JPH08166657A - Method for developing and processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To obtain an image having ultrahigh-contrast by using an ecologically favorable developing solution containing a specified developing agent and a specified auxiliary developing agent and incorporating a specified hydrazine derivative in a silver halide emulsion layer or the like. CONSTITUTION: At least one of the silver halide emulsion layers and other hydrophilic colloidal layers contains at least one kind of hydrazine derivative represented by formula I and the developing solution contains at least one of the developing agent selected from ascorbic acid, erysorbic acid, and the alkali metal salts of these acids, but substantially no dihydroxybenzene derivative, and the developing agent represented by formula II, and the superadditive auxiliary developing agent. In formulae I and II, R1 is an aliphatic or aromatic group; R2 is an H atom or an alkyl group or the like: G1 is a -CO- or -SO2 - group or the like; both of A1 and A2 are an H atom or one of them is an H atom and the other is an alkylsulfonyl group or the like; and X is an H atom or an aryl or heterocyclic group or the like.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a development processing method for forming an ultrahigh contrast image using a silver halide photographic light-sensitive material and a developer containing no dihydroxybenzene type developing agent.

[0002]

2. Description of the Related Art In the field of graphic arts, photographic characteristics of ultra-high contrast (especially gamma of 10 or more) are used in order to improve reproduction of continuous tone images or halftone images by halftone dot images. Is required. As a method for obtaining high-contrast photographic characteristics, a lithographic development method utilizing a so-called "infectious development effect" has been used for a long time, but it has a drawback that the developer is unstable and difficult to use.

On the other hand, as a method using a more stable developing solution, US Pat. Nos. 4,224,401, 4,168,977, and 4,166,742 have been proposed.
No. 4,311,781, No. 4,272,606
No. 4, No. 4,221,857, No. 4,332,87
No. 8, No. 4,634, 661, No. 4,618, 5
No. 74, No. 4,269, 922, No. 5,650,
No. 746, No. 4,681,836 and the like. This image forming system comprises a surface latent image type silver halide photographic light-sensitive material containing a hydrazine derivative, a stable MQ developer having a pH of 11 to 12.3 (a developer using a combination of hydroquinone and p-aminophenols) or PQ developer (hydroquinone and 1-phenyl-3-
And a γ value of 10
It is a system that obtains negative images of super-high contrast exceeding, and by this method, photographic characteristics with high super-high contrast and high sensitivity can be obtained.
Since it is permissible to add a high concentration of sulfite to the developer, the stability of the developer against aerial oxidation is dramatically improved as compared with the conventional lith developer. These systems use hydroquinone as a developing agent, and there is concern that hydroquinone is unfavorable from an ecological and toxicological standpoint, and there is a processing method that can obtain super-high contrast images with a developer that does not use hydroquinone. Is desired.

With respect to the light-sensitive material for light room used in the plate collecting and returning process, for example, when the halftone dot original and the line drawing original are faithfully overlapped on the original, a super-high contrast image forming method is required. The image forming system using a hydrazine derivative is also effective for this purpose.
2-640, 62-235938, 62-23
No. 5939, No. 63-104046, No. 63-103.
235, 63-296031, 63-3145.
No. 41, No. 64-13545 and the like disclose specific application examples thereof.

US 4998604, US 4949436
No. 5 discloses a hydrazine compound having a repeating unit of ethylene oxide and a hydrazine compound having a pyridinium group. However, as is clear from these examples, the high contrast is not sufficient, and it is difficult to obtain the high contrast and the required Dmax under practical development processing conditions.

On the other hand, it is known that enediole such as ascorbic acid functions as a developing agent, and it is attracting attention as a developing agent free from the above ecological or toxicological problems. For example, U.S. Pat. No. 2,688,54
9 and 3,826,654 at least pH 1
It is said that image formation is possible under a highly alkaline condition of 2 or more. However, it is impossible to obtain a high-contrast image by these image forming methods. Some attempts have been made to increase the contrast in development systems using ascorbic acid. For example, Zwicky says that when ascorbic acid is used as the only developing agent, a type of squirrel effect appears (J. Phot. Sc. 27, 185).
Page (1979)), the contrast was considerably lower than that of the hydroquinone developing system. Further, U.S. Pat. No. T896,022 and Japanese Patent Publication No. 49-46939 disclose a system in which a bis quaternary ammonium salt and ascorbic acid are used in combination. Absent. In addition, JP-A-3-2
No. 49756 and No. 4-32838 describe the combined effect of ascorbic acid and a quaternary salt, but the contrast of the obtained image is not sufficient. Furthermore, JP-A-5-88
No. 306 ascorbic acid as the only developing agent, p
It is said that a high contrast can be obtained by keeping H at 12.0 or more, but there is a problem in the stability of the developer. In addition, using a special developer containing ascorbic acid and a hydrazine derivative as main components, high sensitivity, stain,
Example of developing a development system with low fog (US Pat. No. 3,
No. 730,727), but no mention is made of improvement in contrast.

It is known to process sensitizers containing hydrazine with ascorbic acid developers, US Pat.
No. 6, WO93 / 11456, etc.,
None of them are sufficient in terms of contrast, and in the latter case, the developer is made to contain an amine to increase the contrast.
Environmentally unfavorable. From the viewpoint of toxicology, a development processing method for obtaining a high-contrast image by using ascorbic acid, which is preferable as a developing agent, is desired, but sufficient contrast is not obtained. Further, when an ascorbic acid developing agent is used, the pH is greatly decreased by air oxidation, and the photographic performance is greatly deteriorated, which is a practical problem. Further, the high-contrast image required for the printing plate-making film requires a treatment with a relatively high developing solution having a pH of 11 or more, and the air oxidation stability was not sufficient.

[0008]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a development processing method for a silver halide black-and-white photographic light-sensitive material, which does not use a dihydroxybenzene compound and can obtain an ultrahigh contrast image with an ecologically preferable developer. Is to provide.

[0009]

The object of the present invention is to provide a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer and at least one protective layer on the same surface of a support. In the method of developing treatment with a developing solution after exposure, at least one hydrazine derivative represented by the general formula (I) is contained in at least one of the silver halide emulsion layer and / or other hydrophilic colloid layer. And containing substantially no dihydroxybenzene compound in the developer, (1) at least one developing agent selected from ascorbic acid, erythorbic acid and alkali metal salts thereof, (2) the general formula ( II) a developing agent and
(3) It was achieved by a development processing method of a silver halide black-and-white photographic light-sensitive material characterized by containing an auxiliary developing agent exhibiting superadditivity.

[0010]

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In the formula, R ₁ represents an aliphatic group or an aromatic group, R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an unsaturated heterocyclic group, an alkoxy group, an aryloxy group, an amino group, Or represents a hydrazino group, G ₁ is a —CO— group,
-SO ₂ group, -SO- group,

[0012]

[Chemical 6]

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

[0014]

[Chemical 7]

In the formula, X represents a hydrogen atom, an aryl group, a heterocyclic group, or a group represented by the general formula (A). General formula (A)

[0016]

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In the formula, R ₁ , R ₂ and R ₃ may be the same or different and each represents a substituent other than a hydroxy group or a hydrogen atom.

