JPH09160156A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the silver halide photographic sensitive material, for photomechanical process, high in aptitude to rapid processability and processing stability by incorporating at least one kind of specified compound in an emulsion layer or another hydrophilic colloidal layer. SOLUTION: The silver halide photographic sensitive material contains the compound represented by the formula in which each of R1 -R4 is, independently, an H atom or an aliphatic or aromatic group and each of R1 and R2 , R2 and R3 , and R3 and R4 may combine with each other to form a cyclic structure; X is a divalent aliphatic or aromatic group; L is -SO2 NR6 - or -NR6 -SO2 NR6 - or the like; R6 is an H atom or an aliphatic or aromatic group; Y is a substitutable group; (n) is 0-4; G is a carbonyl or sulfonyl group or the like; (m) is 0 or 1; and R5 is an H atom or an aliphatic or alkoxy or aryloxy group or the like.

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 bright room light-sensitive material that can be handled even in a bright room, it is difficult for the nucleating agent to cause a high contrast, and it is desired to develop a highly active nucleating agent.

[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 general formula (1), R ₁ , R ₂ , R ₃ and R _{4, which} may be the same or different, each represents a hydrogen atom, an aliphatic group or an aromatic group, and R ₁ , R ₂ , R ₂ And R ₃ and R ₃ and R ₄ may be connected to each other to form a cyclic structure. X represents a divalent aliphatic group or an aromatic group, L is -SO ₂ NR ₆ -, - NR
₆ SO ₂ NR _6- , -CONR _6- , -CSNR _6- , -N
_{R 6 CONR 6 -, - NR} 6 CSNR 6 -, - G 1 P (O)
(G ₁ R ₁ ) NR ₆ −. G ₁ represents a single bond, an —O— group or a —NR ₆ — group, and R ₆ represents a hydrogen atom, an aliphatic group or an aromatic group. Y represents a substitutable group. n is 0 to 4
It is. G represents a carbonyl group, a sulfonyl group, a sulfinyl group, an oxalyl group or a phosphoryl group, and m is 0
Or 1. R ₅ represents a hydrogen atom, an aliphatic group, an alkoxy group, an aryloxy group, an aromatic group, an amino group or the general formula (2).

Embedded image In the general formula (2), Q ⁺ represents a group containing a cationic group and A ⁻ represents an anion, but it is not necessary when Q ⁺ contains a sulfo group.

The compound represented by the general formula (1) will be described in more detail. In the general formula (1), R ₁ , R ₂ , R
_The aliphatic group represented by ₃ and R ₄ is preferably an aliphatic group having 1 to 30 carbon atoms, and particularly preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. R ₁ , R ₂ , R ₃ and R ₄
Is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic ring. Here, the unsaturated heterocyclic group may be condensed with the aryl group. R ₁ , R ₂ , R ₃ and R ₄
The aliphatic group or aromatic group of may be substituted, and as a typical substituent, for example, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, an aryloxy group, a sulfamoyl group, a ureido group, Urethane group, carbamoyl group, alkyl or arylthio group,
Alkyl or aryl sulfonyl group, hydroxy group,
Examples thereof include a halogen atom, a cyano group, an aryloxycarbonyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group, an amide group, a sulfonamide group and a carboxy group. Each of R ₁ , R ₂ , R ₃ and R ₄ may have a ballast group incorporated therein which is commonly used in a non-moving photographic additive such as a coupler. 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 , R ₂ , R ₃ and R ₄ may be those in which a group for enhancing adsorption to the surface of the silver halide grain is incorporated. Examples of the adsorptive group include thiourea, heterocyclic thioamide group, mercaptoheterocyclic group, and triazole group, which are disclosed in US Pat. No. 4,385,10.
8, No. 4,459,347, JP-A-59-195.
233, 59-200231, 59-2010.
No. 45, No. 59-201046, No. 59-20104
No. 7, No. 59-201049, No. 61-170733.
No. 61-270744, No. 62-948, No. 6
No. 3-234244, No. 63-234245, No. 63
-234246.

