JPH09127632A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a sensitive material for a process excellent in rapid processability and having high processing stability by incorporating a specified compd. into an emulsion layer or the other hydrophilic colloidal layer. SOLUTION: This sensitive material with at least one silver halide emulsion layer on the substrate contains at least one kind of compd. represented by the formula in the emulsion layer or the other hydrophilic colloidal layer. In the formula, R is an aliphatic or arom. group, L1 is -NR3 -, -O- or -S-, L2 is a divalent combining group, G is carbonyl, sulfonyl, sulfinyl, oxalyl or phosphoryl, R2 is H, alkyl, alkoxy, aryloxy, aryl or amino and R3 is H, an aliphatic or arom. group.

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 superhard tone negative image forming method 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.
As a method for obtaining high contrast photographic characteristics using a stable developing solution, US Pat. Nos. 4,166,742, 4,168,977, 4,211,857, and 4,224 are known. No. 401, No. 4,311,781,
No. 4,272,606, No. 4,912,016
No. 4,998,604, JP-A-3-25924.
No. 0, JP-A-5-45761, JP-A-7-5610 and the like are known methods using a hydrazine derivative. 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, it has been found that hitherto known hydrazine compounds have some drawbacks. That is, it has been attempted to make the structure of the hydrazine compound a diffusion-resistant structure with a conventionally known hydrazine compound for the purpose of reducing the adverse effect on other photographic light-sensitive materials caused by flowing out 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 was also found that a sufficient hardness could not be obtained when a large amount of a light-sensitive material was treated with a fatigue developing solution. Further, 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 handling risk, and the BOD at the time of waste liquid treatment. And has a high COD. In addition, since it is necessary to use a large amount of pH buffering agent to keep the pH of the developer constant, the solid concentration of the developer becomes high, the solution becomes sticky, and the scattered solution is difficult to wipe off. was there. Therefore, there has been a demand for the development of a hydrazine compound capable of increasing the contrast with a developer having a lower pH. 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, and in this field, there is a demand for a high blank character quality capable of reproducing a thin Mincho character. Therefore, development of a nucleating agent having higher activity has been desired. In particular, in a low-sensitivity light-sensitive material which can be handled even in a light room, hardening by a nucleating agent hardly occurs, and the development of a more active nucleating agent is desired.

[0003]

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

[0004]

These objects of the present invention have been attained by a silver halide photographic material comprising a compound represented by the following general formula (1).

Embedded image In the formula, R ₁ represents an aliphatic group or an aromatic group, and L ₁ is —NR
₃ -group, -O- group, -S- group, L ₂ represents a divalent linking group, G represents a carbonyl group, a sulfonyl group, a sulfinyl group, an oxalyl group or a phosphoryl group, and R ₂ represents a hydrogen atom. , An alkyl group, an alkoxy group, an aryloxy group, an aryl group, or an amino group, and R ₃ represents a hydrogen atom, an aliphatic group, or an aromatic group.

The compound represented by the general formula (1) will be described in more detail. In the formula, L ₁ is a —NR ₃ — group, —O—
Represents a group and a -S- group. R ₃ represents a hydrogen atom, an aliphatic group or an aromatic group. Of these, preferred is a hydrogen atom. L ₂
Represents a divalent linking group. Among them, the arylene group is preferable, and the phenylene group is particularly preferable. Further, the carbon atom may have a substituent well known in the art (for example, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a hydroxy group, a halogen atom, an amide group, a sulfonamide group, and the like). 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. The aliphatic group represented by R ₁ has 1 to 3 carbon atoms.
It is 0, and is particularly a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. 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 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 aralkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, a ureido group and a urethane group. Group, aryloxy group, sulfamoyl, carbamoyl group, alkyl or arylthio group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, aryl group Oxycarbonyl group, acyl group, carbamoyl group, alkoxycarbonyl group, acyloxy group,
Carbonamide group, sulfonamide group, carboxy group,
Examples thereof include a phosphoric acid amide group, a diacylamino group and an imino group.

