JP3371647B2 - Silver halide photographic materials - Google Patents

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. Particularly, when a halftone image and a line image original as a return original are superposed and exposed, a photosensitive material is desired that has good reproduction performance of the halftone image and the line image. However, in recent years, high-definition printing in which the number of lines forming a halftone image is fine has become popular due to the high quality of printed matter. Therefore, in the conventional light-sensitive materials, there arises a problem that the halftone dot area easily changes due to the change in the exposure amount of the printer. Furthermore, in a light-sensitive material having ultra-high contrast photographic characteristics,
Since a so-called large dot having a large halftone dot area% is easily crushed in a high-definition image, a super-high-contrast photosensitive material suitable for high-definition printing is required.

In general, silver halide emulsions for bright room use are not chemically sensitized because high sensitivity is not required. Further, from the viewpoint of safelight safety, silver halide emulsions having a high silver chloride content are used, but these emulsions tend to increase fog due to chemical sensitization and deteriorate storage stability. For this reason, chemical sensitization, particularly gold-sulfur sensitization with gold and sulfur compounds, has not been used so far for high-silver chloride emulsions for light room use, particularly silver chloride emulsions.

[0005]

SUMMARY OF THE INVENTION The first object of the present invention is to obtain a super-high tone photograph which can be handled under a bright safelight (substantially bright room), has a high blackening density, and has little fog. An object of the present invention is to provide a silver halide photographic light-sensitive material for return, which has characteristics. A second object of the present invention is to provide a return halogen which can be handled under a bright safelight (substantially bright room) and has a good halftone dot area reproducibility even in a high-definition image and has a small halftone dot area with respect to an exposure amount. It is to provide a silver halide photographic light-sensitive material.

[0006]

These objects of the present invention
Means that at least one silver halide emulsion layer is formed on the support.
In the silver halide photographic light-sensitive material having the emulsion layer
Heavy metal selected from Ir, Ru, Rh, ReionHa
At least 1 x 10 per mole of silver rogenide⁻⁶Including mole
Have,pH 3.0-1.5Particle formation under acidic conditions
And then chemically sensitized with gold and sulfur compounds
Silver halide grains having a silver chloride content of 98 mol% or more.
SeeGrain formation and / or chemical increase of the silver halide grains
In the process of feeling, the following general formulas (1), (2) or
At least one of the compounds represented by (3) is added.
AndOther hydrophilicity of the emulsion layer or the side having the emulsion layer
The optical density at 360 nm in the colloid layer is greater than 0.2
Halogen characterized by containing a certain amount of water-soluble dye
Achieved by a silver halide photographic light-sensitive material.(1) R-SO ₂ S-M (2) R-SO ₂ SR ¹ (3) R-SO ₂ SL _m -SSO ₂ -R ² In the formula, R, R ¹ And R ² May be the same or different,
Represents an aliphatic group, an aromatic group, or a heterocyclic group, and M is a cation
Represents a divalent linking group, m represents 0 or 1
Therefore, the compounds of the general formulas (1) to (3) are
The divalent group derived from the structure shown in Ishi (3)
It may be a polymer contained as a return unit.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The silver halide emulsion of the present invention comprises Ir, Ru, Rh, Re
Contains at least one heavy metal ion selected from
Preferred as these heavy metal ions 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 ion selected from Ir, Ru, Rh, and Re. 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 are halide ligands (fluoride, chloride, bromide and iodide), cyanide ligands, cyanate ligands, thiocyanate ligands, selenocyanate ligands, 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. (Ir (NO) Cl ₅ ) ^-1

The above metal complex can be added to the silver halide during grain preparation. The content of the heavy metal ion in the silver halide grain of the present invention is 1 × 10 ⁻⁶ mol to 1 × 10 ⁻² mol per mol of silver halide. It is preferably 1 × 10 ^{−6 to} 3 × 10 ⁻⁴ mol. Further, the above heavy metal ions may be used in combination. The distribution of the heavy metal ion in the silver halide grain is not particularly limited, but it is preferable that the heavy metal ion is present in a larger amount outside the grain.

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 98 mol% or more, particularly 99 mol% or more, is composed of silver chloride. . Most preferred is silver chloride. If the proportion of silver bromide or silver iodide is increased, the safety of safelight in a bright room is deteriorated or γ is decreased, which is not preferable.

The silver halide emulsion of the 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 and an octahedron, and a cube is particularly preferable.

In the present invention, the grain formation of the silver halide emulsion is carried out under acidic conditions. This is effective in suppressing the fog due to the chemical sensitization by the gold-sulfur sensitizer performed thereafter. The acidic conditions include pH 3.0 to pH 1.
It is 5.

The silver halide emulsion of the silver halide photographic light-sensitive material used in the present invention is chemically sensitized after grain formation, that is, gold-sulfur sensitization with a gold sensitizer and a sulfur sensitizer. As the above gold sensitizer, + even if the oxidation number of gold is +1
A trivalent compound may be used, and a gold compound usually used as a gold sensitizer can be used. Representative examples include chloroauric acid salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, pyridyl trichlorogold and the like. The amount of the gold sensitizer added varies depending on various conditions, but as a guide, it is preferably 1 × 10 ^{−7 to} 5 × 10 ⁻⁴ mol per mol of silver halide.
Known sulfur sensitizers can be used. For example, thiosulfate, thioureas, allylisothiocyanate, cystine, p-toluenethiosulfonate,
Examples include rhodanine. Other US Patent No. 1,5
74,944, 2,410,689, 2,
278,947, 2,728,668, 3,501,313, 3,656,955, German Patent 1,422,869, Japanese Patent Publication No. 56-
The sulfur sensitizers described in JP-A-24937, JP-A-55-45016 and the like can also be used. The amount of the sulfur sensitizer added varies over a considerable range under various conditions such as pH, temperature, and size of silver halide grains, but 1 × 10 ⁻⁷ mol or more per mol of silver halide, 5x
It is preferably 10 ^-4 mol or less. Chemical sensitization with these sensitizers is performed by adding the sensitizer and stirring the emulsion at a high temperature, preferably 40 ° C. or higher, for a certain period of time.

The silver halide emulsion of the silver halide photographic light-sensitive material used in the present invention is more preferably subjected to gold sulfur selenium sensitization in combination with a selenium sensitizer. As the selenium sensitizer preferably used in the present invention, the selenium compounds disclosed in the conventionally known patents can be used. That is, it is usually used by adding an unstable selenium compound and / or a non-unstable selenium compound and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. As the unstable selenium compound, Japanese Patent Publication No. 44-
No. 15748, Japanese Examined Patent Publication No. 43-13489, JP-A-4-
No. 25832, JP-A-4-109240, and Japanese Patent Application No. 3-
It is preferable to use the compounds described in No. 92929 and the like. Specific examples of the unstable selenium sensitizer include isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenamides, selenocarboxylic acids (for example, 2- Selenopropions, 2-selenobutyric acid), selenoesters, diacyl selenides, (for example, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, colloidal metal selenium, etc. Can be given. The preferred types of labile selenium compounds have been described above, but are not limiting. Stable selenium compounds as sensitizers for photographic emulsions are known to those skilled in the art, as long as selenium is unstable, the structure of the compounds is not so important, and organic compounds of selenium sensitizer molecules are not important. It is generally understood that the moieties carry selenium and play no role other than allowing it to be present in the emulsion in an unstable form. In the present invention, the labile selenium compound having such a broad concept is advantageously used. Examples of the non-labile selenium compound used in the present invention are JP-B-46-4553,
JP-B-52-34492 and JP-B-52-3449
The compound described in No. 1 is used. Examples of non-labile selenium compounds include selenious acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenides, diaryl diselenides, dialkyl selenides, dialkyl diselenides, 2-selenazolidinediones, Examples include 2-selenooxazolidinethione and derivatives thereof. Of these selenium compounds, the following general formulas (4) and (5) are preferable. General formula (4)

