JP3473826B2 - Silver halide photographic material and processing method thereof - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material and a superhigh contrast 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 recent years, colorization and complexity of printed matter have been rapidly progressing in the field of printing photoengraving. Therefore, demands for improving the quality and stabilizing the quality of the silver halide light-sensitive material for printing (hereinafter referred to as a printing light-sensitive material), which is an intermediate medium for printing, are increasing year by year. Conventionally, a general printing photosensitive material has been imparted with so-called lith development processing suitability in order to achieve high quality. However, in the lith development, it is mechanically impossible to contain a high concentration of a sulfite ion, which is a preservative, in the developing processing solution, and therefore it is not known to those skilled in the art that the stability of the developing solution is very poor. Then it is a well-known fact. As a technique for eliminating the instability of the lith development and obtaining a high-contrast image similar to the lith development processing, the disclosure of the patent document can be seen for some attempts. For example, a technique for obtaining a high-contrast image using a hydrazine compound is disclosed in JP-A-53-16623, JP-A-53-20921, and JP-A-53-20922.
No. 53-49429, No. 53-66732, No. 55-90940,
56-67843, 57-99635, 62-73256, 62
-275247, 62-178246, 62-180361, 63-
121838, 63-223744, 63-234244, 63-25
No. 3357, No. 64-90439, JP-A No. 1-105943, No. 2-25
No. 843, No. 2-120736, No. 2-37, No. 2-8834, No. 3-125134, No. 3-184039, No. 4-51143. The pH of the developer containing these hydrazine compounds is required to be at a relatively high level in order to obtain a high contrast image, and the developer having this high pH absorbs carbon dioxide in the air. However, there is a drawback that the pH tends to decrease and the stability against air oxidation is not always sufficient, and the effective life of the developer is short.

To overcome these drawbacks, a lower p
For example, as disclosed in JP-A-60-179734,
62-948, U.S. Pat.Nos. 4,385,108 and 4,269,929.
No. 4,988,604, No. 4,994,365, No. 5,104,769, and the like, attempts have been made to make the hydrazine derivative more active, but improvement of the hydrazine derivative alone makes it difficult to achieve high contrast at low pH. There was a limit. Therefore, the development of a contrast enhancing agent has been conventionally advanced.
As described in JP-A-56-106244, JP-A-60-218642, JP-A-61-267759, etc., a method of adding a secondary or tertiary amino compound to a developing solution, JP-A-60-140340. , Ibid 62
There is known a method of adding an amino compound to a light-sensitive material as disclosed in Nos. -222241 and 63-124045 and U.S. Pat. No. 4,975,354. However, none of them have the drawbacks that they still do not exhibit satisfactory contrast, or that they must be used in large amounts, and that the photographic performance changes greatly when the composition of the developer changes due to running or air oxidation. Therefore, it has been desired to develop a more effective accelerator.

[0004]

SUMMARY OF THE INVENTION The first object of the present invention is to provide a light-sensitive material having a high contrast and a high image density by using a developing solution which is stable at a low pH. A second object of the present invention is to provide a photosensitive material for printing plate making containing an effective accelerator having an effect of promoting contrast enhancement in a small amount. A third object of the present invention is to provide a silver halide photographic light-sensitive material which has little change in photographic performance due to change in developer composition.

[0005]

A method of processing a silver halide photographic light-sensitive material, which comprises subjecting an exposed silver halide photographic light-sensitive material to development processing in the presence of a compound represented by the following general formula (1). Achieved by the method.

[0006]

[Chemical 2]

