JP2000275768A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide photographic sensitive material for a photomechanical process excellent in rapid processability and processing stability by incorporating a hydrazine compound having an isothioureido group and an onium group into an emulsion layer or another hydrophilic colloidal layer. SOLUTION: The silver halide photographic sensitive material contains at least one compound of the formula in an emulsion layer or another hydrophilic colloidal layer. In the formula, R1 is an aliphatic or aromatic group, R2 is a divalent combining group, R3 is H, an aliphatic or aromatic group, R4 is an aliphatic group, L is a divalent combining group, G is carbonyl, sulfonyl or the like, R5 is H, an alkyl, alkoxy, aryloxy or the like, A+ is a quaternary ammonium cation, a tertiary sulfonium cation or a quaternary phosphonium cation and X is a counter anion or a counter anion part in the case where an inner salt is formed. The isothioureido group in the formula may be in the form of a salt of a protonic acid.

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 risk of 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, 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, development of a silver halide photographic light-sensitive material for plate making having excellent rapid processing properties and high processing stability has been 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]

These objects of the present invention have been achieved by the following methods. (A) a silver halide photographic material characterized by containing a hydrazine compound having an isothioureido group and an onium group (b) silver halide characterized by containing a compound represented by the general formula (1) Photosensitive material

Embedded image In the general formula (1), R ₁ represents an aliphatic group or an aromatic group, and R ₂ represents a divalent linking group. R ₃ represents a hydrogen atom, an aliphatic group or an aromatic group, and R ₄ represents an aliphatic group. L represents a divalent linking group; G represents a carbonyl group, a sulfonyl group, a sulfinyl group, an oxalyl group or a phosphoryl group; R ₅ represents a hydrogen atom, an alkyl group, an alkoxy group,
Represents an aryloxy group, an aryl group, or an amino group. A ⁺ represents a quaternary ammonium cation group, a tertiary sulfonium cation group or a quaternary phosphonium cation group. X ^- represents a counter anion or a counter anion moiety when forming an inner salt. The isothioureido group in the general formula (1) may be a salt of a protonic acid.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The compound represented by formula (1) will be described in more detail. In the formula, L represents a divalent linking group. Among them, an arylene group is preferable, and a 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. R ₁
Is an aliphatic group having 1 to 30 carbon atoms, 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 the aryl group. The aliphatic group or aromatic group for R ₁ may be substituted, and typical substituents include, for example, an alkyl group,
Aralkyl, alkenyl, alkynyl, aryl, amino, ureido, urethane, alkoxy, aryloxy, sulfamoyl, carbamoyl, alkyl or arylthio, alkyl or arylsulfonyl, alkyl or arylsulfinyl, Hydroxy group, halogen atom, cyano group, sulfo group, aryloxycarbonyl group, acyl group, carbamoyl group, alkoxycarbonyl group, acyloxy group,
Carbonamide group, sulfonamide group, carboxy group,
Examples thereof include a phosphoric amide group, a diacylamino group, and an imino group.

The divalent linking group represented by R ₂ represents a divalent aliphatic group or a divalent aromatic group. The divalent aliphatic group represented by R ₂ has 1 to 30 carbon atoms, and is particularly a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms. The aromatic group represented by R ₂ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with the aryl group.
R ₂ is preferably an alkylene group, particularly preferably an ethylene group or a propylene group. The aliphatic group represented by R ₃ is an alkyl group of 1 to 5, and may have a substituent such as an aryl group. Preferably, they are a methyl group, an ethyl group, and a benzyl group. The aliphatic group represented by R ₄ has 1 to 30 carbon atoms, and is particularly a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms. R ₅ 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 ₅ are a hydrogen atom, an alkyl group (for example, a methyl group, a trifluoromethyl group, a 3-hydroxypropyl group,
Methanesulfonamidopropyl group, phenylsulfonylmethyl group, 2-hydroxybenzyl group, trimethylammoniomethyl group, triethylammoniomethyl group, (1
A (pyridinio) methyl group, a (4-methyl-1-pyridinio) methyl group, a (3-methyl-1-imidazolio) methyl group, and the like, an aryl group (for example, a phenyl group, 3,5
-Dichlorophenyl group, o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, 2-hydroxymethylphenyl group, etc.), particularly a hydrogen atom and a substituted alkyl having a quaternized nitrogen atom in the structure. Groups are preferred. When G is a sulfonyl group, a sulfinyl group or an oxalyl group, of the groups represented by R ₅ , preferred are an alkoxy group (for example, a methoxy group, an ethoxy group, etc.) and an aryloxy group (for example, a phenoxy group, 4- Chlorophenoxy group, etc.), amino group, etc., and particularly a substituted amino group having at least one hydroxy group or amino group in the structure (for example, 2-hydroxyethylamino group, 3-hydroxypropylamino group, 3
-Hydroxy-2,2-dimethylpropylamino group,
2,3-dihydroxypropylamino group, 2-hydroxymethylanilino group, 2-dimethylaminoethylamino group, 2-diethylaminoethylamino group, 2-dipropylaminoethylamino group, 2-dibutylaminoethylamino group, 3 A dimethylaminopropylamino group, a 3-diethylaminopropylamino group, a 3-dipropylaminopropylamino group, a 3-dibutylaminopropylamino group, and the like; and a substituted amino group having a quaternized nitrogen atom (for example, 2 -Trimethylammonioethylamino group, 2-triethylammonioethylamino group, 2-tripropylammonioethylamino group, 2-tributylammonioethylamino group, 3-trimethylammoniopropylamino group, 3-triethylammonio Propylamino group, 3-to Propyl ammonio-propylamino group, 3-tributyl ammonio propylamino group, (1
-Methyl-3-pyridinio) amino group, (1-ethyl-
A 3-pyridinio) amino group, a (1-propyl-3-pyridinio) amino group, a (1-butyl-3-pyridinio) amino group and the like are preferable. When G is a phosphoryl group, R ₅ is preferably a methoxy group, an ethoxy group, a butoxy group, a phenoxy group, a phenyl group or the like. A ⁺ represents a quaternary ammonium cation group, a tertiary sulfonium cation group or a quaternary phosphonium cation group, and is preferably the following general formula (2), general formula (3), general formula (4) or general formula (5) It is represented by