[0014]

[Chemical 1]

In the formula, Z ₁ and Z _{2, which} may be the same or different, each represents an alkyl group (for example, a methyl group,
Ethyl group, t-butyl group, adamantyl group, t-octyl group), alkenyl group (eg vinyl group, propenyl group), aralkyl group (eg benzyl group, phenethyl group), aryl group (eg phenyl group, penta) Fluorophenyl group, 4-chlorophenyl group, 3-nitrophenyl group, 4-octylsulfamoylphenyl group, α-
Naphthyl group), heterocyclic group (for example, pyridyl group, thienyl group, furyl group, imidazolyl group), -MR ₁ (R ₂ ),-
Represent OR ₃ or -SR _4. R ₁ , R ₂ , R ₃ and R _{4, which} may be the same or different, each represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. Examples of the alkyl group, aralkyl group, aryl group or heterocyclic group are the same as those for Z ₁ . However, R
₁ and R ₂ are a hydrogen atom or an acyl group (for example, acetyl group, propanoyl group, benzoyl group, heptafluorobutanoyl group, difluoroacetyl group, 4-nitrobenzoyl group, α-naphthoyl group, 4-trifluoromethylbenzoyl group ) May be sufficient. In formula (4), Z ₁ is preferably an alkyl group, an aryl group or —NR
₁ (R ₁ ) and Z ₂ represents —NR ₅ (R ₆ ). R ₁ ,
R ₂ , R ₅ and R _{6, which} may be the same or different, each represents a hydrogen atom, an alkyl group, an aryl group or an acyl group. In the general formula (4), more preferably N,
N-dialkylselenourea, N, N, N'-trialkyl-N'-acylselenourea, tetraalkylselenourea, N, N-dialkyl-arylselenoamide, N-
Represents an alkyl-N-aryl-arylselenoamide. General formula (5)

[0016]

[Chemical 2]

In the formula, Z ₃ , Z ₄ and Z _{5, which} may be the same or different, each represents an aliphatic group, an aromatic group, a heterocyclic group,
-OR ₇ , -MR ₈ (R ₉ ), -SR ₁₀ , -SeR ₁₁ , X,
Represents a hydrogen atom. R ₇ , R ₁₀ and R ₁₁ are aliphatic groups,
It represents an aromatic group, a heterocyclic group, a hydrogen atom or a cation, R ₈ and R ₉ represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and X represents a halogen atom. In the general formula (5), Z ₃ , Z ₄ , Z ₅ , R ₇ , R ₈ ,
The aliphatic group represented by R ₉ , R ₁₀ and R ₁₁ is a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group, aralkyl group (eg, methyl group, ethyl group, n-group).
Propyl group, isopropyl group, t-butyl group, n-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopentyl group, cyclohexyl group, allyl group, 2-butenyl group, 3-pentenyl group, A propargyl group, a 3-pentynyl group, a benzyl group, a phenethyl group). In the general formula (5), Z ₃ , Z ₄ , Z ₅ , R
_The aromatic group represented by ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a monocyclic or condensed aryl group (for example, a phenyl group,
Pentafluorophenyl group, 4-chlorophenyl group, 3
-Sulfophenyl group, α-naphthyl group, 4-methylphenyl group). In the general formula (5), Z ₃ ,
The heterocyclic group represented by Z ₄ , Z ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a saturated or 3- to 10-membered ring containing at least one of a nitrogen atom, an oxygen atom or a sulfur atom. Unsaturated heterocyclic groups (eg, pyridyl group, thienyl group,
Furyl group, thiazolyl group, imidazolyl group, benzimidazolyl group). In the general formula (5), R ₇ ,
The cation represented by R ₁₀ and R ₁₁ represents an alkali metal atom or ammonium, and the halogen atom represented by X represents, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. In the general formula (5), Z ₃ , Z ₄ or Z ₅ is preferably an aliphatic group, an aromatic group or —O.
Represents R _7, R ₇ represents an aliphatic group or an aromatic group. In formula (5), trialkylphosphine selenide, triarylphosphine selenide, trialkylselenophosphate or triarylselenophosphate is more preferable. Specific examples of the compounds represented by formulas (4) and (5) are the compound examples I-1 to I-20 and II-21 to II- described in Japanese Patent Application No. 6-250156.
43 can be mentioned.

Specific examples of selenium sensitizers which are particularly preferable for exhibiting the effects of the present invention are shown below, but the present invention is not limited thereto.

[0019]

[Chemical 3]

[0020]

[Chemical 4]

[0021]

[Chemical 5]

[0022]

[Chemical 6]

The addition amount of the selenium sensitizer varies over a considerable range under various conditions such as pH, temperature and size of silver halide grains, but it is 1 × 10 ⁻ per mol of silver halide. ^It is preferably ⁷ mol or more and 5 × 10 ⁻⁴ mol or less.

In addition to these sensitizers, noble metals such as platinum and palladium, primary tin salts, amines, reduction sensitizers such as formamidinesulfinic acid and silane compounds may be used in combination.

To the silver halide grain of the present invention, a thiosulfonic acid compound represented by the following general formulas (1), (2) and (3) is added in the step of grain formation and / or gold sulfur sensitization. This makes it possible to obtain an emulsion with further reduced fog. _{(1) R-SO 2 S} -M (2) R-SO 2 S-R 1 (3) R-SO 2 S-L m -SSO in ₂ -R ² Formula, R, R ^1, R ² are the same However, they may be different and represent an aliphatic group, an aromatic group, or a heterocyclic group, and M represents a cation. L represents a divalent linking group, and m is 0 or 1. The compounds represented by the general formulas (1) to (3) may be polymers containing a divalent group derived from the structures represented by (1) to (3) as a repeating unit. Specific examples of the general formulas (1) to (3) are shown below.

[0026]

[Chemical 7]

[0027]

[Chemical 8]

[0028]

[Chemical 9]

[0029]

[Chemical 10]

[0030]

[Chemical 11]

[0031]

[Chemical 12]

[0032]

[Chemical 13]

The water-soluble dye of the present invention may be any one as long as it has absorption in the ultraviolet region, but the absorption maximum is 330 to 44.
It is preferably 0 nm and has a molecular extinction coefficient of 8,000 or more. It is preferable that these water-soluble dyes do not substantially remain after the treatment, and those having a solubility in water of 0.1% or more are preferable. Specific examples of preferable dyes are shown below.

[0034]

[Chemical 14]

In addition to the above, JP-A-5-249624
Formulas [3a], [3b], [3c] and [3
d], specifically, exemplified compounds 3-1 to 3
The dye of 3-33 is preferred.

