JP2794254B2 - Silver halide photographic material - 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 photographic light-sensitive material, and more particularly to a super-high contrast silver halide photographic light-sensitive material used for photolithography.

[0002]

2. Description of the Related Art In the field of graphic arts,
In order to improve the reproduction of continuous tone images or the reproduction of line images using halftone images, images developed with a processing solution having good storage stability and exhibiting ultra-high contrast (especially γ of 10 or more) photographic characteristics There is a need for a forming system. One of them is disclosed in U.S. Pat. Nos. 4,166,742 and 4,168,97.
No. 7, 4,221,857, 4,224,401
Nos. 4,243,739 and 4,272,606
No. 4,311,781, a surface latent image type silver halide photographic material to which a specific acylhydrazine compound is added, and a sulfite preservative at pH 11.0 to 12.3. There has been proposed a system for forming a super-hard negative image in which γ exceeds 10 by processing with a developer containing 15 mol / l or more and having good storage stability. However, an alkaline developer having a pH of 11 or more is susceptible to air oxidation, and a silver halide photosensitive material containing a hydrazine compound is developed with a developer having a lower pH to produce a high contrast image. . JP-A-1-17993
9, and JP-A-1-179940, a nucleating development accelerator having an adsorptive group for silver halide emulsion grains and a nucleating agent having the same adsorptive group are used.
A processing method of developing with a developer of 11.0 or less is described. However, when a compound having an adsorptive group is added to a silver halide emulsion, if the amount exceeds a certain limit, photosensitivity is impaired, development is suppressed, or the action of other useful adsorptive additives is hindered. Since it is harmful, the amount used is limited, and sufficient high contrast cannot be exhibited.

[0003] US Patent Nos. 4,998,604 and 4,994
No. 365 discloses a hydrazine compound having a repeating unit of ethylene oxide and a hydrazine compound having a pyridinium group. However, as is apparent from these examples, the high contrast is not sufficient, and it is difficult to obtain the high contrast and the necessary Dmax under practical development conditions. Further, the nucleation-sensitive material using a hydrazine derivative has a large change in photographic properties due to a change in pH of the developer. The pH of the developing solution fluctuates greatly due to an increase due to air oxidation of the developing solution and concentration due to evaporation of water, or a decrease due to absorption of carbon dioxide in the air. Accordingly, attempts have been made to reduce the dependence of photographic performance on the developer pH. Japanese Patent Application No. 1799963 discloses a photosensitive material in which the pH of a developing solution is reduced to 11.0 or less and the pH of the developing solution is small. There is a problem that the pot is deteriorated or the performance fluctuates greatly when running a large amount of film.

[0004]

Accordingly, an object of the present invention is to firstly provide a silver halide photographic light-sensitive material capable of obtaining extremely hard photographic properties having a gamma exceeding 10 using a stable developing solution. That is. A second object of the present invention is to provide a silver halide photographic light-sensitive material having less fluctuation in performance even after long-term storage. A third object of the present invention is to provide a silver halide photographic light-sensitive material which is hardened by a developer having a pH of 11 or less and has small fluctuation in performance even when a large amount of film is processed.

[0005]

SUMMARY OF THE INVENTION The object of the present invention is to provide a silver halide photographic material having at least one silver halide emulsion layer on a support.
Alternatively, the hydrazine derivative represented by the general formula (I) and the hydrazine derivative represented by the general formula (II), (III) or (I)
This has been attained by a silver halide photographic material characterized by containing at least one compound represented by the formula (V).
General formula (I)

[0006]

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[0007] R ¹ represents an aliphatic group, an aromatic group or a heterocyclic group, and may be substituted. G represents a -CO- group, R ² represents a substituted alkyl group in which the carbon atom substituted by G is substituted with at least one electron withdrawing group. R
⁴ represents a hydrogen atom, an aliphatic group, an aromatic group, an alkoxy group, an aryloxy group or an amino group.

[0008]

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Z represents an alkyl group (1 to 18 carbon atoms), an aryl group, (6 to 18 carbon atoms), or a heterocyclic group, and Y represents an aromatic ring (6 to 18 carbon atoms) or a heterocyclic group. Represents required atoms. M is a metal atom or an organic cation;
n represents an integer of 2 to 10.

Next, the compound represented by formula (I) will be described in more detail. In the general formula (I), R
^The aliphatic group represented by ¹ is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group. R ¹
The aromatic group represented by is a monocyclic or bicyclic aryl group, such as a phenyl group and a naphthyl group. The hetero ring of R ¹ is a 3- to 10-membered saturated or unsaturated hetero ring containing at least one of N, O, and S atoms, which may be a single ring, A condensed ring may be formed with an aromatic or hetero ring. The heterocyclic ring is preferably a 5- or 6-membered aromatic heterocyclic group, and includes, for example, a pyridine group, an imidazolyl group, a quinolinyl group, a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, an isoquinolinyl group, a thiazoline group, and a benzothiazolyl group. Are preferred. R
Preferred as ¹ is an aromatic group, a nitrogen-containing heterocyclic ring and a group represented by the general formula (b). General formula (b)

[0011]