[0007]

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In these formulas, R ₆ represents an aliphatic group or an aromatic group. The aliphatic group represented by R ₆ preferably has 1 to 30 carbon atoms, and is particularly a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. The aromatic group represented by R ₆ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group is
It may be condensed with an aryl group. Two R ₆ in the general formulas (2) and (5) may be the same or different, and may be bonded to each other to form a ring. Z ₁ represents a group of atoms necessary for forming a nitrogen-containing heteroaromatic ring. Examples of the nitrogen-containing heteroaromatic ring formed by Z ₁ and a nitrogen atom include a pyridine ring, a pyridazine ring, a pyrazine ring, an imidazole ring, an oxazole ring, and a thiazole ring. . R ₆ and Z ₁ may be substituted, and those listed as substituents of R ₁ in formula (1) apply. 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, which is relatively inert to photographic properties, and can be selected from, for example, an alkyl group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group and the like. . R ₁ may have a group in which a group that enhances adsorption to the surface of silver halide grains 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.
No. 1, No. 59-201045, No. 59-201046
Nos. 59-201047 and 59-201049
No. 61-170733, No. 61-270744
No. 62-948, No. 63-234244, No. 6
Groups described in JP-A-3-234245 and JP-A-63-234246.

The isothioureido group in the formula may be a salt of a protonic acid (eg, hydrochloric acid, hydrobromic acid, hydroiodic acid, perchloric acid, methanesulfonic acid, 4-toluenesulfonic acid, sulfuric acid). .

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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[0015]

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

Synthesis Example: Synthesis of Exemplified Compound H-1

4.5 g of 1- (4-aminophenyl) -2-ethoxalylhydrazine is dissolved in 20 ml of ethanol, 4.6 g of 3-di-n-butylaminopropylisothiocyanate is added, and the mixture is heated under reflux for 1 hour. did. After the reaction,
Ethanol was distilled off to obtain 9.0 g of compound A.

9.0 g of Compound A was dissolved in 20 ml of methanol, 1.6 g of 3-aminopropanol was added, and the mixture was heated under reflux for 1 hour. After the reaction, methanol was distilled off, and the residue was treated with a mixed solvent of isopropanol and isopropyl ether for crystallization. The precipitated crystals were collected by filtration and washed with isopropyl ether to obtain 5.7 g of Compound B.

To 4.8 g of Compound B, 10 ml of sulfolane and 4.1 g of methyl p-toluenesulfonate were added.
Heated at 00 ° C. for 1 hour. After the reaction, dichloromethane 10
0 ml and 1N-sodium bicarbonate 100 ml were added, and the mixture was stirred at room temperature for 15 minutes. The dichloromethane layer was separated, washed with water and dried over magnesium sulfate, and then dichloromethane was distilled off. The residue was isolated and purified by column chromatography to obtain 2.1 g of Exemplified Compound H-1 as a target substance.

[0021]

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Other exemplified compounds were synthesized in the same manner.

The hydrazine derivative of the present invention can be used in a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, etc.), ketones (acetone, acetone).
Methyl ethyl ketone), N, N-dimethylformamide, dimethyl sulfoxide, methyl cellosolve, etc. Further, 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 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
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. In particular,
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 composed of silver halide grains having a surface sensitivity higher than the internal sensitivity. 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. 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 general 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. 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.- ⁸ 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.
Combinations of sensitizing dyes are often used, especially for supersensitization. In addition to 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, gelatin is advantageously used, 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 (such as chrome alum), aldehydes (such as formaldehyde and glyoxal), N-methylol compounds, dioxane derivatives (such as 2,3-dihydroxydioxane), active vinyl compounds, and active halogen compounds (such as 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, antistatic, slipperiness improvement, emulsification dispersion, adhesion prevention and photographic property improvement (for example, 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 hardly soluble synthetic polymer decomposition product in a photographic emulsion layer or another hydrophilic colloid layer for the purpose of improving dimensional stability or the like. 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 /
It is appropriate that m ^{2 be} present.