The divalent aliphatic group represented by X in the general formula (1) is preferably an aliphatic group having 1 to 30 carbon atoms, and particularly preferably a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms. . The aromatic group represented by X is a monocyclic or bicyclic arylene group or an unsaturated heterocycle. Here, the unsaturated heterocyclic group may be condensed with the aryl group. Preferred as X is an arylene group, particularly preferably a phenylene group or a naphthylene group. When G is a carbonyl group, preferred ones of the groups represented by R ₅ are
Hydrogen atom, alkyl group (eg, methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, 2-hydroxybenzyl group, etc.), aryl group (eg, phenyl group) , 3,5-dichlorophenyl group, 2-
Methanesulfonamidophenyl, 4-methanesulfonylphenyl, 2-hydroxymethylphenyl, etc.)
And a hydrogen atom and a trifluoromethyl group are particularly preferable. When G is a sulfonyl group, a sulfinyl group or an oxalyl group, preferable groups among R ₅ are an alkoxy group (for example, a methoxy group, an ethoxy group, etc.), an aryloxy group (for example, a phenoxy group, 4-
Chlorophenoxy group etc.), amino group, especially substituted amino group (eg methylamino group, 3-hydroxypropylamino group, 3-diethylaminopropylamino group, 3
-Methylthiopropylamino group, 2-hydroxymethylanilino group, etc.) are preferred. R ₅ may have a ballast group, which is commonly used in a non-moving photographic additive such as a coupler, incorporated therein or a group which enhances adsorption to the surface of silver halide grains. When G is a phosphoryl group, R ₅ is preferably a methoxy group, an ethoxy group, a butoxy group, a phenoxy group or a phenyl group. Further, R ₅ may be such as to rise to cyclization reaction to form a cyclic structure containing -G-R ₅ moiety of atoms disrupt portions of G-R ₅ from the remainder molecule, examples For example, JP-A-63-2
No. 9751 and the like. L is -SO
₂ NR _6- , -NR ₆ SO ₂ NR _6- , -CONR _6- , -C
SNR _6- , -NR ₆ CONR _6- , -NR ₆ CSNR
_{6 -, - G 1 P (} O) (G 1 R 1) NR 6 - represents a. R ₆ is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group, and particularly preferably a hydrogen atom. The substitutable group represented by Y is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, an alkynyl group, an alkenyl group,
Alkoxy, acyloxy, acylamino, sulfonamide, ureido, thioureido, oxamoylamino, alkylamino, dialkylamino, sulfonyl, sulfamoyl, carbamoyl, aryl, aryloxy, arylamino Examples thereof include groups, amino groups, hydroxyl groups, halogen atoms, mercapto groups, sulfo groups, carboxyl groups and cyano groups. These groups may be further substituted with appropriate substituents. Y may have a ballast group commonly used in a non-moving photographic additive such as a coupler incorporated therein, or a group that enhances adsorption to the surface of silver halide grains. When the guanidino group in the general formula (1) forms a salt of a protic acid, examples of the protic acid include hydrochloric acid, sulfuric acid, p-toluenesulfonic acid and the like, and hydrochloric acid and p-toluenesulfonic acid are preferable.

Q ⁺ in the general formula (2) is a group containing a cationic group having at least one quaternary nitrogen atom, and is a straight chain or branched hydrocarbon chain having 1 to 4 carbon atoms. Through G, and part or all of this chain may form part of a heterocycle having a quaternary nitrogen atom. Preferred examples of Q ⁺ include trialkylammonium alkyl group, pyridinium-1-ylalkyl group,
1-alkylpyridinium-2-yl group, 1-alkylpyridinium-3-yl group, 1-alkylpyridinium-4-yl group, thiazolinium-3-ylalkyl group,
Examples thereof include an oxazolinium-3-ylalkyl group and a 1-alkylimidazolium-3-ylalkyl group. These groups may be substituted, and as the substituents, those mentioned as the substituents for R ₁ , R ₂ , R ₃ and R ₄ are preferable. Further, when these groups form a ring structure,
It may be condensed with another ring. A ^- is a counter anion of Q ^+, Cl preferred examples ^-, Br -, ^{p-toluenesulfonate,} but like methyl sulfonate, having a sulfo group as a Q ⁺ substituents, inner salt Is not present when forming

[0008] The compounds used in the present invention are listed below, but the present invention is not limited thereto.

