2-sulfate 7.5 g Sodium ascorbate 30.0 g Potassium bromide 1.0 g Anhydrous sodium carbonate 53.0 g 5-Nitroindazole 0. The pH was adjusted to 10.2 by adding 1 g water to a total volume of 1.0 liter.

Formulation of Developer 3 N-Methylparaaminophenol.1 / 2 Sulfate 7.5 g Sodium Ascorbate 30.0 g Potassium Bromide 1.0 g Sodium Metaborate Tetrahydrate 70.0 g 5- Nitroindazole 0.1 g Water was added to make the total volume 1.0 liter, and the pH was adjusted to 10.2.

Note) * The pH of each developer was adjusted with 50% potassium hydroxide or 5% sulfuric acid aqueous solution. Table 2 shows the results of the obtained photographic characteristics.

[0133]

[Table 2]

The relative sensitivity in Table 2 is the relative value of the reciprocal of the exposure amount at which a density of 3.0 excluding fogging is obtained, and the sensitivity when film No. 3 is developed with Developer 1 at 35 ° C. for 30 seconds is 100. It is shown. Gamma represents the average gradient between blackened densities of 0.5 and 3.0 excluding fog, and fog represents the density of unexposed areas.

In the case of the film No. 1 in which no hydrazine compound was added, no tone increase occurred in any developer. In the case of the film No. 2 to which the comparative compound was added, a relatively good image was obtained in the developing treatment with the developing solution 1, but a good high contrast image could not be obtained with the developing solution 2 and the developing solution 3.

However, the film No. 3, the film No. 4, the film No. 5, and the film No. 6 which are the films of the present invention to which the hydrazine compound of the general formula (I) is added.
In the case, no matter which of the developing solution 1, the developing solution 2 and the developing solution 3 is used for development, both gamma and sensitivity are high and a stable and good image can be obtained.

As described above, the film according to the present invention to which the hydrazine compound represented by the general formula (I) is added can be developed by using a reductone as a developing agent even when the film is developed by a developing solution containing dihydroxybenzenes as a developing agent. It can be seen that a good image can be obtained even when the development processing is carried out by. Further, the film of the present invention to which the hydrazine compound represented by the general formula (I) is added may be developed with a developing solution containing dihydroxybenzenes as a developing agent, or with a developing solution containing reductones as a developing agent. It can be seen that there is no difference in photographic characteristics between the two, and stable photographic performance can be obtained with any developer.

Example 2 Using the developer 1 of Example 1, an automatic development processor (LD-220-QT manufactured by Dainippon Screen Mfg. Co., Ltd.) was used.
Film No. 3, film No. 4, film No. 5 and film No. 6 of the present invention produced by the above-mentioned formulation were processed and a running test was conducted. The automatic development processor is 1
The film No. 3, the film No. 4, the film No. 5 and the film No. 6 produced in Example 1 which were operated for 8 hours a day and kept at a temperature of 35.degree. A total of 60 sheets of 15 sheets were processed.

The replenishment rate was set to 5.6 ml / dm ² . The photographic performance of the film was compared at the start of evaluation and after one month. As an evaluation method, each film was exposed for 5 seconds through a step wedge having a step of 0.15 with a tungsten light source of 2666K using an LB-200 filter. The development was carried out by the above-mentioned automatic development processor, and the development time was 35 ° C. and 30 seconds.
The fixing tank and the fixing replenishing tank were filled with a 1: 2 diluted Rapid Access RA Fixer and Replenisher manufactured by Kodak Co., and a fixing process was performed. Further, the washing tank was filled with tap water that had been passed through a filter for washing treatment. The drying was performed by setting the temperature to 45 ° C. The results are shown in Table 3.
Shown in

[0140]

[Table 3]

In Table 3, the relative sensitivity is the relative value of the reciprocal of the exposure amount at which the density of the evaluation sample excluding fog is 3.0, and the sensitivity when the film is treated with each developing solution at the start of evaluation is 100. did. Gamma represents the average gradient between blackened densities of 0.5 and 3.0 excluding fog, and fog represents the density of unexposed areas.

