JP2001109097A - Silver halide photographic sensitive material and photographic image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photographic sensitive material which attains rapid progress of development and high contrast even in the case of processing with a developing solution of a low pH and is less liable to a change of its photographic performance due to a pH change and to provide an image forming method. SOLUTION: At least one diazonium salt or its precursor is incorporated into a silver halide photographic sensitive material containing at least one hydrazine derivative or development is carried out in the presence of these compounds.

Description

DETAILED DESCRIPTION OF THE INVENTION TECHNICAL FIELD OF THE INVENTION

[0001] The present invention relates to a silver halide photographic material which is processed with a developer and a photographic image forming method.

[Prior art]

[0002]

2. Description of the Related Art A method for producing a high contrast image using a hydrazine derivative is well known and widely used for photoengraving. However, since a high pH is generally required, the developer is easily oxidized by air and is unstable.

[0003] Attempts have been made to develop a silver halide photosensitive material containing a hydrazine compound with a developer having a lower pH to produce a high-contrast image. JP-A-1-17993
No. 9 and JP-A-1-179940, a photosensitive material containing a nucleation developing accelerator having an adsorptive group for silver halide emulsion grains and a nucleating agent also having an adsorptive group has a pH of 11.0. A processing method of developing with the following developer is described. U.S. Pat. Nos. 4,998,604 and 4,994,365 disclose a hydrazine compound having a repeating unit of ethylene oxide and a hydrazine compound having a pyridinium group. However, as is apparent from these examples, the high contrast is not sufficient, and the high contrast and the necessary D
It is difficult to get max.

In addition, the pH of a developer rises due to concentration of the developer due to air oxidation or evaporation of moisture, or decreases due to absorption of CO ₂ gas in the air or development processing of an exposed photosensitive material. It is not always kept constant. When the pH of the developing solution changes, the photographic performance changes, and particularly the high contrast performance changes. Therefore, it is necessary to add a large amount of replenisher.

[0005] As described above, there has been a demand for an image forming method in which the development pH is further reduced and the change in photographic performance due to the pH fluctuation is small. However, the prior art could not be satisfied.

[0006] On the other hand, in order to reduce the influence on the environment, attempts have been made to substitute hydroquinone, which has been conventionally and generally used, with ascorbic acid. Tokiohei 6
No. 505574 (corresponding to International Patent Publication No. 93/1145)
6), US Pat. Nos. 5,236,816 and 5,26.
No. 4,323 discloses an image forming method in which a silver halide photosensitive material containing a hydrazine derivative is processed with a developing solution containing ascorbic acid. According to the description, a high-contrast image cannot be obtained unless a 3-pyrazolidone derivative is used in combination with an ascorbic acid developing agent as a super-additive auxiliary developing agent and the pH of the developing solution is relatively high. In fact, as a result of additional tests, ultrahigh contrast performance could not be obtained unless the pH was as high as pH 11.0. As a serious drawback of this system, it has been found that when the developer is oxidized by air or fatigued by film processing, the pH is significantly lowered, and the ultra-high contrast performance is extremely impaired.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide an improved silver halide photographic light-sensitive material and a photographic image forming method. In particular, it is an object of the present invention to provide a light-sensitive material which can obtain a high contrast even when processed with a low pH developer, develops quickly, and is excellent in development processing.

[0008]

The above objects of the present invention are attained in a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support and containing a hydrazine derivative. This has been achieved by a silver halide photographic material characterized by containing at least one diazonium salt or a precursor thereof. Further, the above objects of the present invention are to provide a silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support and containing a hydrazine derivative, at least one kind of diazonium salt, or This has also been achieved by an image forming method characterized in that development is performed in the presence of the precursor. In the above development, ascorbic acid containing, pH
Is preferably developed using a developer having a pH of 9.5 to 10.5.

The diazonium salt of the present invention or a precursor thereof will be described below. The diazonium salt of the present invention or a precursor thereof is preferably selected from the group represented by the following general formula (1) or (2).

Embedded image Here, R ₁ and R ₂ represent an aliphatic group or an aromatic group.
n is an integer of 1 or more. X ^n- is a counter anion;
Y is a group selected from the group consisting of a sulfonic acid group, a phosphoric acid group, and a carboxyl group.

[0010] n is preferably an integer of 1 to 3.
The aliphatic group represented by R ₁ preferably has 1 to 30 carbon atoms, and is particularly a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. This alkyl group may have one or more substituents. The aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with an aryl group. R
Preferred as ₁ is an aryl group, particularly preferably a group containing a benzene ring. The aliphatic group and the aromatic group of R ₁ may be substituted with one or more substituents,
Representative substituents include, for example, alkyl, alkenyl, alkynyl, alkoxy, aryl, substituted amino, ureido, aryloxy, sulfamoyl, carbamoyl, alkylthio, arylthio, alkylsulfonyl Group, arylsulfonyl group, alkylsulfinyl group, arylsulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamide group,
Examples include a sulfonamide group, a carboxyl group, a phosphoramide group, a diacylamide group, and an imide group. Preferred substituents include an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a substituted amino group substituted with an alkyl group having 1 to 20 carbon atoms, carbon atom Acylamino group having 2 to 30 carbon atoms, 1 to 3
0 sulfonamide group, ureido group having 1 to 30 carbon atoms,
And a phosphoric amide group having 1 to 30 carbon atoms.

R ₁ may have incorporated therein a ballast group or a polymer commonly used as a diffusion-resistant photographic additive such as a coupler. The ballast group is a group having a carbon number of 8 or more, which is relatively inert to photographic properties. For example, the ballast group is selected from an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group, and the like. Can be. Further, as the polymer, for example, those described in JP-A-1-100530 can be used.