[0009]

Embedded image

[0010]

[Chemical 6]

[0011]

Embedded image

[0012]

Embedded image

The synthesis examples of the present invention will be described below. Synthesis Example 1 Synthesis of H-2 Synthesis of 1,3-dimethyl-2-chloro-1,3-imidazolinium chloride (intermediate A) 1,3-Dimethyl-equivalent to 50 ml of 1,2-dichloroethane
2-Imidazolidinone (10.00 g) was added, and oxalyl chloride (6.2 ml) was added dropwise at room temperature over 15 minutes. Later 8
Heat at 0 ° C. for 4 hours. After standing to cool, the crystallized product was filtered off
-Washing with dichloroethane gave 6.75 g of the desired product.
To 160 ml of N, N-dimethylformamide was added 6.75 g of the intermediate A, and the mixture was stirred at room temperature.
80 ml of dimethylformamide and 2- [4- (3-aminobenzenesulfonamide) phenyl] -1- (3-diethylaminopropyloxamoyl) hydrazine 21.
92 g of the mixed solution was added dropwise. After stirring at room temperature for 30 minutes, the mixture was concentrated under reduced pressure and 5% sodium hydrogen carbonate solution 135 m
1 was added and the mixture was heated at 60 ° C. Chloroform (135 ml) was added, the chloroform layer was extracted, dried over magnesium sulfate, concentrated under reduced pressure, and purified by silica gel chromatography to obtain 10.79 g of a candy-like target product.

Synthesis Example 2 Synthesis of H-4 Synthesis of 2- (p-guanidinophenyl) -1- (ethoxalyl) hydrazine hydrochloride (Intermediate B) 2- (p-aminophenyl) -1- (ethoxalyl) hydrazine 5.50 g, 1H-pyrazole-1-carboxamidine hydrochloride 3.00 g, diisopropylethylamine 2.79 g, N, N-dimethylformamide 40 m
The mixture of 1 was stirred at room temperature under a nitrogen atmosphere for 12 hours.
After concentration under reduced pressure, the residue was purified by silica gel chromatography to obtain 4.03 g of the desired product. Melting point 68 [deg.] C. Intermediate B 4.03 g, 3-aminopropanol 1.
A mixed solution of 00 g and methanol (25 ml) was heated under reflux for 1 hour, insoluble materials were filtered off, and the residue was concentrated under reduced pressure. The residue was purified by silica gel chromatography to obtain 2.68 g of a candy-like target product. Other exemplified compounds were synthesized by the same method.

The hydrazine derivative of the present invention is 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 preferable, and the silver halide type is silver chloride or salt. Although 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 means an emulsion composed of silver halide grains having a surface sensitivity higher than the internal sensitivity, and this emulsion is preferably US Pat. No. 4,224,224. It has a difference between the surface sensitivity and the internal sensitivity defined in the specification of 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 formula (1) is preferably contained in the surface latent image type silver halide emulsion layer, but it is adjacent to the surface latent image type silver halide emulsion layer. It may be contained in the 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. In layer 1
The appropriate content can vary over a wide range because the content of the silver halide emulsion used varies depending on the characteristics of the silver halide emulsion, the chemical structure of the compound and the development conditions. About 1 × 10 ^-6 to 1 per mole
A range of x10 ^-2 mol is practically useful.

The photographic emulsion used in the present invention may be spectrally sensitized with methine dyes and 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.