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(Where X is_bIs an aromatic group or a nitrogen-containing complex
A ring group;_b ¹~ R_b ^FourAre hydrogen and halogen
X represents an alkyl atom or an alkyl group;_bAnd R_b ¹
~ R _b ^FourMay have a substituent if possible.
r and s represent 0 or 1. ) R¹Is more preferably an aromatic group, especially an aryl group.
Preferred is a thiol group. R¹May be substituted with a substituent
No. Examples of the substituent include, for example, an alkyl group and an aralkyl
Group, alkenyl group, alkynyl group, alkoxy group,
Reel group, substituted amino group, aryloxy group, sulfa
Moyl group, carbamoyl group, alkylthio group, aryl
Thio group, sulfonyl group, sulfinyl group, hydroxy
Group, halogen atom, cyano group, sulfo group or carboxyl
Groups, alkyl and aryloxycarbonyl groups, acyl
Group, alkoxycarbonyl group, acyloxy group,
Bonamide group, sulfonamide group, nitro group, alkyl
In addition to a thio group and an arylthio group, the following general formula (c)
And the group represented by General formula (c)

[0013]

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In the formula (c), Y _c is -CO-, -SO
_2- , -P (O) (R _c3 )-(where R _c3 is an alkoxy group,
Or an aryloxy group. ) Or -OP
(O) (R _c3 )-, wherein L is a single bond, -O-, -S-
Or -NR _c4- (wherein R _c4 is a hydrogen atom, an alkyl group,
Represents an aryl group. ). R _c1 and R _c2 represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group,
They may be the same or different, and may combine with each other to form a ring. R ¹ may include one or more of the general formula (c).

In the general formula (c), the aliphatic group represented by R _c1 is a linear, branched or cyclic alkyl, alkenyl or alkynyl group. The aromatic group represented by R _c1 is a monocyclic or bicyclic aryl group, such as a phenyl group and a naphthyl group. The hetero ring of R _c1 is a 3- to 10-membered saturated or unsaturated hetero ring containing at least one of N, O, and S atoms, which may be a single ring, or other ring. A condensed ring may be formed with an aromatic or hetero ring. The heterocycle is preferably a 5- or 6-membered aromatic heterocyclic group, and includes, for example, a pyridine group, an imidazolyl group, a quinolinyl group, a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, an isoquinolinyl group, a thiazolyl group, and a benzothiazolyl group. Are preferred. R _c1 may be substituted with a substituent. Examples of the substituent include the following. These groups may be further substituted. For example, an alkyl group, an aralkyl group, an alkenyl group,
Alkynyl, alkoxy, aryl, substituted amino, acylamino, sulfonylamino, ureido, urethane, aryloxy, sulfamoyl, carbamoyl, alkylthio, arylthio, sulfonyl, sulfinyl, hydroxy , Halogen atom, cyano group, sulfo group or carboxyl group, alkyl and aryloxycarbonyl group, acyl group,
Examples thereof include an alkoxycarbonyl group, an acyloxy group, a carbonamido group, a sulfonamido group, a nitro group, an alkylthio group, and an arylthio group. When possible, these groups may be linked to each other to form a ring.

The aliphatic group represented by R _c2 in the general formula (c) is a linear, branched or cyclic alkyl, alkenyl or alkynyl group. The aromatic group represented by R _c2 is a monocyclic or bicyclic aryl group, such as a phenyl group. R _c2 may be substituted with a substituent. Examples of the substituent include those listed as R _c1 and the substituent in the general formula (c). R _c1 and R _c2 may be linked to each other to form a ring, if possible. R _c2 is more preferably a hydrogen atom.
In formula (c), Y _c represents —CO— or —SO ₂
Is particularly preferred, and L is preferably a single bond or -NR _c4- .

The aliphatic group represented by R _c4 in formula (c) is a linear, branched or cyclic alkyl, alkenyl or alkynyl group. The aromatic group represented by R _c4 is a monocyclic or bicyclic aryl group, such as a phenyl group. R _c4 may be substituted with a substituent. Examples of the substituent include those listed as the substituent of R _c1 in the general formula (c). R
_c4 is more preferably a hydrogen atom.

R ^{2 in the} general formula (I) represents a substituted alkyl group in which a carbon atom substituted by G is substituted with at least one electron-withdrawing group, preferably two electron-withdrawing groups, particularly preferably Represents a substituted alkyl group substituted by three electron withdrawing groups. The electron withdrawing group for substituting the carbon atom substituted with G of R ² preferably has a σ _p value of 0.2 or more,
σ _m value of 0.3 or more, for example, halogen, cyano, nitro, nitrosopolyhaloalkyl, polyhaloaryl, alkyl or arylcarbonyl group, formyl group, alkyl or aryloxycarbonyl group,
Alkylcarbonyloxy group, carbamoyl group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, alkyl or arylsulfonyloxy group, sulfamoyl group, phosphino group, phosphine oxide group, phosphonate ester group, phosphonamide group, arylazo group, It represents an amidino group, an ammonio group, a sulfonio group, or an electron-deficient heterocyclic group. R ^{2 in the} general formula (I) particularly preferably represents a trifluoromethyl group.

R ¹ and R ^{2 in} the general formula (I) may have a ballast group or polymer commonly used in immobile photographic additives such as couplers incorporated therein. The ballast group is a group having a carbon number of 8 or more, which is relatively inert to photographic properties. For example, the ballast group is selected from an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group. Can be. Further, as a polymer, for example,
No. 0. R ^{1 of} the general formula (I),
R ² may have a group in which a group that enhances adsorption to the surface of silver halide grains is incorporated. Examples of such adsorptive groups include thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, and triazole groups.
Nos. 5,108 and 4,459,347;
195,233, 59-200,231, 59
-201,045, 59-201,046, 5
Nos. 9-201,047, 59-201,048, 59-201,049, 61-170,733,
Nos. 61-270,744, 62-948, 63
-234,244, 63-234,245, 6
The groups described in 3-234,246 are mentioned. The compounds used in the present invention are listed below, but the present invention is not limited thereto.