These dyes are used in such amounts that the optical density at 360 nm is greater than 0.2, preferably greater than 0.3. The upper limit is an amount such that the optical density at 360 nm is less than 1.5, preferably less than 1.0. When the addition amount is expressed by weight, it is usually added in the range of 10 ^{−5 to 1} g / m ² , though it depends on the molar absorption coefficient. The dye may be a suitable solvent (eg water, alcohol (eg methanol, ethanol, etc.), acetone,
Etc. or a mixed solvent thereof) and added to the constituent layer of the present invention, but it is preferable to add it to the emulsion layer or a layer (for example, a protective layer) in which the water-soluble dye can diffuse to the emulsion layer. .

The hydrazine derivative used in the present invention is preferably represented by the following general formula (6). General formula (6)

[0038]

[Chemical 15]

In the formula, R ₁ represents an aliphatic group or an aromatic 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 or a hydrazino group. And G ₁ is a —CO— group,
-SO ₂ - group, -SO- group,

[0040]

[Chemical 16]

Represents a --CO--CO-- group, a thiocarbonyl group, or an iminomethylene group, wherein 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 Alternatively, it represents an unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. R ₃ is selected from the same range as the groups defined in R _2, may be different from R _2.

In the general formula (6), the aliphatic group represented by R ₁ preferably has 1 to 30 carbon atoms,
Particularly, it is a linear, 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 (6),
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, for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a group containing a heterocycle,
Pyridinium group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, alkyl or arylsulfonyloxy group, amino group, carbonamido group, sulfonamide group, ureido group, thioureido group, semicarbazide group, thiosemicarbazide group, urethane group, hydrazide Group having structure, group having quaternary ammonium structure, alkyl or arylthio group, alkyl or aryl sulfonyl group, alkyl or aryl sulfinyl group, carboxyl group, sulfo group, acyl group, alkoxy or aryloxycarbonyl group, carbamoyl group, sulfamoyl Group, halogen atom, cyano group, phosphoric acid amide group, diacylamino group, imide group, group having acylurea structure, group containing selenium atom or tellurium atom, tertiary sulfonium structure or Include a group having a quaternary sulfonium structure, and preferable substituents include a linear, branched or cyclic alkyl group (preferably having a carbon number of 1 to 20) and an aralkyl group (preferably having a carbon number of an alkyl portion). 1 to 3 monocyclic or bicyclic), alkoxy group (preferably having 1 to 20 carbon atoms), substituted amino group (preferably amino group substituted by alkyl group having 1 to 20 carbon atoms), acylamino Group (preferably having 2 to 30 carbon atoms), sulfonamide group (preferably having 1 to 3 carbon atoms)
Those having 0), ureido groups (preferably having 1 to 3 carbon atoms)
Those having 0), phosphoric acid amide groups (preferably having 1 carbon atom)
~ 30) and the like.

In the general formula (6), 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, monofluoromethyl group, difluoromethyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc.),
Aralkyl group (eg, o-hydroxybenzyl group), aryl group (eg, phenyl group, 3,5-dichlorophenyl group, o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, 2-hydroxymethylphenyl group, etc. ) Etc. Also, G ₁ is -SO
_In the case of a 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 _{1 in the} general formula (6), a —CO— group and a —COCO— group are preferable, and a —CO— group is the most preferable. Also, R ₂ is G ₁
Portions of -R ₂ disrupts the residual molecules may be such as to rise to cyclization reaction to form a cyclic structure containing a -G ₁ -R ₂ moiety of atoms, examples of which include, for example, Examples thereof include those described in JP-A No. 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 a 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 A hydrogen atom is most preferable as A ₁ and A ₂ .

The substituents of R ₁ and R _{2 in} the general formula (6) 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 (6) may have a ballast group or polymer 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 (6) 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 U.S. Pat. Nos. 4,385,108 and 4,459,34.
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.

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, a group having a quaternary ammonium structure or an alkylthio group. A phenyl group having a group, G
_A hydrazine derivative in which ₁ is a -CO- group and 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). Any combination of the above R ₁ and R ₂ alternatives is possible and preferred.

In the present invention, a hydrazine derivative characterized by having an anionic group or a nonionic group forming an intramolecular hydrogen bond with a hydrogen atom of hydrazine in the vicinity of the hydrazine group is particularly preferably used.

Specific examples of the anionic group include carboxylic acid, sulfonic acid, sulfinic acid, phosphoric acid, phosphonic acid and salts thereof. Here, the vicinity of the hydrazine group means that an atom 2 to 5 selected from at least one of a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom is present between the nitrogen atom close to the anionic group of hydrazine and the anionic group.
It means that there is an intervening bond chain formed by individuals. More preferably as a neighborhood, there is an intervening bond chain formed of 2 to 5 atoms selected from at least one of carbon and nitrogen atoms, and even more preferably a bond chain formed of 2 to 3 carbon atoms. This is when intervening. The nonionic group forming an intramolecular hydrogen bond with hydrazine hydrogen is a group in which a lone pair of electrons forms a hydrogen bond with hydrazine hydrogen in a 5- to 7-membered ring, and contains at least an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom. A group having one. Examples of the nonionic group include an alkoxy group, an amino group, an alkylthio group, a carbonyl group, a carbamoyl group, an alkoxycarbonyl group, a urethane group, a ureido group, an acyloxy group and an acylamino group. Of these, anionic groups are preferred, and carboxylic acids and salts thereof are most preferred. Preferred nucleating agents used in the present invention are those represented by the following general formulas (7) to (9). General formula (7)

[0051]

[Chemical 17]

(In the formula, R ¹ represents an alkyl group, an aryl group or a heterocyclic group, L ¹ represents a divalent linking group having an electron-withdrawing group, Y ¹ represents an anionic group or a hydrogen atom of hydrazine, and Represents a nonionic group forming an intramolecular hydrogen bond.) General formula (8)

[0053]

[Chemical 18]

(In the formula, R ² represents an alkyl group, an aryl group or a heterocyclic group, L ² represents a divalent linking group, and Y
² represents an anionic group or a nonionic group that forms an intramolecular hydrogen bond with a hydrogen atom of hydrazine. ) General formula (9)

[0055]

[Chemical 19]

(Wherein X ³ represents a group capable of substituting on the benzene ring, R ³ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group or an amino group, and Y ³ represents An anionic group or a nonionic group that forms an intramolecular hydrogen bond with a hydrogen atom of hydrazine, m ³ is an integer of 0 to 4, n ³ is 1 or 2. When n ³ is 1, R ³ is It has an electron-withdrawing group.)

The general formulas (7) to (9) will be described in more detail. The alkyl group of R ¹ and R ² is a linear, branched or cyclic alkyl group having 1 to 16 carbon atoms, preferably 1 to 12 carbon atoms, such as methyl, ethyl,
Propyl, isopropyl, t-butyl, allyl, propargyl, 2-butenyl, 2-hydroxyethyl, benzyl, benzhydryl, trityl, 4-methylbenzyl,
2-methoxyethyl, cyclopentyl and 2-acetamidoethyl.

The aryl group is an aryl group having 6 to 24 carbon atoms, preferably 6 to 12 carbon atoms, for example, phenyl, naphthyl, p-alkoxyphenyl, p-sulfonamidophenyl, p-ureidophenyl, p-amidophenyl. Is. The heterocyclic group is a 5-membered or 6-membered saturated or unsaturated heterocycle containing at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, and the number of heteroatoms constituting the ring. The type of the element may be one or plural, and examples thereof include 2-furyl, 2-thienyl, and 4-pyridyl.

