JPH0895185A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To obtain the silver halide photographic sensitive material which can be handled in a well-lighted room and has very high-contrast photographic characteristics and good reproducibility with respect to line drawing by using a specific heavy metal and specific silver halide grains as components of the emulsion layer of the sensitive material and adding a specific hydrazine derivative and a specific nucleation promoter to the emulsion layer or other hydrophilic colloidal layers of the material. CONSTITUTION: In this sensitive material, the emulsion layer contains a heavy metal such as Ir, Ru of at least 1×10<-5> mol per mol of silver and silver halide having >=95mol% content of silver chloride contg. an iron compound, and also the emulsion layer or other hydrophilic colloidal layers contain(s) a hydrazine derivative represented by the formula I and a nucleation promoter represented by the formula II. In the formula I: R1 is an aliphatic or aromatic group substituted by a sulfonamide group; R2 is a hydrogen atom, alkyl group or the like; and both of A1 and A2 are hydrogen atoms, or one of A1 and A2 is a hydrogen atom and the other is an alkylsulfonyl group or the like. In the formula II: each of R1 to R3 is an alkyl or aryl group or the like; L is an organic group linked to a P atom through one of its own carbon atom; and X is an anion.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide black and white photographic light-sensitive material for forming a silver image as a final image, and more specifically, it is handled in an environment which can be called a bright room. The present invention relates to a reversal silver halide black-and-white photographic light-sensitive material suitable for use in the field of photoengraving, capable of forming a negative tone silver image having high contrast.

[0002]

2. Description of the Related Art Among photoengraving processes in the field of print reproduction, particularly in the work processes of collecting and returning plates, the work efficiency and work environment are improved by working in a brighter environment. That is, there is provided a silver halide light-sensitive material for plate making that can be handled in an environment that can be called a bright room. As a method of making a light-sensitive material that can be handled in a bright room by lowering its sensitivity to visible light, a silver halide emulsion mainly containing silver chloride, a rhodium salt, an iridium salt,
A method using an emulsion to which inorganic and organic desensitizers such as pinacryptol yellow and phenosafranine are added is well known. 0.05 to 0.5 without chemical sensitization
A method of using a rhodium salt and / or an organic desensitizer in a fine grain silver chloride or fine grain silver chlorobromide emulsion having a size of μm is preferably used. Furthermore, in combination with these emulsions,
A method of incorporating a yellow dye or an ultraviolet absorbing dye into a light-sensitive material is used for the purpose of sensitivity adjustment and safelight safety.

On the other hand, the light-sensitive material used in the plate-collecting and reversing process has the following features:
There is a demand for what has a so-called ultra-high contrast photographic property, which has a high blackening density in which image areas and non-image areas are clearly distinguished. In particular, the halftone image and the line image original as the return original are overlapped and exposed (so-called character image formation is performed).
In this case, there is a demand for a light-sensitive material having good line drawing reproduction performance (extracted character quality).

As a method for imparting ultra-high contrast photographic characteristics to a light-sensitive material, a method of incorporating a vitrazine derivative or a tetrazolium compound into the light-sensitive material is known, and the above-mentioned inorganic and organic desensitizers and yellow. When the method of incorporating a dye or an ultraviolet absorbing dye into the light-sensitive material is combined, there may be a problem that the effect of the hydrazine derivative or the tetrazolium compound on the contrast enhancement is hindered or the good reproducibility of the line drawing is lost. It was

As an image system capable of obtaining ultra-high contrast photographic characteristics in a silver halide black and white photographic light-sensitive material for return,
JP-A-60-140338, JP-A-61-238049
No. 63-183438, No. 63-296034.
No. 61-198147, No. 61-198148.
No. 61-240235. However, the pH of the developer used in these inventions is 11 or more. A developer with a pH of 11 or more is easily oxidized by air and is unstable and cannot withstand long-term storage. Therefore, a silver halide photographic light-sensitive material containing a hydrazine derivative is developed with a developer having a lower pH to obtain a high contrast image. Is required.

However, when the pH of the developing solution is low, the effect of increasing the contrast of the hydrazine derivative is lowered, and a high contrast image cannot be obtained. Although attempts have been made to develop more active hydrazine derivatives and nucleation accelerators in order to promote higher contrast, the long-term storage stability of the light-sensitive material may be reduced in some cases.

[0007]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a reversal silver halide photographic light-sensitive material which can be handled under bright safelight (substantially bright room) and has ultrahigh contrast photographic characteristics. To provide. A second object of the present invention is to provide a light-sensitive material which can be handled under a bright safelight (substantially in a bright room) and has good line drawing reproduction performance (extracted character quality). A third object of the present invention is to provide a light-sensitive material which has a super-hard tone photographic property even when processed with a low pH developer having a pH stable to 11 or less against air oxidation, and which has good extracted character quality. Especially.
A fourth object of the present invention is to provide a light-sensitive material having good long-term storage stability.

[0008]

These objects of the present invention are directed to a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the emulsion layer having an I
Halogenation containing at least 1 × 10 ⁻⁵ mol of a heavy metal selected from r, Ru, Rh, Re and Cr per mol of silver halide, and containing at least one iron compound in a silver chloride content of 95 mol% or more. At least one of the emulsion layers or other hydrophilic colloid layers containing silver particles and at least one hydrazine derivative represented by the following general formula (I) and a nucleating agent represented by the following general formulas (II) to (V) It has been achieved by a silver halide photographic light-sensitive material characterized by containing at least one accelerator.

The present invention will be described in detail below. The silver halide emulsion of the present invention contains at least one heavy metal selected from Ir, Ru, Rh, Re and Cr. Preferred as these heavy metals are metal coordination complexes, and hexacoordination complexes represented by the following general formula. [M (NY) _m L _6-m ] ⁿ (In the formula, M is a heavy metal selected from Ir, Ru, Rh, Re, and Cr. L is a bridging ligand. Y is oxygen or sulfur. M = 0, 1, 2 and n = 0, -1,-.
2 and -3. ) Preferred examples of L include halide ligands (fluoride, chloride, bromide and iodide), cyanide ligand, cyanate ligand, thiocyanate ligand, selenocyanate ligand, tellurocyan Nate ligands, acid ligands and aco ligands. When an aco ligand is present, it preferably occupies one or two of the ligands. Specific examples of the metal coordination complex are shown below. 1. [Rh (H ₂ O) Cl ₅ ] ^-2 2. [RuCl ₆ ] ^-3 3. [Ru (NO) Cl ₅ ] ^-2 4. [RhCl ₆ ] ^-3 5. [Ru (H ₂ 0) Cl ₅ ] ^-2 6. [Ru (NO) (H ₂ O) Cl ₄ ] ^-1 7. [Re (NO) Cl ₅ ] ^-2 8. [Ir (NO) Cl ₅ ] ^-2 9. [Ir (H ₂ 0) Cl ₅ ] ^-2 10. [Re (H ₂ 0) Cl _5] ^-2 11. [RhBr _6] ^-3 12. [ReCl _6] ^-3 13. [IrCl _6] ^-3 14. _{[Re (NS) Cl 4 (SeCN} ) ] ^{- 2} 15. [Cr (CN) ₆ ] ^-3

The above metal complex can be added to the silver halide during grain preparation. The content of the heavy metal in the silver halide grains of the present invention is 1 × 10 ⁻⁵ mol to 1 × 10 ⁻² mol per mol of silver halide. It is preferably 10 ^{−5 to} 3 × 10 ⁻⁴ mol. Further, the above heavy metals may be used in combination. The distribution of the heavy metal in the silver halide grain is not particularly limited, but it is preferable that the heavy metal is more present outside the grain.