In the formula, R ¹ , R ² and R ³ represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ¹ and R ² may be linked to form a ring. L represents a divalent linking group, E is ^{-N (CSNR 11 R 12) -} , - NR 13 CSNR 14 - represents a. R ^{11 to} R ¹⁴ are a hydrogen atom, an alkyl group, an aryl group,
It represents a heterocyclic group, and R ¹¹ and R ¹² may combine to form a ring.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The general formula (1) will be described in detail below. The alkyl group represented by R ¹ , R ² , R ³ and R ^{11 to} R ¹⁴ has a substituted or unsubstituted carbon number of 1 to 3
Represents an alkyl group of 0, which may be linear, branched or cyclic. Examples of the unsubstituted alkyl group include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, a hexyl group, a cyclohexyl group, and an n-decyl group. R ¹ and R ² , and R ¹¹ and R ¹² may combine to form a ring, and a saturated heterocycle containing a hetero atom (eg, nitrogen atom, oxygen atom, sulfur atom, etc.) therein,
For example, a piperidine ring, a 2-methylpiperidine ring, a morpholine ring, a piperazine ring or the like may be formed. The substituent as the substituted alkyl group includes an aryl group (eg, phenyl group, naphthyl group, etc.), an alkenyl group (eg, vinyl group,
Allyl group, butenyl group etc.), alkynyl group (eg ethynyl group etc.), heterocyclic group (pyridyl group, tetrahydropyranyl group, sulforanyl group etc.), hydroxy group, alkoxy group (eg methoxy group, ethoxy group, benzyloxy group) , Polyethyleneoxyalkyl group etc.), alkoxycarbonyl group (eg ethoxycarbonyl group, benzyloxycarbonyl group etc.), carboxy group, sulfo group, halogen atom (eg chlorine atom, bromine atom etc.), cyano group,
Aryloxy group (eg, phenoxy group, p-tolyloxy group, etc.), acyloxy group (eg, acetyloxy group, propionyloxy group, etc.) Acyl group (eg, acetyl group, propionyl group, benzoyl group, mesyl group, etc.), carbamoyl A group (eg, carbamoyl group, N,
N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, etc.), sulfamoyl group (for example, sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group, etc.), acylamino group (For example, acetylamino group, propionylamino group, mesylamino group, etc.), sulfonamide group (ethylsulfonamide group, p-toluenesulfonamide group, etc.), ureido group (for example, methylureido group, phenylureido group, etc.), Examples thereof include an amino group (eg, diethylamino group). R ¹ ,
Examples of the aryl group represented by R ² , R ³ and R ^{11 to} R ¹⁴ include a phenyl group and a naphthyl group, which have a substituent (the same as those described in the section of the substituted alkyl group). May be. Examples of the heterocyclic group represented by R ¹ , R ² , R ³ and R ^{11 to} R ¹⁴ include a piperidyl group, a morpholinyl group, a furyl group, a thienyl group, a tetrahydropyranyl group,
Examples thereof include a pyridyl group, which may have a substituent (the same as those described in the section of the substituted alkyl group) L
Is an optionally substituted alkylene group having 1 to 10 carbon atoms,
For example, it represents a methylene group, an ethylene group, a propylene group and the like, and examples of the substituent include an aryl group, an alkoxy group, a hydroxy group and a halogen atom. General formula
The compound represented by the formula (1) is particularly preferably the following general formula
In the compound of (2), R ¹ , R ² , R ³ , L and E are the same as those described in the general formula (1).

[0009]

[Chemical 3]

Specific examples of the compound represented by the general formula (1) are shown below, but the present invention is not limited to the following compounds.

[0011]

[Chemical 4]

[0012]

[Chemical 5]

[0013]

[Chemical 6]

[0014]

[Chemical 7]

[0015]

[Chemical 8]

[0016]

[Chemical 9]

Next, specific synthesis examples of the contrast enhancing agent represented by the general formula (1) will be shown. Synthesis Example 1 Synthesis of Exemplified Compound A-11 To 1600 ml of acetonitrile, 920 ml of N, N-diethylethylenediamine, 371 g of triethylene glycol-ditosylate and 215 g of sodium carbonate were added, and the mixture was stirred under reflux for 28 hours. The insoluble material was filtered off, and acetonitrile and excess N, N-diethylethylenediamine were distilled off under reduced pressure. The residue was dissolved in 1000 ml of water and washed with isopropyl ether, and the aqueous layer was washed with chloroform 1000
Extracted with ml. The chloroform layer was washed with brine, dried over magnesium sulfate, and the chloroform was distilled off to obtain 221 g of ethylene glycol-O, O'-bis (2- (2-diethylaminoethylamino) ethyl) ether as an oily substance. Next, this oily substance was dissolved in 500 ml of acetonitrile, and 2-dibutylaminoethylisocyanate 260 was dissolved.
g was added, and the mixture was stirred on a water bath at 80 ° C. for 30 minutes. After distilling off acetonitrile, the residue was dissolved in 1600 ml of 2N-hydrochloric acid and washed with ethyl acetate. 128 g of sodium hydroxide was added to the aqueous layer, and the separated oily matter was mixed with 100 ml of ethyl acetate.
The mixture was extracted with 0 ml, washed with brine, dried over magnesium sulfate, the solvent was distilled off, and Exemplified compound A-1 was obtained as an oily product 392.
g was obtained.