It is also preferred that R ₁ incorporates a group that enhances adsorption to the surface of silver halide grains. Examples of such adsorptive groups include thiourea groups, heterocyclic thioamide groups, mercapto groups, and heterocyclic groups such as imidazole, triazole and tetrazole.
Nos. 5,108 and 4,459,347;
Nos. 195233, 59-200231 and 59-2
No. 01045 to No. 59-201049, No. 61-17
Nos. 0733, 61-270744, 62-948
The adsorbing groups described in (1) are mentioned.

The diazonium salt of the present invention and its precursor are present in a molar ratio of 1/100 to the hydrazine derivative.
To 100/1, preferably 1/10 to 10/1.

The diazonium salt and the precursor thereof according to the present invention may be dissolved in water or an organic solvent (methanol, ethanol, acetone, DMF, ethyl acetate, etc.), added as an emulsified dispersion or a solid dispersion. May be. The layer to be added is preferably a photosensitive emulsion layer or another non-photosensitive hydrophilic colloid layer.

Next, specific examples of the diazonium salt of the present invention and its precursor are shown, but the present invention is not limited to these compounds.

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[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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The hydrazine derivative used in the present invention is
Although any of them can be used, a compound represented by the following general formula (I) is preferable. General formula (I)

[0023]

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In the formula (I), R ₁ is an aliphatic group, an aromatic group,
Or a heterocyclic group, and R ₂ is a hydrogen atom or a block group. G ₁ is a —CO— group, a —SO ₂ — group, a —S
O- group, -CO-CO- group, a thiocarbonyl group, an iminomethylene group or _{-P (O) (R 3)} - represents a group, R ₃
It is selected from the same range as the groups defined in R _2, may be different from R _2.

A ₁ and A _{2 each} represent a hydrogen atom, or one of them represents a hydrogen atom and the other represents a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. In the general formula (I), the aliphatic group represented by R ₁ is preferably a hydrocarbon group having 1 to 30 carbon atoms, particularly a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms.
Here, the branched alkyl group may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Further, this alkyl group may have a substituent. In the general formula (I), the aromatic group represented by R ₁ 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,
There are pyridine ring, pyrimidine ring, imidazole ring, pyrazole ring, quinoline ring, isoquinoline ring, benzimidazole ring, thiazole ring, benzothiazole ring, etc.
Among them, those containing a benzene ring are preferred.

Particularly preferred as R ₁ is an aryl group. The aliphatic group, aromatic group or heterocyclic group represented by R ₁ may be substituted. Representative examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a group containing a heterocyclic ring, and a pyridinium. Group, hydroxy group,
Groups having an alkoxy group, an aryloxy group, an acyloxy group, an alkyl or arylsulfonyloxy group, an amino group, a carbonamide group, a sulfonamide group, a ureido group, a thioureido group, a semicarbazide group, a thiosemicarbazide group, a urethane group, and a hydrazide structure; A group having a quaternary ammonium structure, an alkyl or arylthio group,
Alkyl or aryl sulfonyl group, alkyl or aryl sulfinyl group, carboxyl group, sulfo group,
Acyl group, alkoxy or aryloxycarbonyl group, carbamoyl group, sulfamoyl group, halogen atom, cyano group, phosphoric amide group, diacylamino group, imide group, group having an acylurea structure, group containing selenium atom or tellurium atom, 3 Groups having a quaternary sulfonium structure or a quaternary sulfonium structure, and preferred substituents are a linear, branched or cyclic alkyl group (preferably having 1 to 20 carbon atoms) and an aralkyl group (preferably having an alkyl moiety). A monocyclic or bicyclic one having 1 to 3 carbon atoms, an alkoxy group (preferably 1 to 20 carbon atoms), a substituted amino group (preferably an amino group substituted with an alkyl group having 1 to 20 carbon atoms) ), An acylamino group (preferably having 2 to 30 carbon atoms), a sulfonamide group (preferably having 1 carbon atom) Those with 30), a ureido group (preferably having 1 to 30 carbon atoms), a phosphoric acid amide group (preferably those having 1 to 30 carbon atoms).

As the blocking group for R ₂ , an alkyl group,
There are an aryl group, an unsaturated heterocyclic group, an alkoxy group, an aryloxy group, an amino group, and a hydrazino group.

In formula (I), the alkyl group represented by R ₂ is preferably an alkyl group having 1 to 4 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group. It contains a ring. At least one nitrogen as an unsaturated heterocyclic group,
5- and 6-membered compounds containing oxygen and sulfur atoms, for example, imidazolyl, pyrazolyl, triazolyl,
Examples include a tetrazolyl group, a pyridyl group, a pyridinium group, a quinolinium group, and a quinolinyl group. Pyridyl or pyridinium groups are particularly preferred.

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 an unsubstituted amino group or an alkylamino having 1 to 10 carbon atoms. And arylamino groups are preferred. R ₂ may be substituted, and preferred examples of the substituent include those exemplified as the substituent of R ₁ .

Among the groups represented by R ₂ , when G 1 is a —CO— group, an alkyl group (eg, a methyl group, a trifluoromethyl group, a 2-carboxy-tetrafluoroethyl group, Hydroxypropyl group,
3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, methyl group substituted with a pyridinium 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-hydroxymethylphenyl group, etc.)
Trifluoromethyl groups are preferred. In addition, G ₁ is -SO ₂
R ₂ represents an alkyl group (eg, a methyl group), an aralkyl group (eg, an o-hydroxybenzyl group), an aryl group (eg, a phenyl group), or a substituted amino group (eg, a dimethylamino group). Are preferred. When G ₁ is a —COCO— group, an alkoxy group, an aryloxy group, and a substituted or unsubstituted amino group are preferred.