Gelatin is advantageously used as the binder or protective colloid that can be used in the emulsion layer and 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, 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 the method of obtaining an ultrahigh 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, mercaptotetrazoles. , Mercaptopyrimidines, mercaptotriazines, thioketo compounds, azaindenes, and many other compounds conventionally known as antifoggants or stabilizers 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 or other hydrophilic colloid layer. 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.) or the like can be used alone or in combination.

In the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced by using the present invention, coating aids, antistatic agents, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement (eg development) A surfactant 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 sparingly soluble synthetic polymer decomposition product in the photographic emulsion layer or other hydrophilic colloid layer 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.
m ² preferably 1.0 × 10 ^{−7 to} 1.0 × 10 ⁻⁵ mol /
It is suitable to allow m ^{2 to} exist.

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, No. 61-167939, No. 62-222241, No. 63-124045, the compounds disclosed in US Pat. No. 4,975,354 and the like, and various kinds containing N or S atom. Are effective. These accelerators, but the optimum amount differs depending on the kind of the compound ^{1.0 × 10 -3 ~0.5g / m 2} , preferably 5.0 × 10 ^- in the range of ³ to 0.1 g / m ² It is desirable to use. These accelerators are suitable solvents (water, alcohols such as methanol and ethanol, acetone, N,
It is dissolved in 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 a filter dye, a dye for further lowering photographic sensitivity, preferably an ultraviolet absorber having a spectral absorption maximum in the intrinsic sensitivity region of silver halide, and safety against safelight light when handled as a light-sensitive room light material 310nm to increase the
A dye having substantial light absorption in the region of up to 600 nm is used. 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. Usually 10 depending on the molar extinction coefficient of the dye
^{-3 to 1} g / m ² is added. Preferably 10
It is 500 mg / m ² . The dye is a suitable solvent (for example, water, alcohols such as methanol and ethanol,
It can be dissolved in acetone, methyl cellosolve or the like, or a mixed solvent thereof and added to the coating solution.
These dyes can be used in combination of two or more. Specific examples of these dyes are shown in Japanese Patent Application No. 61-209169.
No. Others, U.S. Pat. No. 3,314,
No. 794, No. 3,352,681, No. 3,49
9,762, 3,533,794, 3,7
00,455, 3,705,805, 3,
707,375, 4,045,229, JP-A-46-2784, West German patent application publication 1,547,86.
Ultraviolet absorbing dyes described in No. 3 and the like are also used. In addition, pyrazolone oxonol dyes described in U.S. Pat. No. 2,274,782, JP-A Nos. 62-185755 and 63-2045, and U.S. Pat. No. 2,956,8
Diarylazo dyes described in 79, US Pat. No. 3,4
23,207 and 3,384,487, styryl dyes and butadienyl dyes, and US Pat. No. 2,52.
7,583, merocyanine dyes described in U.S. Pat. Nos. 3,486,897, 3,652,284, and 3,718,472, merocyanine dyes and oxonol dyes, and U.S. Pat. , 976, 661 and British Patent No. 58
4,609, 1,177,429, JP-A-48
-85130, 49-99620, 49-11
4420, U.S. Pat. Nos. 2,533,472, 3,148,187, 3,177,078, 3,247,127, 3,540,887,
No. 3,575,704, No. 3,653,905
And the dyes described in JP-A No. 62-133453 can also be used.

To obtain ultrahigh contrast photographic characteristics using the silver halide light-sensitive material of the present invention, a conventional lith developer or pH 13 described in US Pat. No. 2,419,975 is 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, by adding amines to a developing solution, the developing speed can be increased and the developing time can be shortened. 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.

[0029]

[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 the addition of gelatin. 2-Methyl-4-hydroxy-1,3,3a, 7-tetraazaindene was added as a stabilizer without aging. This emulsion has an average grain size of 0.2μ
It was a monodisperse emulsion having a cubic crystal form. Table 1 for this emulsion
After adding the following hydrazine compounds selected from the general formula (1) shown in Table 1 and comparative compounds A, B and C in the amounts shown in Table 1, the nucleation accelerator shown below was added at 30 mg / m 2.
^In addition to ² , polyethyl acrylate latex was added to the solid content of 30% by weight of gelatin to obtain 2,4 as a hardening agent.
-Dichloro-6-hydroxy-s-triazine was added,
It 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.