An aryl group is preferred as R ¹ and R ² .
An aromatic heterocyclic group or an aryl-substituted methyl group,
More preferably, it is an aryl group (eg phenyl, naphthyl). R ¹ and R ² may be substituted with a substituent, and examples of the substituent include an alkyl group, an aralkyl group,
An alkoxy group, an alkyl- or aryl-substituted amino group,
Amido group, sulfonamide group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, aryl group, alkylthio group, arylthio group,
A sulfonyl group, a sulfinyl group, a hydroxy group, a halogen atom, a cyano group, a sulfo group, a carboxyl group, and a phosphorus amide group. These groups may be further substituted. Of these, a sulfonamide group, a ureido group, an amide group, an alkoxy group, and a urethane group are preferable, and a sulfonamide group and a ureido group are more preferable. When possible, these groups may be linked to each other to form a ring.

[0060] alkyl groups R ^3, aryl group, heterocyclic group include those described in R ^1. The alkenyl group has 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms, and examples thereof include vinyl and 2-styryl. The alkynyl group has 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms, and examples thereof include ethynyl and phenylethynyl. The alkoxy group has 1 to 16 carbon atoms, preferably 1 to 10 carbon atoms.
Is a linear, branched or cyclic alkoxy group, and is, for example, methoxy, isopropoxy or benzyloxy.
The amino group has 0 to 16 carbon atoms, preferably 1 carbon atom
-10, and are ethylamino, benzylamino and phenylamino. When n ³ = 1, R ³ is preferably an alkyl group, an alkenyl group or an alkynyl group. n ³ =
When 2, R ³ is preferably an amino group or an alkoxy group.

The electron-withdrawing group of R ³ has a Hammett σ _m value of 0.2 or more, preferably 0.3.
Examples of the above include halogen atoms (fluorine, chlorine, bromine), cyano groups, sulfonyl groups (methanesulfonyl, benzenesulfonyl), sulfinyl groups (methanesulfinyl), acyl groups (acetyl, benzoyl), oxycarbonyl groups (methoxycarbonyl). ), Carbamoyl group (N-methylcarbamoyl), sulfamoyl group (methylsulfamoyl), halogen-substituted alkyl group (trifluoromethyl), heterocyclic group (2-benzoxazolyl, pyrrolo), quaternary onium group (tri Phenylphosphonium, trialkylammonium, pyridinium). Examples of R ³ having an electron-withdrawing group include trifluoromethyl, difluoromethyl, monofluoromethyl, pentafluoroethyl, cyanomethyl, methanesulfonylmethyl, acetylethyl, trifluoromethylethynyl and ethoxycarbonylmethyl.

L ¹ and L ² represent a divalent linking group, and include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, a divalent heterocyclic group, and -O-, -S-,
It is a group in which groups such as —NH—, —CO—, and —SO ₂ — are used alone or in combination. L ¹ and L ² are R
^It may be substituted with the group described as the substituent of ¹ . Examples of the alkylene group include methylene, ethylene, trimethylene, propylene, 2-butene-1,4-yl, 2
-Butyn-1,4-yl. The alkenylene group is, for example, vinylene. The alkynylene group is ethynylene. The arylene group is, for example, phenylene. The divalent heterocyclic group is, for example, furan-1,4-diyl. L ¹ is an alkylene group,
An alkenylene group, an alkynylene group and an arylene group are preferable, and an alkylene group is more preferable. Further, an alkylene group having a chain length of 2 to 3 carbon atoms is most preferable. L ² is an alkylene group, an arylene group, —NH-alkylene-,
-O-alkylene- and -NH-arylene- are preferable, and -NH-alkylene- and -O-alkylene- are more preferable.

The electron-withdrawing group of L ¹ is R ³
Examples of the electron-withdrawing group of the above include.
Examples of L ¹ include tetrafluoroethylene, fluoromethylene, hexafluorotrimethylene, perfluorophenylene, difluorovinylene, cyanomethylene, and methanesulfonylethylene.

Y ¹ to Y ^{3 are} as described above, and are anionic groups or nonionic groups in which a lone pair of electrons forms a hydrogen bond with hydrazine hydrogen in a 5- to 7-membered ring. More specifically, examples of the anionic group include carboxylic acid, sulfonic acid, sulfinic acid, phosphoric acid, phosphonic acid and salts thereof. Examples of the salt include alkali metal ions (sodium and potassium), alkaline earth metal ions (calcium and magnesium), ammonium (ammonium, triethylammonium, tetrabutylammonium, pyridinium) and phosphonium (tetraphenylphosphonium). The nonionic group is a group having at least one of an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom, an alkoxy group, an amino group, an alkylthio group, a carbonyl group, a carbamoyl group,
Examples thereof include an alkoxycarbonyl group, a urethane group, a ureido group, an acyloxy group and an acylamino group. As Y ¹ to Y ³ , an anionic group is preferable, and a carboxylic acid and its salt are more preferable.

Examples of the group capable of substituting on the benzene ring of X ³ and its preferable groups include those mentioned as the substituents of R ^{1 in the} general formula (1). When m ³ is 2 or more, they may be the same or different.

R ¹ to R ³ or X ³ may have a diffusion resistant group used in a photographic coupler or may have an adsorption promoting group to silver halide. The diffusion resistant group has 8 to 30 carbon atoms, preferably 12 to 25 carbon atoms. The adsorption promoting group for silver halide is preferably a thioamide (eg thiourethane,
Thioureido, thioamide), mercaptos (eg 5
-Mercaptotetrazole, 3-mercapto-1,2,
Heterocyclic mercapto such as 4-triazole, 2-mercapto-1,3,4-thiadiazole, and 2-mercapto-1,3,4-oxadiazole, alkylmercapto,
Aryl mercapto) and a 5- or 6-membered nitrogen-containing heterocycle (eg benzotriazole) which produces silver imino
Is. Examples of those having a silver halide adsorption promoting group include those having a structure in which the adsorbing group is protected and the protecting group is removed during the development processing to enhance the adsorptivity to silver halide.

In the general formulas (7) to (9), radicals from which the hydrogen atoms of two compounds are removed may combine with each other to form a bis type. In the general formulas (7) to (9), the general formulas (7) and (8) are preferable, and the general formula (7) is more preferable. Further, in the general formulas (7) to (9), the following general formula (10)
To (12) are more preferable, and general formula (10) is the most preferable. General formula (10)

[0068]

[Chemical 20]

(In the formula, R ⁴ , X ⁴ and m ⁴ are respectively synonymous with R ³ , X ³ and m ^{3 in the} general formula (9), and L ⁴ , Y ^{4 and}
Is synonymous with L ¹ and Y ^{1 in} the general formula (7). ) General formula (11)

[0070]

[Chemical 21]

(In the formula, R ⁵ , X ⁵ and m ⁵ are respectively synonymous with R ³ , X ³ and m ^{3 of the} general formula (9), and L ⁵ , Y ^{5 and}
Is synonymous with L ² and Y ^{2 in} the general formula (8). ) General formula (12)

[0072]

[Chemical formula 22]

(Wherein R ⁶¹ , R ⁶² , X ⁶ , m ⁶ , n ⁶ ,
Y is R ³ , R ³ , X ³ , m ³ , n ³ or Y in the general formula (9).
Synonymous with ³ . )

Specific examples of the hydrazine derivative used in the present invention are shown below, but the present invention is not limited thereto.