G _{1 in the} general formula (I) represents a —CO— group,
-COCO- groups are preferred and -CO- groups are most preferred. R ₂ may also be such as to cause a cyclization reaction that cleaves the G ₁ -R ₂ moiety from the residual molecule to form a cyclic structure containing atoms of the -G ₁ -R ₂ moiety. Examples thereof include those described in JP-A-63-29751.

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

R ₁ or R _{2 in} the general formula (I) may have a ballast group or polymer commonly used in immobile photographic additives such as couplers incorporated therein. A ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, for example, an alkyl group,
It can be selected from aralkyl groups, alkoxy groups, phenyl groups, alkylphenyl groups, phenoxy groups, alkylphenoxy groups and the like. Examples of the polymer include those described in JP-A-1-100530.

R ₁ or R _{2 in} the general formula (I) may have a group in which a group which enhances adsorption to the surface of silver halide grains is incorporated. Examples of such an adsorbing group include U.S. Pat. Nos. 4,385,108 and 4,459,34 such as an alkylthio group, an arylthio group, a thiourea group, a heterocyclic thioamide group, a mercapto heterocyclic group, and a triazole group.
7, JP-A-59-195233 and JP-A-59-2002.
No. 31, No. 59-201045, No. 59-20104
No. 6, No. 59-201047, No. 59-201048
No. 59-201049, JP-A-61-17073.
Nos. 3, 61-270744, 62-948, 63-234244, 63-234245, and 6
The group described in 3-234246 is mentioned.

Particularly preferred hydrazine derivatives in the present invention are those wherein R ₁ is a ballast group via a sulfonamide group, an acylamino group or an 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 is a —CO— group or —COCO— group, and R ₂ is a substituted alkyl group or a substituted aryl group (an electron-withdrawing group or a hydroxymethyl A hydrazine derivative which is a substituted or unsubstituted amino group. It should be noted that any combination of the above-mentioned options of R ₁ and R ₂ is possible and preferable.

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

[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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In the present invention, as the hydrazine derivative, 1
A compound having a plurality of acylhydrazino groups in the molecule can be used. Such hydrazine derivatives are disclosed in JP-B-7-82220, JP-A-4-16938,
197991, JP-A-9-235266, JP-A-9-
179229. Next, specific examples will be given, but the present invention is not limited to these.

[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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The amount of the hydrazine derivative to be added in the present invention is preferably 1 × 10 ^-6 mol to 5 × 10 ^-2 mol, and more preferably 1 × 1 ^-6 mol per mol of silver halide.
The range of 0 ^-5 mol to 2 × 10 ^-2 mol is a preferable addition amount. The hydrazine derivative in the present invention is contained in the emulsion layer and / or another hydrophilic colloid layer. Here, examples of the other hydrophilic colloid layer include a protective layer, a layer provided between the emulsion layer and the support, and an intermediate layer.

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

The silver halide photographic light-sensitive material of the present invention comprises, as a development accelerator, an amine derivative, an onium salt, a disulfide derivative and hydroxymethyl in at least one layer of a silver halide emulsion layer or another hydrophilic colloid layer. It may contain a nucleation accelerator selected from derivatives. One of these nucleation accelerators may be used alone, or a plurality thereof may be used in combination. Examples of the amine derivative include, for example,
-140340, 62-50829, 62-2
No. 22241, No. 62-250439, No. 62-28
No. 0733, No. 63-124045, No. 63-133
145, 63-286840 and the like. More preferably, the amine derivative is described in JP-A-63-1224045 and JP-A-63-1331,1.
No. 45, 63-286840, etc., compounds having a group which adsorbs to silver halide;
The sum of the number of carbon atoms described in No. 2-222241 is 2
0 or more compounds. As the onium salt, an ammonium salt or a phosphonium salt is preferable. Preferred examples of ammonium salts are described in JP-A-62-250439.
And No. 62-280733. Examples of preferred phosphonium salts include JP-A-61-167939 and JP-A-62-2.
80733 and the like. Examples of the disulfide derivative include, for example,
The compound described in 1-198,147 can be mentioned. Examples of hydroxymethyl derivatives include, for example, U.S. Pat. Nos. 4,693,956 and 4,777,118;
P231, 850, JP-A-62-50829, and the like, and more preferred are diarylmethanol derivatives.

The optimum addition amount of these accelerators varies depending on the type thereof, but 1.0 × 1 per mol of the hydrazine compound.
0 ^-2 mol to 1.0 × 10 ² mol, preferably 1.0 × 10 ² mol
It is desirable to use in the range of 10 ^-1 mol to 1.0 × 10 mol. These compounds are dissolved in an appropriate solvent (H ₂ O) such as alcohols such as methanol and ethanol, acetone, dimethylformamide, and methylcellosolve, and added to the coating solution.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention may be silver chloride, silver bromide, or a mixed silver halide such as silver chlorobromide, silver iodobromide, or silver halide. Silver iodobromide and the like can be used. Silver chlorobromide and silver iodochlorobromide having a silver chloride content of 50 mol% or more are preferred. The silver iodide content is preferably 3 mol% or less, more preferably 0.5 mol or less. The shape of the silver halide grains may be any of cubic, tetradecahedral, octahedral, irregular, and tabular, but a cubic is preferred. The average grain size of the silver halide is preferably 0.01 μm to 0.7 μm, more preferably 0.05 to 0.5 μm, and {(standard deviation of grain size) / (average grain size)} × 100. It is preferable that the expressed coefficient of variation is 15% or less, more preferably 10% or less, with a narrow particle size distribution. The silver halide grains may have a uniform inner or surface layer or different layers. The photographic emulsion used in the present invention is described by P. Glafkides.
Chimie et Physique Photographique (Paul Montel, 1967), PhotographicEmuls by GF Dufin
ion Chemistry (The Focal Press, 1966),
Making and Coating Photogr by VL Zelikman etal
It can be prepared using a method described in, for example, aphic Emulsion (The Focal Press, 1964).