[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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The compound used in the present invention is preferably a hydrazine derivative of the present invention, in which the corresponding hydrazine is reacted with a corresponding carboxylic acid in the presence of a condensing agent such as dicyclohexylcarbodiimide, or an acid halide such as sulfonyl chloride or acyl chloride. Alternatively, it was synthesized by reacting with an acid anhydride, an active ester or the like. When the EWG is R ₃ SO ₂ —, a method of reacting the corresponding haloacetylhydrazide derivative with R ₃ SO ₂ H in the presence of a base was also used. Specific examples are shown below.

Synthesis Example: Synthesis of Exemplified Compound 16 Under a nitrogen atmosphere, triethylamine (15.3 ml) was added to a mixed solution of the starting compound A (63.2 g) and tetrahydrofuran (200 ml), and the mixed solution was cooled to 5 ° C. ,
Trifluoroacetic anhydride (16.9 ml) was added and stirred at room temperature overnight. The reaction solution was poured into 0.1N HCl aqueous solution, extracted with ethyl acetate, and the organic layer was washed with saturated saline. It was dried over anhydrous magnesium sulfate, ethyl acetate was distilled off, and the residue was isolated and purified by silica gel chromatography to obtain the desired product (52.1 g). The structure of the compound was confirmed by an nmr spectrum and an ir spectrum. The structure of the starting compound A is shown below.

[0031]

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The compound of the formula (I) of the present invention may be added in an amount of 1 × 10 ^-6 to 5 × per mol of silver halide.
It is preferably contained in an amount of 10 ⁻² mol, and particularly preferably in the range of 1 × 10 ⁻⁵ mol to 2 × 10 ⁻² mol.

The compounds of the general formula (I) according to the present invention can be used in suitable water-miscible organic solvents such as alcohols (methanol, ethanol, propanol, fluorinated alcohols), ketones (acetone, methyl ethyl ketone), dimethylformamide, It can be used by dissolving it in dimethyl sulfoxide, methyl cellosolve or the like. Also, by well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate,
It can also be dissolved using an auxiliary solvent such as ethyl acetate or cyclohexanone to mechanically prepare and use an emulsified dispersion. Alternatively, by a method known as a solid dispersion method, the powder of the redox compound is ball milled in water,
A colloid mill or a dispersion using an ultrasonic wave can be used.

Next, the general formulas (II) to (IV) will be described in detail.
In general formulas (II), (III) and (IV), the alkyl group, aryl group, heterocyclic group, aromatic ring and heterocyclic ring represented by Z and Y may be substituted. As the substituent,
Examples thereof include a lower alkyl group such as a methyl group and an ethyl group, an aryl group such as a phenyl group, an alkoxy group having 1 to 8 carbon atoms, a halogen atom such as chlorine, a nitro group, an amino group, and a carboxyl group. Examples of the hetero ring represented by Z and Y include thiazole, benzthiazole, imidazole, benzimidazole, oxazole ring and the like. The metal atom represented by M is preferably an alkali metal atom such as a sodium ion or a potassium ion, and the organic cation is preferably an ammonium ion or a guanidine group. General formula (II), (III)
Or, specific examples of the compound represented by (IV) include the following, but are not limited thereto.

[0035]

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[0036]

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The halogen composition of the silver halide emulsion used in the present invention is not particularly limited, but the silver chloride content is 50 mol% or more, and either silver chlorobromide or silver iodochlorobromide is preferred. The silver iodide content is 3 mol% or less, more preferably,
0.5 mol% or less. Various methods known in the field of silver halide photographic materials are used for preparing the monodispersed silver halide emulsion used in the present invention. For example,
"Simmy &Physik" by P. Glafkides
Photographic (Chimie et PhysiquePhotographiq
ue) "(Paul Montel, 1967)
GFDuffin, Photographic Emulsion Chemistry (Photog)
raphic Emulsion Chemistry) (The Focal Press), 1966)
VLZelikman et al.
Making and Coating Photographic Emulsion "
(The Focal Press, 196
4 years).

The silver halide emulsion in the present invention is preferably a monodispersed emulsion, and has a coefficient of variation of 20% or less, particularly preferably 15% or less. Here, the variation coefficient (%) is a value obtained by dividing the standard deviation of the particle diameter by the average value of the particle diameter and multiplying the result by 100.
The average grain size of the grains in the monodispersed silver halide emulsion is 0.5 μm or less, particularly preferably 0.1 μm to
0.4 μm.

As a method of reacting a water-soluble silver salt (aqueous silver nitrate solution) with a water-soluble halogen salt, any one of a one-side mixing method, a simultaneous mixing method, and a combination thereof may be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a control double jet method can be used. Further, it is preferable to form grains using a so-called silver halide solvent such as ammonia, thioether, or tetra-substituted thiourea. More preferred are tetrasubstituted thiourea compounds, which are described in JP-A-53-82408 and JP-A-55-77737. Preferred thiourea compounds are tetramethylthiourea and 1,3-dimethyl-2-imidazolidinthione. In the control double jet method and the grain formation method using a silver halide solvent, it is easy to produce a silver halide emulsion having a regular crystal form and a narrow grain size distribution. It is a useful tool. The monodispersed emulsion preferably has a regular crystal form such as a cubic, octahedral, or tetradecahedral, and particularly preferably a cubic. In the silver halide grains, the inside and the surface layer may be composed of a uniform phase or may be composed of different phases.