[0075]

[Chemical formula 23]

[0076]

[Chemical formula 24]

[0077]

[Chemical 25]

[0078]

[Chemical formula 26]

[0079]

[Chemical 27]

[0080]

[Chemical 28]

[0081]

[Chemical 29]

[0082]

[Chemical 30]

[0083]

[Chemical 31]

[0084]

[Chemical 32]

[0085]

[Chemical 33]

[0086]

[Chemical 34]

[0087]

[Chemical 35]

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 per mol of silver halide, and 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 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.

The silver halide photographic light-sensitive material of the present invention preferably contains a nucleation accelerator in at least one of the emulsion layer and other hydrophilic colloid layers.

The nucleation accelerator preferably used in the present invention is represented by the following general formulas (13), (14), (15) and (16).
Is a compound represented by.

[0093]

[Chemical 36]

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.

[0095]

[Chemical 37]

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.

For details of the compounds of the general formulas (13) to (16) and compound examples, the description in Japanese Patent Application No. 6-250136 and the compound examples A201 to A262 therein can be mentioned. Many of the compounds represented by the general formula (13) are known and are 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.

Further, the general formula (14), the general formula (15),
The compound represented by the general formula (16) can be synthesized by a generally well-known method (for example, Quart. Rev., 16, 163 (1
962))).

The addition amount of the compounds of the general formula (13), the general formula (14), the general formula (15) and the general formula (16) is as follows.
There is no particular limitation, but 1 × 10 1 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 (15).

Further, the general formula (13), the general formula (14),
When the compounds of the general formulas (15) and (16) are contained in the photographic light-sensitive material, they are water-soluble when they are water-soluble, and alcohols (for example, methanol and ethanol) and esters (when they are water-insoluble). For example, it may be added to the silver halide emulsion solution or the hydrophilic colloid solution as a solution of a water-miscible organic solvent such as 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.

Specific examples of the nucleation accelerator include JP-A-62-62
-250439, compound examples IV-1 to IV-29, JP-A-5-273710, compound examples 1-29, U.S. Pat.
Compound Examples II-1 to II-17 of No. 847,180 and Compound Examples A-1 to A-47, B-1 of Japanese Patent Application No. 6-46604.
To B-21, C-1 to C-20 and the like.

Although gelatin is used as a binder for the silver halide emulsion layer and other hydrophilic colloid layers of the present invention, other hydrophilic colloids can be used in combination. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol. Use of various kinds of synthetic hydrophilic polymer substances such as single or copolymers of polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. You can As the gelatin, acid-treated gelatin may be used in addition to lime-treated gelatin, and gelatin hydrolyzate and gelatin enzyme-decomposed product may also be used. In the present invention, the coating amount of gelatin as the binder is such that the total hydrophilic colloid layer on the side having the silver halide emulsion layer has a gelatin amount of 3 g / m ² or less and the total hydrophilic side on the side having the silver halide emulsion layer. total gelatin sex colloid layer and all hydrophilic colloid layers on the opposite surface is at 6 g / m ² or less, preferably 2.0 to 6.0 g / m ^2.

Using the silver halide light-sensitive material of the present invention,
In order to obtain photographic characteristics that are safe and have a safelight safety that can withstand bright room applications, use of the above-mentioned hydrazine derivatives and nucleation accelerators makes it possible to use conventional infectious developers and US Pat. No. 2,419,975. It is not necessary to use a highly alkaline developing solution close to pH 13 described in 1., but it is sufficient to use a developing solution stable at a lower pH. 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 by using the above-mentioned hydrazine derivative and nucleation accelerator, and has a pH of 9.5 to 11.
With a developer of 0, a super high contrast image can be obtained.

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-
Containing 1.2 mol / l of free sulfite ion, (4) the compound represented by the general formula (17),
And the dihydroxybenzene-based developing agent have a concentration ratio of 0.03 to 0.12 and a pH of 9.0 to 1
The developer is 1.0, and particularly preferably 9.5 to 10.7. General formula (17)

[0105]

[Chemical 38]

In the formula, R ₁ and R ₂ each represent a hydroxy group, amino group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkoxycarbonylamino group, mercapto group or 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 = O 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 (17) 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 (17) is the concentration ratio of (the compound represented by the general formula (17) / hydroquinone-based developing agent) (the general formula (1
The value obtained by dividing the concentration of the compound represented by 7) by the concentration of the dihydroxybenzene type developing agent) 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. 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.

The p-aminophenol-based developing agent used in the present invention includes N-methyl-p-aminophenol and p-aminophenol.
-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 a reductone is used as a developing agent, it can be used as the reductone represented by the general formula (17).
It is preferable to use the compound (1), and ascorbic acid or erythorbic acid (stereoisomer) is particularly preferable. In this case, the same auxiliary developing agent as the dihydroxybenzene type developing agent can be used, and a p-aminophenol type and / or 1-phenyl-3-pyrazolidone type auxiliary developing agent is preferable. When the compound of the general formula (17) is used as a developing agent, the general range of the amount used is from 5 × 10 ⁻³ mol to 1 liter of the developing solution.
It is 1 mol, particularly preferably 10 ^-2 mol to 0.5 mol.

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.

In the developing solution used in the present invention, a dialdehyde type hardener or a bisulfite adduct thereof may be used. Specific examples thereof include glutaraldehyde, α-methylglutaraldehyde, β-methylglutaraldehyde, maleindialdehyde, succindialdehyde, methoxysuccindialdehyde, methylsuccindialdehyde, α-methoxy-β-ethoxyglutaraldehyde, α. -N-butoxyglutaraldehyde,
Examples include α, α-diethylsuccindialdehyde, butylmalein dialdehyde, or 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, 1 to 50 g, preferably 3 to 1 liter of the developer is used.
It is 10 g.

An antifoggant is used in the developer used in 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] butanesulfonate sodium, 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 per liter of the developing solution, and more preferably 0.1 to 10 mmol.
It is 2 mmol. 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 present invention may optionally contain a buffering agent (eg, carbonate, alkanolamine), an alkaline agent (eg, hydroxide, carbonate),
Dissolution aids (eg polyethylene glycols, esters thereof), pH adjusters (eg organic acids such as acetic acid), development accelerators (eg US Pat. No. 2,648,604,
Various pyridinium compounds and other cationic compounds described in JP-B-44-9503 and US Pat. No. 3,171,247, cationic dyes such as phenosafranine,
Neutral salts such as thallium nitrate and potassium nitrate, JP-B-44
-9304, U.S. Pat.
No. 832, No. 2950970, No. 2577127, polyethylene glycol and its derivatives, nonionic compounds such as polythioethers, JP-B-44-950.
9, an organic solvent described in Belgian Patent 682862, a thioether compound described in U.S. Pat. No. 3,012,242, etc., particularly preferably a thioether compound), a surfactant and the like can be contained.

The development processing temperature and time are related to each other 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.

