JPH11194441A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance rapid processing and processing stability by incorporating a specified compound in an emulsion layer or another hydrophilic colloidal layer. SOLUTION: The emulsion layer or another hydrophilic colloidal layer contains at least one of the compounds represented by formula I in which M<+> is a cationic 5-membered hetero ring consisting of C, N, O, S, and Se atoms; A1 * is O* or S* or N-R; R is an aliphatic or aromatic or heterocyclic group; L1 is a divalent bonding group; (m) 0 or 1; L2 is a divalent aliphatic or aromatic group; G is a carbonyl, sulfonyl, sulfinyl group or the like; R1 is an H atom or an aliphatic or alkoxy group or the like or a group represented by formula II; and in formula II, Q<+> is a group containing a cationic group; and A2 is an anionic group but unnecessary when Q<+> has an anionic group and forms an intramolecular salt.

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 a method for forming an ultra-high contrast negative image using the same, and more particularly to a silver halide photographic light-sensitive material used in a photomechanical process. .

[0002]

2. Description of the Related Art In the field of graphic arts, an image forming system exhibiting photographic characteristics of ultra-high contrast (particularly, gamma of 10 or more) is required in order to improve reproduction of continuous tone images or line images by halftone images. is necessary.
Methods for obtaining high-contrast photographic characteristics using a stable developer are described in U.S. Pat. Nos. 4,166,742, 4,168,977, 4,211,857, and 4,224. No. 4,401, No. 4,311,781,
Nos. 4,272,606 and 4,912,016
No. 4,998,604, JP-A-3-25924
No. 0, JP-A-5-45761, JP-A-7-5610 and the like using a hydrazine derivative are known. According to this method, ultra-high contrast and high-sensitivity photographic characteristics can be obtained, and the addition of a high concentration of sulfite to the developer is allowed. And improve dramatically. However, conventionally known hydrazine compounds have been found to have several disadvantages. In other words, an attempt was made to make the structure of the hydrazine compound diffusion resistant in order to reduce the adverse effect on other photographic light-sensitive materials caused by the hydrazine compound flowing into the developing solution. These diffusion-resistant hydrazine compounds are required in large amounts for sensitization and high contrast, and have the problems of deteriorating the physical strength of the obtained photosensitive layer and causing the hydrazine compound to precipitate in the coating solution. Further, it has been found that when the photosensitive material is processed in a large amount with a fatigued developer, sufficient contrast cannot be obtained. Conventionally, a super-high contrast system using a hydrazine compound requires a developer having a relatively high pH, for example, 11.5 or 11.8, which increases the danger in handling. And high COD. Also, it is necessary to use a large amount of a pH buffer to keep the pH of the developer constant, so that the solid concentration of the developer becomes high, the solution becomes sticky, and the scattered solution is difficult to wipe off. was there. Therefore, development of a hydrazine compound which can be hardened by a developer having a lower pH has been desired. In addition, a returned photographic material generally handled in a light room occupies a large field as one of the photographic materials for plate making. In this field, a high blank character quality which reproduces a thin Mincho character is demanded. Therefore, development of a nucleating agent having higher activity has been desired. In particular, in a low-sensitivity bright room light-sensitive material that can be handled even in a bright room, development of a nucleating agent that is less likely to be hardened by a nucleating agent and has higher activity is desired.

[0003]

SUMMARY OF THE INVENTION It is a first object of the present invention to provide a silver halide photographic light-sensitive material for plate making which has excellent rapid processing and high processing stability. A second object of the present invention is to provide a silver halide photographic material for plate making which can be developed at a lower pH.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photographic material having at least one silver halide emulsion layer on a support, the emulsion layer or another hydrophilic colloid layer. This has been attained by a silver halide photographic material characterized by containing at least one compound represented by the above formula (1).