The silver halide emulsion of the present invention contains at least one iron compound.

The iron compound used in the present invention is a divalent or trivalent iron ion-containing compound, and is preferably an iron salt or an iron complex salt having water solubility in the concentration range used in the present invention. Specifically, ferrous arsenate ferrous bromide ferrous carbonate ferrous chloride ferrous citrate ferrous fluoride ferrous formate ferrous gluconate ferrous hydroxide iodide ferrate Ferrous lactate ferrous lactate ferrous phosphate ferrous succinate ferrous sulfate ferrous thiocyanate ferrous nitrate ferrous ammonium nitrate basic ferric acetate ferric albuminate Ferric acetate ammonium ferric bromide ferric chloride ferric chloride ferric citrate ferric fluoride ferric formate ferric chryserophosphate ferric hydroxide ferric hydroxide acidic phosphate ferric Ferric nitrate ferric nitrate ferric phosphate ferric pyrophosphate sodium ferric pyrophosphate ferric thiocyanate ferric sulfate ammonium ferric sulfate ammonium ferric sulfate guanidine ferric ammonium citrate hexane cyanoferrate (II) Potassium bentacyanoammine ferrous potassium Chirenjinitoriro tetraacetate sodium ferric potassium hexacyanoferrate (III) chloride tris (dipyridyl) ferric preventor cyano nitrosyl ferric potassium chloride Hekisarea ferric particularly hexacyanoferrate (II), hexacyanoferrate (III)
Acid salts, ferrous thiocyanate and ferric thiocyanate show remarkable effects.

The iron compound can be added to the silver halide during grain preparation. The distribution of iron in the silver halide grain is not particularly limited, but it is preferable that the iron be present in a larger amount outside the grain or localized outside the grain.

The content of iron in the silver halide grains of the present invention is 1 × 10 ^-7 mol to 1 × 1 mol per mol of silver halide.
0 ^-2 mol, preferably 1 x 10 ^-5 mol to 5 x 10
^-3 mol.

The silver halide emulsion of the silver halide photographic light-sensitive material used in the present invention is silver chlorobromide, silver chloroiodobromide or silver chloride in which 95 mol% or more, particularly 99 mol% or more, is composed of silver chloride. . 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 of the silver halide photographic light-sensitive material used in the present invention has an average grain size of 0.20.
μm or less. It is particularly preferably 0.08 to 0.16 μm. If the particle size exceeds 0.2μ, γ decreases and Dmax of the practical skill decreases. In the present invention, the reaction temperature is 5 as a mixing condition for adjusting the silver halide grains.
The silver potential is 70 mV or more, preferably 300 mV to 500 mV, or 5,6-cyclopentane-4-hydroxy-1,3 at 0 ° C. or lower, preferably 40 ° C. or lower, under a condition that the stirring speed is sufficiently high for uniform mixing. 80 mV in the presence of a stabilizer such as 1,3a, 7-tetrazaindene
Good results can be obtained by adjusting at ~ 120 mV. The particle size distribution is basically not limited, but it is preferably monodisperse. Here, the monodispersion means that at least 95% of the weight or the number of particles is ± 4 of the average particle size.
It is composed of particle groups having a size within 0%, more preferably within ± 20%. The silver halide grain of the present invention preferably has a regular crystal such as a cube, an octahedron and a tetradecahedron, and a cubic is particularly preferable.

The silver halide emulsion used in the method of the present invention may not be chemically sensitized, but may be chemically sensitized. As a method of chemically sensitizing a silver halide emulsion, sulfur sensitization, reduction sensitization and noble metal sensitization are known, and any of these may be used alone or in combination. Good. Among the noble metal sensitizing methods, the gold sensitizing method is a typical one, which uses a gold compound, mainly a gold complex salt. Noble metals other than gold, for example, complex salts of platinum, palladium, iridium, etc. may be contained. Specific examples are US Pat.
No. 8,060, British Patent 618,061 and the like. As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanins and the like can be used in addition to the sulfur compounds contained in gelatin. As the reduction sensitizer, a first tin salt, an amine, formamidinesulfinic acid, a silane compound or the like can be used. Since the silver halide emulsion of the present invention contains an iron compound, chemical sensitization may be hindered. For chemical sensitization, Japanese Patent Application No. 5-35
It is preferable to use a zinc compound in combination as described in No. 605.

In the present invention, the grain formation of the silver halide emulsion is preferably carried out under acidic conditions. The acidic condition is pH 4.0 or less, preferably pH
The pH is 3.0 to 1.5.

The hydrazine derivative used in the present invention is
It is a compound represented by the following general formula (I).

[0020]

[Chemical 4]

In the formula, R ₁ represents an aliphatic group or an aromatic group substituted with a sulfonamide group, and R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an unsaturated heterocyclic group, an alkoxy group or an aryloxy group. Represents a group, an amino group or a hydrazino group. A ₁ and A ₂ both represent a hydrogen atom, or one 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 formula (I), the aliphatic group substituted with the sulfonamide group represented by R ₁ preferably has 1 to 1 carbon atoms.
30 is a straight chain, branched or cyclic alkyl group having 1 to 20 carbon atoms. The branched alkyl groups herein 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 substituted by the sulfonamide 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, pyridine ring, pyrimidine ring, imidazole ring,
There are a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, a benzothiazole ring, and the like, and among them, those containing a benzene ring are preferable. Of these, an aryl group is particularly preferable.

In the general 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 preferable typical substituents are, for example, alkyl group, alkenyl group, alkynyl group, aryl group, group containing heterocycle, pyridinium group, hydroxy group, alkoxy group and aryloxy group. Groups, acyloxy groups, alkyl or aryl sulfonyloxy groups, amino groups, carbonamido groups, sulfonamide groups, ureido groups, thioureido groups, semicarbazide groups, thiosemicarbazide groups, urethane groups, hydrazide groups, quaternary ammonium structures Group having, alkyl or arylthio group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group, carboxyl group, sulfo group, acyl group, alkoxy or aryloxycarbonyl group, carbamoyl group, sulfamoyl group, halogen Child, a cyano group, a phosphoric acid amide group,
Examples thereof include 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 preferable substituents are linear, branched or cyclic. An 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.

Preferred among the groups represented by R ₂ are a hydrogen atom, an alkyl group (eg, methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc.). ), An aralkyl group (for example, an o-hydroxybenzyl group), an aryl group (for example, a phenyl group,
3,5-dichlorophenyl group, o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, 2-
(E.g., a hydroxymethylphenyl group) and the like, and a hydrogen atom and a trifluoromethyl group are particularly preferable. Also, R ₂ is C
The portion of OR ₂ is split from the rest of the molecule, and -CO-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 ₁ , A ₂
Is most preferably a hydrogen atom.

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

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 silver halide grains 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.

In the present invention, a particularly preferred hydrazine derivative is that R ₁ is a ballast group, a group that promotes adsorption to the surface of silver halide grains, a group having a quaternary ammonium structure, or a phenyl group having an alkylthio group,
A hydrazine derivative in which 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). Note that any combination of the above R ₁ and R ₂ options is possible and preferred. A hydrazine derivative in which R ₁ is a phenyl group having an alkylthio group or a group that promotes adsorption on the surface of silver halide grains and R ₂ is a substituted alkyl group is particularly preferable.