The hardening agent in the fixing solution used in the present invention includes 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 to 45 ° C, and the 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, especially 300 ml / m ^{2 with} respect to the processing amount of the light-sensitive material.
It is preferably m ² or less.

The light-sensitive 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,
It is possible to eliminate the need for piping for the automatic processor. When the washing with water is carried out with a small amount of water, JP-A-63-18350 and JP-A-6-18350.
It is more preferable to provide a squeeze roller septic tank described in JP-A-2-287252. 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 the whole 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 JP-A-60-
As described in No. 235133, it can also be used for a processing liquid 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, to prevent contamination by dyes eluted from a light-sensitive material, JP-A-63-16
The dye adsorbent described in No. 3456 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, and as an example, there is JP-A-2-201357.
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 the 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 US Pat. Nos. 3,025,779 and 3,545,971 and the like.
It is possible to preferably use those comprising four steps of fixing, washing with water and drying. Further, the above treatment liquid may be used as a solid treatment agent. The solid processing agent preferably used in the present invention is powder, tablet, granule, powder, lump or paste, and the preferred form is JP-A-61-2599.
The form or tablet described in No. 21. The method for producing tablets is described in, for example, JP-A Nos. 51-61837 and 54-155.
038, 52-88025, British Patents 1,21
It can be produced by a general method described in No. 3,808,
Further, the granule treating agent is, for example, JP-A No. 2-109042,
2-109043, 3-39735 and 3-
It can be produced by a general method described in No. 39739 or the like. Furthermore, powder treating agents are disclosed in, for example, JP-A-54-133.
No. 332, British Patents 725,892 and 729,86.
No. 2 and German Patent No. 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 , particularly from the viewpoint of solubility and the effect of the object of the present invention. 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 sensitization described in JP-A Nos. 1-112235, 2-124560, 3-79928, 5-11389, and 4-330434. Pigment. 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, and compounds described in JP-A-5-257239 and JP-A-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, in Japanese Patent Publication No. 46-22507, Japanese Patent Publication No. 50-73625, US Pat. Nos. 34 88708, 3939130, 392 9482, and Japanese Patent Application No. 5-300182, or in the specification. 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 described in detail with reference to Examples, but the present invention is not limited thereto.

[0129]

【Example】

Example 1 <Emulsion preparation> Emulsion A: 3 × 10 ⁻⁵ mol of the exemplified compound (1-1) per mol of sodium chloride and silver kept at 38 ° C.
6) 5 × 10 ⁻³ mol of 4-hydroxy-6-methyl-
PH containing 1,3,3a, 7-tetrazaindene = 2.
An aqueous solution of sodium chloride containing 5 × 10 ⁻⁵ mol of K ₂ Ru (NO) Cl ₅ per mol of silver in a 1.5% gelatin aqueous solution of 0 by a double jet method at a potential of 95 mV for 3 minutes and 30 seconds. Half of the silver amount of the final particles was added at the same time to prepare core particles of 0.12 μm. Then, an aqueous silver nitrate solution and an aqueous sodium chloride solution containing 5 × 10 ⁻⁵ mol of K ₂ Ru (NO) Cl ₅ per mol of silver were added in the same manner as above for 7 minutes,
Cubic silver chloride grains having an average grain size of 0.13 μm 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, gelatin was added, and compound-F and phenoxyethanol as preservatives were added at 60 mg per 1 mol of silver, respectively, and then pH 5.5, Adjusted to pAg = 7.5 and silver 1
4 × 10 ⁻⁵ mol of chloroauric acid, 1 × 10 ⁻⁵ mol of selenium compound SE-4 and 1 × 10 ⁻⁵ mol of sodium thiosulfate were added per mol, and the mixture was heated at 60 ° C. for 60 minutes to chemically increase the amount. After being sensitized, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene as a stabilizer was added in an amount of 1 × 10 ⁻³ mol per mol of silver.
5.7, pAg = 7.5, Ru = 5 × 10 ⁻⁵ mol / Ag
Became a silver chloride containing moles).

Emulsions B to G were prepared in the same manner as Emulsion A, except that K ₂ Ru (NO) Cl ₅ in Emulsion A was changed to the heavy metal species and amount shown in Table 1.

Emulsion H: Emulsion A sodium thiosulfate , ce
Except that the len compound SE-4 and chloroauric acid were not added, everything else was prepared exactly like Emulsion A.

Emulsions I and J: The selenium compound S was prepared by ^{adjusting the} amount of sodium thiosulfate in the preparation of Emulsion A to 2 × 10 ^-5 mol.
Emulsion A was prepared exactly as in Emulsion A, except that E-4 was removed and the heavy metal species and amounts shown in Table 1 were changed. Emulsion K: 2 × sodium thiosulfate when preparing Emulsion A
The emulsion was prepared in the same manner as in Emulsion A, except that the amount of chloroauric acid and the selenium compound SE-4 were removed to 10 ^-5 mol. Emulsion L: Prepared in the same manner as Emulsion A except that sodium thiosulfate in the preparation of Emulsion A was removed and the selenium compound was changed to SE-4 in an amount of 2 × 10 ⁻⁵ mol. Emulsion M: Prepared in the same manner as Emulsion A, except that sodium thiosulfate in the preparation of Emulsion A was removed and the selenium compound was SE-3 and the amount thereof was 2 × 10 ^-5 mol.

<Preparation of Emulsion Layer Coating Liquid and Its Coating> The following compounds were added to the emulsions shown in Table 1 and coated on a support described below including an undercoat layer at a gelatin coating amount of 0.9 g / m ² A silver halide emulsion layer was coated so that the amount of silver would be 2.75 g / m ² . N-oleyl-N-methyltaurine sodium salt 19 mg / m ² hydrazine derivative (A-23) 15 mg / m ² Nucleation accelerator Z 20 mg / m ² 3- (5-mercaptotetrazole) -benzenesulfonic acid sodium 11 mg / m ² compound A 13 mg / m ² ascorbic acid 1 mg / m ² compound B 15 mg / m ² compound C 70 mg / m ² acetic acid Amount that makes the film surface pH 5.2 to 6.0 compound D 950 mg / m ² ribolane-1400 ( Lion fat and oil) 47 mg / m ² Compound E (hardener) Amount that makes the swelling rate in water 80%

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

<Preparation of Emulsion Protecting Lower Layer Coating Liquid and Its Coating>
The following compounds were added to an aqueous gelatin solution and coated so that the gelatin coating amount would be 0.8 g / m ² . Gelatin (Ca ⁺⁺ content 2700 ppm) 0.8 g / m ² compound F 1 mg / m ² 1,5-dihydroxy-2-benzaldoxime 14 mg / m ² C ₂ H ₅ SO ₂ SNa 3 mg / m ² compound C 3 mg / M ² sodium p-dodecylbenzenesulfonate 7 mg / m ² Water-soluble dye of the present invention (D-2) Amount shown in Table 1.