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The compound represented by the general formula (1) will be described below. M ⁺ represents a cationic 5-membered heterocyclic ring formed by a group consisting of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom and a selenium atom. Examples thereof are, for example, imidazolium, oxazolium, thiazolium, 1,3,4-triazolium, 1,3,4
-Oxadiazolium, 1,3,4-thiadiazolium ring and the like. A ₁ ^- is ^{O -,} S ^{-, N} - represents a -R. R represents an aliphatic group (eg, methyl, ethyl, allyl group, etc.), an aromatic group (eg, phenyl, naphthyl group, etc.), or a heterocyclic group (eg, pyridyl group, etc.). L ₁ represents a divalent linking group. Examples thereof include an alkylene group (eg, methylene, ethylene, propylene group, etc.), an arylene group (eg, phenylene, naphthylene group, etc.),
_{-SO 2 NR 2 -, - NR} 2 SO 2 NR 2 -, - CONR
_{2 -, - CSNR 2 -,} - NR 2 CONR 2 -, - NR 2 C
SNR ₂ —, —G ₁ P (O) (G ₁ R ₂ ) NR ₂ —, and the like, and a plurality of these may be combined.
Here, G ₁ represents a single bond, an —O— group, or an —NR ₂ — group, and R ₂ represents a hydrogen atom, an aliphatic group (synonymous with R), an aromatic group (synonymous with R), a heterocyclic group (R Synonymous with). Preferred examples of R ₂ include a hydrogen atom and an alkyl group having 5 or less carbon atoms, with a hydrogen atom being particularly preferred. m represents 0 or 1. L ₂ represents a divalent aliphatic group or an aromatic group. Among them, an arylene group is preferred, and particularly, p-
Phenylene groups are preferred.

G represents a carbonyl group, a sulfonyl group, a sulfinyl group, an oxalyl group or a phosphoryl group. Among them, preferred are a carbonyl group and an oxalyl group,
Particularly, an oxalyl group is preferable. R ₁ represents a hydrogen atom, an aliphatic group, an alkoxy group, an aryloxy group, an aromatic group, an amino group or the general formula (2). When G is a carbonyl group, preferred among the groups represented by R ₁ are a hydrogen atom, an alkyl group (for example, a methyl group, a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group,
-Hydroxypropyl group, 3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, 2-hydroxybenzyl group, etc., aryl group (for example, phenyl group, 3,5-dichlorophenyl group, 2-methanesulfonamidophenyl group, 4 -A methanesulfonylphenyl group,
2-hydroxymethylphenyl group), general formula (2)
In particular, a hydrogen atom, a difluoromethyl group, a trifluoromethyl group, and a group represented by the following general formula (2) are preferable. When G is an oxalyl group, R ₁
Preferred among the groups represented by are an alkoxy group (for example, a methoxy group, an ethoxy group, and the like), an aryloxy group (for example, a phenoxy group, a 4-chlorophenoxy group, and the like), an amino group, and the like. A substituted amino group substituted with an alkyl group or a heterocyclic group having two hydroxy groups, a tertiary amino group, a basic nitrogen-containing heterocyclic group or the like as a substituent is preferred. Further, a substituted amino group directly substituted with a basic nitrogen-containing heterocyclic group or a group represented by the following general formula (2) is also preferable. Specific examples of these include, for example, a 2-hydroxyethylamino group, a 3-hydroxypropylamino group, a 2,3-dihydroxypropylamino group, a 2-dimethylaminoethylamino group,
-Diethylaminopropylamino group, 2- (2-diethylaminoethylthio) ethylamino group, 2-trimethylammonioethylamino group, 3-triethylammoniopropylamino group, 2-picolylamino group, 3-picolylamino group, 4-pyridylamino Group, (1-methyl-2
-Pyridinio) methylamino group, (1-ethyl-3-pyridinio) amino group and the like.