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.
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} 0.
It is desirable to use in the range of 1 g / m ² . These accelerators can be used in suitable solvents (water, alcohols such as methanol and ethanol, acetone, N, N-dimethylformamide,
Dissolved in methylcellosolve) 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 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 are
Depending on the purpose, it may be added to the emulsion layer or may be added and fixed together with a 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. preferable. 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 from 10 to 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 can be used in combination of two or more kinds. Specific examples of these dyes are described in Japanese Patent Application No. 61-209169. Others
U.S. Pat. Nos. 3,314,794 and 3,352,6
No. 81, No. 3,499,762, No. 3,533,
No. 794, No. 3,700,455, No. 3,70
No. 5,805, No. 3,707,375, No. 4,0
No. 45,229, JP-A-46-2784, and West German Patent Application Publication No. 1,547,863. Other US Patent No. 2,27
4,782, JP-A-62-185755, JP-A-63-185755.
No. 2045, pyrazolone oxonol dyes described in U.S. Pat. No. 2,956,879, diarylazo dyes described in U.S. Pat. Nos. 3,423,207 and 3,38.
No. 4,487, styryl dyes and butadienyl dyes, U.S. Pat. No. 2,527,583, merocyanine dyes, U.S. Pat. Nos. 3,486,897, 3,3.
Nos. 652,284 and 3,718,472, merocyanine dyes and oxonol dyes, U.S. Pat.
No. 977,661 and the enaminohemioxonol dyes described in British Patent Nos. 584,609 and 1,177,
No. 429, JP-A-48-85130 and JP-A-49-996.
No. 20, No. 49-114420, U.S. Pat.
No. 3,472, No. 3,148,187, No. 3,1
No. 77,078, No. 3,247,127, No. 3,
Dyes described in 540,887, 3,575,704, 3,653,905 and JP-A-62-133353 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, 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 and the development time can be shortened by adding amines to the developer. 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.

[0037]

[Example 1]

1) Preparation of coating sample 5.0 × / mol of silver was added to an aqueous gelatin solution kept at 40 ° C.
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 a comparative compound represented by the following formulas (10), (11) and (12)
Was added in an amount shown in Table 1, 30 mg / m ² of the following chemical formula 13 was added as a nucleation accelerator, and further, a polyethyl acrylate latex was added at 30 wt% of solid content with respect to gelatin, and 2,2 was used as a hardening agent. 4-dichloro-6-hydroxy-
2. Add s-triazine and add 3 on polyester film.
The coating was performed so that the Ag amount was 8 g / m ² . Gelatin is 1.
It was 8 g / m ² . On top of this, gelatin 1.
A layer of 5 g / m ² and 0.3 g / m ² of polymethyl methacrylate having a particle size of 2.5 μm was applied.

[0038]

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[0039]

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[0040]

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[0041]

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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., developed with a developer having the following composition at 35 ° C. for 30 seconds, and processed by Mitsubishi Paper Mills ( The solution was fixed with a fixing solution PURCF901 of Co., Ltd., washed with water and dried. Table 1 shows the results of evaluating the Dmax and the quality of the blank characters of each sample. The blank character image quality 5 is an image quality at which a character having a width of 30 μm is reproduced when properly exposed so that a halftone dot area of 50% becomes a halftone dot area of 50% on a return photosensitive material using a halftone dot document. Very good character image quality. On the other hand, the blank character image quality 1 is an image quality that can reproduce only characters having a width of 150 μm or more when the same proper exposure is given.
2 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-Hudroxymethyl-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 10.5.

[0044]

[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
Was prepared by the 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 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 compounds represented by the formulas
1, and then added with 5-methylbenzothiazole, 2-methyl-4-hydroxy-1,3,3a, 7-
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 . A gelatin was applied thereon as a protective layer at a rate of 1.5 g / m ² to obtain a sample.

[0046]

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2) Evaluation of photographic properties After exposing these samples to tungsten light of 3200 ° K through an optical wedge and a 150-line gray contact screen, the samples were developed with the above 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.

[0048]

[Table 2]

[0049]

The silver halide photographic light-sensitive material of the present invention is excellent in rapid processing property, and can obtain good image quality and halftone dot quality and high Dmax with a small amount of addition and a stable developing solution. it can.

Claims (2)

[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 hydrazine compound having an isothioureido group and an onium group in the emulsion layer or another hydrophilic colloid layer. 2. 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 general formula (1), R ₁ represents an aliphatic group or an aromatic group, and R ₂ represents a divalent linking group. R ₃ represents a hydrogen atom, an aliphatic group or an aromatic group, and R ₄ represents an aliphatic group. L represents a divalent linking group; G represents a carbonyl group, a sulfonyl group, a sulfinyl group, an oxalyl group or a phosphoryl group; R ₅ represents a hydrogen atom, an alkyl group, an alkoxy group,
Represents an aryloxy group, an aryl group, or an amino group. A ⁺ represents a quaternary ammonium cation group, a tertiary sulfonium cation group or a quaternary phosphonium cation group. X ^- represents a counter anion or a counter anion moiety when forming an inner salt. The isothioureido group in the general formula (1) may be a salt of a protonic acid.