When the compound of the general formula (1) of the present invention is added to the photographic light-sensitive material, it is preferable to add it to the silver halide emulsion layer, but the other non-photosensitive hydrophilic colloid layer ( (Eg, protective layer, intermediate layer, filter layer, antihalation layer, etc.). Specifically, when the compound used is water-soluble, as an aqueous solution, and when it is poorly water-soluble, a water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone). , Methyl ethyl ketone), dimethylacetamide, dimethyl sulfoxide,
It may be added to the hydrophilic colloid solution as a solution of an organic solvent such as methyl cellosolve. When it is added to the silver halide emulsion layer, it can be added at any time during emulsion preparation, but it is preferably added after the completion of chemical ripening and before coating. Particularly preferably, it is added to the coating solution prepared for coating. The amount of addition is 1 mol of silver halide,
It is used in the range of 1.0 × 10 ^{−4 to} 1.0 × 10 ⁻¹ mol, more preferably 5.0 × 10 ^{−4 to} 5.0 × 10 ⁻² mol. When the compound is added to the developer, it is preferably 5 × 10 ^{−3 to} 0.30 mol per liter of the developer.
The compound represented by the general formula (1) of the present invention has the effect of accelerating the enhancement of contrast when used in a system for obtaining a so-called contrast-rich silver image. The compound represented by the general formula (1) of the present invention is most effective in a system using a hydrazine derivative as a nucleating agent. Examples of the hydrazine derivative used in the present invention include compounds represented by the following general formula (3).

[0019]

[Chemical 10]

In the general formula (3), A ₁ and A ₂ are both hydrogen atoms or one is a hydrogen atom and the other is a sulfonyl group or an acyl group, and R ₂₁ is an aliphatic group, an aromatic group or a heterocycle. Represents a group, G ₁ represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group, an oxalyl group or an iminomethylene group, and R ₂₂ represents a hydrogen atom, an aliphatic group, an aromatic group, an alkoxy group, an aryloxy group, amino. Group or general formula (4)
Represents

[0021]

[Chemical 11]

In the general formula (4), Q ⁺ represents a group containing a cationic group and A ⁻ represents an anion, but it is not necessary when Q ⁺ contains a sulfo group.

Next, the general formulas (3) and (4) will be described in detail. In the general formula (3), A ₁ and A ₂ are hydrogen atoms, an alkylsulfonyl group having 20 or less carbon atoms and an arylsulfonyl group (preferably a phenylsulfonyl group, or the sum of Hammett's σ _p is -0.5 or more). A phenylsulfonyl group substituted so as to be), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or the sum of Hammett's σ _p is -0.5).
A benzoyl group substituted as described above), or a linear, branched or cyclic unsubstituted and substituted aliphatic acyl group (as a substituent, for example, a halogen atom, an ether group,
Examples thereof include sulfonamide group, amide group, hydroxy group, carboxy group, and sulfo group. It is most preferable that A ₁ and A ₂ are hydrogen atoms. The aliphatic group represented by R ₂₁ is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group. The aromatic group represented by R ₂₁ is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group and a naphthyl group. The heterocyclic group for R ₂₁ contains at least one of N, O and S atoms.
It is a 10-membered saturated or unsaturated heterocycle, which may be a monocycle or may further form a condensed ring with another aromatic ring or heterocycle. The heterocycle is preferably a 5- to 6-membered aromatic heterocyclic group, and includes, for example, a pyridyl group, an imidazolyl group, a quinolinyl group, a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, an isoquinolinyl group, a thiazolyl group, a benzthiazolyl group. Those are preferable. R ₂₁ may be substituted with a substituent. Examples of the substituent include the followings. These groups may be further substituted. For example, an alkyl group,
Aralkyl group, alkoxy group, aryl group, substituted amino group, acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group , A halogen atom, a cyano group, a sulfo group, a carboxy group, an ammonium group, a pyridinium group, a thiuronium group, an isothioureido group and the like. When possible, these groups may be linked to each other to form a ring. Preferred as R ₂₁ is an aromatic group, more preferably an aryl group. or,
R ₂₁ may have a ballast group, which is commonly used in a non-moving photographic additive such as a coupler, incorporated therein. The ballast group is a group having a carbon number of 8 or more and relatively inactive for photographic properties, and examples thereof include an alkyl group and
It can be selected from an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group and the like. Q ⁺ in the general formula (4) is a group containing a cationic group having at least one quaternary nitrogen atom,
It may be bonded to G ₁ through a straight or branched hydrocarbon chain having 1 to 4 carbon atoms, and part or all of this chain may form part of a heterocycle having a quaternary nitrogen atom. Good.
Preferred examples of Q ⁺ include trialkylammonioalkyl group, pyridinium-1-ylalkyl group, 1-alkylpyridinium-2-yl group, 1-alkylpyridinium-3-yl group, 1-alkylpyridinium-4-
Examples thereof include an yl group, a thiazolinium-3-ylalkyl group, an oxazolinium-3-ylalkyl group, and a 1-alkylimidazolium-3-ylalkyl group. These groups may be substituted, and as the substituent, those mentioned as the substituent for R ²¹ are preferable. Further, when these groups form a ring structure, they may be condensed with another ring. A ⁻ is a counter anion of Q ⁺ , and preferred examples thereof include Cl ⁻ , Br ⁻ , p-toluene sulfonate, methyl sulfonate and the like, which has a sulfo group as a substituent of Q ⁺ and has an inner salt. It does not exist when forming.