Next, the general formula (2) will be described. Q ⁺ in the general formula (2) is a group containing a cationic group having at least one quaternary nitrogen atom, and has 1 carbon atom.
It is attached to G through a straight or branched hydrocarbon chain having up to 4 carbon atoms, and part or all of this chain may form part of a heterocyclic ring having a quaternary nitrogen atom. Preferred examples of Q ⁺ include a trialkylammonium alkyl group, a pyridinium-1-ylalkyl group, a 1-alkylpyridinium-2-yl group, a 1-alkylpyridinium-3-yl group, and a 1-alkylpyridinium-4-yl Group, thiazolinium-3-ylalkyl group, oxazolinium-3-ylalkyl group, 1-alkylimidazolium-3-ylalkyl group, 1,3,4-triazoliumthiolate-1-ylalkyl group, and the like. Can be
All the groups mentioned above may be substituted by substituents well known in the art. A ₂ ^- is a counter anion of Q ^+, Cl preferred examples ^-, Br -, ^{p-toluenesulfonate,} although methane sulfonate and the like,
It has an anionic group as a substituent of Q ⁺ and does not exist when it forms an inner salt. Of those mentioned above,
Particularly preferred are compounds represented by the following chemical formula 3.

[0008]

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In the formula, R ₃ represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. R ₄ represents an aliphatic group, an aromatic group, or a heterocyclic group. Preferred as the aliphatic group represented by R ₃ and R ₄ are linear, branched or cyclic alkyl and alkenyl groups having 1 to 30 carbon atoms, and preferred as the aromatic group and the heterocyclic group are simple groups. It is cyclic or bicyclic. Further, the aliphatic group, aromatic group and heterocyclic group represented by R ₃ and R ₄ may be substituted by a substituent well known in the art. Examples of the typical substituent include an alkyl group,
Alkenyl, alkynyl, alkoxy, aryl, aryloxy, sulfamoyl, ureido, urethane, carbamoyl, alkyl or arylthio, alkyl or arylsulfonyl, hydroxy, halogen, cyano, aryloxy Examples include a carbonyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group, an amide group, a sulfonamide group, and a carboxy group. Of those described above, particularly preferred are straight-chain, branched or cyclic alkyl and alkenyl groups having a total carbon number of 15 or less including substituents. n represents 0 or 1. G ₂ has the same meaning as G. R ₅ has the same meaning as R ₁ .

The compounds used in the present invention are listed below, but the present invention is not limited thereto.

[0011]

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[0012]

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[0013]

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[0014]

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The synthesis examples of the present invention are described below. Synthesis of H-2 N-acetyl-N-methylhydrazine 1.76 g, 1-
5.30 g of (4-isothiocyanatophenyl) -2-ethoxalylhydrazine and 20 ml of ethanol were mixed,
Stirred at room temperature for 1 hour. Then in this reaction mixture,
N, N-diethyl-1,3-diaminopropane 2.86
g was added and the mixture was heated under reflux for 4 hours. Then, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel chromatography to obtain 2.3 g of H-2.

The hydrazine derivative of the present invention can be prepared from a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, etc.), ketones (acetone,
Methyl ethyl ketone), N, N-dimethylformamide, dimethyl sulfoxide, methyl cellosolve, etc. Also, by an already well-known emulsification dispersion method, dimethyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl terephthalate, and dissolved using an auxiliary solvent such as ethyl acetate or cyclohexanone, mechanically emulsified dispersion. It can also be created and used. A colloid mill, a ball mill, or a method known as a solid dispersion method using ultrasonic waves can be used.