R ₂ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an aryl group or an amino group. When G is a carbonyl group, preferred among the groups represented by R ₂ are a hydrogen atom, an alkyl group (for example, a methyl group, a trifluoromethyl group, a 3-hydroxypropyl group, a 3-methanesulfonamidopropyl group, Phenylsulfonylmethyl group, 2-hydroxybenzyl group, trimethylammoniomethyl group, triethylammoniomethyl group, (1-pyridinio) methyl group, (4-methyl-1-
A pyridinio) methyl group, a (3-methyl-1-imidazolio) methyl group, an aryl group (for example, a phenyl group, a 3,5-dichlorophenyl group, an o-methanesulfonamidophenyl group, a 4-methanesulfonylphenyl group,
2-hydroxymethylphenyl group) and the like, and a hydrogen atom and a substituted alkyl group having a quaternized nitrogen atom in the structure are particularly preferable. When G is a sulfonyl group, a sulfinyl group or an oxalyl group, preferred groups among R ₂ are an alkoxy group (eg, methoxy group, ethoxy group, etc.), an aryloxy group (eg, phenoxy group, 4 -Chlorophenoxy group, etc.), an amino group, etc., and particularly a substituted amino group having at least one hydroxy group or amino group in the structure (eg, 2
-Hydroxyethylamino group, 3-hydroxypropylamino group, 3-hydroxy-2,2-dimethylpropylamino group, 2,3-dihydroxypropylamino group,
-Hydroxymethylanilino group, 2-dimethylaminoethylamino group, 2-diethylaminoethylamino group, 2
-Dipropylaminoethylamino group, 2-dibutylaminoethylamino group, 3-dimethylaminopropylamino group, 3-diethylaminopropylamino group, 3-dipropylaminopropylamino group, 3-dibutylaminopropylamino group), And a substituted amino group having a quaternized nitrogen atom (for example, a 2-trimethylammonioethylamino group, a 2-triethylammonioethylamino group, a 2-tripropylammonioethylamino group,
Tributylammonioethylamino group, 3-trimethylammoniopropylamino group, 3-triethylammoniopropylamino group, 3-tripropylammoniopropylamino group, 3-tributylammoniopropylamino group, (1-methyl-3 -Pyridinio) amino group, (1
-Ethyl-3-pyridinio) amino group, (1-propyl-3-pyridinio) amino group, (1-butyl-3-pyridinio) amino group and the like are preferable. When G is a phosphoryl group, R ₂ is preferably a methoxy group, an ethoxy group, a butoxy group, a phenoxy group, a phenyl group or the like.

Further, R ₁ may have a ballast group 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 and relatively inert to photographic properties, and can be selected from, for example, an alkyl group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group. . Further, R ₁ may be one in which a group which enhances adsorption on the surface of the silver halide grain is incorporated. Examples of such an adsorbing group include, for example, US Pat. Nos. 4,385,108 and 4,459,347 such as a heterocyclic thioamide group, a mercapto heterocyclic group, and a triazole group.
And JP-A-59-195233 and JP-A-59-20023.
1, No. 59-201045, No. 59-201046
Issue No. 59-201047 Issue No. 59-201049
No. 61-170733 and No. 61-270744.
No. 62, No. 62-948, No. 63-234244, No. 6
The groups described in 3-234245 and 63-234246 are mentioned.

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

[0009]

Embedded image

[0010]

Embedded image

[0011]

Embedded image

[0012]

[Chemical 6]

[0013]

Embedded image

Next, representative examples of the synthesis of the hydrazine derivative used in the present invention represented by the above formula 1 will be described.