The general formula (I) will be described in more detail. In the general formula (I), the aliphatic group represented by R ₁ is preferably an aliphatic group having 1 to 30 carbon atoms, and 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. Moreover, 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. Examples thereof include a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, and a benzothiazole ring. Among them, those containing a benzene ring are preferable. Particularly preferred as R ₁ is an aryl group. The aliphatic group or aromatic group of R ₁ may be substituted, and typical examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group-containing group, a pyridinium group and a hydroxy group. Group, alkoxy group, aryloxy group, acyloxy group, alkyl or arylsulfonyloxy group, amino group, carbonamide group, sulfonamide group, ureido group, thioureido group, semicarbazide group, thiosemicarbazide group, urethane group, group having a hydrazide structure A group having a quaternary ammonium structure, an alkyl or aryl thio group, an alkyl or aryl sulfonyl group, an alkyl or aryl sulfinyl group, a carboxyl group, a sulfo group, an acyl group, an alkoxy or aryloxy carbonyl group, a carbamoyl group, a sulfamoyl group, Examples include a rogen atom, a cyano group, a phosphoric acid amide group, a diacylamino group, an imide group, a group having an acylurea structure, a group containing a selenium atom or a tellurium atom, a group having a tertiary sulfonium structure or a quaternary sulfonium structure, and the like. As a preferred substituent, a linear, branched or cyclic alkyl group (preferably having a carbon number of 1 to 20),
Aralkyl group (preferably 1 to 1 carbon atoms in the alkyl part)
3 monocyclic or bicyclic), an alkoxy group (preferably having 1 to 20 carbon atoms), a substituted amino group (preferably an amino group substituted with an alkyl group having 1 to 20 carbon atoms),
Acylamino group (preferably having 2 to 30 carbon atoms), sulfonamide group (preferably having 1 to 30 carbon atoms), ureido group (preferably having 1 to 30 carbon atoms), phosphoric acid amide group (Preferably having 1 to 3 carbon atoms
0) and so on.

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, for example, benzene. It contains a ring. At least one nitrogen as the unsaturated heterocyclic group,
A 5- or 6-membered ring compound containing oxygen and a sulfur atom, for example, an imidazolyl group, a pyrazolyl group, a triazolyl group,
Examples include a tetrazolyl group, a pyridyl group, a pyridinium group, a quinolinium group, and a quinolinyl group. A pyridyl group or a pyridinium group is particularly preferable. The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, the aryloxy group is preferably a monocyclic group, the amino group is an unsubstituted amino group, and an alkylamino group having 1 to 10 carbon atoms, aryl Amino groups are preferred. R ₂ may be substituted, and as the preferable substituent, those exemplified as the substituent of R ₁ are applicable. Preferred among the groups represented by R ₂ is when G ₁ is a —CO— group,
Hydrogen atom, alkyl group (for example, methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc.), aralkyl group (for example, o-hydroxybenzyl group, etc.), Aryl groups (eg phenyl groups, 3,5
-Dichlorophenyl group, o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, 2-hydroxymethylphenyl group and the like), and a hydrogen atom and trifluoromethyl group are particularly preferable. Also, G ₁ is -S
In the case of an O ₂ — group, R ₂ is an alkyl group (eg, methyl group), an aralkyl group (eg, o-hydroxybenzyl group), an aryl group (eg, phenyl group) or a substituted amino group (eg, , Dimethylamino group, etc.) are preferred. When G ₁ is a —COCO— group, an alkoxy group, an aryloxy group and an amino group are preferable.
As G in the general formula (I), a -CO- group and a -COCO- group are preferable, and a -CO- group is most preferable. Also, R ₂ is G
The part of _1- R ₂ is split from the residual molecule, and -G ₁ -R ₂
It may be one that causes a cyclization reaction to form a cyclic structure containing a partial atom, and examples thereof include those described in JP-A-63-29751.

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

The substituents of R ₁ and R _{2 in} the general formula (I) may be further substituted, and preferable examples thereof 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 ...
., May be multiply substituted, and preferred examples are also those exemplified as the substituent of R ₁ .

R ₁ or R _{2 in} the general formula (I) may have a ballast group or a polymer, which is commonly used in a non-moving photographic additive such as a coupler, incorporated therein. The ballast group is a group having a carbon number of 8 or more, which is relatively inert to photographic properties, such as an alkyl group,
It can be selected from aralkyl group, alkoxy group, phenyl group, alkylphenyl group, phenoxy group, alkylphenoxy group and the like. Examples of the polymer include those described in JP-A No. 1-100530.

R ₁ or R _{2 in} the general formula (I) may be one in which a group for enhancing adsorption to the surface of the silver halide grain is incorporated. Examples of the adsorptive group include alkylthio groups, arylthio groups, thiourea groups, heterocyclic thioamide groups, mercaptoheterocyclic groups, and triazole groups, which are disclosed in US Pat.
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.
No. 3, No. 61-270744, No. 62-948, No. 63-234244, No. 63-234245, No. 6
The groups described in 3-234246 are mentioned.

Particularly preferred hydrazine derivatives in the present invention are those in which R ₁ is a ballast group via a sulfonamide group, an acylamino group or a ureido group, a group which promotes adsorption to the surface of a silver halide grain, or a group having a quaternary ammonium structure or It is a phenyl group having an alkylthio group, G is a -CO- group, R ₂ is a hydrogen atom, a substituted alkyl group or a substituted aryl group (the substituent is preferably an electron-withdrawing group or a hydroxymethyl group at the 2-position). ) Is a hydrazine derivative. Any combination of the above R ₁ and R ₂ alternatives is possible and preferred.

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

[0026]

[Chemical 9]

[0027]

[Chemical 10]

[0028]

[Chemical 11]

[0029]

[Chemical 12]

[0030]

[Chemical 13]

[0031]

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[0032]

[Chemical 15]

[0033]

Embedded image

[0034]

[Chemical 17]

[0035]

Embedded image

[0036]

[Chemical 19]

As the hydrazine derivative used in the present invention, in addition to the above, RESEARCH DISCLOSURE Item 2
3516 (November 1983, p. 346) and references cited therein, as well as U.S. Pat. No. 4,080,20.
No. 7, No. 4,269,929, No. 4,276,364
Nos. 4,278,748, 4,385,108
Issue No. 4,459,347 Issue No. 4,478,928
Nos. 4,560,638 and 4,686,167
No. 4,912,016 No. 4,988,604
Issue No. 4,994,365 Issue 5,041,355
No. 5,104,769, British Patent No. 2,011,
391B, European Patent Nos. 217,310 and 301,
799, 356, 898, JP-A-60-1797.
34, 61-170733, 61-27074.
No. 4, No. 62-178246, No. 62-270948.
No. 63, No. 63-29751, No. 63-32538, No. 63-104047, No. 63-121838, No. 6
3-129337, 63-223744, 63
-234244, 63-234245, 63-
234246, 63-294552, 63-3
06438, 64-10233 and JP-A-1-90.
No. 439, No. 1-100530, No. 1-105941
No. 1, No. 1-105943, No. 1-276128, No. 1-280747, No. 1-283548, No. 1-2.
83549, 1-285940, 2-2541.
No. 2, No. 2-77057, No. 2-139538, No. 2
-196234, 2-196235, 2-19
No. 8440, 2-198441, 2-198442.
No. 2-220042, No. 2-221953, No. 2-221954, No. 2-285342, No. 2-2.
85343, 2-289843, 2-3027.
No. 50, No. 2-304550, No. 3-37642,
No. 3-54549, No. 3-125134, No. 3-1
No. 84039, No. 3-240036, No. 3-2400.
No. 37, No. 3-259240, No. 3-280038.
No. 3, No. 3-228536, No. 4-51143, No. 4
-56842, 4-84134, 2-2302
No. 33, No. 4-96053, No. 4-216544,
No. 5-45761, No. 5-45762, No. 5-45
No. 763, No. 5-45764, No. 5-45765,
The thing described in Japanese Patent Application No. 5-94925 can be used.