The silver halide used in the photosensitive silver halide emulsion layer of the light-sensitive material of the present invention is not particularly limited, but a surface latent image type silver halide emulsion is preferred. Silver bromide, silver chloroiodobromide, silver iodobromide, silver bromide and the like can be used. When silver iodobromide or silver chloroiodobromide is used, the content of silver iodide is 5%. It is preferably in the range of mol% or less. The form, crystal habit, size distribution and the like of the silver halide grains are not particularly limited, but the grain size is 0.7
Submicron ones are preferred. The silver halide emulsion is
Rhodium, gold compounds such as chloroaurate, gold trichloride, etc.
Sensitivity can be increased without coarsening particles by a sulfur compound which forms silver sulfide by reacting with a salt or silver salt of a noble metal such as iridium, or a stannous salt or an amine. Further, an iron compound such as a salt of a noble metal such as rhodium or iridium, or a red blood salt may be present during physical ripening or nucleation of silver halide grains. Especially,
Addition of a rhodium salt or a complex salt thereof is preferable because the effect of the present invention of achieving ultra-high contrast photographic characteristics in a short development time is further promoted.

In the present invention, the surface latent image type silver halide emulsion is an emulsion comprising silver halide grains having a surface sensitivity higher than the internal sensitivity. This emulsion is preferably a US Pat. It has a difference between the surface sensitivity and the internal sensitivity defined in the specification of Japanese Patent No. 401. The silver halide emulsion is desirably monodispersed, especially in the above-mentioned U.S. Pat.
Emulsions having the monodispersity specified in JP-A-224,401 are preferred. The silver halide emulsion used in the present invention preferably contains a water-soluble rhodium salt (for example, rhodium dichloride, rhodium trichloride, potassium hexachloride (III), ammonium rhodium (III) hexachloride, etc.). It is preferable to add these rhodium salts before the completion of the first ripening at the time of emulsion production. The addition amount of the rhodium salt is preferably from 1 × 10 ⁻⁷ mol to 1 × 10 ⁻⁴ mol per mol of silver halide. The average grain size of the silver halide used in the present invention is preferably 0.5 μm or less, particularly preferably 0.1 to 0.4 μm. The shape of the silver halide grains may be a regular one such as cubic or octahedral, or a mixed crystal, but it is preferably a so-called monodisperse emulsion having a relatively narrow grain size distribution. The term "monodisperse emulsion" as used herein means an emulsion in which 90%, more preferably 95%, of the total number of grains falls within a grain size range of ± 40% of the average grain size. The method of reacting the soluble silver salt with the soluble halide salt for preparing the silver halide emulsion in the present invention may be any of a single jet method, a double jet method, and a back mixing method of forming under excess silver ions. For the purpose of the present invention, a double jet method in which a soluble silver salt and a soluble halogen salt are simultaneously added in an acidic solution to form grains is particularly preferable. The silver halide emulsion prepared in this manner may or may not be chemically sensitized. From the viewpoint of improving the handleability in a safelight environment, which can be called a bright room, the chemical sensitization is effective. It is rather preferable not to sensitize. In the case of chemical sensitization, usual sulfur sensitization, selenium sensitization, reduction sensitization and the like are used.

In the light-sensitive material of the present invention, the compound represented by the formula (1) is preferably contained in a surface latent image type silver halide emulsion layer, but is adjacent to the surface latent image type silver halide emulsion layer. It may be contained in a hydrophilic colloid layer. Such a layer is not particularly limited as long as it does not prevent the compound represented by the general formula (1) from diffusing into the silver halide grains, such as an undercoat layer, an intermediate layer, a filter layer, a protective layer, and an antihalation layer. It may be a layer having a function. In-layer formation 1
Content varies depending on the characteristics of the silver halide emulsion to be used, the chemical structure of the compound and the development conditions. Therefore, the appropriate content may vary over a wide range, but the silver content in the surface latent image type silver halide emulsion may vary. About 1 × 10 ^-6 to 1 per mole
A range of x10 ^-2 moles is practically useful.

The photographic emulsion used in the present invention may be spectrally sensitized with a methine dye or the like. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are
It is a dye belonging to a cyanine dye, a merocyanine dye, and a complex merocyanine dye. These sensitizing dyes may be used alone or in combination.
Combinations of sensitizing dyes are often used, especially for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosure 176, 17643 (1978).
(Issued December 2013), page 23, IV, section J.