As a method of reacting the soluble silver salt with the soluble halogen salt, any of a one-side mixing method, a simultaneous mixing method, a combination thereof and the like may be used. Method of forming grains in excess of silver ions (so-called reverse mixing method)
Can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. Further, it is preferable to form grains using a so-called silver halide solvent such as ammonia, thioether, or tetra-substituted thiourea. More preferred are tetra-substituted thiourea compounds.
No. 08, 55-77737. Preferred thiourea compounds are tetramethylthiourea, 1,3-
Dimethyl-2-imidazolidinthione. According to the controlled double jet method and the grain forming method using a silver halide solvent, it is easy to produce a silver halide emulsion having a regular crystal form and a narrow grain size distribution, and the silver halide used in the present invention is easy to produce. It is a useful tool for making emulsions. Further, in order to make the particle size uniform, British Patent No. 1,535,016, JP-B-48-3689.
No. 0 and No. 52-16364,
A method in which the addition rate of silver nitrate or alkali halide is changed according to the grain growth rate, and a method disclosed in British Patent No. 4,242,4
No. 45 and Japanese Patent Application Laid-Open No. 55-158124, it is preferable to use a method of changing the concentration of the aqueous solution and to grow the solution quickly within a range not exceeding the critical saturation.

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

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

As the selenium sensitizer used in the present invention, known selenium compounds can be used. That is, usually, an unstable type and / or an unstable type selenium compound is added, and the emulsion is stirred at a high temperature, preferably at 40 ° C. or higher for a certain period of time. Examples of unstable selenium compounds include JP-B-44-15748 and JP-B-43-1.
No. 3489, JP-A-4-25832, JP-A-4-1092
Compounds described in Nos. 40 and 4-324855 can be used. It is particularly preferable to use the compounds represented by 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 silver halide grains. The formation rate of silver telluride in a silver halide emulsion is described in
It can be tested by the method described in US Pat.
Specifically, U.S. Pat. Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211 and 1,121,496
No. 1,295,462, No. 1,396,69
No. 6, Canadian Patent No. 800,958, JP-A No. 4-20
No. 4640, No. 4-271341, No. 4-33304
No. 3, 4-129787, J. Chem. Soc. Chem. Co.
mmun., 635 (1980), 1102 (1979),
645 (1979), J. Chem. Soc. Perkin. Tran
s., 1, 191 (1980), edited by S. Patai, TheChem
istry of Organic Serenium and Tellurium Compounds,
The compounds described in Vol. 1 (1986) and Vol. 2 (1987) can be used. In particular, JP-A-5-31328
Compounds represented by formulas (II), (III) and (IV) in No. 4 are preferred.

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

The noble metal sensitizer used in the present invention includes gold, platinum, palladium and the like, and gold sensitization is particularly preferable. Specific examples of the gold sensitizer used in the present invention include chloroauric acid, potassium chlorate, potassium aurithiocyanate, and gold sulfide, and about 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, a lead salt, a thallium salt and the like may coexist in the process of forming silver halide grains or physical ripening. In the present invention, reduction sensitization can be used. Stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used as the reduction sensitizer. A thiosulfonic acid compound may be added to the silver halide emulsion of the present invention by the method described in EP 293,917. The silver halide emulsion in the light-sensitive material used in the present invention may be only one kind or two or more kinds (for example, those having different average grain sizes, those having different halogen compositions, those having different crystal habits, those having chemical sensitization, Those with different conditions) may be used in combination.

The silver halide photographic light-sensitive material of the present invention preferably contains 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, rhodium (III) halide compounds or rhodium complex salts having halogens, amines, oxalates and the like as ligands, for example, hexachlororhodium (III) complex salt, hexabromorhodium (III) complex salt, hexaamminerhodium ( III) complex salts and trizalatrodium (III) complex salts. These rhodium compounds are used by dissolving them in water or a suitable solvent, and are generally used to stabilize the solution of the rhodium compound, that is, a hydrogen halide aqueous solution (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid) Etc.) or alkali halides (eg KCl, NaCl: KBr, Na
(Br, etc.) can be used. Instead of using water-soluble rhodium, it is also possible to add and dissolve another silver halide grain doped with rhodium in the preparation of silver halide.

The total amount of the rhodium compound added is from 1 × 10 ^{−8 to} 5 × 1 per mol of silver halide finally formed.
0 ^-6 mol are suitable, preferably 5 × 10 ^-8 ~1 × 1
0 ^-6 mol. These compounds can be appropriately added at the time of production of silver halide emulsion grains and at each stage before coating the emulsion. Particularly, they can be added at the time of emulsion formation and incorporated into silver halide grains. preferable.

The silver halide photographic material of the present invention preferably contains an iridium compound in order to achieve high sensitivity and high contrast. Various compounds can be used as the iridium compound used in the present invention,
For example, hexachloroiridium, hexaammineiridium, trioxalatoiridium, hexacyanoiridium and the like can be mentioned. These iridium compounds are used after being dissolved in water or a suitable solvent. However, a method generally used to stabilize the solution of the iridium compound, that is, a hydrogen halide aqueous solution (for example, hydrochloric acid, bromic acid, hydrofluoric acid) is used. Etc.) or a method of adding an alkali halide (for example, KCl, NaCl, KBr, NaBr, etc.). Instead of using water-soluble iridium, it is also possible to add and dissolve another silver halide grain doped with iridium in advance during the preparation of 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, preferably 5 × 10 ^-8 to 1 ×.
10 ^-6 mol. These compounds can be appropriately added at the time of production of silver halide emulsion grains and at each stage before coating the emulsion, but it is particularly preferable to add them at the time of emulsion formation and to incorporate them into silver halide grains. .