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

[0031]

[Chemical 5]

[0032]

[Chemical 6]

[0033]

[Chemical 7]

[0034]

[Chemical 8]

[0035]

[Chemical 9]

[0036]

[Chemical 10]

[0037]

[Chemical 11]

[0038]

[Chemical 12]

As the hydrazine derivative used in the present invention, in addition to the above, RESEARCH DISCLOSURE Item 2
3516 (November 1983, p. 346) and references cited therein, as well as U.S. Pat. No. 4,080,20.
No. 7, No. 4,269,929, No. 4,276,364
Nos. 4,278,748, 4,385,108
Issue No. 4,459,347 Issue No. 4,478,928
Nos. 4,560,638 and 4,686,167
No. 4,912,016, 4,988,604
Issue No. 4,994,365 Issue 5,041,355
No. 5,104,769, British Patent No. 2,011,
391B, European Patent Nos. 217,310 and 301,
799, 356, 898, JP-A-60-1797.
34, 61-170733, 61-27074.
No. 4, No. 62-178246, No. 62-270948.
No. 63, No. 63-29751, No. 63-32538, No. 63-104047, No. 63-121838, No. 6
3-129337, 63-223744, 63
-234244, 63-234245, 63-
234246, 63-294552, 63-3
06438, 64-10233 and JP-A-1-90.
No. 439, No. 1-100530, No. 1-105941
No. 1, No. 1-105943, No. 1-276128, No. 1-280747, No. 1-283548, No. 1-2.
83549, 1-285940, 2-2541.
No. 2, No. 2-77057, No. 2-139538, No. 2
-196234, 2-196235, 2-19
No. 8440, No. 2-198441, No. 2-19844
No. 2, No. 2-220042, No. 2-221953,
2-221954, 2-285342, 2-
285343, 2-289843, 2-302
No. 750, No. 2-304550, No. 3-37642
No. 3, No. 3-54549, No. 3-125134, No. 3
-184039, 3-240036, 3-24
No. 0037, No. 3-259240, No. 3-28003
No. 8, No. 3-228536, No. 4-51143, No. 4-56842, No. 4-84134, No. 2-230.
No. 233, No. 4-96053, No. 4-216544.
No. 5, No. 5-45761, No. 5-45762, No. 5-
No. 45763, No. 5-45764, No. 5-45765.
And those described in Japanese Patent Application No. 5-94925 can be used in combination.

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

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

The nucleation accelerator used in the present invention is a compound represented by the following general formulas (II), (III), (IV) and (V).

[0043]

[Chemical 13]

In the formula, R ₁ , R ₂ and R ₃ are alkyl groups,
It represents a cycloalkyl group, an aryl group, an alkenyl group, a cycloalkenyl group or a heterocyclic residue, which may further have a substituent. m represents an integer of 1 to 4, L represents an m-valent organic group bonded to the P atom by its carbon atom, n represents an integer of 1 to 3, X represents an n-valent anion, and X represents May be linked to L.

[0045]

[Chemical 14]

In the formula, A represents an organic group for completing the heterocycle. B and D each represent a divalent group.
R ₁ and R ₂ each represent an alkyl group or an aryl group,
R ₃ and R ₄ represent a hydrogen atom or a substituent. R ₅ represents an alkyl group. X represents an anion group, but X is not necessary in the case of an inner salt.

The general formula (II) will be described in detail.

[0048]

[Chemical 15]

In the formula, R ₁ , R ₂ and R ₃ represent an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, a cycloalkenyl group or a heterocyclic residue, which may further have a substituent. . m represents an integer, L represents an m-valent organic group which is bonded to a P atom and its carbon atom, n represents an integer of 1 to 3, X represents an n-valent anion, and X is linked to L. You may have.

Examples of the groups represented by R ₁ , R ₂ and R ₃ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group and tert group.
-A straight-chain or branched alkyl group such as a butyl group, an octyl group, a 2-ethylhexyl group, a dodecyl group, a hexadecyl group, and an octadecyl group; an aralkyl group such as a substituted or unsubstituted benzyl group; a cyclopropyl group, a cyclopen Cycloalkyl groups such as teal and cyclohexyl, aryl groups such as phenyl, naphthyl and phenanthryl; alkenyl groups such as allyl, vinyl and 5-hexenyl; cyclopentenyl, cyclohexenyl and other cyclo groups Alkenyl group; pyridyl group, quinolyl group,
Furyl group, imidazolyl group, thiazolyl group, thiadiazolyl group, benzotriazolyl group, benzothiazolyl group,
Heterocyclic residues such as a morpholyl group, a pyrimidyl group and a pyrrolidyl group are mentioned. Examples of the substituents substituted on these groups include, in addition to the groups represented by R ₁ , R ₂ and R ₃ , halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, nitro group, 1 2, a tertiary amino group, an alkyl or aryl ether group, an alkyl or aryl thioether group, a carbonamido group, a carbamoyl group,
Examples thereof include sulfonamide group, sulfamoyl group, hydroxyl group, sulfoxy group, sulfonyl group, carboxyl group, sulfonic acid group, cyano group and carbonyl group. Examples of the group represented by L include a group having the same meaning as R ₁ , R ₂ and R ₃ , as well as a trimethylene group, a tetramethylene group,
Polymethylene group such as hexamethylene group, pentamethylene group, octamethylene group and dodecamethylene group, divalent aromatic group such as phenylene group, biphenylene group and naphthylene group, polyvalent fat such as trimethylenemethyl group and tetramethylenemethyl group Examples thereof include polyvalent aromatic groups such as group groups, phenylene-1,3,5-toluyl group, and phenylene-1,2,4,5-tetrayl group.

Examples of the anion represented by X include halogen ions such as chlorine ion, bromine ion and iodine ion, carboxylate ion such as acetate ion, oxalate ion, fumarate ion and benzoate ion, and p-toluenesulfonate. , Methane sulfonate, butane sulfonate, benzene sulfonate and other sulfonate ions, sulfate ions, perchlorate ions,
Examples thereof include carbonate ion and nitrate ion.

In the general formula (II), R ₁ , R ₂ , R ₃
Is preferably a group having 20 or less carbon atoms, and an aryl group having 15 or less carbon atoms is particularly preferable. m is preferably 1 or 2, and when m is 1, L is preferably a group having 20 or less carbon atoms, and particularly preferably an alkyl group or aryl group having 15 or less total carbon atoms. When m represents 2, the divalent organic group represented by L is preferably an alkylene group, an arylene group or a divalent group formed by combining these groups, and further, these groups and a -CO- group. , -O- group, -N
R ₄ — group (provided that R ₄ is a hydrogen atom or R ₁ , R ₂ , R
₃ represents a group having the same meaning as _3, and when a plurality of R _4's are present in the molecule, they may be the same or different and may be bonded to each other), —S— group, — SO-
It is a divalent group formed by combining a group and a —SO ₂ — group. When m represents 2, L is particularly preferably a divalent group having a total carbon number of 20 or less, which is bonded to a P atom at that carbon atom. When m represents an integer of 2 or more, R ₁ in the molecule,
R _2, R ₃ are each plurality of, the plurality of R _1, R _2, R ₃ may be different even in the same, respectively. n is preferably 1 or 2 and m is 1 or 2
Is preferred. X may combine with R ₁ , R ₂ , R ₃ or L to form an inner salt.

Since it is added as a part of the substituents of R ₁ , R ₂ and R ₃ to a specific layer of a silver halide light-sensitive material, it promotes adsorption to a ballast group or silver halide for reducing diffusibility. It is preferable to have a group. The ballast group has a total number of carbon atoms of 15 or more and is preferably used in a silver halide photographic coupler. The adsorption promoting group for silver halide is preferably thioamides (eg thiourethane, thioureido, thioamide), mercaptos (eg 5-mercaptotetrazole, 3-mercapto-1,2,4-triazole, 2-
Heterocycles such as mercapto-1,3,4-thiadiazole, 2-mercapto-1,3,4-oxadiazole, etc., and 5- to 6-membered nitrogen-containing heterocycles that form iminosilver. (For example, benzotriazole).