The monodispersed emulsion of the present invention is preferably subjected to chemical sensitization, and known methods such as sulfur sensitization, reduction sensitization, and gold sensitization can be used, and these can be used alone or in combination. A preferred chemical sensitization method is gold sulfur sensitization. As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines and the like can be used in addition to the sulfur compounds contained in gelatin. Specific examples are described in U.S. Pat.
No. 78,947, No. 2,410,689, No. 2,72
8,668, 3,501,313, 3,65
No. 6,955. Preferred sulfur compounds are thiosulfates and thiourea compounds, and the pAg at the time of chemical sensitization is preferably 8.3 or less, more preferably 7.3 to 8.0. Moisar, Kl
ein Gelatine. Proc. Syme. 2nd, 301-309 (197
0) et al. Also use polyvinylpyrrolidone and thiosulfate in combination to give good results. Among the noble metal sensitization methods, the gold sensitization method is a typical one and uses a gold compound, mainly a gold complex salt. Precious metals other than gold,
For example, complex salts such as platinum, palladium, and iridium may be contained. A specific example is described in U.S. Pat. No. 2,448,
060, British Patent 618,061 and the like. As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines and the like can be used in addition to the sulfur compounds contained in gelatin. Stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used as the reduction sensitizer.

As the selenium sensitizer used in the present invention, selenium compounds disclosed in conventionally known patents can be used. That is, usually, an unstable selenium compound and / or a non-unstable selenium compound is added,
It is used by stirring the emulsion at a high temperature, preferably at 40 ° C. or higher for a certain period of time. Unstable selenium compounds include JP-B-44-15748 and JP-B-43-13489.
No., Japanese Patent Application No. 2-130976, Japanese Patent Application No. 2-2930
It is preferable to use the compounds described in No. 0 or the like. Specific examples of unstable selenium sensitizers include isoselenocyanates (eg, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenoamides, and selenocarboxylic acids (for example,
2-selenopropionic acid, 2-selenobutyric acid), selenoesters, diacylselenides (eg, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, colloidal metal selenium And so on. Although the preferred types of unstable selenium compounds have been described above, they are not intended to be limiting. Skilled artisans say that an unstable selenium compound as a sensitizer for a photographic emulsion is not very important as long as selenium is unstable,
It is generally understood that the organic portion of the selenium sensitizer molecule carries selenium and has no role other than to make it present in the emulsion in an unstable form. In the present invention, an unstable selenium compound having such a broad concept is advantageously used. Non-labile selenium compounds used in the present invention include JP-B-46-4553 and JP-B-52-344.
No. 92 and Japanese Patent Publication No. 52-34491 are used. Examples of the non-labile selenium compound include selenous acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenide, diaryl diselenide, dialkyl selenide, dialkyl diselenide, 2-selenazolidinedione, 2-selenooxazolidinethione and derivatives thereof.

As the tellurium sensitizer used in the present invention, US Pat. Nos. 1,623,499 and 3,320,
Nos. 069 and 3,772,031, British Patent No. 23
Nos. 5,211, 1,121,496 and 1,29
No. 5,462, No. 1,396,696, Canadian Patent No. 800,958, Journal of Chemical Society Chemical Communication (J. Chem.
Soc. Chem. Commun.) 635 (1980), ibid 11.
02 (1979), ibid 645 (1979), Journal of Chemical Society Perkin Trans. (J. Chem. Soc. Perkin Trans.) 1,2
191 (1980) and the like. Specific examples of tellurium sensitizers include colloidal tellurium and telluroureas (eg, allyl tellurourea, N, N
-Dimethyltellurourea, tetramethyltellurourea, N-
Carboxyethyl-N ′, N′-dimethyltellurourea,
N, N'-dimethylethylene tellurourea, N, N'-diphenylethylene tellurourea), isotellurocyanates (e.g. allyl isotellurocyanate), telluroketones (e.g. telluroacetone, telluroacetophenone), telluramides (e.g. telluroacetamide) ,
N, N-dimethyltellurobenzamide), tellurohydrazide (e.g., N, N ', N'-trimethyltellurobenzhydrazide), telluroester (e.g., t-butyl-t)
-Hexyl telluride esters), phosphine tellurides (e.g. tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), other tellurium compounds (e.g. UK) Patent No. 1,295,462, negatively charged telluride ion-containing gelatin, potassium telluride, potassium tellurocyanate, sodium telluropentathionate, allyl tellurocyanate) and the like.

The emulsion of the present invention preferably contains a transition metal complex selected from the elements of Groups V to VIII of the periodic table. A preferred transition metal coordination complex is a hexacoordination complex represented by the following general formula. [ML ₆ ] ^m (where M is a transition metal selected from the elements of Groups V to VIII of the Periodic Table of the Elements, and L is a bridging ligand. M =
0, -1, -2, and -3. Preferred bridging ligands are nitrosyl and thionitrosyl,
Halide ligands (fluoride, chloride, bromide and iodide), cyanide ligand, cyanate ligand, thiocyanate ligand, selenocyanate ligand, tellurocyanate ligand, azide ligand And aquo ligands. If an aquo ligand is present, it preferably occupies one or two of the ligands. Particularly preferred examples of M are rhodium, ruthenium, rhenium, osmium,
Iridium.