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

Further, a contact film or a contact paper which can be handled in a bright room is generally called a bright room return light-sensitive material. For such a light-sensitive material, a silver chloride emulsion is preferable.

The various additives used in the light-sensitive material of the present invention are not particularly limited, and for example, those described in the following places can be preferably used. Item: 1) Silver halide emulsion JP-A-2-97937, page 20, lower right column, line 12 and its production method, page 21: lower left column, line 14; JP-A-2-122236 The selenium sensitization method described on page 7, upper right column, line 19 to page 8, lower left column, line 12, and Japanese Patent Application No. 2-189532. 2) Spectral sensitizing dyes JP-A-2-12236, page 8, lower left column, line 13 to lower right column, line 4; JP-A-2-103536, page 16, lower right column, lines 3 to page 17 Spectroscopy described in the lower left column, line 20, further described in JP-A-1-112235, JP-A-2-124560, JP-A-3-7928, JP-A-3-189532, JP-A-3-411106, and JP-A-6-103272. Sensitizing dye. 3) Surfactant JP-A-2-12236, page 9, upper right column, line 7 to lower right column, line 7, and JP-A-2-18542, page 2, lower left column, line 13 to page 4, right The bottom line, line 18, Japanese Patent Application No. 5-204325. 4) Antifoggants JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5, furthermore, JP-A-1-237538. Thiosulfinic acid compound described in Japanese Patent Publication No. 5) Polymer latex JP-A-2-103536, page 18, lower left column, lines 12 to 20. 6) Compound having an acid group From page 6, lower right column, line 6 to page 19, upper left column, line 1 of JP-A-2-103536. 7) Matting agent, slipping agent JP-A-2-103536, page 19, upper left column, line 15 Plasticizer to page 19, upper right column, line 15 9) Hardener JP-A-2-103536, page 18, right upper column, 5th line to 17th line. 9) Dyes Dyes described in JP-A-2-103536, page 17, lower right column, lines 1 to 18; solid dyes described in JP-A-2-294638 and Japanese Patent Application No. 3-185773. 10) Binder JP-A-2-18542, page 3, lower right column, 1st line to 20th line. 11) Black spot inhibitors Compounds described in U.S. Pat. No. 4,956,257 and JP-A-1-18832. 12) Monomethine compounds Compounds of the general formula (II) described in JP-A-2-287532 (especially compound examples II-1 to II-26). 13) Dihydroxy Compounds described in JP-A-3-39948, page 11, upper left column to first benzenes, page 2, lower left column, and EP 452772A.

The developer (development start solution and development replenisher) of the present invention contains at least one ascorbic acid or a derivative thereof as a developing agent. Preferred ascorbic acid or a derivative thereof is a compound represented by the general formula (II).

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

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

Examples of the 5- to 7-membered ring include a dihydrofuranone ring, a dihydropyrone ring, a pyranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrrolinone ring, a pyrazolinone ring, a pyridone ring, an azacyclohexenone ring, and a uracil ring. And as an example of a preferred 5- to 7-membered ring,
Dihydrofuranone ring, cyclopentenone ring, cyclohexenone ring, pyrazolinone ring, azacyclohexenone ring,
A uracil ring can be mentioned.

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

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Among them, preferred is ascorbic acid or erythorbic acid (a diastereomer of ascorbic acid). The general range of the amount of ascorbic acid used is 5 × 10 ⁻³ mol to 1 mol, particularly preferably 10 ⁻² mol to 0.5 mol, per liter of the developer.

As the auxiliary developing agent, 3-pyrazolidones and aminophenols can be used, but it is preferable to use aminophenols. As aminophenols, 4-aminophenol, 4-amino-3
-Methylphenol, 4- (N-methyl) aminophenol, 2,4-diaminophenol, N- (4-hydroxyphenyl) glycine, N- (2'-hydroxyethyl) -2-aminophenol, 2-hydroxymethyl −
4-aminophenol, 2-hydroxymethyl-4-
(N-methyl) aminophenol, 2-amino-6-phenylphenol, 2-amino-4-chloro-6-phenylphenol, N-β-hydroxyethyl-4-aminophenol, N- (4′-hydroxyphenyl) ) Pyrrolidine, N-γ-hydroxypropyl-4-aminophenol, 6-hydroxyl-1,2,3,4-tetrahydroquinoline, N, N-dimethyl-4-aminophenol, N, N-diethylaminophenol and the like Hydrochlorides and sulfates of the compounds can be mentioned.

The general range of the amount of the aminophenol used is 5 × 10 ^-4 mol to 0.5 mol, preferably 10 ^-3 mol to 0.1 mol per liter of the developing solution.

The addition ratio of the developing agent and the auxiliary developing agent can be arbitrarily selected as long as it is within the range of the respective addition amounts described above.

The developer of the present invention further comprises hydroquinone or a derivative thereof (hydroquinone monosulfonic acid, hydroquinone disulfonic acid, methylhydroquinone, chlorohydroquinone, etc.), or 3-pyrazolidone or a derivative thereof (eg, 1-phenyl-3-pyrazolidone). , 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1
-Phenyl-4-methyl-hydroxymethyl-3-pyrazolidone). The addition amount is 1 ×
10 ^-3 to 0.8 mol / l, preferably 1 × 10
^-2 to 0.4 mol / l.