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

The hydrazine derivative of the present invention is a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve. It can be used by dissolving it in Further, by a well-known emulsification dispersion method, it is dissolved by using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. An object can be produced and used. Alternatively, the hydrazine derivative powder may be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method. Further, as described in JP-A-2-948, it can be used by being contained in fine polymer particles.

Particularly when processed with the developer of the present invention having a pH of less than 11, the silver halide photographic light-sensitive material contains an amine derivative, an onium salt or a disulfide in a silver halide emulsion layer or other hydrophilic colloid layer. Derivatives and nucleation accelerators such as hydroxylamine derivatives are preferably added.

As the amine derivative, for example, JP-A-60 is used.
-140,340, 62-50,829, 62
-222, 241, 62-250, 439, 6
The compounds described in 2-280,733, 63-124,045, 63-133,145, 63-286,840 and the like can be mentioned. More preferably as the amine derivative, JP-A-63-124,045 and JP-A-63-133,1
No. 45, No. 63-286,840, etc., and compounds having a group capable of adsorbing to silver halide, or JP-A-62-22.
Compounds having 20 or more carbon atoms, such as those described in US Pat. No. 2,241, US Pat. No. 4,975,354, EP458P70
6A and the like, amine compounds having an ethylene group, compounds described in JP-A-62-50829 and the like can be mentioned. The onium salt is preferably a pyridinium salt, an ammonium salt or a phosphonium salt. Examples of preferable pyridinium salts include the compounds described in Japanese Patent Application No. 5-97866. Also,
Examples of preferable ammonium salts include JP-A-62-2
The compounds described in Nos. 50,439 and 62-280,733 can be mentioned. Further, examples of preferable phosphonium salts include JP-A-61-167,93.
The compounds described in No. 9, No. 62-280, 733 and the like can be mentioned. Examples of the disulfide derivative include compounds described in JP-A No. 61-198,147. Examples of hydroxymethyl derivatives include, for example, U.S. Pat. Nos. 4,698,956, 4,777,118 and EP23.
Examples thereof include compounds described in JP-A No. 1,850 and JP-A No. 62-50,829, and more preferably a diarylmethanol derivative. Examples of the acetylene derivative include, for example, JP-A-3-168735 and JP-A-2-27.
Examples thereof include compounds described in No. 1351. Examples of the urea derivative include compounds described in JP-A-3-168736.

Specific examples of the nucleation accelerator are shown below. However, the present invention is not limited to the following compounds.

[0043]

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[0044]

[Chemical 21]

[0045]

[Chemical formula 22]

[0046]

[Chemical formula 23]

[0047]

[Chemical formula 24]

[0048]

[Chemical 25]

[0049]

[Chemical formula 26]

[0050]

[Chemical 27]

[0051]

[Chemical 28]

[0052]

[Chemical 29]

[0053]

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The optimum addition amount of these compounds varies depending on the kind thereof, but is 1.0 × 1 per mol of the hydrazine compound.
0 ⁻² mol to 1.0 × 10 ² mol, preferably 1.0 ×
It is preferably used in the range of 10 ^-1 mol to 5.0 x 10 mol. These compounds are suitable water-miscible organic solvents such as alcohols (methanol, ethanol, propanol, fluorinated alcohols), ketones (acetone,
Methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve, etc. can be used after dissolving. 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, powders of these compounds may be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method.

The halogen composition of the silver halide emulsion used in the present invention is such that silver chloride having a silver chloride content of 50 mol% or more, silver chlorobromide, and chloroiodo are more effective in achieving the object of the present invention. Silver bromide is preferred. The silver iodide content is preferably less than 5 mol%, particularly preferably less than 2 mol%.

In the present invention, a light-sensitive material suitable for high-illuminance exposure such as scanner exposure and a light-sensitive material for line drawing are
It 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, a rhodium (III) halide compound, or a rhodium complex salt having a halogen, an amine, oxalate, etc. as a ligand, for example, hexachlororhodium (III) complex salt, hexabromorhodium (III) complex salt, hexaaminerhodium ( III) Complex salt, trisalathodium (II
I) Complex salts and the like can be mentioned. These rhodium compounds are
It is used by dissolving it in water or an appropriate solvent, but it is generally used to stabilize the solution of the rhodium compound, that is, an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid, etc.), or halogenation. A method of adding an alkali (for example, KCl, NaCl, KBr, NaBr, etc.) can be used. Instead of using water-soluble rhodium, it is also possible to add and dissolve another silver halide grain which has been previously doped with rhodium when preparing the silver halide. The addition amount is 1 × 10 ^{−8 to} 5 × 10 ⁻⁶ mol, preferably 5 × 10 ⁻⁸ to 1 × 10 ⁻⁶ mol, per mol of silver in the silver halide emulsion. The addition of these compounds can be appropriately carried out during the production of silver halide emulsion grains and before each step of coating the emulsion, but it is particularly preferable to add these compounds at the time of emulsion formation and to incorporate them into the silver halide grains. . The photographic emulsion used in the present invention is Chimie et Physique Photograp by P. Glafkides.
hique (Paul Montel, 1967), GFDufin
By Photographic Emulsion Chemistry (The Focal Pres
s, 1966), by VL Zelikman et al Making and
Coating Photographic Emulsion (The Focal Press
, 1964) and the like.

As the method for reacting the soluble silver salt and the soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. Method of forming grains in the presence of excess silver ion (so-called reverse mixing method)
Can also be used. As one form of the simultaneous mixing method, a method of keeping pAg constant in the liquid phase in which silver halide is produced, 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 preferably, it is a tetra-substituted thiourea compound and is disclosed in JP-A-53-824.
08, 55-77737. Preferred thiourea compounds are tetramethylthiourea, 1,3-
Dimethyl-2-imidazolidinethione. In the controlled double jet method and the grain forming method using a silver halide solvent, it is easy to prepare a silver halide emulsion having a regular crystal form and a narrow grain size distribution. It is a useful tool for making emulsions. Further, in order to make the particle size uniform, British Patent No. 1,535,016 and Japanese Examined Patent Publication No. 48-3689.
0, No. 52-16364, a method of changing the addition rate of silver nitrate or an alkali halide according to the grain growth rate, and British Patent No. 4,242,44.
As described in JP-A-55-158124 and JP-A-55-158124, it is preferable to use the method of changing the concentration of the aqueous solution to grow it quickly within a range not exceeding the critical saturation. The emulsion of the present invention is preferably a monodisperse emulsion and has a coefficient of variation of 2
It is 0% or less, particularly preferably 15% or less. Average grain size of grains in monodisperse silver halide emulsion is 0.5 μm
It is below, and particularly preferably 0.1 μm to 0.4 μm.

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

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

As the selenium sensitizer used in the present invention, known selenium compounds can be used. That is, it is usually carried out by adding an unstable and / or non-unstable selenium compound and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain time. As unstable selenium compounds, JP-B-44-15748 and 43-13489,
Japanese Patent Application Nos. 2-13097, 2-229300, and 3
The compounds described in No. 121798 and the like can be used. Especially, the general formula (VIII) in Japanese Patent Application No. 3-121798.
It is preferable to use the compounds represented by and (IX).

The tellurium sensitizer used in the present invention is a compound capable of producing silver telluride which is presumed to serve as a sensitizing nucleus on the surface or inside of the silver halide grain. Regarding the rate of silver telluride formation in a silver halide emulsion, Japanese Patent Application No. 4-
It can be tested by the method described in 146739.
Specifically, U.S. Patent Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211 and 1,121,496.
No. 1, No. 1,295,462, No. 1,396,69
6, Canadian Patent No. 800,958, Japanese Patent Application No. 2-33
No. 3819, No. 3-53693, No. 3-131598.
No. 4-129787, Journal of Chemical Society Chemical Communication (J.Chem.Soc.Chem.Commun.) 635 (1980), ibid
1102 (1979), ibid 645 (1979),
Journal of Chemical Society Perkin Transaction (J.Chem.Soc.Perkin.Trans.)
1, 191 (1980), edited by S. Patai, The Chemistry of Organic Selenium and Tellurium Campounds
rganic Serenium and Tellunium Compounds), Vol 1
(1986) and the same Vol 2 (1987) can be used. Particularly preferred are the compounds represented by the general formulas (II) (III) (IV) in Japanese Patent Application No. 4-146739.