Gelatin is advantageously used as a binder or protective colloid which can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol Polyacetal partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, and various kinds of synthetic hydrophilic polymer materials such as copolymers such as polyvinylimidazole can be used. . As gelatin, in addition to lime-processed gelatin, acid-processed gelatin and Bull.Soc.Sci.Phot.Japan, No.
16, P30 (1966) may be used, and hydrolyzate or enzymatic degradation of gelatin may also be used.

In a method for obtaining a super-high contrast image using a hydrazine compound, a conventional safelight dye is added to an emulsion layer or another hydrophilic colloid layer in order to enable handling in a bright room. Is also good. The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, mercaptotetrazole And many compounds conventionally known as antifoggants or stabilizers such as mercaptopyrimidines, mercaptotriazines, thioketo compounds, and azaindenes. Among these, particularly preferred are benzotriazoles (eg, 5-methylbenzotriazoles) and nitroindazoles (eg, 5-nitroindazole). These compounds may be contained in the processing solution.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers. For example, chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glyoxal, etc.), N-methylol compounds, dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds, active halogen compounds (2,4-dichloro- 6-
Hydroxy-S-triazine, etc.) alone or in combination.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared by using the present invention may contain a coating aid, an antistatic agent, an improvement in slipperiness, an emulsification / dispersion, an adhesion prevention and an improvement in photographic properties (for example, development Surfactants may be included for various purposes such as acceleration, contrast enhancement, and sensitization. For example, saponins (steroids), alkylene oxide derivatives (polyethylene glycol, polyethylene glycol / polypropylene glycol condensate, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl) Amines or amides, silicone polyethylene oxide adducts, etc.), glycidol derivatives (alkenyl succinic polyglycerides,
Alkylphenol polyglycerides), nonionic surfactants such as fatty acid esters of polyhydric alcohols, alkyl esters of sugars, alkyl carboxylate, alkyl sulfate, alkyl benzene sulfonate,
Carboxy group, sulfo group, phospho group, sulfate group, phosphate group such as alkyl phosphates, sulfosuccinates, sulfoalkylpolyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc. Anionic surfactants containing an acidic group such as an amino group, amphoteric surfactants such as amino acids, aminoalkylsulfonic acids, aminoalkylsulfuric acid or phosphate esters, aliphatic or aromatic quaternary ammonium salts, pyridinium, imidazolium And cationic surfactants such as heterocyclic quaternary ammonium salts.

The photographic light-sensitive material used in the present invention may contain a water-insoluble or sparingly soluble synthetic polymer decomposition product in a photographic emulsion layer or other hydrophilic colloid layers for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide,
Vinyl acetate, acrylonitrile, olefins, styrene and the like alone or in combination, or acrylic acid,
A polymer having a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, styrene sulfonic acid and the like as a monomer component can be used.

The light-sensitive material of the present invention may contain an organic desensitizer. Preferred organic desensitizers have at least one water-soluble or alkali-dissociable group. These preferred organic desensitizers are described in U.S. Pat. No. 4,908,293.
No. When an organic desensitizer is used, 1.0 × 10 ^{−8 to} 1.0 × 10 ⁻⁴ mol / mol is added to the silver halide emulsion layer.
m ^2, preferably 1.0 × 10 ^{−7 to} 1.0 × 10 ⁻⁵ mol / m ²
It is appropriate to make it exist.