Synthetic Example: Synthesis of Exemplified Compound H-7 N- (4-aminophenyl) -N'-ethogizalylhydrazine (4.5 g) was dissolved in THF (50 ml), triethylamine (3 ml) was added and the mixture was stirred at an internal temperature of 0 ° C or lower. While N
-Chlorosulfonylcarbamic acid phenyl ester 5.
0 g of THF solution (5.0 g / 10 ml) was added dropwise.
After the dropping was completed, the mixture was stirred at the same temperature for 30 minutes and at room temperature for 1 hour. After completion of the reaction, THF was distilled off, and the residue was stirred in 100 ml of chloroform at room temperature for 1 hour. The precipitated crystals were collected by filtration, washed with chloroform, dried, and 4.2 g
Compound A of was obtained. 90-92 ° C

4.2 g of compound A was dissolved in 50 ml of THF, 1.8 g of compound B was added, and the mixture was stirred at room temperature for 1 hour.
After the reaction was completed, THF was distilled off, and the residue was chloroform 1
It stirred at room temperature in 00 ml for 1 hour. The precipitated crystals were collected by filtration, washed with chloroform and dried to obtain 3.2 g of compound C. Melting point 127-129 ° C

4.3 g of the compound C was dissolved in 50 ml of methanol, 1.1 g of diethylaminopropylamine was added, and the mixture was heated under reflux for 30 minutes. After completion of the reaction, methanol was distilled off, and the residue was purified by silica gel column chromatography (developing solvent chloroform / methanol: 1/1) to obtain 2.9 g of Exemplified compound H-7. Melting point 114 ° C
(Disassembly)

[0018]

Embedded image

Other exemplified compounds were synthesized by the same method.

The hydrazine derivative of the present invention can be prepared by using 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. It can be used by a method known as a solid dispersion method using a colloid mill, a ball mill or ultrasonic waves.

The silver halide used in the light-sensitive 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
Gold compounds such as chloroaurate and gold trichloride, rhodium,
A sulfur compound that reacts with a salt of a noble metal such as iridium or a silver salt to form silver sulfide, or a reducing substance such as a stannous salt or amines can increase the sensitivity without coarsening the particles. Further, an iron compound such as a salt of a noble metal such as rhodium or iridium or a red blood salt may be allowed to 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 it further promotes the effect of the present invention of achieving ultrahigh contrast photographic characteristics in a short development time.

In the present invention, the surface latent image type silver halide emulsion is an emulsion composed of silver halide grains having a surface sensitivity higher than the internal sensitivity, and this emulsion is preferably US Pat. It has a difference between the surface sensitivity and the internal sensitivity defined in the specification of Japanese Patent No. 401. It is desirable that the silver halide emulsion be monodisperse, and in particular, the above-mentioned US Pat.
An emulsion having the monodispersity defined in No. 224,401 is preferable. It is preferable that the silver halide emulsion used in the present invention contains a water-soluble rhodium salt (eg, rhodium dichloride, rhodium trichloride, potassium hexachloride rhodium (III) acid, ammonium hexachloride rhodium (III) acid). The rhodium salt is preferably added before 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 and the soluble halogen salt for the preparation of the silver halide emulsion in the present invention may be a single jet method, a double jet method, a reverse mixing method of forming in the presence of excess silver ions, or the like. However, 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 particles is particularly preferable. The silver halide emulsion thus prepared 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, it is chemically sensitized. It is rather preferable that it is not sensitized. 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 may be an undercoat layer, an intermediate layer, a filter layer, a protective layer, an antihalation layer, or the like as long as it does not prevent the compound represented by the general formula (1) from diffusing into silver halide grains. It may be a layer having a function. Since the content of the compound represented by the formula (1) in the layer varies depending on the characteristics of the silver halide emulsion used, the chemical structure of the compound and the development conditions, the appropriate content can vary over a wide range. Is the silver 1 in the surface latent image type silver halide emulsion.
A range of about 1.times.10.sup.- ⁶ to 1.times.10.sup.- ² mole per mole 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.
A combination of sensitizing dyes is often used especially for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosure 176, 17643 (1978).
(Issued December 2013), page 23, IV, section J.