As the binder or protective colloid of the photographic emulsion, gelatin is advantageously used, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, albumin, protein hydroxyethylcellulose such as casein, carboxymethylcellulose, cellulose derivatives such as cellulose sulfates, sodium alginate, sugar derivatives such as starch derivatives, polyvinyl alcohol, Polyvinyl alcohol partial acetal, poly-N
-Various kinds of synthetic hydrophilic high-molecular substances such as homo- or copolymers such as vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole can be used.

In order to obtain ultra-high-contrast, high-sensitivity photographic characteristics using the silver halide light-sensitive material of the present invention, a conventional infectious developer or a pH 13 described in US Pat. No. 2,419,975 can be used.
It is not necessary to use a highly alkaline developer close to the above, and a stable developer can be used. That is, the silver halide light-sensitive material of the present invention contains 0.1% of sulfite ion as a preservative.
With a developer containing 15 mol / l or more and having a pH of 9.6 to 11.0, a negative image having a sufficiently high contrast can be obtained. The developing agent used in the developing solution used in the present invention is not particularly limited, but preferably contains dihydroxybenzenes in that good halftone dot quality can be easily obtained. Combinations of pyrazolidones or combinations of dihydroxybenzenes and p-aminophenols may be used. As the dihydroxybenzene developing agent used in the present invention, hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone,
2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,
Although there is 5-dimethylhydroquinone and the like, hydroquinone is particularly preferable. 1-phenyl-3- used in the present invention
Examples of the developing agents of pyrazolidone or a derivative thereof include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-4-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, Phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1
-P-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4,4-dimethyl-3-pyrazolidone and the like. Examples of the p-aminophenol-based developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, and N- (4-hydroxyphenyl) glycine. , 2-methyl-p-aminophenol and p-benzylaminophenol, among which N-methyl-p-aminophenol is preferred. The developing agent is preferably used in an amount of usually 0.05 mol / l to 0.8 mol / l. Dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p
When the combination with amino-phenols is used, the former is 0.05 mol / l to 0.5 mol / l,
The latter is preferably used in an amount of 0.06 mol / l or less.

The sulfite preservatives used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite,
Examples include ammonium sulfite, sodium bisulfite, potassium metabisulfite, and sodium formaldehyde bisulfite. The sulfite is preferably at least 0.15 mol / l, particularly preferably at least 0.3 mol / l. The upper limit is 2.
Preferably it is up to 5 mol / l. The alkaline agent used for setting the pH includes a pH adjuster or a buffer such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate and potassium triphosphate. The pH of the developer is set between 9.6 and 11.0. Additives other than the above-mentioned components include compounds such as boric acid and borax, and development inhibitors such as sodium bromide, potassium bromide and potassium iodide: ethylene glycol, diethylene glycol, toluethylene glycol, dimethylformamide, methyl cellosolve , Organic solvents such as hexylene glycol, ethanol and methanol: 1-phenyl-5-mercaptotetrazole, 5-
An antifoggant or a black pepper inhibitor such as an indazole compound such as nitroindazole, a benzotriazole compound such as 5-methylbenztriazole, and a color tone agent and a surfactant, if necessary. , Defoamer, water softener, hardener, JP-A-56-10
It may contain an amino compound described in No. 6244 and the like.

In the developing solution of the present invention, compounds described in JP-A-56-24347 can be used as silver stain inhibitors. Japanese Patent Application No. Sho 6 as a dissolution aid added to the developer
Compounds described in No. 0-109,743 can be used. Further, as a pH buffering agent used for a developer,
Compounds described in Japanese Patent Application No. 0-93,433 or Japanese Patent Application No.
The compounds described in -28708 can be used.
As the fixing agent, those having a commonly used composition can be used. As a fixing agent, thiosulfates and thiocyanates, and organic sulfur compounds known to have an effect as a fixing agent can be used. The fixing solution may contain water-soluble aluminum (for example, aluminum sulfate, bright bun, etc.) as a hardener. Here, the amount of the water-soluble aluminum salt is usually 0.4 to 2.0 g-Al / liter. Further, a trivalent iron compound can be used as an oxidizing agent as a complex with ethylenediaminetetraacetic acid. The development temperature is usually selected between 18 ° C and 50 ° C, but is more preferably 25 ° C to 43 ° C.