The light-sensitive material of the present invention may contain a development accelerator. Examples of development accelerators suitable for use in the present invention or accelerators for nucleation transmission development include JP-A-53-7761.
6, No. 53-137133, No. 54-37732.
Nos. 60-140340, 61-167939, 62-222241, 63-1224045, U.S. Pat. No. 4,975,354 and various compounds containing N or S atoms in addition to the compounds disclosed in U.S. Pat. Are effective. The optimum amount of these accelerators varies depending on the type of the compound, but is in the range of 1.0 × 10 ^{−3 to} 0.5 g / m ² , preferably 5.0 × 10 ^{−3 to} 0.1 g / m ² . It is desirable to use. These accelerators can be used in a suitable solvent (water, alcohols such as methanol and ethanol, acetone, N, N-
Dimethylformamide, methylcellosolve, etc.) and added to the coating solution. A plurality of these additives may be used in combination. The emulsion layer or other hydrophilic colloid layer of the present invention may contain a water-soluble dye as a filter dye or for various purposes such as prevention of irradiation. As the filter dye, a dye for further lowering the photographic sensitivity, preferably, an ultraviolet absorber having a spectral absorption maximum in the specific sensitivity range of silver halide,
310 nm to 6 nm for improving safety against safelight light when handled as a light room photosensitive material
A dye having substantial light absorption in the region of 00 nm is used. These dyes are added to the emulsion layer depending on the purpose, or added together with the mordant to the upper part of the silver halide emulsion layer, that is, the non-photosensitive hydrophilic colloid layer farther from the silver halide emulsion layer with respect to the support, and fixed. It is preferable to use them. Different by the molar extinction coefficient of the dye is usually 10 ^-3
It is added in the range of １1 g / m ² . Preferably 10 to 50
0 mg / m ² . The above dye is a suitable solvent (for example,
Water, alcohols such as methanol and ethanol, acetone, methyl cellosolve and the like, or a mixed solvent thereof) and added to the coating solution. These dyes can be used in combination of two or more kinds.
Specific examples of these dyes are described in Japanese Patent Application No. 61-209169. In addition, US Pat. No. 3,314,79
No. 4, No. 3,352,681, No. 3,499,7
No. 62, No. 3,533, 794, No. 3,700,
No. 455, No. 3,705,805, No. 3,70
No. 7,375, No. 4,045,229, JP-A-46
No. 2784, West German Patent Application Publication No. 1,547,863, and the like can also be used. In addition, U.S. Pat. No. 2,274,782,
Nos. 185755 and 63-2045, pyrazolone oxonol dyes described in U.S. Pat. No. 2,956,879, diarylazo dyes described in U.S. Pat.
No. 207, No. 3,384,487, styryl dyes and butadienyl dyes, US Pat. No. 2,527,58.
3, the merocyanine dye described in U.S. Pat.
No. 6,897, No. 3,652,284, No. 3,7
No. 18,472, merocyanine dyes and oxonol dyes, U.S. Pat. No. 3,976,661, enaminohemioxonol dyes and British Patent 584,60.
9, No. 1,177,429, JP-A-48-851.
No. 30, No. 49-99620, No. 49-114420
Nos. 2,533,472 and 3,14
No. 8,187, No. 3,177,078, No. 3,2
No. 47,127, No. 3,540,887, No. 3,
Dyes described in 575,704, 3,653,905 and JP-A-62-133453 can also be used.

In order to obtain ultra-high contrast photographic characteristics using the silver halide light-sensitive material of the present invention, a conventional lith developer and 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 photographic light-sensitive material of the present invention can use a developer sufficiently containing (especially, 0.15 mol / l or more) a sulfite ion as a preservative, and has a pH of 9.5 or more. Especially 10-11.
With the developing solution of No. 5, a negative image having a sufficiently high contrast can be obtained. There is no particular limitation on the developing agent that can be used in the method of the present invention, and examples thereof include dihydroxybenzenes (for example, hydroquinone) and 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone, 4,4-dimethyl-1). -Phenyl-3-pyrazolidone), aminophenols (eg, N-methyl-p-aminophenol) and the like can be used alone or in combination. The silver halide light-sensitive material of the present invention is particularly suitable to be processed with a developer containing dihydroxybenzenes as a main developing agent and 3-pyrazolidones or aminophenols as an auxiliary developing agent. Preferably, the developer contains 0.05 to 0.5 of dihydroxybenzenes.
The moles / liter, 3-pyrazolidones or aminophenols are used together in the range of 0.06 mol / liter or less.