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, it is advantageous to use gelatin, 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, an enzyme-treated gelatin as described in P30 (1966) may be used, or a hydrolyzed product or an enzymatically decomposed product of gelatin may 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 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, azols such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, mercaptos. Many compounds conventionally known as antifoggants or stabilizers such as tetrazoles, mercaptopyrimidines, mercaptotriazines, thioketo compounds and azaindenes can be added. 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 coating aids, antistatic agents, improving slipperiness, emulsifying and dispersing, preventing adhesion and improving photographic characteristics (for example, developing 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 condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl) Amines or amides, polyethylene oxide adducts of silicone, etc.), glycidol derivatives (alkenyl succinic acid polyglyceride,
Alkylphenol polyglycerides), nonionic surfactants such as fatty acid esters of polyhydric alcohols, alkyl esters of sugars, alkyl carboxylate, alkyl sulfate, alkyl benzene sulfonate,
Alkyl phosphates, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates, etc., carboxy, sulfo, phospho, sulfate, phosphate Surfactants containing acidic groups such as groups, amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid esters, aliphatic or aromatic quaternary ammonium salts, pyridinium, imidazolium Cationic surfactants such as heterocyclic quaternary ammonium salts such as can be used.

The photographic light-sensitive material used in the present invention may contain a water-insoluble or hardly 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 group 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, the silver halide emulsion layer contains 1.0 × 10 ^{−8 to} 1.0 × 10 ⁻⁴ mol / mol.
It is appropriate that m ² , preferably 1.0 × 10 ^{−7 to} 1.0 × 10 ⁻⁵ mol / m ^{2 is} present.

The light-sensitive material of the present invention may contain a development accelerator. Suitable development accelerators or nucleation infectious development accelerators for use in the present invention are those disclosed in JP-A-53-7761.
No. 6, No. 53-137133, No. 54-37732,
No. 60-140340, U.S. Pat. No. 4,975,35
In addition to the compounds disclosed in No. 4, etc., various compounds containing an N or S atom are effective. These accelerators
Although the optimum amount varies depending on the type of compound, it is 1.0 × 1
0 ^{−3 to} 0.5 g / m ² , preferably 5.0 × 10 ⁻³ to
It is desirable to use in the range of 0.1 g / m ² . These accelerators are dissolved in a suitable solvent (water, alcohols such as methanol or ethanol, acetone, N, N-dimethylformamide, methyl cellosolve, etc.) and added to the coating solution. You may use these additives together in multiple types. The emulsion layer of the present invention or the other hydrophilic colloid layer 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 intrinsic sensitivity range of silver halide, or safety against safelight light when handled as a light room photosensitive material Dyes having substantial light absorption mainly in the region of 310 nm to 600 nm are used to increase the light absorption. These dyes may be added to the emulsion layer depending on the purpose, or may be fixed together with a mordant in the upper part of the silver halide emulsion layer, that is, in the non-photosensitive hydrophilic colloid layer farther than the silver halide emulsion layer with respect to the support. It is preferable to use it. Depending on the molar extinction coefficient of the dye, it is usually added in the range of 10 ^{-3 to 1} g / m ² . Preferably it is 10-500 mg / m < ² >. The dye can be dissolved in 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 are 2
It is also possible to use a combination of two or more species. Specific examples of these dyes are described in Japanese Patent Application No. 61-209169. In addition, U.S. Patent Nos. 3,314,794, 3,352,681, 3,499,762, 3,533,794, 3,700,455,
Nos. 3,705,805 and 3,707,375
No. 4,045,229, JP-A-46-2784.
And ultraviolet absorbing dyes described in West German Patent Application Publication No. 1,547,863. In addition, U.S. Pat. No. 2,274,782, JP-A-62-18755
5, pyrazolone oxonol dyes described in 63-2045, diarylazo dyes described in U.S. Pat. No. 2,956,879, U.S. Pat. No. 3,423,207,
No. 3,384,487, styryl dyes and butadienyl dyes, U.S. Pat. No. 2,527,583, merocyanine dyes, U.S. Pat. No. 3,486,897.
No. 3,652,284, No. 3,718,47
No. 2, merocyanine dyes and oxonol dyes, US Pat. No. 3,976,661, enaminohemioxonol dyes, and British Patents 584,609 and 1,177,429, and JP-A No. 48-85130, 49-99620, 49-114420, US Pat. Nos. 2,533,472, 3,148,187, 3,177,078, and 3,247. , 12
No. 7, No. 3,540, 887, No. 3, 575, 7
No. 04, No. 3,653,905, JP-A-62-13
The dyes described in No. 3453 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 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, for the silver halide photographic light-sensitive material of the present invention, a developer containing sufficient sulfite ion as a preservative (especially 0.15 mol / l or more) can be used, and a pH of 9.5 or more, Especially 10-11.
With the developing solution of No. 5, a sufficiently high-contrast negative image 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 (eg, hydroquinone), 3-pyrazolidones (eg, 1-phenyl-3-pyrazolidone, 4,4-dimethyl-1). -Phenyl-3-pyrazolidone), aminophenols (for example, N-methyl-p-aminophenol), etc. 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.
Mol / liter, 3-pyrazolidones or aminophenols are used together in the range of 0.06 mol / liter or less.