The amounts of the selenium and tellurium sensitizers used in the present invention vary depending on the silver halide grains used, chemical ripening conditions and the like, but generally 10 ^-8 to 10 ^-2 mol per mol of silver halide, Preferably, about 10 ^-7 to 10 ^-3 mol is used. The conditions of the chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to. It is 85 ° C. Examples of the noble metal sensitizer used in the present invention include gold, platinum, palladium and iridium, with gold sensitization being particularly preferred. Specific examples of the gold sensitizer used in the present invention include chloroauric acid, potassium chlorate, potassium aurithiocyanate, and gold sulfide.
About 10 ⁻⁷ to 10 ⁻² mol can be used per mol. In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite salt, a lead salt, a thallium salt and the like may coexist in the process of forming silver halide grains or physically ripening. Reduction sensitization can be used in the present invention. As the reduction sensitizer, stannous salt, amines, formamidinesulfinic acid, silane compound and the like can be used. To the silver halide emulsion of the present invention, a thiosulfonic acid compound may be added according to the method disclosed in European Patent Publication (EP) -293,917. The silver halide emulsion in the light-sensitive material used in the present invention may be of one kind or two or more kinds (for example, those having different average grain sizes,
Different halogen compositions, different crystal habits, different chemical sensitization conditions) may be used together.

In the present invention, a silver halide emulsion particularly suitable as a reversal light-sensitive material is a silver halide comprising 90 mol% or more, more preferably 95 mol% or more, and silver bromide of 0 to 10 is contained. It is silver chlorobromide or silver chloroiodobromide containing mol%. If the ratio of silver bromide or silver iodide increases, the safety of safelight in a bright room deteriorates, or γ
Is lowered, which is not preferable.

The silver halide emulsion used in the light-returning light-sensitive material of the present invention preferably contains a transition metal complex. Transition metals include Rh, Ru, Re, Os, I
r, Cr, and the like. The ligands include nitrosyl and thionitrosyl bridging ligands, halide ligands (fluoride, chloride, bromide and iodide), cyanide ligands, cyanate ligands, thiocyanate ligands, seleno Cyanate ligands, tellurocyanate ligands, acid ligands and aco ligands. When an aco ligand is present, it preferably occupies one or two of the ligands.

Specifically, in order to contain a rhodium atom, a metal salt in any form such as a single salt or a complex salt can be added and added at the time of grain preparation. Examples of the rhodium salt include rhodium monochloride, rhodium dichloride, rhodium trichloride, ammonium hexachlororhodate, and the like, preferably a water-soluble trivalent rhodium complex compound such as hexachlororhodium (III) acid or a salt thereof ( Ammonium salts, sodium salts, potassium salts, etc.). The amount of these water-soluble rhodium salts added is in the range of 1.0 × 10 ⁻⁶ mol to 1.0 × 10 ⁻³ mol per mol of silver halide. Preferably 1.0 × 10 ⁻⁵ mol to 1.0
× 10 ⁻³ mol, particularly preferably 5.0 × 10 ⁻⁵ mol
It is 5.0 × 10 ⁻⁴ mol.

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

The spectral sensitizing dye used in the present invention is not particularly limited. The addition amount of the sensitizing dye used in the present invention varies depending on the shape, size, etc. of the silver halide grains, but it is used in the range of 4 × 10 ⁻⁶ to 8 × 10 ⁻³ mol per mol of silver halide. For example, when the silver halide grain size is 0.2 to 1.3 μm, the addition amount range of 2 × 10 ^{−7 to} 3.5 × 10 ⁻⁶ mol is preferable per 1 m ² of the surface area of the silver halide grain. , Especially 6.5 × 10 ^{−7 to} 2.0 ×
The addition amount range of 10 ⁻⁶ mol is preferable.

The photosensitive silver halide emulsion of the present invention may be spectrally sensitized by a sensitizing dye to blue light, green light, red light or infrared light having a relatively long wavelength. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holoholer cyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hemioxonol dye and the like can be used. Useful sensitizing dyes used in the present invention are, for example, RESEARCH DISCLOSURE Item 17643 IV-
Item A (p.23, December 1978), Item 1831
Section X (p.437, Aug. 1978) or cited. In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, (A) Argon laser light source, JP-A-60-162247, JP-A-2-48653, US Pat. No. 2,161,331, West German Patent 936,071, and Japanese Patent Application No. 3-189532. For the described simple merocyanines and (B) helium-neon laser light source, JP-A-50-62425,
54-18726 and 59-102229, trinuclear cyanine dyes, sensitizing dyes described as the general formula (I) in JP-A-6-75322, and specific examples thereof.
(C) Japanese Patent Publication Nos. 48-42172, 51-9609 and 55 for LED light sources and red semiconductor lasers
No. 39818, JP-A No. 62-284343, JP-A No. 2-105135, and thiacarbocyanines, and (D) infrared semiconductor laser light source.
9-191032, tricarbocyanines described in JP-A-60-80841, JP-A-59-19224.
No. 2, dicarbocyanines containing a 4-quinoline nucleus described in the general formula (IIIa) and the general formula (IIIb) of JP-A-3-67242, and (E) for a white light source such as a camera image General formula (IV) described in Japanese Patent Application No. 5-201254
The sensitizing dye and its specific examples are advantageously selected. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosure 176, 176.
43 (issued in December 1978), page 23, IV, paragraph J.

Next, the developing solution used in the present invention will be described. The developer used in the development processing of the light-sensitive material according to the present invention may contain additives which are usually used (for example, a developing agent, an alkaline agent, a pH buffering agent, a preservative and a chelating agent). Any known method can be used for the development processing of the present invention, and a known development processing solution can be used. As described above, the developer of the present invention contains substantially no dihydroxybenzene-based developing agent, and the main developing agents are (1) ascorbic acid and erythorbic acid (geometric isomers of ascorbic acid) and those At least one selected from the alkali metal salts of (2) and the compound represented by the general formula (II). Further, the developing solution of the present invention contains the developing agents (1) and (2) and an auxiliary developing agent exhibiting superadditivity. As the auxiliary developing agent, a 1-phenyl-3-pyrazolidone type auxiliary developing agent and / or a p-aminophenol type auxiliary developing agent is preferable.

The amount of ascorbic acid, erythorbic acid or their alkali metal salts used is generally in the range of 5 × 10 ^-3 mol to 1 mol, and particularly preferably 10 ^-2 mol to 0, per liter of the developing solution. 0.5 mol.

The general formula (II) will be described in detail below. In the formula, the aryl group represented by X has 6 to 1 carbon atoms.
An aryl group of 0, such as a phenyl group and a naphthyl group. These groups may have a substituent, and as the substituent, an alkyl group, an alkenyl group, an aryl group, a halogen atom, a nitro group, a hydroxy group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, Acyloxy group, amino group, alkylamino group,
Examples thereof include carbonamido group, sulfonamide group, ureido group, acyl group, oxycarbonyl group, carbamoyl group, sulfinyloxy group, carboxyl group (including salt), and sulfo group (including salt) hydroxyamino group. Are, for example, phenyl, p-methylphenyl, anisyl, p-carboxyphenyl, p-sulfonylphenyl and the like.