[0030]

Embedded image

[0031]

Embedded image

2) Evaluation of Photographic Property The coated sample thus obtained was imagewise exposed by a bright room printer P-627GA manufactured by Dainippon Screen Co., Ltd., and developed with a developer having the following composition at 35 ° C. for 30 seconds to obtain Mitsubishi Paper Mills ( It 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 extracted character image quality 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. Similarly, Dmax is 50% of the original and halftone dot area is 50%.
Is Dmax when the exposure is performed so that the halftone dot area becomes. The sample of the present invention has a high Dmax and is excellent in character image quality. Further, compared to the comparative compound, it works effectively even when added in a small amount.

[Developer] Hydroquinone 30.0 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-plaseridone 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-Benzene sulfone amido-2-mercaptopentimimizosol 0.5 g Water is added to adjust to pH 10.6 to 1 liter.

[0034]

[Table 1]

Example 2 1) Preparation of coating sample 4 × 10 ⁻⁷ mol of iridium (III) hexachloride per mol of silver
97 mol% AgBr in the presence of potassium and ammonia,
A cubic iodobromide emulsion containing 3 mol% AgI and having an average grain size of 0.25 μ 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 ° C.
5'-Dichloro-9-ethyl-3,3'-bis (4-sulfobutyl) oxacarbocyanine was added, and the mixture was allowed to stand 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 further 5-methylbenzothiazole and 2-methyl-
4-Hydroxy-1,3,3a, 7-tetraazaindene was added. Also, 20 mg of the contrast enhancing agent shown below is used.
/ M ² and 1,3-divinylsulfonyl-2-propanol were added and coated on a polyethylene terephthalate film so that the amount of silver was 3.7 g / m ² . A gelatin was applied thereon as a protective layer so as to be 1.5 g / m ² to obtain a sample.

[0036]

Embedded image

[0037]

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, developed with the developing solution at 35 ° C for 30 seconds, fixed, washed with water and dried. 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 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 the amount of exposure (log which gives 1.5 as the optical density of a sample which 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 a good halftone dot quality is provided as compared with the comparative compound.

[0038]

[Table 2]

[0039]

INDUSTRIAL APPLICABILITY The silver halide photographic light-sensitive material of the present invention can obtain good image quality of printed letters and halftone dots and 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 general formula (1), R ₁ , R ₂ , R ₃ and R _{4, which} may be the same or different, each represents a hydrogen atom, an aliphatic group or an aromatic group, and R ₁ , R ₂ , R ₂ And R ₃ and R ₃ and R ₄ may be connected to each other to form a cyclic structure. X represents a divalent aliphatic group or an aromatic group, L is -SO ₂ NR ₆ -, - NR
₆ SO ₂ NR _6- , -CONR _6- , -CSNR _6- , -N
_{R 6 CONR 6 -, - NR} 6 CSNR 6 -, - G 1 P (O)
(G ₁ R ₁ ) NR ₆ −. G ₁ represents a single bond, an —O— group or a —NR ₆ — group, and R ₆ represents a hydrogen atom, an aliphatic group or an aromatic group. Y represents a substitutable group. n is 0 to 4
It is. G represents a carbonyl group, a sulfonyl group, a sulfinyl group, an oxalyl group or a phosphoryl group, and m is 0
Or 1. R ₅ represents a hydrogen atom, an aliphatic group, an alkoxy group, an aryloxy group, an aromatic group, an amino group or the general formula (2). Embedded image In the general formula (2), Q ⁺ represents a group containing a cationic group and A ⁻ represents an anion, but it is not necessary when Q ⁺ contains a sulfo group.