Further, as described in US Pat. No. 4,269,929, the development speed can be increased by adding amines to a developer to shorten the development time. The developer may also include other pH buffering agents such as alkali metal sulfites, carbonates, borates and phosphates,
Development inhibitors such as bromides, iodides and organic antifoggants (particularly preferably nitroindazoles or benzotriazoles) or antifoggants can be contained. 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), a defoaming agent, a hardener, and a silver stain preventing agent for the film. (For example, 2-mercaptobenzimidazole sulfonic acids, etc.) may be included. The processing temperature in the process according to the invention is usually chosen between 18 ° C and 50 ° C. Although it is preferable to use an automatic processor for photographic processing, the total processing time from putting the light-sensitive material into the automatic developing machine until it comes out is 90 to 12 by the method of the present invention.
Even if it is set to 0 second, a photographic characteristic of a super gradation of 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. As a dissolution aid to be added to the developer, Japanese Patent Application No. 60
The compounds described in No. 109743 can be used. Further, as a pH buffer agent used in a developing solution, JP-A-60-
93433 or Japanese Patent Application No. 61-28
The compounds described in No. 708 can be used.

[0034]

[Example 1]

1) Preparation of coating sample 5.0 × / mol of silver was added to an aqueous gelatin solution kept at 40 ° C.
The aqueous solution of silver nitrate and the aqueous solution of sodium chloride were simultaneously mixed in the presence of 10 ⁻⁶ mol of (NH ₄ ) ₃ RhCl ₆ , and then the soluble salt was removed by a method well known in the art, followed by addition of gelatin, followed by chemical treatment. 2-Methyl-4-hydroxy-1,3,3a, 7-tetraazaindene was added as a stabilizer without aging. This emulsion had an average grain size of 0.2
It was a monodisperse emulsion having a cubic crystal shape of μ. A hydrazine compound selected from the general formula (1) shown in Table 1 and a comparative compound represented by the following chemical formulas 9, 10 and 11,
After the addition of Chemical Formula 12 in the amount shown in Table 1, 30 mg / m ² of Chemical Formula 13 below was added as a nucleation promoting agent, and polyethyl acrylate latex was further added at a solid content of 30 wt% to gelatin.
%, And 2,4-dichloro-6-hydroxy-s-triazine was added as a hardener, and the mixture was coated on a polyester film so as to have an Ag amount of 3.8 g / m ² . Gelatin was 1.8 g / m ² . On this, a layer of 1.5 g / m ² of gelatin and 0.3 g / m ² of polymethyl methacrylate having a particle size of 2.5 μm was applied as a protective layer.

[0035]

Embedded image

[0036]

Embedded image

[0037]

Embedded image

[0038]

Embedded image

[0039]

Embedded image

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 developer 1 having the following composition. The image was fixed with a fixing solution PURCF901 from Paper Manufacturing Co., Ltd., washed with water and dried. Table 1 shows the results of evaluating the Dmax and the extracted character image quality of each sample. The blank character image quality 5 is 50 using a halftone original.
%, Which is an image quality in which a character having a width of 30 μm is reproduced when properly exposed so that a halftone dot area becomes 50% halftone dot area on the return photosensitive material. on the other hand,
150μ when the same proper exposure is given as the character image quality 1
The image quality is such that the image quality is such that only characters with a width of m or more can be reproduced. This is a poor character quality, and a rank of 4 or 2 is provided between 5 and 1 in the sensory evaluation. Three or more is a practical level. Similarly, Dmax is 50% of the original and the halftone dot area is 50.
It is Dmax when exposed so that the halftone dot area may be%.
The sample of the present invention has high Dmax and excellent character image quality. Further, compared to the comparative compound, it works effectively even when added in a small amount.