<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 gelatin coating amount would be 0.45 g / m ² . Gelatin (Ca ⁺⁺ content 2700 ppm) 0.45 g / m ² amorphous silica matting agent (average particle size 4.4 μm) 40 mg / m ² amorphous silica matting agent (average particle size 3.6 μm) 10 mg / m ² compound F 1 mg / m ² compound C 8 mg / m ² solid disperse dye -G ₁ 68mg / m ² Liquid paraffin 21 mg / m ² N-perfluorooctane sulfonyl -N- propyl glycine Potassium 5 mg / m ² p-dodecylbenzenesulfonate Sodium 29 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 Liquid for Conductive Layer and Coating> The following compounds were added to a gelatin aqueous solution to give a gelatin coating amount of 0.
It was applied so that the amount would be 06 g / m ² . SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μm) 186 mg / m ² gelatin (Ca ⁺⁺ content 2700 ppm) 0.06 g / m ² sodium p-dodecylbenzenesulfonate 13 mg / m ² dihexyl- α-sulfosuccinate sodium 12 mg / m ² compound C 12 mg / m ² compound F 1 mg / m ²

<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 1.94 g / m ² . Gelatin (Ca ⁺⁺ content 30ppm) 1.94g / m ² of polymethyl methacrylate particles (average particle size 4.7μ) 7mg / m ² Compound -H 233 mg / m ² Compound -I 21 mg / m ² Compound -G 146 mg / m ² compound -F 3 mg / m ² p-dodecylbenzenesulfonate sodium 68 mg / m ² dihexyl -α- sulfosuccinates sodium _{^{21mg / m 2 C 8 F 17}} SO 3 Li 4mg / m 2 N- perfluorooctanesulfonyl - the amount of N- propyl glycine Potassium 6 mg / m ² sodium sulfate 177 mg / m ² compound -E (hardener) swelling rate in water is 90%

(Support, Undercoat Layer) Biaxially stretched polyethylene terephthalate supports (thickness: 100 μm) were coated with the first and second undercoat layers having the following compositions on both sides. <Undercoat layer 1 layer> Core-shell type vinylidene chloride copolymer 15 g 2,4-dichloro-6-hydroxy-s-triazine 0.25 g Polystyrene fine particles (average particle size 3 μ) 0.05 g Compound-M 0.20 g Colloidal silica (Snowtex ZL: particle size 70 to 100 μm, manufactured by Nissan Kagaku Co., Ltd.) 0.12 g Water added 100 g Further, 10 wt% KOH was added to adjust the pH = 6, and the coating liquid was dried at 180 ° C. The dry film thickness was 0.
It was applied so as to be 9μ.

<Undercoat Layer Second Layer> Gelatin 1 g Methylcellulose 0.05 g Compound-J 0.02 g C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 0.03 g Compound-F 3.5 × 10 ⁻³ g Acetic acid 0.2 g Water was added 100 g This coating solution was applied at a drying temperature of 170 ° C. for 2 minutes so that the dry film thickness was 0.1 μm, to prepare a support with an undercoat layer.

[0142]

[Chemical Formula 39]

[0143]

[Chemical 40]

[0144]

[Chemical 41]

Samples 1 to 18 were manufactured as described above.

The coating method and drying conditions were as follows. <Coating method> On the support having the above-mentioned undercoat layer, first, from the side closer to the support as the emulsion surface side, the emulsion layer, the emulsion protection lower layer,
Simultaneous multilayer coating while adding the hardener solution by the slide hopper method while maintaining at 35 ° C in the order of the emulsion protection upper layer,
After passing through the cold air set zone (5 ° C.), the conductive layer and the back layer were arranged in this order from the side closer to the support on the side opposite to the emulsion surface.
Similarly, simultaneous multilayer coating was performed by adding a hardener solution by a slide hopper method, and a cold air set zone (5 ° C.) was applied. The coating liquid exhibited sufficient setting properties when it passed through each setting zone. Subsequently, both sides were simultaneously dried in the drying zone under the following drying conditions. In addition, after applying the back surface side, it was conveyed in a state in which there was no contact with the roller and the rest until winding. The coating speed at this time is 120 m / m
It was in.

<Drying conditions> After setting, the product was dried with a dry air at 30 ° C. until the weight ratio of water / gelatin reached 800%, and then 8
Dry 0 to 200% with 35 ° C 30% dry air, apply the air as it is, and after 30 seconds from the time when the surface temperature reaches 34 ° C (it is considered that the drying is completed), dry with 48 ° C 2% air for 1 minute. did. At this time, the drying time is 50 seconds from the start of drying to a water / gelatin ratio of 800% and 35 seconds from 800 to 200%.
5 seconds from 200% to the end of drying.

This photosensitive material was wound up at 40 ° C. at 23 ° C., cut in the same environment, and placed in a barrier bag conditioned for 6 hours to give 4
After the humidity was controlled at 0 ° C. and 10% for 8 hours, the sample was sealed together with the thick paper that was controlled at 23 ° C. and 40% for 2 hours to prepare the samples shown in Table 1. When the humidity in the barrier bag was measured, it was 40%.

Samples 1 to 23 were evaluated by the following methods. <Evaluation Method> (Evaluation of Practical Technique Dmax and Fog Value) In order to evaluate the practical technique Dmax, a manuscript “transparent embedment base / line drawing positive image” having the configuration shown in FIG. 1 of Japanese Patent Publication No. 2-288,56. Film (line drawing original) / transparent sticking base / film on which halftone image is formed (halftone original) "in this order." Closely attach to P made by Dainippon Screen
It was exposed with a -627FM printer, processed with an automatic developing machine FG-680AG manufactured by Fuji Photo Film Co., Ltd., at 38 ° C. for 20 seconds with the following developer 1, and then fixed, washed with water and dried.
The following fixer 1 was used as the fixer. The amount of replenisher for developer 1 and fixer 1 was 162 m / m ² for each sample.
l, 260 ml. The exposure time of each sample is halftone dot area ratio 5
A 0% halftone dot original portion was determined so as to form an image on each sample as a halftone dot having a halftone dot area ratio of 50%, and the maximum blackening density at this time was defined as the practical technique Dmax. For the fog value,
Evaluation was made by subtracting the base density from the density of the unexposed area when the above treatment was performed.

[0150] (Developer 1)   Potassium hydroxide 40.0g   Diethylenetriamine-pentaacetic acid 2.0 g   Potassium carbonate 60.0g   Sodium metabisulfite 70.0g   Potassium bromide 7.0g   Hydroquinone 40.0g   5-methylbenzotriazole 0.35 g   4-hydroxymethyl-4-methyl-1-phenyl-3-     Pyrazolidone 1.50g   2-Mercaptobenzimidazole-5-sulfonic acid     Sodium 0.30g   3- (5-mercaptotetrazol-1-yl) benzene     Sodium sulfonate 0.10g   Sodium erythorbate 6.0 g   5.0 g of diethylene glycol   Add potassium hydroxide and add water to 1 liter     Adjust the pH to 10.65. 1 liter

[0151] (Fixer 1)   Ammonium thiosulfate 119.7 g   Ethylenediaminetetraacetic acid 2Na dihydrate 0.03g   Sodium thiosulfate pentahydrate 10.9g   Sodium sulfite 25.0g   12.4g of NaOH (in pure content)   Glacial acetic acid 29.1g   Tartaric acid 2.92g   Sodium gluconate 1.74g   Aluminum sulfate 8.4g   pH (adjusted with sulfuric acid or sodium hydroxide) 4.8   1 liter with water

(Evaluation of halftone dot area variation) Amount of variation in halftone dot area ratio when the exposure Dx is doubled and the exposure amount is tripled (how much it changes from 50%) )
Was evaluated. The smaller this value, the less likely the halftone dots are collapsed in a high definition image. The results obtained are shown in Table 1.