G ₁ represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group, an oxalyl group or an iminomethylene group, and G ₁ is preferably a carbonyl group or an oxalyl group. The aliphatic group represented by R ₂₂ is preferably an alkyl group having 1 to 5 carbon atoms, and the aromatic group is preferably a monocyclic or bicyclic aryl group (for example, one containing a benzene ring). When G ₁ is a carbonyl group, R
Preferred among the groups represented by ₂₂ are a hydrogen atom, an alkyl group (eg, methyl group, trifluoromethyl group, 3
-Hydroxypropyl group, 3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc.), aralkyl group (eg, 2-hydroxybenzyl group, etc.), aryl group (eg, phenyl group, 3,5-dichlorophenyl group, 2- Methanesulfonamidophenyl group, 4-methanesulfonamidophenyl group, 2-hydroxymethylphenyl group, etc.), general formula (4), and the like, with a hydrogen atom and general formula (4) being particularly preferable. R ₂₂ may be substituted, and as the substituent, the substituents listed for R ₂₁ can be applied. When G ₁ is an oxalyl group, preferred as R ₂₂ are an alkoxy group (eg, a methoxy group, an ethoxy group, an isopropoxy group, a methoxyethoxy group, etc.), an aryloxy group (eg, a phenoxy group, 2-
Hydroxymethylphenoxy group, 4-chlorophenoxy group), amino group (for example, 3-hydroxypropylamino group, 2,3-dihydroxypropylamino group, 2-dimethylaminoethylamino group, 3-diethylaminopropylamino group, etc.), Formula (4) and the like are preferable, and an amino group is particularly preferable. R ₂₁ and R ₂₂ may be those in which a group that enhances adsorption to the surface of the silver halide grain is incorporated. Examples of the adsorptive group include groups described in US Pat. No. 4,355,105 such as thiourea group, heterocyclic thioamide group, mercaptoheterocyclic group, and triazole group. Also, R ₂₂ disrupts the portion of the G ₁ -R ₂₂ from the remainder molecule may be such as to rise to cyclization reaction to form a cyclic structure containing a -G ₁ -R ₂₂ moiety of atoms Examples thereof include those described in JP-A-63-29751. Specific examples of the compound represented by the general formula (3) are shown below, but the present invention is not limited to the following compounds.

[0025]

[Chemical 12]

[0026]

[Chemical 13]

[0027]

[Chemical 14]

[0028]

[Chemical 15]

[0029]

[Chemical 16]

The hydrazine compound of the present invention is described in, for example, JP-A Nos. 61-213847, 62-178246, 62-180361 and 62-178361.
62-260153, 63-253357, U.S. Patent No. 4,684,604
Issue No. 3,379,529, No. 4,377,634, No. 4,332,87
No. 8, No. 4,937,160, Japanese Patent Application No. 63-98803 and the like can be used for the synthesis.

The hydrazine compound of the present invention is a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethylacetamide, dimethylsulfoxide,
It can be used by dissolving it in methyl cellosolve or the like.
Further, by a well-known emulsification dispersion method, oil such as dimethyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate is dissolved using an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. Objects can be created and used. Alternatively, the hydrazine compound powder may be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method, and then used.