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 the sulfite include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium bisulfite, and potassium metabisulfite. The larger the amount of preservative added, the better the preservative properties of the developer, but on the other hand, the amount of silver ions dissolving out of the photosensitive material into the developer increases, so that silver sludge gradually accumulates in the developer. Have negative effects. Since the developer of the present invention has high stability, sufficient preservation can be obtained with a small amount of sulfite added. Therefore, the amount of sulfite added is preferably 0.5 mol or less per liter of developer. More preferably, 0.0
2 to 0.4 mol / liter is preferred. Particularly preferably, it is 0.
It is preferably from 02 to 0.3 mol / liter.

The additives used other than those described above include:
Development inhibitors such as sodium bromide and potassium bromide; organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide; development accelerators such as alkanolamines such as diethanolamine and triethanolamine, imidazole and derivatives thereof; mercapto A compound, an indazole compound, a benzotriazole compound, or a benzimidazole compound may be contained as an antifoggant or a black pepper inhibitor. Specifically, 5-nitroindazole,
5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-nitroindazole, 3-methyl-5-nitroindazole, 5-nitrobenzimidazole, 2-isopropyl-5-nitrobenzimidazole, 5- Nitrobenztriazole, 4
-[(2-mercapto-1,3,4-thiadiazole-
Sodium 2-yl) thio] butanesulfonate, 5-amino-1,3,4-thiadiazole-2-thiol, methylbenzotriazole, 5-methylbenzotriazole, 2-mercaptobenzotriazole and the like can be mentioned. The amount of these antifoggants is usually 0.01 to 10 mmol, more preferably 0.05 to 2 mmol, per liter of developer. In order to suppress the accumulation of silver sludge in the developer, a known silver sludge inhibitor can be used.

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

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

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

Examples of the organic phosphonocarboxylic acid include JP-A-52-102726, JP-A-53-42730, and JP-A-54-42730.
No. 121127, No. 55-4024, No. 55-40
No. 25, No. 55-126241, No. 55-65555
And the compounds described in Research Disclosure No. 55-65556, and Research Disclosure No. 18170 described above. These chelating agents may be used in the form of an alkali metal salt or an ammonium salt. The amount of the chelating agent to be added is preferably 1 × 10 ^-4 to 1 × 10 ^-1 mol, more preferably 1 × 10 ^-1 mol per liter of the developer.
It is 10 ^-3 to 1 × 10 ^-2 mol.

Further, if necessary, a color tone agent, a surfactant,
It may contain an antifoaming agent, a hardening agent and the like.

The developing solution used in the present invention contains carbonate, boric acid and borate (for example, boric acid,
Borax, sodium metaborate, potassium borate) Sugars (for example, saccharose), oximes (for example, acetoxime), phenols (for example, 5-sulfosalicylic acid), and tertiary phosphate described in JP-A-60-93433 (Eg, sodium salt, potassium salt), aluminate (eg, sodium salt) and the like, and preferably carbonate and borate. The pH buffer is 0.1-1.
5 mol / l, preferably 0.2 to 1.2 mol / l is used. More preferably, it is used in an amount of 0.3 to 1.0 mol / liter. The development processing temperature and time are interrelated and 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 50 ° C.
At 45 ° C., the development time is 5 seconds to 2 minutes, preferably 7 seconds to 6 minutes.
0 seconds.

The pH of the developing solution of the present invention is 9.0-1.
0.5. As the alkali agent used for setting the pH, a usual water-soluble inorganic alkali metal salt (for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate) can be used.

The composition of the development replenisher is basically the same as the composition of the development initiator except for the pH. The pH of the developing replenisher is set higher than the pH of the developing solution. Preferably, the pH of the developing replenisher is 0.2 to
It is set at 1.5 units, particularly preferably 0.3 to 1.0 units higher. However, if the pH of the replenisher is too high, the replenisher itself is likely to be oxidized by air.
The upper limit of H is preferably about 11.2. By performing the running process while replenishing such a development replenisher, the fluctuation of the pH value of the developer actually processing the photographic material can be almost eliminated, and the p value set at the start of development can be reduced.
The photosensitive material is processed at a pH value substantially similar to H (that is, the pH value of the development start solution). The pH of the development start solution and the development replenisher may be adjusted by adding the above-mentioned alkali agent to the development start solution in excess, or may be used as a development replenisher, or acetic acid, glacial acetic acid, sulfamic acid and the like. Alternatively, an acid such as sulfuric acid may be added to lower the pH to make a development start solution.
Alternatively, the development start solution and the development replenisher may be separately prepared so as to have a composition optimized within the above-mentioned range.

In the present invention, the processing is performed while replenishing the developing replenisher in accordance with the processing amount of the silver halide light-sensitive material. The replenishing amount of the developing replenisher is usually 500 ml or less per square meter of the photosensitive material, but can be made smaller than usual according to the present invention, and the replenishment amount is as low as 200 ml or less, more preferably 150 ml or less per square meter of the photosensitive material. However, stable processing is possible.

The photosensitive material after the development is usually fixed, washed (stabilized), and dried. The fixing solution used in the fixing step includes sodium thiosulfate, ammonium thiosulfate, and, if necessary, tartaric acid, citric acid, gluconic acid, boric acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid,
It is an aqueous solution containing these salts, such as tiron, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and nitrilotriacetic acid. From the viewpoint of environmental protection in recent years, it is preferable that boric acid is not contained. The fixing agent of the fixing solution used in the present invention is sodium thiosulfate, ammonium thiosulfate or the like, and ammonium thiosulfate is preferable from the viewpoint of fixing speed, but sodium thiosulfate may be used from the viewpoint of environmental protection in recent years. . The amount of these known fixing agents can be varied as appropriate, and is generally about 0.1 to about 2 mol / l. Particularly preferably, 0.2 to 1.5 mol /
Liters. The fixing solution may optionally contain a hardener (eg, a water-soluble aluminum compound), a preservative (eg, sulfite, bisulfite), a pH buffer (eg, acetic acid), and a pH adjuster (eg, ammonia, sulfuric acid). ), Chelating agents, surfactants, wetting agents, fixing promoters.