The various additives used in the light-sensitive material of the present invention are not particularly limited, and for example, those described in the following places can be preferably used. Item 1) Nuclear nucleation accelerators From page 13, upper right column, line 13 to page 16, upper left column, line 10 of JP-A-2-103536, the general formulas (II-m) to (II-p) ) And Compound Examples II-1 to II-22 and compounds described in JP-A-1-179939. 2) Spectral sensitizing dye JP-A-2-12236, page 8, lower left column, line 13 to lower right column, line 4, JP-A-2-103536, page 16, lower right column, line 3 to page 17, lower left Column 20, line 20. Further, spectral sensitizing dyes described in JP-A-1-112235, JP-A-2-124560, JP-A-3-7928, Japanese Patent Application Nos. 3-189532 and 3-411046. 3) Surfactant JP-A-2-12236, page 9, upper right column, line 7 to lower right column, line 7, and JP-A-2-18542, page 2, lower left column, line 13 to line 4 Line 18 in the lower right column of the page. 4) Antifoggants JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5, and JP-A 1-237538. Thiosulfinic acid compounds described in the official bulletin. 5) Polymer latex: JP-A-2-103536, page 18, lower left column, lines 12 to 20. 6) Compound having an acid group From page 6, lower right column, line 6 to page 19, upper left column, line 1 of JP-A-2-103536. 7) Matting agent, slip agent, JP-A-2-103536, page 19, upper left column, 15 plasticizer line to page 19, upper right column, 15th line. 8) Hardener From page 5, right upper column, line 5 to line 17, JP-A-2-103536. 9) Dyes Dyes on page 17, right lower column, lines 1 to 18 of JP-A-2-103536, solid dyes described in JP-A-2-29438 and JP-A-3-185773. 10) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 20. 11) Black spot inhibitors Compounds described in U.S. Pat. No. 4,956,257 and JP-A-1-118832. 12) Redox compound A compound represented by the general formula (I) of JP-A-2-301743 (especially, compound examples 1 to 50), and a compound represented by the general formula (3) of JP-A-3-174143, pp. 3 to 20: (R-1), (R-2), (R-3), compounds described in Compound Examples 1 to 75, and further described in Japanese Patent Application Nos. 3-69466 and 3-15648. 13) Monomethine compounds Compounds of the general formula (II) described in JP-A-2-287532 (especially compound examples II-1 to II-26). 14) Dihydroxybenze Compounds described in JP-A-3-39948, from page 11, upper left column to class II, page 12, lower left column, and EP 452772A.

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

[0050]

EXAMPLES Example 1 Emulsion A was prepared by the following method. Emulsion A: a silver nitrate solution of 0.13M, K ₃ RhCl ₆ and 2 × K ₃ corresponding to 10 ^-7 mol equivalent to 1 mol of silver per 1 × 10 ^-7 mol
0.04M potassium bromide containing IrCl ₆ and 0.09M
An aqueous solution of a halogen salt containing sodium chloride of M is added to an aqueous solution of gelatin containing sodium chloride and 1,3-dimethyl-2-imidazolidinethione at 38 ° C. while stirring.
For 12 minutes by a double jet method to obtain silver chlorobromide grains having an average grain size of 0.15 μm and a silver chloride content of 70 mol%, thereby forming nuclei. Subsequently, similarly, a 0.87 M silver nitrate aqueous solution, a 0.26 M potassium bromide solution, and a 0.65 M sodium chloride aqueous solution containing sodium chloride were added by a double jet method over 20 minutes. Thereafter, a KI solution of 1 × 10 ⁻³ mol was added to perform conversion, washed with water by a flocculation method according to a conventional method, 40 g of gelatin was added, and pH 6.5 and pAg were added.
The mixture was adjusted to 7.5, and 5 mg of sodium thiosulfate and 8 mg of chloroauric acid were added per 1 mol of silver, and the mixture was heated at 60 ° C. for 60 minutes, subjected to a chemical sensitization treatment, and treated with 6-methyl- as a stabilizer.
150 mg of 4-hydroxy-1,3,3a, 7-tetrazaindene were added. The obtained particles have an average particle size of 0.1.
The particles were silver chlorobromide cubic grains having a particle size of 27 μm and a silver chloride content of 70 mol%. (Coefficient of variation 10%).

Emulsion A was divided and used as a sensitizing dye at 1 × 10 ^-3 mol of 5-{[3- (4-sulfobutyl) -5-chloro-2-benzooxazolidylidene] ethylidene} per mol of silver. -1-hydroxyethoxyethyl-3- (2
-Pyridyl) -2-thiohydantoin K ⁺ salt, and 2 × 10 ⁻⁴ mol of 1-phenyl-5-mercaptotetrazole, 5 × 10 ⁻⁴ mol of short-wave cyanine dye represented by the following structural formula (a) , (b) a water-soluble latex represented by (200mg / m ²⁾ and a dispersion of polyethyl acrylate (200mg / m ²⁾ as a hardener 1,3-vinylsulfonyl-2-propanol (200mg / m ^2),
As a nucleation accelerator, an amine compound (20 mg / m ² ) represented by the following structural formula (c), a hydrazine compound of the present invention, comparative compounds A and B, and compounds of general formulas (II) to (IV) of the present invention were used. It was added as shown in Table 1.

[0052]

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[0053]

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[0054]

[Table 1]

Further, as a protective layer, gelatin 1.0 g /
m ^2, atypical of SiO ₂ matting agent 40 mg / m ² of particle size of about 3.5 [mu], methanol silica 0.1 g / m ^2, polyacrylamides 100 mg / m ^2, hydroquinone 200 mg / m ²
And a silicone oil (20 mg / m ² ) and a fluorine surfactant (5 mg / m ² ) represented by the following structural formula as a coating aid

[0056]

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And a layer containing sodium dodecylbenzenesulfonate (100 mg / m ² ) were simultaneously applied to prepare samples as shown in Table 1. Table 2 shows the evaluation results. The back layer and the back layer protective layer were applied according to the following formulation.