The silver halide used in the light-sensitive silver halide emulsion 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 is selected from silver chloride and salts. Although silver bromide, silver chloroiodobromide, silver iodobromide, silver bromide or the like can be used, when silver chloroiodobromide or silver iodobromide 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, etc. of the silver halide grains are not particularly limited, but the grain size is 0.7.
It is preferably μm or less. A silver halide emulsion is a sulfur compound that reacts with a gold compound such as chloroaurate or gold trichloride, a salt of a noble metal such as rhodium or iridium or a silver salt to form silver sulfide, a stannous salt, The sensitivity can be increased with a reducing substance such as amines without coarsening the particles. Also, salts of precious metals such as rhodium and iridium,
An iron compound such as 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 it further promotes the effect of the present invention of achieving photographic characteristics of ultrahigh contrast in a short developing 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 the US Pat.
It has a difference between the surface sensitivity and the internal sensitivity defined in the specification of 4,224,401. The silver halide emulsion is preferably monodispersed, and particularly preferably an emulsion having monodispersity defined in the above-mentioned US Pat. No. 4,224,401. The silver halide emulsion used in the present invention preferably contains a water-soluble rhodium salt (e.g., rhodium dichloride, rhodium trichloride, potassium hexachloride rhodium (III) acid, ammonium hexachloride rhodium (III) acid, etc.). 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 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 0.7 μm or less, particularly preferably in the range of 0.1 to 0.4 μm. The silver halide grains may have a regular shape such as a cube or an octahedron or a mixed crystal form, but a so-called monodisperse emulsion having a relatively narrow grain size distribution is preferable. The monodisperse emulsion referred to 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. But for the purposes 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 thus prepared may or may not be chemically sensitized. The so-called bright room light-sensitive material to be handled in a safe light environment which can be called a bright room is easy to handle. From the viewpoint of improving the quality, it is rather preferable not to perform chemical sensitization. For chemical sensitization, ordinary sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization and the like are used.

In the light-sensitive material of the present invention, the hydrazine compound is preferably contained in the silver halide emulsion layer.
It may be contained in a hydrophilic colloid layer adjacent to the surface latent image type silver halide emulsion layer. Such a layer is a layer having any function, such as a subbing layer, an intermediate layer, a filter layer, a protective layer, or an antihalation layer, as long as it does not prevent the hydrazine compound from diffusing into the silver halide grains. Good. Since the content of the hydrazine compound 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, but for the hydrazine compound the surface can be varied. About 1 x 10 per mol of silver in latent image type silver halide emulsion
A range of ^-6 to 1 x 10 ^-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
Cyanine dyes, merocyanine dyes, and composite merocyanine dyes. 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, a dye having no spectral sensitizing effect itself or a substance that does not substantially absorb visible light and exhibits supersensitization may be included in the emulsion.

As the binder or protective colloid that 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 hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol. It is possible to use various kinds of synthetic hydrophilic polymer substances such as a partial or acetal of polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, and other single or copolymers. . Examples of gelatin include lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Phot. Japan,
The enzyme-treated gelatin as described in No. 16, p. 30 (1966) may be used, or a hydrolyzed product or an enzymatically decomposed product of gelatin may also be used.

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

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.) or the like can be used alone or in combination. A compound described in Research Disclosure No. 17465, Sections XXI, B to D is added to the photosensitive silver halide emulsion layer or its adjacent layer for the purpose of increasing sensitivity, increasing contrast, or promoting development. In particular, it is preferable to add polyethylene glycol or its derivative. The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced by using the present invention may include a coating aid, an antistatic agent,
Surfactants may be included for various purposes such as improving slipperiness, emulsifying and dispersing, preventing adhesion and improving photographic characteristics (for example, development acceleration, hardening, and sensitization). Non-ionics such as saponins (steroids), alkylene oxide derivatives (polyethylene glycol, polyethylene glycol alkyl ethers, etc.), glycidol derivatives (alkenyl succinic acid polyglycerides, etc.), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Surfactants, alkyl carboxylates, alkyl sulfates,
Carboxy group, such as alkyl phosphates,
Anionic surfactants containing amino groups such as sulfo group, phospho group, sulfate group, and phosphate group, amino acids,
Amphoteric surfactants such as aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid esters, cationic surfactants such as aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium 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, olefin, styrene, etc., alone or in combination, or with these, acrylic acid,
A polymer having a monomer component of a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, styrene sulfonic acid and the like can be used.

To obtain ultrahigh contrast photographic characteristics using the silver halide light-sensitive material of the present invention, a conventional lith developer or a highly alkaline developer near pH 13 described in US Pat. No. 2,419,975 is used. It is not necessary and a stable developing solution can be used. That is, for the silver halide photographic light-sensitive material of the present invention, a developer containing a sufficient amount of sulfite ion as a preservative (especially 0.15 mol / l or more) can be used, and a pH of 9.5 or more, Particularly, a developing solution of 10 to 11.0 can sufficiently obtain a super-high contrast negative image.
Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.