Examples of the surfactant include anionic surfactants such as sulfates and sulfonates, polyethylene surfactants, and amphoteric surfactants described in JP-A-57-6740. In addition, a known antifoaming agent may be added. Examples of the wetting agent include alkanolamine and alkylene glycol. Examples of the fixing accelerator include JP-B-45-35754 and JP-B-5-35754.
Thiourea derivatives described in JP-A Nos. 8-122535 and 58-122536, alcohols having a triple bond in the molecule, thioether compounds described in U.S. Pat. And the compounds described in JP-A-2-44355 may be used. In addition, as a pH buffer,
For example, acetic acid, malic acid, succinic acid, tartaric acid, citric acid,
Organic acids such as oxalic acid, maleic acid, glycolic acid and adipic acid, and inorganic buffers such as boric acid, phosphate and sulfite 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.
0.01 to 1.0 mol / l, more preferably 0.1 to 1.0 mol / l.
Use about 02 to 0.6 mol / liter. Fixer pH
Is preferably 4.0 to 6.5, particularly preferably 4.5 to 6.5.
It is in the range of 6.0. Further, compounds described in JP-A-64-4739 can be used as the dye elution accelerator.

The hardener in the fixing solution includes water-soluble aluminum salts and chromium salts. Preferred compounds are water-soluble aluminum salts, such as aluminum chloride, aluminum sulfate and potassium alum. A preferable addition amount is 0.01 mol to 0.2 mol / l, and more preferably 0.03 to 0.08 mol / l. The fixing temperature is about 20C to about 50C, preferably 25C to 45C.
The fixing time is 5 seconds to 1 minute, preferably 7 seconds to 50 seconds. The replenishment amount of the fixing solution is 50 times the processing amount of the photosensitive material.
0 ml / m ² or less, particularly 300 ml / m ² or less.

As processing proceeds, silver salts accumulate in the fixing solution. The tired fixer can be recycled by removing silver salts by known silver recovery means. A method of converting silver ions into metallic silver by electrolytic reduction and removing them by filtration with a filter, a method of removing silver ions by adsorbing them on a compound that strongly adsorbs them, and a method of depositing and removing silver ions on the surface of a metal filament can be used. These silver recovery devices may be installed in a circulation line for the fixing solution, or may be processed off-line.

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

The processing solution used in the present invention is disclosed in
It is preferable to store in a packaging material having low oxygen permeability described in No. 73147. It is preferable that the processing liquid is concentrated and diluted at the time of use for the purpose of transporting the processing liquid, packaging material cost, space saving, and the like. For concentration of the developer, it is effective to convert a salt component contained in the developer into potassium salt. The treatment liquid used in the present invention may be in the form of a powder and solidified. As the method, a known method can be used.
JP-A-259921, JP-A-4-85533, JP-A-4-
It is preferable to use the method described in US Pat. 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. As for the roller transport type automatic developing machine, U.S. Pat.
No. 45971 and the like, and are simply referred to as a roller transport type processor in this specification. The roller transport type processor has four steps of development, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, a stop step), but most preferably follows these four steps. . Four steps of a stabilization step may be used instead of the washing step.

In the silver halide photographic light-sensitive material or the photographic image forming method of the present invention, any combination of usable elements, preferred embodiments of each, preferred addition amounts, and numerically limited ranges is also described in the present invention. This is a further preferred embodiment of the invention. Examples include diazonium salts,
Or a preferable substituent group that can be taken by R ₁ , R ₂ , Y and the like in the general formula (1) or (2) representing the precursor thereof, and R ₁ , R ₂ and A in the general formula (I) representing the hydrazine derivative ₁ , A ₂
And G1, preferred substituent groups that can be respectively taken, preferred nucleation accelerators, preferred silver halide emulsions, rhodium compounds and iridium compounds preferably added thereto,
Any combination of these and the preferable addition ranges of these compounds is a further preferred embodiment.

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

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

Thereafter, the resultant was washed with water by a flocculation method according to a conventional method, 40 g of gelatin was added per 1 mol of silver, and 7 mg of sodium benzenethiosulfonate and 2 mg of benzenesulfinic acid were added per 1 mol of silver. The pAg was adjusted to 7.5, and 2 mg of sodium thiosulfate and 4 mg of chloroauric acid were added per mole of silver, followed by chemical sensitization at 60 ° C. for optimum sensitivity. Thereafter, 150 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added as a stabilizer, and 100 mg of proxel was further added as a preservative. Each of the obtained particles has an average particle size of 0.25 μm.
m, silver chlorobromide cubic grains having a silver chloride content of 70 mol%. (Coefficient of variation 10%)

Preparation of Coated Sample A polyethylene terephthalate film support having a moisture-proof layer undercoat containing vinylidene chloride was placed on a support from the support side.
Samples were prepared by applying sequentially to form a layer structure of an UL layer, an EM layer, a PC layer, and an OC layer. The preparation method and application amount of each layer are shown below.

(UL layer) A dispersion of polyethyl acrylate in an amount of 30% by weight based on gelatin was added to an aqueous gelatin solution, and the mixture was applied so that the gelatin became 0.5 g / m ² .