Many of the compounds represented by the general formula (II) of the present invention are known and commercially available as reagents. As a general synthetic method, there is a method of reacting a phosphinic acid with an alkylating agent such as an alkyl halide or a sulfonate: or a method of exchanging a counter anion of a phosphonium salt by a conventional method.

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

[0056]

[Chemical 16]

[0057]

[Chemical 17]

[0058]

[Chemical 18]

[0059]

[Chemical 19]

[0060]

Embedded image

[0061]

[Chemical 21]

[0062]

[Chemical formula 22]

[0063]

[Chemical formula 23]

[0064]

[Chemical formula 24]

Next, the general formulas (III), (IV) and (V) will be described in more detail.

[0066]

[Chemical 25]

In the formula, A represents an organic group for completing the heterocycle, which may contain a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom or a sulfur atom, and the benzene ring may be condensed. . As a preferred example, A can be a 5- or 6-membered ring, and more preferred examples are a pyridine ring, a quinoline ring and an isoquinoline ring. In addition, A may be substituted, and as a preferable substituent,
Halogen atom (eg chlorine atom, bromine atom), substituted or unsubstituted alkyl group (eg methyl group, hydroxyethyl group etc.), substituted or unsubstituted aralkyl group (eg bezyl group, p-methoxyphenethyl group etc.) A substituted or unsubstituted aryl group (eg, phenyl group, tolyl group, p-chlorophenyl group, furyl group,
Thienyl group, naphthyl group, etc.), substituted or unsubstituted acyl group (eg, benzoyl group, p-bromobenzoyl group, acetyl group, etc.), sulfo group, carboxy group, hydroxy group, alkoxy group (eg, methoxy group, ethoxy group) Group), an aryloxy group, an amide group, a sulfamoyl group, a carbamoyl group, a ureido group, an unsubstituted or alkyl-substituted amino group, a cyano group, a nitro group, an alkylthio group, and an arylthio group. Examples of particularly preferable substituents include an aryl group, a sulfo group, a carboxy group, and a hydroxy group. 2 represented by B and D
The valent group is alkylene, arylene, alkenylene, -S
_{O 2 -, - SO -,} - O -, - S -, - N (R 6) - those constituted singly or in combination are preferred. However, R ₆ represents an alkyl group, an aryl group, or a hydrogen atom. As a particularly preferable example, B and D include alkylene, arylene, -O-, and -S-, which may be used alone or in combination. R ₁ and R ₂ are preferably alkyl groups having 1 to 20 carbon atoms and may be the same or different. The alkyl group may be substituted with a substituent, and examples of the substituent include a halogen atom (eg, chlorine atom, bromine atom), a substituted or unsubstituted aryl group (eg, phenyl group, tolyl group, p-chlorophenyl group). ,
Furyl group, thienyl group, naphthyl group, etc.), substituted or unsubstituted acyl group (eg, benzoyl group, p-bromobenzoyl group, acetyl group, etc.), sulfo group, carboxy group, hydroxy group, alkoxy group (eg, methoxy group) Group, ethoxy group, etc.), aryloxy group, amide group, sulfamoyl group, carbamoyl group, ureido group,
It represents an unsubstituted or alkyl-substituted amino group, a cyano group, a nitro group, an alkylthio group, and an arylthio group. In particular,
As a preferred example, R ₁ and R ₂ each represent an alkyl group having 1 to 10 carbon atoms. Examples of preferred substituents include an aryl group, a sulfo group, a carboxy group, and a hydroxy group.

R ₃ and R ₄ represent a hydrogen atom or a substituent, and examples of the substituent are selected from the above-mentioned substituents of the alkyl group of R ₁ and R ₂ . As preferred examples, R ₃ and R ₄ have 0 to 10 carbon atoms, and specific examples thereof include an aryl-substituted alkyl group and a substituted or unsubstituted aryl group. R ₅ has 1 to 2 carbon atoms
An alkyl group of 0 is preferable, and whether it is linear or branched,
Further, it may be a cyclic alkyl group. The alkyl group may be substituted with a substituent, and examples of the substituent are selected from the substituents mentioned above as the substituents of the alkyl group of R ₁ and R ₂ . X represents an anion group, but X is not necessary in the case of an inner salt. Examples of X are chlorine ion, bromine ion, iodine ion, nitrate ion, sulfate ion, p-toluenesulfonate ion, and oxalate. R ₃ , R
_As a part of the substituents of ₄ and R ₅ , it is preferable to have a ballast group for reducing the diffusibility or an adsorption promoting group for silver halide in order to add it to a specific layer of the silver halide photosensitive material. . The ballast group has a total number of carbon atoms of 15 or more and is preferably used in a silver halide photographic coupler. The adsorption promoting group for silver halide is preferably thioamides (eg thiourethane, thioureido, thioamide), mercaptos (eg 5-mercaptotetrazole, 3-mercapto-).
1,2,4-triazole, 2-mercapto-1,3
4-thiadiazole, 2-mercapto-1,3,4-oxadiazole and other heterocycles such as mercapto, alkylmercapto, arylmercapto) and a 5- or 6-membered nitrogen-containing heterocycle (eg benzotriazole) which produces imino silver. is there.

The compounds represented by the general formulas (III), (IV) and (V) of the present invention can be easily synthesized by well-known methods. (For example, see Quart. Rev., 16, 163 (1962))

Specific examples of the compounds represented by the general formula (III), the general formula (IV) and the general formula (V) are shown below. However, the present invention is not limited to the following compounds.

[0071]

[Chemical formula 26]

[0072]

[Chemical 27]

[0073]

[Chemical 28]

[0074]

[Chemical 29]

[0075]

[Chemical 30]

[0076]

[Chemical 31]

[0077]

[Chemical 32]

[0078]

[Chemical 33]

[0079]

Embedded image

The addition amount of the compounds of the general formula (II), general formula (III), general formula (IV) and general formula (V) of the present invention is as follows.
There is no particular limitation, but 1 × 10 per mol of silver halide
^-5 to 2 × 10 ^-2 mol is preferable, and a particularly preferable range is 2 × 10 ^-5 to 1 × 10 ^-2 mol. The nucleation accelerator used particularly preferably in the present invention is a compound represented by the general formula (IV).

The general formula (II) and the general formula (II
When the compound of the formula (I), the general formula (IV) or the general formula (V) is contained in the photographic light-sensitive material, it is an aqueous solution when it is water-soluble, and alcohols (for example, methanol, ethanol) when it is water-insoluble. It may be added to a silver halide emulsion solution or a hydrophilic colloid solution as a solution of a water-miscible organic solvent such as esters (eg ethyl acetate) and ketones (eg acetone). 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, it can be used as a fine dispersion by a method known as a solid dispersion method.

Using the silver halide light-sensitive material of the present invention,
It is necessary to use a conventional infectious developer or a highly alkaline developer close to pH 13 described in US Pat. No. 2,419,975 in order to obtain photographic characteristics having a safe light safety that can withstand ultra-high contrast and bright room applications. Instead, a stable developer can be used. That is, the silver halide light-sensitive material of the present invention contains 0.15 mol / liter or more of sulfite ion as a preservative, and a sufficiently high-contrast image can be obtained by a developer having a pH of 9.5 to 11.0.