[0153]

[Table 1]

[0154]

[Table 2]

As is clear from the results shown in Table 1, the samples 4 to 7, 9 to 12, 14, and 15 of the present invention had a fog value and a practical skill Dmax.
It can be seen that the dot area variation amount is excellent. Further, when the optical density at 360 nm is larger than 0.3, the halftone dot variation becomes smaller (Samples 5 and 6).
I understand from.

Example 2 The pH of the emulsion A of Example 1 during grain formation and the amount and kind of the exemplary compound (1-16) of the thiosulfonic acid compound are shown in the table below.
3 is changed to indicate the emulsion N~S prepared, other samples were prepared 19-24 was exactly the same as Sample 5 of Example 1. The fog value of the obtained sample was evaluated in the same manner as in Example 1. In addition, the sample at 60 ℃, 30
After left under the condition of% RH for 3 days, the fog value was evaluated in the same manner. The same evaluation was performed for Sample 5 of Example 1. The developing solution 1 and the fixing solution 1 were used as the following developing solution 2 and fixing solution 2 for the above evaluation, and the replenishing solution amounts of the developing solution and the fixing solution were exactly the same as in Example 1.

(Developer 2) A solution to be used was prepared by adding water to the following storage form of a solid developer to make it 10 liters. In the method for producing a solid developer, a container made of high-density polyethylene (average wall thickness = 500 μm, partially 200 to 1000 μm) was filled with 10 liters of developing components as a working solution in solid form. At this time, the components were mixed and then filled in a container. Table 2 shows the composition of 10 liter of the developer used and the form of the raw material.

[0158]

[Table 3]

Regarding the raw material form, the bulk powder is used as it is as a general industrial product, and alkali metal salt beads,
Commercially available products were used for both pellets. When the raw material form was briquette, it was pressed and compressed using a briquetting machine to prepare an irregular rugby ball shape having a length of about 4 to 6 mm, which was crushed and used. For minor components, each component was blended before briquetting.

(Fixing Solution 2) The following solid agent and liquid agent were added to water to make 10 liters to prepare a working solution. The fixing solution is made of high-density polyethylene in the following formulation for both the solid agent portion and the liquid agent portion (average wall thickness = 500 μm, width 200-
What was filled in a container of 1000 μm) was used. The liquid volume after dissolution was 10 liters, and the pH was 4.85.

[0161] <Solid agent part>   Ammonium thiosulfate 1200g   Sodium thiosulfate 150g   400 g of sodium acetate   Sodium metabisulfite 200g <Liquid part>   Aluminum sulfate (27%) 300g   Sulfuric acid (75%) 30g   Sodium gluconate 20g   EDTA 0.3g   Citric acid 40g   The solid agent parts are mixed and filled.

The results obtained are shown in Table 3.

[0163]

[Table 4]

From the results of Table 3, Samples 5 and 20 of the present invention were obtained.
Is superior in terms of fog value. That is, it is found that particle formation under acidic conditions (pH 3.0 to 1.5 ) and addition of a thiosulfonic acid compound are effective.

Example 3 Samples 25 to 29 were prepared in exactly the same manner as Sample 5 of Example 1 except that the halogen composition of Emulsion A used in Example 1 was changed as shown in Table 4. The following samples were evaluated for safelight safety. <Safelight Safety Evaluation> Toshiba anti-fading fluorescent lamp (F
(LR40SW-DL-X NU / M) When irradiated and exposed with about 400 Lux, the fog value was evaluated by the irradiation time of the fluorescent lamp to be 0.02. Regarding the post-exposure treatment,
The developer 1 was replaced with the developer 3 below, and the other conditions were the same as in Example 1. The longer this time is, the easier it is to handle in a bright room environment.

[0166] <Developer 3>   1.71 g of sodium hydroxide   Diethylenetriamine-5 acetic acid 4 g   27.5g potassium carbonate   Sodium carbonate 25.5g   Sodium erythorbate 30g   N-methyl-P-aminophenol 7.5 g   KBr 2g   5-methylbenzotriazole 0.1 g   1-phenyl-5-mercaptotetrazole 0.02 g   Sodium sulfite 5g   Glacial acetic acid 9g   Add water to 1 liter and adjust the pH to 9.8.

The results obtained are shown in Table 4.

[0168]

[Table 5]

From Table 4, it is understood that the silver chloride content of the present invention of 98 mol% or more is excellent as the halogen composition from the viewpoint of safelight safety, and silver chloride is particularly effective.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI G03C 1/83 G03C 1/83 5/31 5/31 (56) Reference JP-A-7-234472 (JP, A) JP JP-A-7-239524 (JP, A) JP-A-7-175148 (JP, A) JP-A-6-82944 (JP, A) JP-A-60-83028 (JP, A) JP-A-4-307535 (JP , A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03C 1/06 501 G03C 1 / 035,1 / 09 G03C 1 / 34,5 / 31

Claims (6)

(57) [Claims] 1. At least one layer of halogenation on a support.
In a silver halide photographic light-sensitive material having a silver emulsion layer,
Heavy metal selected from Ir, Ru, Rh, Re in the emulsion layer
ionIs at least 1 × 10 per mol of silver halide.
^-6Contains moles,pH 3.0-1.5Particles under acidic conditions
Formed and then chemically enhanced by gold and sulfur compounds
Detected silver halide grains with a silver chloride content of 98 mol% or more
Including children,Grain formation of the silver halide grains and / or
In the process of chemical sensitization, the following general formulas (1), (2) and
Is at least one of the compounds represented by (3)
IsOther hydrophilicity of the emulsion layer or the side having the emulsion layer
The optical density at 360 nm is greater than 0.2 in the organic colloid layer.
A halo characterized by containing an amount of a water-soluble dye
Silver photographic light-sensitive material.(1) R-SO ₂ S-M (2) R-SO ₂ SR ¹ (3) R-SO ₂ SL _m -SSO ₂ -R ² In the formula, R, R ¹ And R ² May be the same or different,
Represents an aliphatic group, an aromatic group, or a heterocyclic group, and M is a cation
Represents a divalent linking group, m represents 0 or 1
Therefore, the compounds of the general formulas (1) to (3) are
The divalent group derived from the structure shown in Ishi (3)
It may be a polymer contained as a return unit. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide grains are chemically sensitized with a selenium compound. 3. A silver halide photographic material as claimed in claim 1 or 2, characterized in that at least one at least in more hydrazine derivatives of the emulsion layer or other hydrophilic colloid layer. 4. The optical density at 360 nm in the emulsion layer or the other hydrophilic colloid layer on the side having the emulsion layer is 0.
The silver halide photographic material according to any one of claims 1 to 3, characterized in that it contains an amount of water-soluble dye to be greater than 3. 5. The silver halide grain has a silver chloride content of 10
The silver halide photographic material according to any one of claims 1 to 4, characterized in that 0 mol%. 6. The replenishing amount of the developing solution when processed by an automatic processor is 2 per square meter of the silver halide photographic light-sensitive material.
The amount is less than 00 milliliters.
The current of the silver halide photographic light-sensitive material according to any one of 1 to 5
Image processing method .