When the film of the present invention was developed with Developer 1, even after one month, the gamma was not decreased and the sensitivity was changed less than at the start of evaluation, and a good and high-contrast image was obtained without problems in photographic performance. You can see that it is being done.

Example 3 An automatic development processor (LD-220-Q manufactured by Dainippon Screen Mfg. Co., Ltd.) was used by using Developer 4 having the following formulation.
In T), the film No. 3, the film No. 4, the film No. 5 and the film No. 6 produced in Example 1 were processed and a running test was conducted.

Formulation of Developer 4 N-Methylparaaminophenol.1 / 2 Sulfate 7.5 g Sodium Ascorbate 30.0 g Potassium Bromide 1.0 g Potassium Metaborate.4 / 3 Hydrochloride 54.0 g Sodium sulfite 13.0 g Water was added to make the total volume 1.0 liter, and the pH was adjusted to 10.2.

The automatic processor is operated for 8 hours a day, the temperature is kept at 35 ° C., and the paper size (50.8 c
m × 61 cm), which were exposed to the entire surface, were treated with the film number 3, the film number 4, the film number 5, and the film number 6 produced by the above-mentioned prescription, 15 sheets each, for a total of 60 sheets. The replenishment rate was set to 5.6 ml / dm ² . The photographic performance of the film was compared at the start of evaluation and after one month.

As an evaluation method, each film was exposed for 5 seconds using a LB-200 filter with a tungsten light source of 2666K through a step wedge having a step of 0.15. The development was carried out by the above-mentioned automatic development processor, and the development time was 35 ° C. and 30 seconds.
The fixing tank and the fixing replenishing tank were filled with a 1: 2 diluted Rapid Access RA Fixer and Replenisher manufactured by Kodak Co., and a fixing process was performed. Further, the washing tank was filled with tap water that had been passed through a filter for washing treatment. The drying was performed by setting the temperature to 45 ° C. Table 4 shows the results
Shown in

[0147]

[Table 4]

In Table 4, the relative sensitivity is the relative value of the reciprocal of the exposure dose at which the density of the evaluation sample excluding fog is 3.0, and the sensitivity when the film is treated with each developing solution at the start of evaluation is 100. did. Gamma represents the average gradient between blackened densities of 0.5 and 3.0 excluding fog, and fog represents the density of unexposed areas.

When the film of the present invention was developed with the developing solution 4, there was little reduction in gamma and change in sensitivity even after one month from the start of evaluation, and a good and high-contrast image was obtained with no problems in photographic performance. You can see that it is being done. Also, Table 3 and Table 4
In comparison, the photographic performance is almost the same, and similar photographic performance can be obtained with different developers.

[0150]

By using the silver halide photographic light-sensitive material of the present invention, a method using a developing solution containing dihydroxybenzenes as a developing agent and a method using a developing solution containing reductones as a developing agent after exposing an image. In any of the development processing methods described above, it is possible to obtain a hard tone and good image exhibiting the same photographic performance.

Claims (19)