There is no particular limitation on the development and fixing in the present invention, but it is preferable to use a dihydroxybenzene compound or reductone as a developing agent as a developing solution. Among these, a preferable developing solution in the case of using a dihydroxybenzene type developing agent has the following composition. (1) 0.2 to 0.75 mol / liter of dihydroxybenzene type developing agent, (2) 0.001 to 0.06 mol / liter of 1-phenyl-3-pyrazolidone type or p-type
Aminophenol-based auxiliary developing agent, (3) 0.15-
It contains 1.2 mol / liter of free sulfite ion, (4) the compound represented by the general formula [IX], and the concentration ratio of the compound represented by the general formula [IX] and the dihydroxybenzene-based developing agent is 0.03. .About.0.12 and the pH is 9.0-12.
The developer is 0, and particularly preferably 10.0 to 10.8. General formula [VI]

[0084]

Embedded image

In the formula, R ₁ and R ₂ each represent a hydroxy group, an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group or an alkylthio group. P and Q represent a hydroxy group, a carboxyl group, an alkoxy group, a hydroxyalkyl group, a carboxyalkyl group, a sulfo group, a sulfoalkyl group, an amino group, an aminoalkyl group, an alkyl group or an aryl group, or P and Q are It represents an atomic group which is bonded to each other to form a 5- to 8-membered ring with two vinyl carbon atoms substituted by R ₁ and R ₂ and a carbon atom substituted by Y. Y represents = 0 or = N-R _3,. R ₃ represents a hydrogen atom, a hydroxyl group, an alkyl group, an acyl group, a hydroxyalkyl group, a sulfoalkyl group or a carboxyalkyl group.

Detailed description of the general formula [VI] and specific compounds are described in Japanese Patent Application No. 5-282101.
Of these, ascorbic acid and erythorbic acid (stereoisomers) are preferable. The addition amount of the compound of the general formula [VI] is such that the concentration ratio of the compound represented by the general formula [VI] / hydroquinone-based developing agent is the concentration of the compound represented by the general formula [VI] of the dihydroxybenzene-based developing agent. The value divided by the concentration) is in the range of 0.03 to 0.12. A preferable concentration ratio is 0.03 to 0.10. A particularly preferable concentration ratio is 0.05 to 0.09.

Examples of the dihydroxybenzene type developing agent used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dibromohydroquinone, and 2,5-dimethylhydroquinone, but hydroquinone is particularly preferable. preferable. The concentration of the hydroquinone derivative in the developer is 0.2 to 0.75 mol / liter, preferably 0.2 to 0.5 mol / liter, particularly preferably 0.2 to 0.4 mol / liter. is there.

As the 1-phenyl-3-pyrazolidone derivative developing agent used in the present invention, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone and 1-phenyl-4-methyl- 4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-
Dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p-
Trilyl-4,4-dimethyl-3-pyrazolidone, 1-p
-Tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and the like are preferable, and 1-phenyl-3-pyrazolidone and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone are preferable.

As the p-aminophenol type developing agent used in the present invention, N-methyl-p-aminophenol, p
-Aminophenol, N- (β-hydroxyethyl)-
There are p-aminophenol, N- (4-hydroxyphenyl) glycine and the like, and among them, N-methyl-p-aminophenol is preferable. When the combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is 0.05
Mol / liter to 0.5 mol / liter, the latter of 0.0
It is preferably used in an amount of 6 mol / liter or less.

When the reductone is used as the developing agent, the compound of the above-mentioned general formula (VI) is preferably used as the reductone, and ascorbic acid or erythorbic acid (stereoisomer) is particularly preferable. In this case, as the auxiliary developing agent, the same ones as the dihydroxybenzene type developing agent can be used, and the p-aminofer type and / or 1-phenyl-3-pyrazolidone type auxiliary developing agent is preferable. When the compound of the general formula (VI) is used as a developing agent, the amount used is generally 5 × 10 ⁻³ mol to 1 mol, and particularly preferably 10 ⁻² mol to 0.5, per liter of the developing solution. It is a mole.

The preservative used in the developing solution preferred in the present invention is free sulfite ion, and the form of addition to the developing solution is sodium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite and the like. The free sulfite ion concentration is 0.15 to 1.2 mol / liter,
It is preferably 0.3 to 1.0 mol / liter, and particularly preferably 0.3 to 0.8 mol / liter. The pH of the developer used in the developing treatment of the present invention is in the range of 9.0 to 11.0, preferably 9.5 to 10.7. Sodium hydroxide is used as the alkaline agent to set the pH.
It contains pH adjusters such as sodium carbonate, sodium triphosphate, potassium hydroxide, potassium carbonate, boric acid and the like.

Further, a dialdehyde type hardener or a bisulfite adduct thereof may be used in the developing solution used in the method of the present invention. Specific examples thereof include glutaraldehyde, α-methylglutaraldehyde, β-methylglutaraldehyde, maleindialdehyde, succindialdehyde, methoxysuccindialdehyde, methylsuccindialdehyde, α-methoxy-β-ethoxyglutaraldehyde, α. Examples include -n-butoxyglutaraldehyde, α, α-diethylsuccindialdehyde, butylmaleindialdehyde, and bisulfite adducts thereof. Of these, glutaraldehyde or its bisulfite adduct is most commonly used. The dialdehyde compound is used in such an amount that the sensitivity of the photographic layer to be processed is not suppressed and the drying time is not significantly prolonged. Specifically, it is 1 to 50 g, preferably 3 to 10 g per liter of the developing solution.

An antifoggant is used in the developer used in the method of the present invention, and examples thereof include indazole type, benzimidazole type and benztriazole type. 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] butane Sodium sulfonate, 5-amino-1,
3,4-thiadiazole-2-thiol and the like can be mentioned. The amount of these antifoggants is usually 0.01 to 10 mmol, and more preferably 0.1 to 2 mmol, per liter of the developing solution. In addition to these organic antifoggants, for example, halides such as potassium bromide and sodium bromide can be used.

Further, various organic and inorganic chelating agents can be used in combination in the developing solution used in 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, corkic acid, acieleic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, maleic acid , Itaconic acid, malic acid, citric acid,
Examples include tartar and the like, but the invention is not limited thereto.

Examples of aminopolycarboxylic acids include iminodiacetic acid, nitriloacetic acid, nitrilopropionic acid, ethylenediaminomonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycol ether tetraacetic acid, 1,2-diaminopropanetetraacetic acid, diethylenetriamine. Pentaacetic acid,
Triethylene tetramine hexaacetic acid, 1,3-diamino-2
-Propanol tetraacetic acid, glycol ether diamino 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), ethylenediaminotetramethylenephosphonic acid, aminotrimethylenephosphonic acid, and the like. In addition to 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.

In addition to the above composition, the developer used in the method of the present invention may optionally have a buffer (eg, carbonate, alkanolamine), an alkaline agent (eg, hydroxide, carbonate), and a solubilizing agent. (For example, polyethylene glycols,
These esters), pH adjusters (eg organic acids such as acetic acid), development accelerators (eg US Pat. No. 2,648,604).
No. 4, Japanese Patent Publication No. 4-9503, US Pat. No. 3,171,247.
Various pyridinium compounds and other cationic compounds described in No. 5, cationic dyes such as phenosafranine, neutral salts such as thallium nitrate and potassium nitrate, JP-B-44-9304, US Pat.
31832, 2950970, and 2577127.
Polyethylene glycol and its derivatives, nonionic compounds such as polythioethers described in JP-B-44-9
509, Belgian Patent 682862, organic solvents described in U.S. Pat. No. 3,012,242, thioether compounds, etc., especially thioether compounds are preferable), and surfactants may be contained.