In the formula, the heterocyclic group represented by X is a 5- or 6-membered heterocyclic group composed of a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom, for example, a furyl group,
Examples thereof include a benzofuryl group, a pyranyl group, a pyrrolyl group, an imidazolyl group, a pyrazolyl group, a triazolyl group, a pyridyl group, a pyrimidyl group, a pyridazyl group, a thienyl group and an isothiazolyl group. These groups may have a substituent,
As the substituent, the substituents listed for the aryl group can be applied, and preferably, for example, furyl, 5-methylfuryl, benzofuryl, pyridyl, 5-chloropyridyl, 3
-Carboxypyridyl, 5-sulfonylpyridyl, 1-phenyltriazolyl and the like.

Next, R ₁ , R ₂ and R ₃ in the compound represented by the general formula (A) will be described in detail. R ₁ ,
R ₂ and R ₃ may be the same or different and each represents a substituent other than a hydroxy group or a hydrogen atom. More specifically, examples of the substituents of R ₁ , R ₂ and R ₃ include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyloxy group, an amino group, an alkylamino group and a carboxylic group. Examples thereof include an amide group, a sulfonamide group, a ureido group, an oxycarbonyl group, a carbamoyl group, a sulfinyloxy group, a carboxyl group (including a salt), and a sulfo group (including a salt).
If possible, these groups may be further substituted, and as the substituents, the substituents mentioned for the aryl group can be applied.

More specific examples of the substituents of R ₁ , R ₂ and R ₃ will be shown. The alkyl group is a linear, branched or cyclic alkyl group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, and these groups may have a substituent. The substituents mentioned for the aryl group can be applied, for example, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, cyclohexyl, benzyl, hydroxymethyl, methoxymethyl, phenoxymethyl, methylthiomethyl, phenylthiomethyl, acetoxymethyl,
1,2-diacetoxyethyl, 1,2,3-triacetoxypropyl, aminomethyl, dimethylaminomethyl,
Acetamidomethyl, methanesulfonylamidomethyl,
Examples thereof include ureidomethyl, methoxycarbonylmethyl, carbamoylmethyl, carboxymethyl and sulfonylmethyl.

The aryl group is an aryl group having 6 to 10 carbon atoms, and these groups may have a substituent. As the substituent, the substituents mentioned in the aryl group can be applied.
For example, phenyl, naphthyl, p-methylphenyl and the like. The alkoxy group is an alkoxy group having 1 to 19 carbon atoms, preferably 1 to 8 carbon atoms, and these groups may have a substituent. As the substituent, the substituents described in the aryl group are applied. Examples thereof include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, octyloxy, 2-methoxyethoxy and the like.

The aryloxy group has 6 to 10 carbon atoms.
In these aryloxy groups, these groups may have a substituent, and as the substituent, the substituents mentioned in the aryl group can be applied, and examples thereof include phenoxy, o-hydroxyphenoxy, o-carboxyphenoxy, Examples thereof include o-sulfonylphenoxy. The alkylthio group is an alkylthio group having 1 to 16 carbon atoms, preferably 1 to 8 carbon atoms, and these groups may have a substituent, and as the substituent, the substituents described in the aryl group are applied. It can be, for example, methylthio, octylthio and the like. The arylthio group is an arylthio group having 6 to 10 carbon atoms, and these groups may have a substituent. As the substituent, the substituents listed for the aryl group can be applied, and examples thereof include phenylthio and 4- Examples thereof include hydroxyphenylthio. 1 carbon atom as an acyloxy group
To 17, preferably an acyloxy group having 1 to 8 carbon atoms,
These groups may have a substituent, and as the substituent, the substituents listed for the aryl group can be applied, and examples thereof include acetoxy, propanoyloxy, butanoyloxy, octanoyloxy, carboxyacetoxy, and 3 -Sulfonylpropanoyloxy and the like can be mentioned.

The alkylamino group is an alkylamino group having 1 to 6 carbon atoms, and examples thereof include a dimethylamino group and a diethylamino group. 1 carbon atom as a carbonamido group
The carbonamido groups of 6 are, for example, an acetamido group and a propionamido group. The sulfonamide group is a sulfonamide group having 1 to 6 carbon atoms, and is, for example, a methanesulfonamide group. The ureido group is a ureido group having 1 to 6 carbon atoms, and examples thereof include ureido and methylureido. The oxycarbonyl group is an oxycarbonyl group having a carbon number of 1 to 6, and examples thereof include methoxycarbonyl and ethoxycarbonyl. The carbamoyl group has 1 to 1 carbon atoms.
The carbamoyl group of 6 is, for example, carbamoyl or N, N-dimethylcarbamoyl. The sulfinyloxy group is a sulfinyloxy group having 1 to 6 carbon atoms, for example,
It is a methanesulfinyloxy group. These substituents may be further substituted, if possible.

R _{1 of} the group represented by the general formula (A),
Preferred as R ₂ and R ₃ are a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an acyloxy group, an oxycarbonyl group and a sulfinyloxy group.

Among the compounds represented by the general formula (II),
The compound represented by the following general formula (B) is particularly preferable. General formula (B)

[0080]

[Chemical 31]

In the formula, Y represents a hydrogen atom or a group represented by the general formula (C). General formula (C)

[0082]

Embedded image

In the formula, R ₁₁ and R ₁₂ may be the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group or an oxycarbonyl group.

Preferred combinations of R ₁₁ and R ₁₂ in the general formula (C) are described below. R ₁₁ is a hydrogen atom, an alkoxy group, or an acyloxy group, and R ₁₂
Is preferably a hydrogen atom, an alkyl group, or an oxycarbonyl group. In this combination, the alkyl group of R ₁₂ includes those substituted with other substituents, more preferably an alkyl group substituted with an alkoxy group or an acyloxy group, and these substituents are if possible. , May be further substituted.

More preferably, R ₁₁ is an alkoxy group or an acyloxy group, and R ₁₂ is a combination of alkyl groups substituted with an alkoxy group or an acyloxy group, and particularly preferably, the alkoxy group and the acyloxy group have 1 to 1 carbon atoms. 8 is an alkoxy group or an acyloxy group, the alkyl group is an alkyl group having 1 to 6 carbon atoms, and most preferably, the alkyl group of R ₁₂ is a methyl group. These substituents may be further substituted, if possible, and as the substituent, the substituents mentioned for the aryl group can be applied.

Among the compounds represented by the general formula (B),
The compound represented by the following general formula (D) is most preferable. General formula (D)

[0087]

[Chemical 33]

In the formula, R ₄ and R ₅ may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group or an alkenyl group, and the alkyl groups represented by R ₄ and R ₅ are linked to each other. You may form a ring structure. Where an alkyl group,
The aryl group and the alkenyl group include those substituted with other substituents, and the substituents include an alkyl group,
Alkenyl group, aryl group, halogen atom, nitro group,
Examples thereof include a hydroxy group, an alkoxy group, an acyl group, a carboxyl group (including a salt), a sulfo group (including a salt), and a hydroxyamino group.

R ₄ and R ₅ in the compound represented by the general formula (D) are preferably a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, an aryl group having 6 to 10 carbon atoms, and 2 to 2 carbon atoms. 7
Alkenyl group, particularly preferably a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, an aryl group having 6 to 10 carbon atoms, and most preferably a hydrogen atom or 1 to 7 carbon atoms.
The alkyl groups represented by R ₄ and R ₅ may be linked to form a ring structure, and at least one of them is more preferably not a hydrogen atom. These groups may have a substituent, and as the substituent, the substituents described in the general formula (D) can be applied, for example, a hydrogen atom,
Methyl group, ethyl group, propyl group, butyl group, phenyl group, chloromethyl group, methoxymethyl group, 2-methoxyethyl group, 1-hydroxyamino-1-methyl-methyl group, 2-carboxyethyl group, or R ₄ and R ₅ Examples thereof include a cyclopentyl ring and a cyclohexyl ring formed by connecting the alkyl groups represented by these, and if possible, these groups may be further substituted. The compound of the general formula (II) is described as a so-called enol form, but the keto form isomerized thereof is virtually the same compound, and the compound in which the hydrogen atom is isomerized is also within the scope of the claims in the present application.