[Claims] 1. A negative-type silver halide photographic light-sensitive material having at least one negative-type silver halide emulsion layer on a support and, if necessary, another hydrophilic colloid layer, the emulsion layer or another hydrophilic colloid. In at least one of the layers,
A silver halide photographic light-sensitive material containing at least one hydrazine compound represented by formula (I). Embedded image (In the formula, R ₁ represents a hydrogen atom, an optionally substituted aliphatic group, an optionally substituted aromatic group or an optionally substituted heterocyclic group. R ₂ is a hydrogen atom or a blocking group. A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is a sulfonyl group, an acyl group or an oxalyl group, and E is a carbonyl group, a sulfonyl group,
It represents a sulfoxy group, a phosphoryl group, an oxalyl group or an iminomethylene group. G ₁ represents a divalent optionally substituted aliphatic group, an optionally substituted aromatic group or an optionally substituted heterocyclic group. G ₂ represents a divalent aromatic group which may be substituted or an unsaturated heterocyclic group which may be substituted. L is a divalent linking group. R ₃ ⁺ represents a nitrogen-containing 6-membered aromatic quaternary base whose reduction potential is less than -0.6 V, and may be further substituted with a substituent. Substituents that may be substituted include alkyl groups, alkenyl groups, alkynyl groups, aralkyl groups, alkoxy groups, substituted amino groups, acylamino groups, sulfonylamino groups, ureido groups, urethane groups, aryloxy groups, sulfamoyl groups, carbamoyl groups. , Ester group, sulfonate group, aryl group, alkylthio group, arylthio group, carboxyalkyl group, sulfoxyalkyl group, acyl group, substituted sulfonyl group, sulfinyl group, hydroxy group, cyano group, sulfoxyl group, carboxyl group, halogen Is an atom. These substituents may be further substituted and may be connected to each other to form an aliphatic ring, aromatic ring or hetero ring. X ⁻ is a counter anion,
An inner salt may be formed. ) 2. A high contrast image forming method, wherein the alkaline developing solution used in the development processing of the silver halide photographic light-sensitive material is an alkaline developing solution containing dihydroxybenzenes as a main developing agent. 3. The high contrast image forming method according to claim 2, wherein the alkaline developer containing dihydroxybenzenes as a main developing agent contains 3-pyrazolidones as an auxiliary developing agent. 4. The high contrast image forming method according to claim 2, wherein the alkaline developer containing dihydroxybenzenes as a main developing agent contains aminophenols as an auxiliary developing agent. 5. The high contrast image forming method according to claim 2, wherein the alkaline developer containing dihydroxybenzenes as a main developing agent contains sulfite as a preservative. 6. A high contrast image forming method, wherein the alkaline developer used in the development processing of the silver halide photographic light-sensitive material is an alkaline developer containing a reductone as a main developing agent. 7. The high contrast image forming method according to claim 6, wherein the alkaline developer containing the reductone as a main developing agent contains dihydroxybenzenes as an auxiliary developing agent. 8. The high contrast image forming method according to claim 6, wherein the alkaline developer containing the reductone as a main developing agent contains 3-pyrazolidones as an auxiliary developing agent. 9. The high contrast image forming method according to claim 6, wherein the alkaline developer containing the reductone as a main developing agent contains 3-aminopyrazoline as an auxiliary developing agent. 10. The high contrast image forming method according to claim 6, wherein the alkaline developer containing the reductone as a main developing agent contains phenylenediamines as an auxiliary developing agent. 11. The high contrast image forming method according to claim 6, wherein the alkaline developer containing the reductone as a main developing agent contains aminophenols as an auxiliary developing agent. 12. The high contrast image forming method according to claim 6, wherein the reductone is an endiol type reductone compound. 13. The high contrast image forming method according to claim 6, wherein the reductones are enaminol type reductone compounds. 14. The high contrast image forming method according to claim 6, wherein the reductone is an enediamine type reductone compound. 15. The high contrast image forming method according to claim 6, wherein the reductones are thiolenol type reductones. 16. The high contrast image forming method according to claim 6, wherein the reductone is an enaminethiol type reductone compound. 17. The high contrast image forming method according to claim 12, wherein the enediol-type reductone compound is a compound represented by the following general formula (II) or a salt thereof. Embedded image (In the formula, Z represents a hydrogen atom or a hydroxyl group, and d represents an integer of 0 to 3.) 18. A photograph which is exactly the same in the case of the developing treatment with either the above-mentioned alkaline developing solution containing dihydroxybenzenes as the main developing agent or alkaline developing solution containing the reductones as the main developing agent. The silver halide photographic light-sensitive material according to claim 1, wherein a high-contrast image showing performance is obtained. 19. In the case of the development processing by any one of the alkaline developing solutions containing dihydroxybenzenes as a main developing agent or the alkaline developing solutions containing reductones as a main developing agent and having different main developing agents. In the above, the image forming method is characterized in that a high contrast image having exactly the same photographic performance is obtained.