The development processing temperature and time are interrelated and are determined in relation to the total processing time. Generally, the processing temperature is about 20 ° C. to about 50 ° C. and the processing time is 10 seconds to 2 minutes. When processing 1 square meter of a silver halide black and white photographic light-sensitive material, the replenisher amount of the developing solution is 400 ml or less, preferably 200 ml or less.

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.
Modifiers (eg ammonia, sulfuric acid), chelating agents, surfactants, wetting agents, fixing accelerators can be included. Examples of the surfactant include anionic surfactants such as sulfates and sulfonates, polyethylene-based surfactants,
Examples thereof include 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. As a fixing accelerator,
For example, Japanese Examined Patent Publication Nos. 45-35754 and 58-12253.
5, thiourea derivatives described in JP-A Nos. 58-122536, alcohols having a triple bond in the molecule, thioether compounds described in US Pat.
Examples include mesoionic compounds described in JP-A-229860, and compounds described in JP-A-2-44355 may be used. The pH of the fixer is preferably 4.0 to 6.5,
Particularly preferably, it is in the range of 4.5 to 6.0. Further, as the dye elution accelerator, the compounds described in JP-A No. 64-4739 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 mol to 0.2 mol / liter, more preferably 0.03 to 0.08 mol / liter. The fixing temperature is about 20 ° C to about 50 ° C, preferably 25 ° C.
~ 45 ° C, fixing time is 5 seconds to 1 minute, preferably 7 seconds to
50 seconds. The replenishing amount of the fixing solution is 600 ml / m ² or less, and particularly preferably 300 ml / m ² or less with respect to the processing amount of the light-sensitive material.

The photosensitive material which has been developed and fixed is then washed with water or stabilized. The washing or stabilizing treatment can be carried out with a replenishing amount of 3 liters or less (including 0, that is, washing with water) per 1 m ^{2 of the} silver halide light-sensitive material. That is, not only is it possible to save water,
The piping for installing the automatic processor can be eliminated. When the washing with water is carried out with a small amount of water, JP-A-63-18350,
It is more preferable to provide a squeeze roller septic tank described in JP-A No. 62-287252. In addition, various oxidants may be added or filter filtration may be combined in order to reduce the pollution load which becomes a problem when washing with a small amount of water. Further, a part or all of the overflow liquid from the washing or stabilizing bath produced by supplementing the washing or stabilizing bath with anti-vibration means according to the process by the method of the present invention is disclosed in Japanese Patent Laid-Open No.
No. 0-235133, 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 a small amount of water is used and / or to prevent the treatment agent component attached to the squeeze roller from being transferred to the treated film. Good. Further, in order to prevent contamination by dyes eluted from the light-sensitive material, JP-A-63-1
The dye adsorbent described in No. 63456 may be installed in the washing tank.

There is also a case where a stabilizing treatment is carried out subsequent to the water washing treatment.
The baths containing the compounds described in JP-A No. 2-132435, JP-A No. 1-125255, and JP-A No. 46-44446 may be used as the final bath of the light-sensitive material. In this stabilizing bath, if necessary, ammonium compounds, metal compounds such as Bi and Al, optical brighteners, various chelating agents, film pH buffers, hardeners, bactericides, fungicides, alkanolamines and surface active agents. As the water used for the agent, tap water, deionized water and halogen, ultraviolet germicidal lamps and various oxidizers (ozone,
It is preferable to use water sterilized by hydrogen peroxide, chlorate, etc.).

The treatment liquid preferably used in the present invention is preferably stored in a packaging material having low oxygen permeability described in JP-A-61-73147. On the other hand, in the case of reducing the replenishment amount, it is preferable to prevent the evaporation and air oxidation of the liquid by reducing the contact area with the air in the processing tank. The roller-conveying type automatic developing machine is described in U.S. Pat. Nos. 3,025,779 and 3,545,971 and the like, and the roller-conveying type automatic developing machine comprises four steps of development, fixing, washing and drying. Can be preferably used. Further, the above treatment liquid may be used as a solid treatment agent. The solid processing agent preferably used in the present invention is in the form of powder, tablets, granules, powder, lumps or pastes, and the preferred form is JP-A-61-25.
The form or tablet described in 9921. The method for producing tablets is described in, for example, JP-A-51-61837 and JP-A-54-1.
55038, 52-88025, British Patents 1, 2
It can be produced by a general method described in JP-A No. 13,808.
No. 2-109043, No. 3-39735, No. 3-39739, and the like. Further, the powder treating agent is, for example, JP-A-54-13.
3332, British Patents 725,892 and 729,8
62 and German Patent 3,733,861 and the like, but can be produced by a general method.

The bulk density of the solid processing agent preferably used in the present invention is preferably 0.5 to 6.0 g / cm ³ , from the viewpoint of its solubility and the effect of the object of the present invention, and particularly, It is preferably 1.0 to 5.0 g / cm ³ .

There are no particular restrictions on the various additives and the like used in the light-sensitive material of the present invention, and for example, those described in the following relevant parts can be preferably used. Item This section 1) Spectral sensitizing dye JP-A-2-12236, page 8, lower left column, line 13 to same, lower right column, line 4, and JP-A-2-103536, page 16, lower right column, line 3 To page 17, lower left column, line 20, and spectral enhancement described in JP-A Nos. 1-112235, 2-124560, 3-79928, 5-11389, and Japanese Patent Application No. 3-411064. Sensitive dye. 2) Surfactants, antistatic From JP-A-2-12236, page 9, upper right column, line 7 or the same, from antistatic agent, lower right column, line 7 and JP-A-2-18542, page 2, lower left column, line 13 Page 4, lower right column, line 18. 3) Antifoggant, Stability JP-A-2-103536, page 17, lower right column 19, agent line to page 18, upper right column, line 4 and lower right column, line 1 to line 5. Further, thiosulfinic acid compounds described in JP-A-1-237538. 4) Compound having an acid group From JP-A-2-103536, page 8, lower right column, line 5 to page 19, upper left column, line 1 and JP-A 2-55349, page 8, lower right column, line 13 Page 11, upper left column, line 8. 5) Matting agent, slipping agent JP-A-2-103536, page 19, upper left column, line 15 to page 19, upper right column, line 15 6) Hardener JP-A-2-103536, page 18, upper right column, line 5 to line 17 7) Dye JP-A-2-103536, page 17, lower right column, line 1 to line 18; JP-A-2-39042, page 4, upper right column, line 1 to page 6, upper right column, line 5 Dyes described in Kaihei 2-294638 and JP-A-63-296039. Further, solids described in WO88 / 04794, European Patent No. 456148, JP-A-5-11382, Japanese Patent Application No. 5-224717, Japanese Patent Application No. 6-117454, and the like. Disperse dye. 8) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 20. 9) Black spot preventing agent Compounds described in U.S. Pat. No. 4,956,257 and JP-A-1-118832. 10) Redox compounds Compounds represented by the general formula (I) in JP-A No. 2-301743 (particularly compound examples 1 to 50), and general compounds described in pages 3 to 20 of JP-A 3-174143. Formulas (R-1), (R-2), (R-3), Compound Examples 1 to 75, compounds described in Japanese Patent Application No. 3-69466 and JP-A No. 4-278939. 11) Monomethine compound A compound of the general formula (II) described in JP-A-2-287532 (particularly compound examples II-1 to II-26). 12) Dihydroxybenze Compounds described in JP-A-3-39948, page 11, upper left column to items, page 12, lower left column, and European Patent No. 452, 772A. 13) Polymer latex JP-A-2-103536, page 18, lower left column, lines 12 to 20. Further, the publications of Japanese Patent Publication No. 46-22507, Japanese Patent Publication No. 50-73625, U.S. Pat. Polymer latices having active methylene groups as described. 14) Organic desensitizers Compounds described in Japanese Patent Publication No. 3-76450, Japanese Patent Application Laid-Open No. 63-64039, Japanese Patent Application No. 6-117454, or the like or the description thereof. 15) Amino group, Ammoni JP-A-63-133145, page 8, line 5 to um group, and nitrogen-containing, page 40, line 5. Compounds containing elementary heterocycles

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.