Specific examples of the compound of the present invention include, but are not limited to, the following compounds.

[0091]

Embedded image

[0092]

Embedded image

[0093]

Embedded image

[0094]

Embedded image

[0095]

[Chemical 38]

[0096]

[Chemical Formula 39]

[0097]

[Chemical 40]

[0098]

Embedded image

[0099]

Embedded image

[0100]

[Chemical 43]

The compound represented by the general formula (II) is ESH
EL.Ashry, A.Mousaad, and N.Rashed, Advances in Het
erocyclic Chemistry, vol.53, 233-302. JP-A-64-4
It can be synthesized according to a general synthesis method such as 5383, JP-A-2-288872, JP-A-4-29985, JP-A-4-364182, and JP-A-5-112594. As a general range of the amount of the compound represented by the general formula (II) used, 5 × 10 ⁻³ mol to 1 mol, and particularly preferably 10 ⁻² per 1 liter of the developing solution.
It is from mol to 0.5 mol.

1-Phenyl-3 as an auxiliary developing agent
Examples of pyrazolidone or a derivative thereof include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone and 1-phenyl-4-methyl-4.
-Hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxylmethyl-3-pyrazolidone,
1-phenyl-5-methyl-3-pyrazolidone, 1-p
-Aminophenyl-4,4 dimethyl-3-pyrazolidone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and the like. As the p-aminophenol-based auxiliary developing agent, N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine, 2- There are methyl-p-aminophenol, p-benzylaminophenol and the like, and among them, N-methyl-p-aminophenol is preferable.
Developing agent and 1-phenyl-3-pyrazolidones or p-
When the combination with aminophenols is used, the latter is usually 10 ^-3 mol / liter to 0.1 mol / liter,
More preferably 10 ⁻³ mol / liter to 0.06 mol /
It is preferably used in an amount of 1 liter.

In the present invention, the term "substantially free of dihydroxybenzenes" means that the concentration of dihydroxybenzenes in the developing solution is determined relative to the amount of the compound of the general formula (VI) or the above-mentioned auxiliary developing agent. Not enough (eg 5 × 1
^0-4 mol / liter or less). The developer of the present invention preferably contains no dihydroxybenzenes.

Sulfite salts such as sodium sulfite, potassium sulfite, lithium sulfite, sodium bisulfite, potassium metabisulfite and formaldehyde sodium bisulfite may be added to the developer of the present invention as a preservative.
The sulfite is used at 0.01 mol / l or more. If used in a large amount, it will dissolve silver halide emulsion grains and cause silver stains. Moreover, since it also causes an increase in COD (chemical oxygen demand), the amount added should be minimized.

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

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

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

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

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

Further, as a silver stain preventing agent in a developing solution, JP-A-56-24347, JP-B-56-46585,
The compounds described in JP-B-62-2849 and JP-A-4-362942 can be used. Further, the compound described in JP-A-62-212651 can be used as the development unevenness preventing agent, and the compound described in JP-A-61-267759 can be used as the dissolution aid. Further, if necessary, a color toning agent, a surfactant, an antifoaming agent, a hardener and the like may be contained.

The developer used in the present invention contains a carbonate as a buffer, boric acid described in JP-A-62-186259, sugars (eg saccharose) described in JP-A-60-93433, and oximes. (Eg acetoxime),
Phenols (for example, 5-sulfosalicylic acid), tertiary phosphates (for example, sodium salt, potassium salt) and the like are used, and carbonate and boric acid are preferably used. The pH of the developer is preferably 9.5 to 11.0, and particularly preferably 9.8 to 10.7. The developing temperature and time are interrelated and are determined in relation to the total processing time. Generally, the developing temperature is about 20 ° C to about 50 ° C, preferably 25 to 45 ° C, and the developing time is 5 seconds to 2 seconds. Minutes, preferably 7 seconds to 1 minute 30 seconds. When processing 1 square meter of the silver halide black and white photographic light-sensitive material, the replenisher amount of the developing solution is 500 ml or less, preferably 350 ml or less. In order to adjust the solid developer, it is effective to potassium salt the salt component contained in the developer from the viewpoint of dissolution rate.

The fixing solution used in the fixing step of the present invention is sodium thiosulfate, ammonium thiosulfate, if necessary tartaric acid, citric acid, gluconic acid, boric acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, tyron, ethylenediamine. Tetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid are aqueous solutions containing these salts.
From the viewpoint of recent environmental protection, it is preferable that boric acid is not contained. As the fixing agent of the fixing solution used in the present invention, sodium thiosulfate, ammonium thiosulfate and the like are used, and ammonium thiosulfate is preferable from the viewpoint of the fixing speed, but sodium thiosulfate may be used from the viewpoint of recent environmental protection. . The use amount of these known fixing agents can be appropriately changed and is generally about 0.1 to about 2 mol / liter. Particularly preferably, it is 0.2 to 1.5 mol / liter. If desired, the fixer may include a hardening agent (eg, water-soluble aluminum compound), preservative (eg, sulfite, bisulfite), pH buffer (eg, acetic acid), pH adjuster (eg, ammonia, sulfuric acid). ), A chelating agent, a surfactant, a wetting agent, and a fixing accelerator. Examples of the surfactant include anionic surfactants such as sulfates and sulfonates, polyethylene surfactants, and amphoteric surfactants described in JP-A-57-6740. Further, a known antifoaming agent may be added. Examples of the wetting agent include alkanolamine and alkylene glycol. Examples of fixing accelerators include JP-B-45-35754 and JP-A-58-122535.
No. 58-122536, thiourea derivatives, alcohol having triple bond in the molecule, US Pat.
A thioether compound described in JP-A-126459, JP-A-4-
The mesoionic compounds described in JP-A No. 229860 and the like may be mentioned, and the compounds described in JP-A-2-44355 may be used. As the pH buffer, for example, acetic acid, malic acid, succinic acid, tartaric acid, oxalic acid citric acid, maleic acid, glycolic acid, organic acids such as adipic acid, boric acid,
Inorganic buffers such as phosphates and sulfites 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 bringing in a developing solution, and is 0.01 to 1.0 mol / liter, more preferably 0.02 to 0.6 mol / l.
Use about 1 liter. The pH of the fixing solution is preferably 4.0 to 6.5, particularly preferably 4.5 to 6.0. Further, as a dye elution accelerator, JP-A 64-473
The compounds described in No. 9 can also be used.

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

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

When the replenishment amount is reduced, it is preferable to prevent the liquid from evaporating and oxidizing by reducing the contact area of the treatment tank with the air. The roller-conveying type automatic developing machine is described in U.S. Pat. Nos. 3,025,779 and 3,545,971, and is referred to simply as a roller-conveying type processor in this specification. Roller transport type processor is for developing, fixing,
Although it comprises four steps of washing and drying, the method of the present invention does not exclude other steps (for example, stopping step), but it is most preferable to follow these four steps. Instead of the water washing step, four stable steps may be used.