As described in US Pat. No. 4,269,929, the development speed can be increased by adding amines to the developer to shorten the development time. Others include pH buffers such as alkali metal sulfites, carbonates, borates and phosphates,
It may contain a development inhibitor such as bromide, iodide and an organic antifoggant (particularly preferably nitroindazoles or benzotriazoles) or an antifoggant. Further, if necessary, a water softener, a dissolution aid, a color tone agent, a development accelerator, a surfactant (particularly preferably the above-mentioned polyalkylene oxides), an antifoaming agent, a hardening agent, a silver stain preventing agent for a film. (For example, 2-mercaptobenzimidazolesulfonic acids). The processing temperature in the process according to the invention is usually chosen between 18 ° C and 50 ° C. It is preferable to use an automatic developing machine for the photographic processing. However, according to the method of the present invention, the total processing time from when the photosensitive material is put into the automatic developing machine to when it comes out is 90 to 12 times.
Even if it is set to 0 second, a photographic characteristic of a sufficiently high contrast negative gradation can be obtained. In the developer of the present invention, compounds described in JP-A-56-24347 can be used as a silver stain inhibitor. Japanese Patent Application Sho 60 as a dissolution aid to be added to the developer
The compounds described in JP-A-109743 can be used. Further, as a pH buffering agent used in a developing solution,
Compounds described in Japanese Patent Application No. 93433 / 61-28
No. 708 can be used.

[0030]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited thereto. Example 1 1) Preparation of a coated sample A gelatin solution maintained at 40 ° C was mixed with 5.0 × / mol of silver.
An aqueous solution of silver nitrate and an aqueous solution of sodium chloride are simultaneously mixed in the presence of 10 ^-6 mol of (NH ₄ ) ₃ RhCl ₆ , and after removing soluble salts by a method well known in the art, gelatin is added thereto, followed by chemical reaction. Without aging, 2-methyl-4-hydroxy-1,3,3a, 7-tetraazaindene was added as a stabilizer. This emulsion had an average grain size of 0.2
This was a monodisperse emulsion having a cubic crystal form of μ. A hydrazine compound selected from the general formula (1) shown in Table 1 and the following A, B, and C as comparative compounds were added to the emulsion in the amounts shown in Table 1, and then the nucleation accelerators shown below were added. 30 mg /
m ² was added, was added to gelatin 30 wt% further polyethyl acrylate latex solids, 2,4 as a hardener
-Dichloro-6-hydroxy-s-triazine,
It was applied on a polyester film so as to have an Ag amount of 3.8 g / m ² . Gelatin was 1.8 g / m ² . As a protective layer, gelatin 1.5 g / m ² , particle size 2.5 μm
A layer of 0.3 g / m ² of polymethyl methacrylate was applied.

[0031]

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[0032]

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2) Evaluation of photographic properties The obtained coated sample was image-exposed with a bright room printer P-627GA manufactured by Dainippon Screen Co., Ltd., and developed at 35 ° C. for 30 seconds with a developing solution having the following composition. The image was fixed with a fixing solution PURCF901 of Co., Ltd., washed with water and dried. Table 1
The results of evaluating the Dmax and the quality of the blank characters of each sample are shown below. 50% of blank character quality using halftone original
Is an image quality in which a character having a width of 30 μm is reproduced when properly exposed such that the halftone dot area becomes 50% halftone dot area on the return photosensitive material. On the other hand, 150 μm when the same proper exposure is given
It is an unsatisfactory character quality, which is an image quality that can reproduce only characters larger than the width.
２2 ranks were provided. Three or more is a practical level. Dmax is also 50% halftone dot area of the document
Dmax when exposure is performed so as to obtain a halftone dot area. The sample of the present invention has a high Dmax and has excellent character image quality. Also, it works effectively with a smaller amount of addition than the comparative compound.