[0108]

【Example】

Example 1 <Emulsion preparation> Emulsion A: in a 1.5% gelatin aqueous solution of pH = 2.0 containing sodium chloride and 3 × 10 ⁻⁵ mol of sodium benzenethiosulfonate per mol of silver kept at 40 ° C. An aqueous solution of silver nitrate and 3.5 × 10 ^-5 mol (N
An aqueous solution of sodium chloride containing H ₄ ) ₂ Rh (H ₂ O) Cl ₅ was simultaneously added by the double jet method at a potential of 95 mV for 3 minutes and 30 seconds so that half of the silver amount of the final particles was simultaneously added.
μm was prepared. Then, an aqueous solution of silver nitrate and an aqueous solution of sodium chloride containing 10.5 × 10 ^-5 mol of (NH ₄ ) ₂ Rh (H ₂ O) Cl ₅ per 1 mol of silver were added in the same manner as above for 7 minutes to obtain an average particle size of 0.15 μm silver chloride cubic grains were prepared.
(Coefficient of variation: 12%) After that, the product was washed with water by a flocculation method well known in the art to remove soluble salts, and then gelatin was added. Compound-A and phenoxyethanol were added as silver preservatives without chemical ripening. 50 mg each per mole,
4-hydroxy-6-methyl-1,3,3 as a stabilizer
10 ⁻³ mol of a, 7-tetrazaindene was added per mol of silver. (PH = 5.7 as final particles, pAg =
7.5, Rh = 7 × 10 ⁻⁵ mol / Ag mol. )

Emulsion B: Core particles (0.12 μm) were prepared in the same manner as Emulsion A, and then an aqueous solution of silver nitrate and 14.0 × 10 ^-5 mol of (NH ₄ ) ₂ Rh (H _An aqueous solution of sodium chloride containing ₂ O) Cl ₅ was applied at a potential of 9 by the table jet method.
1/4 of the silver amount of the final grain in 3 minutes and 30 seconds at 5 mV
Was added at the same time to prepare particles of 0.14 μm, and thereafter, an aqueous silver nitrate solution, 4.0 × 10 ⁻⁴ mol of K ₄ Fe (CN) ₆ per mol of silver and 7.0 × 10 ⁻ per mol of silver were prepared. ⁵ moles
Aqueous sodium chloride solution containing (NH ₄ ) ₂ Rh (H ₂ O) Cl ₅ was added in the same manner as above for 1 minute to 30% of the final amount of silver in the final particles, and silver chloride having an average particle size of 0.15 μm was added. Cubic particles were prepared. Then, the emulsion was washed with water in the same manner as in the emulsion A, gelatin was added, and preservatives and stabilizers were added without chemical ripening. (Variation coefficient 12% as final particles, pH = 5.7, pAg = 7.
5, Rh = 7.0 × 10 ⁻⁵ mol / Ag mol, Fe = 1.
0 × 10 ⁻⁴ mol / Ag mol).

Emulsions C to I: The metal species doped in the silver halide grains, the doping amount thereof and the doping amount of K ₄ Fe (CN) ₆ were added as shown in Table 1, and the other emulsions were designated as Emulsion B. Prepared similarly.

<Preparation of Coating Solution for Emulsion Layer and Coating> The following compounds were added to the emulsions shown in Table 1 to give a gelatin coating amount of 1.1 g / m ² on the following support including an undercoat layer, coated silver. The silver halide emulsion layer was coated so that the amount was 2.5 g / m ² . 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 10 mg / m ² N-oleyl-N-methyltaurine sodium salt 35 mg / m ² compound-B 10 mg / m ² compound-C 20 mg / m ² n-butyl acrylate / 2-acetoacetoxyethyl methacrylate / acrylic acid copolymer (89/8/3) 900 mg / m ² compound-D (hardener) 150 mg / m ² Furthermore, the nucleation accelerator of the present invention and The hydrazine derivative was added as coated as in Table 1.

An emulsion protective lower layer and an upper layer were coated on the above emulsion layer.

<Preparation and Coating of Emulsion Protecting Lower Layer Coating Liquid>
The following compounds were added to a gelatin aqueous solution and coated so that the gelatin coating amount would be 0.7 g / m ² . Gelatin (Ca ⁺⁺ content 2700 ppm) 0.7 g / m ² sodium p-dodecylbenzenesulfonate 15 mg / m ² compound-A 5 mg / m ² compound-E 10 mg / m ² compound-F 20 mg / m ²

<Preparation of Emulsion Protecting Upper Layer Coating Liquid and Its Coating>
The following compounds were added to an aqueous gelatin solution and coated so that the coating amount of gelatin was 0.8 g / m ² . Gelatin (Ca ⁺⁺ content 2700ppm) 0.8g / m ² amorphous silica matting agent 40 mg / m ² (average particle size 3.5 [mu], pore diameter 25 Å, surface area 700m ² / g) amorphous silica matting agent 10mg / m ² (average particle diameter 2.5 μ, pore diameter 170 Å, surface area 300 m ² / g) N-perfluorooctanesulfonyl-N-propyl glycine potassium 5 mg / m ² sodium dodecylbenzenesulfonate 30 mg / m ² compound-A 5 mg / m ² solid disperse dye-G ₁ 100 mg / m ² solid disperse dye-G ₂ 50 mg / m ²

Then, a conductive layer and a back layer shown below were simultaneously coated on the opposite surface of the support.

<Preparation of Coating Solution for Conductive Layer and Coating> The following compounds were added to a gelatin aqueous solution to give a gelatin coating amount of 77.
It was applied so as to be mg / m ² . SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25μ) 200 mg / m ² Gelatin (Ca ⁺⁺ content 3000 ppm) 77 〃 Sodium dodecylbenzene sulfonate 10 〃 Dihexyl-α-sulfosuccinate sodium 40 〃 Sodium polystyrene sulfonate 9〃 Compound-A 7〃

<Preparation of Back Layer Coating Liquid and Its Coating> The following compounds were added to a gelatin aqueous solution and coated so that the gelatin coating amount would be 2.92 g / m ² . Gelatin (Ca ⁺⁺ content 30 ppm) 2.92 g / m ² Polymethylmethacrylate fine particles (average particle size 3.4 μ) 54 mg / m ² Compound-H 140 〃 Compound-I 140 〃 Compound-J 40 〃 Dodecylbenzenesulfonic acid Sodium 75 〃 Dihexyl-α-sulfosuccinate sodium 20 〃 Compound-K 5 〃 N-perfluorooctanesulfonyl-N-propyl glycine potassium 5 〃 Sodium sulfate 50 〃 Sodium acetate 85 〃

(Support, Undercoat Layer) A biaxially stretched polyethylene terephthalate support (thickness: 100 μm) was coated on both sides with the first and second undercoat layers having the following composition. <Undercoat layer 1 layer> Core-shell type vinylidene chloride copolymer 15 g 2,4-dichloro-6-hydroxy-s-triazine 0.25〃 polystyrene fine particles (average particle size 3µ) 0.05〃 compound-L 0 .20〃 colloidal silica (Snowtex ZL; particle size 70 to 100 μm manufactured by Nissan Kagaku Co., Ltd.) 0.12〃 Water added 100〃 Further, 10% by weight KOH was added to adjust the pH to 6 At a drying temperature of 180 ° C. for 2 minutes and a dry film thickness of 0.
It was applied so as to be 9μ.