The supply form of the treatment liquid in the present invention may be a solid treatment agent, and the solid treatment agent may be powder, tablets, granules,
A powder, a lump, or a paste is used, and the preferred form is the form or tablet described in JP-A-61-259921. The method for producing tablets is described in, for example, JP-A-51-51.
61837, 54-155038, 52-88.
No. 025, British Patent No. 1,213,808, and the like, and can be produced by a general method, and granule treating agents include, for example, JP-A Nos. 2-109042, 2-109043, 3-39735, and It can be produced by a general method described in JP-A-3-39739. Furthermore, the powder processing agent is
For example, JP-A-54-133332, British Patent 725,
892, 729,862 and German Patent 3,73.
It can be produced by a general method as described in No. 3,861.

The bulk density of the solid processing agent of the present invention is from 0.5 to 0.5 from the viewpoint of its solubility and the effect of the object of the present invention.
It is preferably 6.0 g / cm ³ , particularly 1.0 to 5.
It is preferably 0 g / cm ³ .

There are no particular restrictions on the various additives used in the light-sensitive material of the present invention, and for example, those described in the following sections can be preferably used. Item This section 1) 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 13 From line 4 to page 4, lower right column, line 18. 2) Antifoggant 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, further JP-A 1-237538. Thiosulfinic acid compounds described in the public notice. 3) Polymer latex JP-A-2-103536, page 18, lower left column, lines 12 to 20. 4) Compounds having an acid group JP-A-2-103536, page 18, lower right column, line 6 to page 19, upper left column, line 1 5) Matting agent, slip agent, JP-A-2-103536, page 19, upper left column 15, plasticizer line to page 19, upper right column, line 15 6) Hardener JP-A-2-103536, page 18, upper right column, line 5 to line 17 thereof. 7) Dyes Dyes in the lower right column, lines 1 to 18 of JP-A-2-103536, solid dyes described in JP-A-2-294638 and Japanese Patent Application No. 3-187573. 8) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 20. 9) Black spot inhibitor The compounds described in U.S. Pat. No. 4,956,257 and JP-A-1-118832. 10) Monomethine compound Compounds of general formula (II) described in JP-A-2-287532 (compound examples II-1 to II-26). 11) Dihydroxybenze Compounds described in JP-A-3-39948, page 11, upper left column to pages 12, page 12 lower left column, and EP452772A.

[0119]

EXAMPLES The present invention will be described in more detail with reference to the following examples. First, a method of making a silver halide emulsion used in the following examples will be described. Emulsion-A 0.13 M silver nitrate aqueous solution and 1.5 × per mol of silver
^Containing K ₂ Rh (H ₂ O) Cl ₅ corresponding to 10 ⁻⁷ mol and K ₃ IrCl ₆ corresponding to 2 × 10 ⁻⁷ mol,
An aqueous solution of a halogen salt containing 04M potassium bromide and 0.09M sodium chloride was added to sodium chloride, and 1,3-
To obtain silver chlorobromide grains having an average grain size of 0.14 μm and a silver chloride content of 70 mol% by adding to a gelatin aqueous solution containing dimethyl-2-imidazolidinethione by a double jet method at 38 ° C. for 12 minutes while stirring. Nucleation was performed by. Subsequently, similarly, a 0.87 M silver nitrate aqueous solution, 0.26 M potassium bromide, and a halogen salt aqueous solution containing 0.65 M sodium chloride were added over 20 minutes by the double jet method. Then, 1 × 10 ⁻³ mol of a KI solution was added for conversion, and subsequently, a copolymer of isobutene and monosodium maleic acid salt was used as a precipitating agent, followed by washing with water by a flocculation method according to a conventional method, and per mol of silver Add 40 g of gelatin, p
Prepared to H6.5 and pAg7.5, and further added 7 mg of sodium benzenethiosulfonate, 2 mg of benzenesulfinic acid, 8 mg of chloroauric acid, 200 mg of potassium thiocyanate and 5 mg of sodium thiosulfate per 1 mol of silver, and added at 60 ° C
After 45 minutes of heating and chemical sensitization, 4 as a stabilizer
150 mg of -hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, and further 100 mg of proxel as a preservative was added. The obtained grains were silver iodochlorobromide cubic grains having an average grain size of 0.25 μm and a silver chloride content of 69.9 mol%. (Coefficient of variation 10%) Emulsion-B 0.37 mol of silver nitrate aqueous solution, and (NH ₄ ) ₃ RhCl ₆ and 2 × corresponding to 1.0 × 10 ⁻⁷ mol per 1 mol of silver in the finished emulsion.
An aqueous solution of a halogen salt containing 10 ⁻⁷ mol of K ₃ IrCl ₆ , 0.11 mol of potassium bromide and 0.27 mol of sodium chloride, sodium chloride and 1,3-dimethyl-2-
The mixture was added to a gelatin aqueous solution containing imidazolidinethione by a double jet method at 45 ° C. for 12 minutes with stirring to give an average particle size of 0.20 μm and a silver chloride content of 70.
Nucleation was performed by obtaining mol% silver chlorobromide grains. Subsequently, a 0.63 mol silver nitrate aqueous solution was added in the same manner as above.
An aqueous solution of halogen salt containing 19 mol of potassium bromide and 0.47 mol of sodium chloride was added over 20 minutes by the double jet method. Then 1 per mole of silver
A KI solution of × 10 ^-3 mol was added for conversion, followed by washing with water by a flocculation method according to a conventional method, 40 g of gelatin was added to adjust pH to 6.5 and pAg to 7.5, and benzenethiosulfonic acid was added per mol of silver. 7 mg of sodium, 5 mg of sodium thiosulfate and 8 mg of chloroauric acid were added, and the mixture was heated at 60 ° C. for 45 minutes for chemical sensitization treatment, and 4-hydroxy-6-methyl-1, as a stabilizer,
150 mg 3,3a, 7-tetrazaindene and proxel as preservative were added. The obtained grains were cubic silver chlorobromide grains having an average grain size of 0.28 μm and a silver chloride content of 70 mol%. (Coefficient of variation 9%)

[0120]

[Table 1]

Example 1 Undercoat layer made of vinylidene chloride copolymer (0.5 μm)
Polyethylene terephthalate film having (150
μm) on the support, from the support side, UL, EM, ML,
It was applied so as to have a PC layer structure. The preparation method and coating amount of each layer are shown below.

(UL) 10 g of gelatin, 50 wt% of gelatin, 3.5 wt% of polyethyl acrylate latex compound (a) were added to gelatin, and water was added so that the final amount was 250 ml. , Gelatin was applied at 0.4 g / m ² .

(EM) The above emulsion-A was mixed with gelatin together with 4
After dissolving at 0 ° C., 3.2 parts of the sensitizing dye (S-1 above) was added.
× 10 ^-4 mol / mol Ag, 2.7 sensitizing dye (S-2)
× 10 ^-4 mol / mol Ag, KBr 3.4 × 10 ^-3 mol /
Mol Ag, compound (b) 3.2 × 10 ⁻⁴ mol / mol A
g, compound (c) 7.4 × 10 ⁻⁴ mol / mol Ag, hydroquinone 9.7 × 10 ⁻³ mol / mol Ag, phosphoric acid 8.
0 × 10 ⁻³ mol / mol Ag, compound I-38 among compounds of general formula (I) 4.5 × 10 ⁻⁴ mol / mol Ag, compound A-12 among compounds of general formula (II) 5.3 x 1
0 ^-4 mol / mol Ag, compound W-1 3 × 10 ^-4 mol / mol
Addition of mol Ag, 15 wt% polyethyl acrylate to gelatin, 15 wt% to gelatin
Latex copolymer (methyl acrylate; 2-acrylamido-2-methylpropanesulfonic acid sodium salt; 2-acetoacetoxyethyl methacrylate = 8)
(8: 5: 7 weight ratio), and 4 wt% of the compound (a) to gelatin was added and coated so as to have Ag of 3.3 g / m ² .