[Developer] Hydroquinone 30.0 g 4-Human peroxymethyl-4-methyl-1-phenyl-3-perazodritone 0.3 g Potassium hydroxide 20.0 g Sodium hydroxide 18.0 g Sodium sulfite 30.0 g EDTA · 2Na 1.0 g Potassium bromide 10.0 g 5-Methylbenzotriazole 0.4 g 5-Phensene sulfonamito-2-mercaphate pentimidate 0.5 g Water is added to adjust to 1 liter pH 10.6.

[0035]

[Table 1]

Example 2 1) Preparation of coating sample 4 × 10 ⁻⁷ mol of iridium hexachloride (III) per mol of silver
97 mole% AgBr in the presence of potassium and ammonia,
A silver iodobromide emulsion comprising cubic crystals having an average grain size of 0.25 µm and containing 3 mol% of AgI was prepared by a double jet method. The emulsion was desalted by flocculation, and 40 g of inert gelatin was added per mole of silver. This emulsion was kept at 50 ° C.
After adding 5'-dichloro-9-ethyl-3,3'-bis (4-sulfobutyl) oxacarbocyanine, the mixture was aged for 20 minutes and then cooled. Using this emulsion, the compounds of the present invention shown in Table 2 and D, E, and F shown below for comparison were added, and 5-methylbenzothiazole, 2-methyl-
4-Hydroxy-1,3,3a, 7-tetraazaindene was added. In addition, 20 mg of the following contrast enhancement agent:
/ M ² and 1,3-divinylsulfonyl-2-propanol were added, and the mixture was coated on a polyethylene terephthalate film so as to have a silver amount of 3.7 g / m ² . A gelatin was applied thereon as a protective layer at a rate of 1.5 g / m ² to obtain a sample.

[0037]

Embedded image

[0038]

Embedded image 2) Evaluation of photographic properties These samples were exposed to tungsten light at 3200 ° K through an optical wedge and a 150-line gray contact screen, developed with the developer at 35 ° C for 30 seconds, fixed, washed and dried. The dot quality and Dma of the obtained sample
x is shown in Table 2. The halftone dot quality is visually evaluated on a five-point scale, where 5 is the best and 1 represents the worst quality. As the halftone dot masters for plate making, 5 and 4 are practically usable, 3 is inferior but can be used just barely, and 2 and 1 are qualities which cannot be practically used. Dmax is the exposure amount (log) that gives 1.5 in terms of the optical density of the sample that was similarly exposed through an optical wedge and developed.
The optical density (Dmax) at a point where exposure (0.5 + logE) was larger than that of E) by 0.5 was shown. It can be seen that when the compound of the present invention is used, a high Dmax is maintained with a small amount of addition, and good dot quality is provided as compared with the comparative compound.

[0039]

[Table 2]

[0040]

As described above, the silver halide photographic light-sensitive material of the present invention can provide good image quality and halftone dot quality and high Dmax with a small amount of addition and using a stable developer.

Claims (1)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support,
A silver halide photographic material comprising at least one compound represented by the following formula 1 in the emulsion layer or another hydrophilic colloid layer. Embedded image In the general formula (1), M ⁺ represents a cationic 5-membered heterocyclic ring formed by a group consisting of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom and a selenium atom. A ₁ ^- is O ^-,
Represents S ^- and N ^-- R. R represents an aliphatic group, an aromatic group, or a heterocyclic group. L ₁ represents a divalent linking group. m represents 0 or 1. L ₂ represents a divalent aliphatic group or an aromatic group. G represents a carbonyl group, a sulfonyl group, a sulfinyl group, an oxalyl group or a phosphoryl group. R ₁ is a hydrogen atom, an aliphatic group, an alkoxy group, an aryloxy group,
It represents an aromatic group, an amino group or the general formula (2). Embedded image In the general formula (2), Q ⁺ is a group comprising a cationic group, A ₂ ^- represents an anion, if Q ⁺ forms an intramolecular salt having an anionic group is not required.