<Undercoat Layer Second Layer> Gelatin 1 Methylcellulose 0.05 〃 Compound-M 0.02 〃 C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 0.03 〃 Compound-A 3.5 × 10 ^-3 〃 acetic acid 0.2 〃 water was added 100 〃 This coating solution was applied at a drying temperature of 170 ° C for 2 minutes so that the dry film thickness was 0.1 µ. Sample 1
18 was produced.

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[Chemical 38]

<Evaluation Method> Photographic Properties The sample thus obtained was exposed through an optical wedge using a P-627FM printer manufactured by Dainippon Screen Co., Ltd., and was developed by Fuji Photo Film Co., Ltd. automatic developing machine FG-680AG and a developing solution. The sample was treated with No. 1 at 38 ° C. for 20 seconds, fixed, washed with water and dried. The fixer used was fixer 1. The following items were evaluated for these samples. 1) Sensitivity (S _1.5 ); logarithmic value of the exposure amount giving a density of 1.5 (the smaller the value, the higher the sensitivity.) 2) γ; (1.5-0.1) / {log (density 1. Exposure dose giving 5) -log (exposure dose giving density 0.1)}

Extracted Character Image Quality To evaluate the extracted character image quality, Japanese Patent Publication No. 2-28,85
No. 6 of the document shown in FIG. 1 "Transparent embedding base / film having line image positive image formed (line image original) / transparent embedding base / film having dot image formed (mesh) Point original), and the emulsion surface of each sample are brought into close contact with each other.
Image development was performed by a 627FM printer, and development processing was performed. (Same processing as above) The exposure time of each sample is as follows:
It was determined to be imaged on each sample as a halftone dot area 50% halftone dot. Here, the first character image quality is the same as the first character quality 5.
When an appropriate exposure is performed using a document as shown in the figure such that 50% halftone dot area is 50% halftone dot area on the return photosensitive material.
It is the image quality with which characters with a width of μm can be reproduced, and it is a very good extracted image quality. On the other hand, the extracted character image quality 1 is an unexplained extracted character quality, which is an image quality that can reproduce only characters having a width of 150 μm or more when the same appropriate exposure is given, and is between 4 and 2 in the sensory evaluation between 5 and 1. Rank is set. A level of 3 or more is a practical level.

Practical technique Dmax The maximum blackening density when a 50% halftone original document described in the evaluation of the character quality without characters is exposed on the film sample so that the halftone dot area is 50%.

Storability ΔS _{1.5 The} sample was left under the condition of 70 ° C. at 50 ° C. for 3 days, and then the treatment described in the evaluation of photographic characteristics was performed to change the sensitivity immediately after coating (S _1.5 immediately after coating−S _1.5 50 ° C.). 70% 3d: The larger the numerical value, the more sensitized there is.)

<Developer 1> Potassium hydroxide 35.0 g Diethylenetriamine-pentaacetic acid 2.0 g Potassium carbonate 12.0 g Sodium metabisulfite 40.0 g Potassium bromide 3.0 g Hydroquinone 25.0 g 5-Methylbenzotriazole 0. 08 g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 0.45 g 2,3,5,6,7,8-hexahydro-2-thioxo-4- (1H) -quinazolinone 0.04 g 2- Mercaptobenzimidazole-5-sulfonic acid sodium salt 0.15 g Sodium erythorbate 3.0 g Potassium hydroxide is added and water is added to 1 liter to adjust the pH to 10.5. 1 liter

<Fixer 1> Ammonium thiosulfate 359.1 g Ethylenediaminetetraacetic acid 2Na dihydrate 2.26 g Sodium thiosulfate pentahydrate 32.8 g Sodium sulfite 64.8 g NaOH 37.2 g Glacial acetic acid 87.3 g Tartaric acid 8.76 g Sodium gluconate 6.6 g Aluminum sulfate 25.3 g pH (adjusted with sulfuric acid or sodium hydroxide) 4.85 Water was added to 1 liter 2 liters of water was added to 1 liter of the above fixing solution for use.

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[Table 1]

As is clear from Table 1, the samples (Nos. 5 to 11 and 15) of the present invention have high photographic characteristics such as high contrast (γ10 or more), excellent image quality of extracted characters, and practical Dm
The ax is as high as 5.0 or higher. It is also excellent in storage stability.

Emulsion B (NH ₄ ) ₂ Rh (H ₂ O) Cl ₅ was added to K ₃ CrCN ₆ , K ₃
The same evaluation as Emulsion B in Table 1 was performed on three types of emulsions prepared by changing to ReCl ₆ and K ₂ Ir (NO) Cl ₅ and found that they had high contrast and high Dm.
It was confirmed that the ax was high, the image quality was high, and the storability was good.

Example 2 The samples (Nos. 1 to 6) of Example 1 were treated with the developer 2 at 38 ° C.
Evaluation was made in the same manner as in Example 1 except that the treatment was performed for 20 seconds (FG-680AG).

<Developer 2> Metol 7.5 g Sodium ascorbate 30.0 g Sodium metaborate 70.0 g Potassium bromide 1.0 g 5-Methylbenzotriazole 10.0 mg Sodium hydrogen sulfite 22.0 g Water was added to 1 liter. pH = 9.8

The evaluation result shows that the contrast becomes even harder than in Example 1 and p
Even in H9.8, the samples of the present invention (numbers 5 and 6) were excellent in the image quality of extracted characters, and the practical skill Dmax was as high as 5.0 or more.

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
A heavy metal selected from Ir, Ru, Rh, Re and Cr is added to the emulsion layer in an amount of at least 1 × 1 per mol of silver halide.
0 ^-5 mol contain, and comprises at least one containing silver halide grains of the silver content of 95 mol% or more chloride to the iron compound, the following formula in at least one layer of the emulsion layer or other hydrophilic colloid layer A silver halide photographic light-sensitive material comprising at least one hydrazine derivative represented by (I) and at least one nucleation accelerator represented by the following general formulas (II) to (V). [Chemical 1] In the formula, R ₁ represents an aliphatic group or an aromatic group substituted with a sulfonamide group, and 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. Represents a group or a hydrazino 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,
Alternatively, it represents a substituted or unsubstituted acyl group. [Chemical 2] In the formula, R ₁ , R ₂ , and R ₃ represent an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, a cycloalkenyl group, or a heterocyclic residue, which may further have a substituent. m is an integer of 1 to 4, L is P
Represents an m-valent organic group that is bonded to an atom and its carbon atom,
n represents an integer of 1 to 3, X represents an n-valent anion, and X may be linked to L. [Chemical 3] In the formula, A represents an organic group for completing the heterocycle.
B and D each represent a divalent group. R ₁ and R ₂ each represent an alkyl group or an aryl group, and R ₃ and R ₄ each represent a hydrogen atom or a substituent. R ₅ represents an alkyl group. X represents an anion group, but X is not necessary in the case of an inner salt. 2. R _{1 of the} hydrazine derivative represented by the general formula (I) is a phenyl group having an alkylthio group or a group that promotes adsorption to the surface of a silver halide grain through a sulfonamide group. The silver halide photographic light-sensitive material according to claim 1. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the nucleation accelerator is a compound represented by the general formula (IV).