Compound (d) 7 was added to (ML) gelatin solution.
mg / m ² , 15 wt% of polyethyl acrylate to gelatin, and 3.5 wt% of compound (a) to gelatin were added so that gelatin was 0.5 g / m ² .

[0125] (PC) to the gelatin solution, the average particle size 3.5μm of an amorphous SiO ₂ matting agent 40 mg / m ^2, silicone oil 20 mg / m ² and the compound as a coating aid (e) 5 mg / m ² and dodecyl 25 mg / m ² of sodium benzenesulfonate was added and coated. 0.3 for gelatin
g / m ² .

Additive for the photosensitive material layer of Example 1

[0127]

[Chemical 44]

[0128]

Embedded image

The back layer and the back protective layer were coated by the following formulation. [Back layer formulation] Gelatin 3 g / m ² latex Polyethyl acrylate 2 g / m ² Surfactant sodium P-dodecylbenzenesulfonate 40 mg / m ² compound [a] 110 mg / m ² 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] 100 mg / m ² dye [c] 50 mg / m ²

[0130]

Embedded image

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

A developing solution was prepared according to the formulation shown in Table 2.

[0133]

[Table 2]

The fixer formulation used in the present invention is shown below. (Fixer formulation) Ammonium thiosulfate 360 g Ethylenediaminetetraacetic acid 2Na dihydrate 2.3 g Sodium thiosulfate pentahydrate 33.0 g Sodium sulfite 75.0 g Sodium hydroxide 37.0 g Glacial acetic acid 87.0 g Tartaric acid 8.8 g Sodium gluconate 6.6 g Aluminum sulfate 25.0 g Water to add 3 liter pH (adjusted with sulfuric acid or sodium hydroxide) 4.85

<Exposure / Development Processing>
Exposure with a tungsten light of 0 ° K for 5 seconds was performed through an optical wedge for sensitometry, and the developing solution shown in Table 2 was developed for 30 seconds at 35 ° C, followed by fixing, washing with water and drying. For processing, an automatic processor FG-680A manufactured by Fuji Photo Film Co., Ltd. was used.

The sensitivity is shown by the relative value of the reciprocal of the exposure amount which gives a density of 1.5. The relative sensitivity is shown with the sensitivity of Experiment No. 1 being 100. Image contrast index (γ)
From the point of fog + density 0.3 of the characteristic curve, fo
Connect the point of g + concentration 3.0 with a straight line, and the slope of this straight line is γ
Expressed as a value. That is, γ = (3.0-0.3) / [l
og (exposure dose giving a density of 3.0) -log (density of 0.
3), and the larger the γ value, the harder the photographic characteristics.

[0137]

[Table 3]

By the processing method of the present invention, a system in which reductones which are environmentally and toxicologically preferable are used as a developing agent, and when two developing agents are used in combination, a high contrast image can be obtained. With ascorbic acid or the compound of the present invention alone, it is not possible to obtain the same high contrast as the hydroquinone developing agent, which is an unexpected effect rather than the effect of superimposing two developing agents.

Example 2 A sample was prepared in the same manner as in Example 1 except that the EM layer formulation of Example 1 was changed to the following.

(EM) The above emulsion-B was mixed with gelatin 4
After dissolving at 0 ° C., the sensitizing dye (S-3 above) was added to 4.6.
× 10 ⁻⁴ mol / mol Ag, sensitizing dye (S-1) 1.7 ×
10 ⁻⁴ mol / mol Ag, KBr4.5 × 10 ⁻³ mol / mol Ag, compound (b) 3.1 × 10 ⁻⁴ mol / mol Ag,
Compound (c) 7.4 × 10 ⁻⁴ mol / mol Ag, hydroquinone 2.9 × 10 ⁻² mol / mol Ag, acetic acid 2.3 × 1
0 ^-3 mol / mol Ag, 10 wt% of colloidal silica with respect to gelatin, the compound I-38 of the general formula (I) 3.
4 × 10 ⁻⁴ mol / mol Ag, compound A-of the general formula (III)
12 was added at 4.9 × 10 ^-4 mol / mol Ag, and compound W-1 was added at 3.4 × 10 ^-4 mol / mol Ag, and further added to gelatin in an amount of 30 wt% of polyethyl acrylate latex polymer and gelatin. On the other hand, 4 wt% compound (a)
Was added and applied. Compounds (a), (b), (c)
Is the same as in Example 1.

[0141]

[Table 4]

A developing solution was prepared according to the formulation shown in Table 4,
The same fixing solution as in Example 1 was used. Using the sample prepared as described above, the sample was exposed to xenon flash light having an emission time of 10 ^-5 sec through an interference filter having a peak at 488 nm and a continuous wedge, and was exposed to 35% with the developer shown in Table 4.
After development at 30 ° C. for 30 seconds, fixing, washing with water and drying were performed. Processing is Fuji Photo Film Co., Ltd. automatic processor F
G-680AG was used. The evaluation was performed in the same manner as in Example 1.

[0143]

[Table 5]

By the processing method of the present invention, a high-sensitivity and high-contrast image can be obtained. The carbonate concentration of the developer is 0.5M
By the above, it is possible to obtain a development processing method with higher sensitivity.

According to the present invention, it is possible to provide a processing method for a silver halide black and white photographic light-sensitive material capable of obtaining a super-high contrast and high-sensitivity image with a developer containing no dihydroxybenzene type developing agent.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] July 7, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0122

[Correction method] Change

[Correction content]

(UL) 10 g of gelatin, 50 wt% of polyethyl acrylate latex with respect to gelatin, and 3.5 wt% of compound (a) with respect to gelatin were added,
Water was added to the final amount of 250 ml to prepare gelatin, and gelatin was coated at 0.4 g / m ² .

Claims (4)

[Claims] 1. A method in which a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support is exposed and then developed with a developer to obtain a silver halide emulsion layer and / or Contains at least one hydrazine derivative represented by the general formula (I) in at least one of the other hydrophilic colloid layers, and the developer contains substantially no dihydroxybenzene compound, ) At least one developing agent selected from ascorbic acid, erythorbic acid and alkali metal salts thereof, (2) a developing agent represented by the general formula (II), and (3) a super-additive auxiliary developing agent. A process for developing a silver halide black and white photographic light-sensitive material, which comprises: Embedded image In the formula, R ₁ represents an aliphatic group or an aromatic group, R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an unsaturated heterocyclic group,
Represents an alkoxy group, an aryloxy group, an amino group, or a hydrazino group, and G ₁ represents a —CO— group, a —SO ₂ group,
-SO- group, , -CO-CO- group, thiocarbonyl group, or iminomethylene group, both A ₁ and A ₂ are hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted It represents a substituted arylsulfonyl group or a substituted or unsubstituted acyl group. R ₃ is selected from the same range as the group defined for R ₂ ,
It may be different from R ₂ . Embedded image In the formula, X represents a hydrogen atom, an aryl group, a heterocyclic group, or a group represented by the general formula (A). General formula (A): In the formula, R ₁ , R ₂ and R ₃ may be the same or different and each represents a substituent other than a hydroxy group or a hydrogen atom. 2. The development processing method according to claim 1, wherein the initial pH of the developer is 9.5 to 11.0. 3. A 1-phenyl-3-pyrazolidone compound and / or as an auxiliary developing agent exhibiting superadditivity to a developing solution.
3. The development processing method according to claim 1, which further comprises a p-aminophenol compound. 4. The development processing method according to claim 1, wherein the developer contains a carbonate in an amount of 0.5 M or more.