[Back Layer Formulation] Gelatin 3 g / m ² Latex Polyethyl acrylate 2 g / m ² Surfactant Sodium p-dodecylbenzenesulfonate 40 mg / m ² SnO ₂ / Sb (9/1 weight ratio, average particle size 0) .20 μm) 190 mg / m ²

[0059]

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Dye Mixture of dyes [a], [b] and [c] Dye [a] 50 mg / m ² Dye [b] 100 mg / m ² Dye [c] 50 mg / m ²

[0061]

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[Back protective layer] Gelatin 0.8 mg / m ² polymethyl methacrylate fine particles (average particle size 4.5 μ) 30 mg / m ² dihexyl-α-sulfosuccinate sodium salt 15 mg / m ² dodecylbenzenesulfonic acid sodium salt 15 mg / m ² sodium acetate 40 mg / m ²

[0063]

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(Evaluation of Photographic Properties 1) Photographic properties were measured using a developer 1 of the following formulation using an FG-460A automatic developing machine (manufactured by Fuji Photo Film Co., Ltd.) to sample a sample with tungsten light at 3200 ° K. 38 ° C 30 after exposure through
Developed for 2 seconds, fixed, washed with water and dried. As the fixer,
GR-F1 manufactured by Fuji Photo Film Co., Ltd. was used.

Developer 1 Hydroquinone 30.0 g N-methyl-p-aminophenol 0.3 Sodium hydroxide 10.0 Potassium sulfite 60.0 Diethylenetriaminepentaacetic acid 1.0 Potassium bromide 10.0 5-Methylbenzotriazole 0 0.4 2-Mercaptobenzimidazole-5-sulfonate 0.3 Sodium 3- (5-mercaptotetrazole) benzenesulfonate 0.2 Sodium toluenesulfonate 8.0 Add water to adjust to 1 liter pH 10.6

(Evaluation of aging property)
After humidifying for 2 hours in an atmosphere of H, heat sealing was performed under the same conditions, and the resultant was left at 50 ° C. for 10 days. Here, the sensitivity was a relative value of a reciprocal of an exposure amount giving a density of 1.5 in development at 34 ° C. for 30 seconds, and the value of Sample 1 was 100. Where γ is represented by the following equation

[0067]

(Equation 1)

Is defined. Black pots were obtained by observing the invisible portion developed at 34 ° C. for 30 seconds by microscopic observation on a 5-point scale. “5” represents the best quality and “1” represents the worst quality. "5" or "4" is practical and "3" is bad, but practically available, "2" or "1" is practically impossible. Those intermediate between "4" and "3" were rated "3.5". As is evident from Table 1, the sample of the present invention is sufficiently hardened even at a low pH, and has a small variation with time and is excellent.

Example 2 Emulsions BF were prepared in the following manner. Emulsion B: 0.13
M silver nitrate aqueous solution, and 0.052 M potassium bromide containing 1 × 10 ⁻⁷ mol of K ₂ Rh (NO) Cl ₅ and 2 × 10 ⁻⁷ mol of K ₃ IrCl ₆ per mol of silver And a halogen salt aqueous solution containing 0.078 M sodium chloride, sodium chloride, 1,3-dimethyl-2
-In an aqueous gelatin solution containing imidazolidinethione,
While stirring, the mixture was added by a double jet method at 45 ° C. for 12 minutes to give an average particle size of 0.15 μm and a silver chloride content of
Nucleation was performed by obtaining 0 mol% of silver chlorobromide grains. Subsequently, a 0.87M aqueous silver nitrate solution and a 0.1.
An aqueous solution of a halogen salt containing 34 M of potassium bromide and 0.52 M of sodium chloride was applied to
Added over 0 minutes. Thereafter, 1 × 10 ⁻³ mol of a KI solution was added to perform conversion, washed with water by a flocculation method according to a conventional method, and 40 g of gelatin was added.
The pH was adjusted to 6.5 and the pAg to 7.5, and 5 mg of sodium thiosulfate and 8 mg of chloroauric acid were added per mole of silver.
The mixture was heated at 60 ° C. for 60 minutes, subjected to a chemical sensitization treatment, and used as a stabilizer, 4-hydroxy-6-methyl-1,3,3a, 7.
-150 mg of tetrazaindene were added. The obtained grains were cubic silver chlorobromide grains having an average grain size of 0.27 μm and a silver chloride content of 60 mol%. (Coefficient of variation 10%).

Emulsion C: 0.13 M aqueous silver nitrate solution and K ₃ RhCl ₆ equivalent to 1 × 10 ⁻⁷ mol per mol of silver
And an aqueous solution of a halogen salt containing 0.078 M of potassium bromide and 0.052 M of sodium chloride containing K ₃ IrCl ₆ corresponding to 2 × 10 ⁻⁷ mol and a gelatin solution containing sodium chloride with stirring. 12 at 45 ° C
The mixture was added by a double jet method for 1 minute to obtain silver chlorobromide particles having an average particle size of 0.15 μm and a silver chloride content of 70 mol%, thereby forming nuclei. Subsequently, 0.
A silver salt aqueous solution containing 87M silver nitrate aqueous solution, 0.522M potassium bromide and 0.348M sodium chloride was added over 20 minutes by a double jet method. Thereafter, a KI solution of 1 × 10 ⁻³ mol was added to perform conversion, washed with water by a flocculation method according to a conventional method, 40 g of gelatin was added, and pH 6.5 and pAg were added.
The mixture was adjusted to 7.5, and 5 mg of sodium thiosulfate and 8 mg of chloroauric acid per 1 mol of silver were added. The mixture was heated at 60 ° C. for 60 minutes, subjected to a chemical sensitization treatment, and 4-hydroxy-6-methyl- as a stabilizer. 150 mg of 1,3,3a, 7-tetrazaindene were added. The obtained particles have an average particle size of 0.1.
The particles were silver chlorobromide cubic grains having a particle size of 27 μm and a silver chloride content of 40 mol%. (Coefficient of variation 11%).