[Developer-1] hydroquinone 30.0 g 4-human peroxymethyl-4-methyl-1-phenyl-3-hydroxyperitone 0.3 g sodium sulfite 75.0 g EDTA · 2Na 1.0 g tripotassium phosphate 80.0 g Potassium bromide 2.0 g Sodium hydroxide 13.0 g 5-methylbenzotriazole 0.3 g 1-diethylamino-2,3-diethylhydroxyfluoropropane 17.0 g sodium p-toluenesulfonate 7.0 g Adjust to pH 11.5 with potassium.

[0042]

[Table 1]

Example 2 1) Preparation of Coated Sample 4 × 10 ^-7 mol of iridium hexachloride (II) per mol of silver
I) 97 mole% AgB in the presence of potassium and ammonia
r, average particle size 0.25μ containing 3 mol% AgI
A silver iodobromide emulsion consisting of cubic crystals was prepared by the double jet method. This emulsion was desalted by the flocculation method, and then 40 g of inert gelatin was added per mol of silver. This emulsion was kept at 50 DEG C., and 5,5'-dichloro-9-ethyl-3,3'-bis (4
(Sulfobutyl) oxacarbocyanine was added, and the mixture was aged for 20 minutes and then cooled. Using this emulsion, the compounds of the present invention shown in Table 2 and the above-mentioned chemical formulas 9 and 10
Chemical formulas 11 and 12 are added, and 5-methylbenzothiazole, 2-methyl-4-hydroxy-1,3,3a, 7 are further added.
-Tetraazaindene was added. Further, 20 mg / m ² of the following chemical formula 14 was added as a nucleation accelerator, and 1,3-divinylsulfonyl-2-propanol was added, and the mixture was coated on a polyethylene terephthalate film so as to have a silver amount of 3.7 g / m ² . On top of this, 1.5 g of gelatin as a protective layer
/ M ² to obtain a sample.

[0044]

Embedded image

2) Evaluation of photographic properties These samples were exposed with a tungsten light of 3200 ° K through an optical wedge and a 150-line gray contact screen, and then developed with the following developer-2 at 35 ° C for 30 seconds, fixed, washed with water and dried. did. The dot quality and Dmax of the obtained sample are 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 a halftone dot plate for plate making, 5 and 4 are practical, 3 is poor but can be used barely, and 2 and 1 are practically unusable qualities. Dmax is indicated by the optical density (Dmax) of a point which is exposed 0.5 times more (0.5 + logE) than the exposure amount (logE) which gives 1.5 as the optical density of the sample which was similarly exposed through an optical wedge. It was It can be seen that the compound of the present invention maintains a high Dmax with a small amount of addition and gives a good halftone dot quality, as compared with the comparative compound.

[Developer-2] 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 1.0g Potassium bromide 10.0g 5-Methylbenzotriazole 0.4g 5-Phensene sulfonamito-2-mercaphate pentimimitazole 0.5g Water is added to adjust to 1 liter pH10.6.

[0047]

[Table 2]

[0048]

INDUSTRIAL APPLICABILITY The silver halide photographic light-sensitive material of the present invention can obtain a good image quality of printed letters and halftone dots and a high Dmax by using a stable developing solution with a small addition amount.

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 general formula (1) in the emulsion layer or another hydrophilic colloid layer. Embedded image In the formula, R ₁ represents an aliphatic group or an aromatic group, and L ₁ is —NR
₃ -group, -O- group, -S- group, L ₂ represents a divalent linkage, G represents a carbonyl group, a sulfonyl group, a sulfinyl group, an oxalyl group or a phosphoryl group, and R ₂ represents a hydrogen atom. , An alkyl group, an alkoxy group, an aryloxy group, an aryl group, or an amino group, and R ₃ represents a hydrogen atom, an aliphatic group, or an aromatic group.