(EM layer) The emulsion A was used as a sensitizing dye.
The following compound (S-1) was added in an amount of 5 × 10^-FourMo
(S-2) is 5 × 10^-FourMole, then 1 mole of silver
3 × 10 per^-FourMole of mercap represented by the following (a)
Compound, 4 × 10^-FourMole of mercap represented by (b)
Compound, 4 × 10^-FourMole of triazine represented by (c)
Compound, 2 × 10^-3Molar 5-chloro-8-hydroxy
Shikinoline, 5 × 10^-FourMol, nucleation
The following compound (A) was used as an accelerator at 4 × 10^-FourAdd mole
did. Furthermore, hydroquinone 100 mg / m^Two, N-
30 mg of oleyl-N-methyltaurine sodium salt
/ M^Two Added as applied. Next, hydrazine induction
1 × 10^-Five mol / m^TwoOf the present invention
Azo compounds (shown in Table 1), water-soluble lanes shown in (d)
Tex 200mg / m^Two , Polyethyl acrylate
200 mg / m^Two , Methyl acrylate and 2
-Acrylamido-2-methylpropanesulfonic acid nato
Lithium salt and 2-acetoacetoxyethyl methacrylate
Latex copolymer (88: 5: 7 by weight) in 200
mg / m ^Two , Colloidal silica having an average particle size of 0.02 μm
200 mg / m^Two , Dodecylbenzenesulfonic acid nato
30 mg / m^Two, And 1,3-divinyl as a hardening agent
Nylsulfonyl-2-propanol at 200 mg / m^Two 
Was added. The pH of the solution was adjusted to 5.65 with acetic acid.
Was. 3.5 g / m of coated silver^Two Apply to become
did.

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

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

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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

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

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[Back protective layer] Gelatin 0.8 mg / m ² polymethyl methacrylate 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 processing The following developer A was used as a developer. Sample 4 above
The resultant was exposed to xenon flash light having an emission time of 10 ^-5 sec through a step wedge through an interference filter having a peak at 88 nm, developed at 35 ° C. for 20 seconds, and then subjected to fixing, washing and drying. Developer A Potassium hydroxide 25.0 g Diethylenetriaminepentaacetic acid 2.0 Potassium carbonate 30.0 Sodium sulfite 10.0 Potassium bromide 2.0 5-Methylbenzotriazole 1.0 N-methyl-p-aminophenol 7.5 Sodium erythorbate 30.0 Boric acid 12.0 Dimercaptothiadiazole 0.08 Add water to make up to 1.0 liter. (PH adjusted to 9.7)

[0119]

[Table 1]

The fixer used had the following formulation. (Formulation of fixing solution) Ammonium thiosulfate 359.1 g Ethylenediaminetetraacetic acid 2Na dihydrate 0.09 g Sodium thiosulfate pentahydrate 32.8 g Sodium sulfite 64.8 g NaOH 37.2 g Glacial acetic acid 87.3 g Tartaric acid 8.76 g Sodium gluconate 6.6 g aluminum sulfate 25.3 g pH (adjusted with sulfuric acid or sodium hydroxide) 4.85 3 liters by adding water

(2) Evaluation of Image Contrast and Sensitivity As an index (gamma) indicating the contrast of an image, a point of fog + density of 0.1 on the characteristic curve from fog + density of 0.1.
Points of 0 were connected by a straight line, and the slope of this straight line was represented as a gamma value. That is, gamma = (3.0−0.1) / [l
og (exposure to give a density of 3.0)-(exposure to give a density of 0.1)], indicating that the larger the gamma value, the harder the photographic characteristics. As a photographic material for graphic arts, gamma is preferably 10 or more, more preferably 15 or more. Photosensitivity is the logarithmic value of the reciprocal of the amount of exposure that gives a density of 1.5,
The value was expressed as a relative value with respect to the developer A after the treatment for 20 seconds. Dmax is the maximum blackening density. 35 ° C.3 to evaluate development progress
A 0 second treatment was performed. The smaller the difference between the sensitivity and the Dmax between the processing for 20 seconds and the processing for 30 seconds, the faster the development. Sensitivity difference (ΔS) = (sensitivity of 30-second processing) − (sensitivity of 20-second processing) Dmax difference (ΔDmax) = (Dmax of 30-second processing) − (Dmax of 20-second processing) The above results are shown in Table 1. It was shown to. By using the compound of the present invention, high sensitivity can be obtained, and high contrast and Dmax can be obtained even in a treatment for 20 seconds. In addition, even if the developing time is extended up to 30 seconds, the increase in sensitivity and Dmax is small, and it can be seen that the current progress is extremely fast. In other words, it shows that stable performance can be obtained with a development time as short as 20 seconds.

Example 2 In Example 1, compound 1 was used as a hydrazine derivative.
Example 7 was carried out in the same manner as in Example 1 except that bis-hydrazine derivative 1C was used instead of 7. The results are shown in Table 2.
Higher contrast and sensitivity were obtained.

[0123]

[Table 2]

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support and containing a hydrazine derivative, comprising at least one diazonium salt or a precursor thereof. A silver halide photographic light-sensitive material, characterized in that: 2. The silver halide photographic material according to claim 1, wherein the diazonium salt or a precursor thereof is a compound selected from the group represented by the following general formula (1) or (2). Embedded image Here, R ₁ and R ₂ represent an aliphatic group or an aromatic group.
n represents an integer of 1 or more. X ^n- is a counter anion;
Is a group selected from the group consisting of a sulfonic acid group, a phosphoric acid group, and a carboxyl group. 3. A silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support and containing a hydrazine derivative in the presence of at least one diazonium salt or a precursor thereof. 3. The image forming method according to claim 1, wherein the developing process is performed using a developing solution containing ascorbic acid and having a pH of 9.5 to 10.5.