(Emulsion D) Grain formation was carried out in exactly the same manner as in Emulsion A, followed by conversion by adding a 1 × 10 ^-3 mol KI solution and washing with flocculation according to a conventional method. In addition, pH5.
5, pAg 7.5, 3 mg of sodium thiosulfate per mole of silver, and 1.5 g of N, N-dimethylselenourea.
0 mg and 8 mg of chloroauric acid were added, and the mixture was heated at 60 ° C. for 60 minutes, subjected to a chemical sensitization treatment, and treated with 6-methyl-4 as a stabilizer.
-Hydroxy-1,3,3a, 7-tetrazaindene 1
50 mg was added. The resulting particles have an average particle size of 0.2
The particles were cubic silver chlorobromide particles having a particle size of 7 μm and a silver chloride content of 70 mol%. (Coefficient of variation 10%). Was prepared (Emulsion E) N in the emulsions D, N-addition of dimethylselenourea _{1.0mg ((i) C 3 H} 7) 3 P = Te3mg Emulsion E by exactly the same method except for changing the addition of .

Emulsion F: 1 mol of an aqueous silver nitrate solution in the presence of 1,8-dihydroxy-3,6-dithiaoctane in an aqueous gelatin solution kept at 50 ° C. and 1.2 × 10 5 per mol of silver
^An aqueous solution of potassium iodide and potassium bromide containing ^-7 mol of K ₃ RhCl ₆ was simultaneously added over 60 minutes, and the pAg was maintained at 7.8 during that period to maintain an average particle size of 0.25 μm and an average silver iodide content of 1 mol. % Of a cubic monodispersed emulsion, desalted by flocculation, added with 40 g of gelatin, adjusted to pH = 6.0 pAg = 8.5, added with 5 mg of sodium thiosulfate and 6 mg of chloroauric acid, and added at 60 ° C. The mixture was heated for 60 minutes, subjected to a chemical sensitization treatment, and 150 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added as a stabilizer. (Coefficient of variation 9%) Emulsions A to F are summarized in Table 2.

[0073]

[Table 2]

Emulsions A to F were divided and silver 1 was used as a sensitizing dye.
1 × 10 ^-3 mole of 5-{[3- (4-sulfobutyl) -5-chloro-2-benzooxazolidylidene] per mole
[Ethylidene] -1-hydroxyethoxyethyl-3-
(2-pyridyl) -2-thiohydantoin K ⁺ salt was added, and 2 × 10 ⁻⁴ mol of 1-phenyl-5-mercaptotetrazole, 5 × 10 ⁻⁵ mol of sodium salt of ethylthiosulfonic acid of the present invention, 5 × 10 ^-4 mol of a short-wave cyanine dye represented by the following structural formula (a), a water-soluble latex represented by (b) (20 mg / m ² ) and a dispersion of polyethyl acrylate (200 mg / m ² ) 1,3-divinylsulfonyl-2-propanol (20
0 mg / m ² ), hydrazine compound of the present invention and Example 1
Comparative Compound A used in Table 2 was added as shown in Table 2. Protective layer,
The back layer and the back protective layer were coated in the same manner as in Example 1. Table 3 shows the evaluation results.

(Evaluation of Photographic Property 2) Each of the 100% blackened samples was processed in the same manner as in Photographic Property 1 after 30 sheets were processed without replenishment in terms of Daizen. Table 3
As is clear, the sample of the present invention has a sufficiently high contrast even in a developing solution having a pH of 11 or less, and has a small change in performance even in a case where a large amount of film is processed. On the other hand, in the present invention, samples using emulsions A and B having a silver chloride content of 50 mol% or more and emulsions D and E sensitized with selenium or tellurium showed particularly good results.

[0076]

[Table 3]

Continuation of the front page (56) References JP-A-1-237538 (JP, A) JP-A-62-235939 (JP, A) JP-A-4-76530 (JP, A) JP-A-3-236044 (JP, A) JP-A-3-237450 (JP, A) JP-A-4-204640 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03C 1/06 501 G03C 1/09 G03C 1/34 G03C 5/29 501

Claims (4)

(57) [Claims] In a silver halide photographic material having at least one silver halide emulsion layer on a support, the emulsion layer and / or another hydrophilic colloid layer may be represented by the following formula (I): At least one derivative
And a compound containing at least one compound represented by formula (II), (III) or (IV). General formula (I) R ¹ represents an aliphatic group, an aromatic group or a heterocyclic group, and may be substituted. G represents a -CO- group, R ² represents a substituted alkyl group in which the carbon atom substituted by G is substituted with at least one electron withdrawing group. R ⁴ represents a hydrogen atom, an aliphatic group, an aromatic group, an alkoxy group, an aryloxy group or an amino group. Embedded image Z is an alkyl group (1 to 18 carbon atoms), an aryl group (6 to 18 carbon atoms), or a heterocyclic group, and Y is an aromatic ring (6 carbon atoms).
-18) or an atom necessary to form a heterocyclic ring. M represents a metal atom or an organic cation, and n represents an integer of 2 to 10. 2. The silver halide photographic material according to claim 1, wherein the silver halide in the emulsion layer is a silver halide having a silver chloride content of 50 mol% or more. 3. The silver halide photographic material according to claim 1, wherein the silver halide in the emulsion layer is chemically sensitized with a selenium and / or tellurium compound. 4. An image forming method, wherein the silver halide photographic light-sensitive material according to claim 1 is developed using a developer having a pH of 9.6 or more and less than 11.0.