[0041]

Example 1 6-Methyl-4-hydroxy-1,3,3a, 7 was added to a monodisperse silver chlorobromide emulsion containing iridium and having an average particle size of 0.25 μm prepared by the control double jet method.
1 g / Ag of tetrazaindene was added. Anhydro-5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine hydroxide pyridinium was used as a sensitizing dye at 300 mg / Ag1.
mol, the exemplified hydrazine compound and the contrast enhancing agent were added as shown in Table 1. 2 g / m ² of polyethylene acrylate dispersion and 2.5 g of gelatin were added to the emulsion thus obtained.
/ M ² , and the coated silver amount was 3.5 g / m ² on the polyethylene terephthalate film. Comparative compounds (1), (2) and (3) were similarly used as comparative samples of the contrast enhancing agent.

[0042]

[Chemical 17]

The sample thus obtained was exposed through a light wedge to a printer using a tungsten lamp as a light source, and then developed with a developer having the following composition at 38 ° C. for 20 seconds, stopped, fixed, washed with water and dried. Their relative photographic speed, contrast and dot quality were evaluated. The contrast is the slope of the straight line of the characteristic curve (tan of optical density 0.1 to 2.50).
θ). The halftone dot quality is a subjective measure and was ranked on a scale of 5 with 1 being extremely poor and 5 being extremely good. Three or more were considered to be practically usable. The results are shown in Table 2.

<Developer (concentrate)> Hydroquinone 65 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-phenylazoline 2.9 g Sodium pyrosulfite 145 g Diethylenetriamine pentaacetic acid pentasodium salt 6.0 g Boric acid 6.9 g Sodium bromide 12 g 1-Phenyl-5-mercaptotetrazole 0.05 g Sodium hydroxide 23 g Benzotriazole 0.4 g Potassium hydroxide 80 g Potassium carbonate 80 g Diethylene glycol 120 g Water was added 1 liter The concentrate was 1 part with respect to 4 parts water 1 part Diluted to a pH of 1
The developing solution was 0.5.

[0045]

[Table 1]

[0046]

[Table 2]

Example 2 The developer used in Example 1 was adjusted to pH values shown in Tables 3 and 4 with an aqueous sodium hydroxide solution and sulfuric acid, and the developing time was set to 40 seconds at 35 ° C. The same items as in 1 and pepper fog were evaluated. Pepper fog
According to the visual judgment, 1 was extremely poor, and 5 was ranked in 5 grades, which means a good state in which pepper was hardly observed. The obtained results are shown in Tables 3 and 4.

[0048]

[Table 3]

[0049]

[Table 4]

It can be seen that when the compound of the general formula (1) of the present invention is used, it exhibits a high effect of promoting high contrast with a small addition amount, and improves the sensitivity, contrast and halftone dot quality. Further, even when the pH of the developing solution is changed, the contrast is kept higher than that of the comparative compound, and the practically preferable photographic characteristics in which the generation of pepper fog is suppressed are provided. Further, it is apparent that the use of the compound of the general formula (1) causes the hydrazine compound to produce a high contrast even in a developer having a low pH.

[0051]

INDUSTRIAL APPLICABILITY The formation of a high-contrast image by a silver halide photographic material containing a hydrazine compound in the presence of a high-contrast accelerator selected from the compounds of the general formula (1) of the present invention is a developer having a pH lower than that of the prior art. However, it is easy to obtain photographic characteristics that are not easily affected by pH changes. In addition, the contrast enhancing agent described in the present specification is easy to synthesize, low in cost, and very effective.

Claims (2)

(57) [Claims] 1. A method for processing a silver halide photographic light-sensitive material, which comprises developing the exposed silver halide photographic light-sensitive material in the presence of a compound represented by the following general formula (1). [Chemical 1] In the formula, R ¹ , R ² and R ³ are a hydrogen atom or an unsubstituted alkyl group.
Group, aryl group, alkenyl group, alkynyl group
Group, heterocyclic group, hydroxy group, alkoxy group, alkoxy group
Sicarbonyl group, carboxy group, sulfo group, halogen source
Child, cyano group, aryloxy group, acyloxy group,
Syl group, carbamoyl group, sulfamoyl group, acyl group
Mino group, sulfonamide group, ureido group or amino
It represents an alkyl group substituted with a group, and R ¹ and R ² may combine to form a ring. L represents a divalent linking group, E is -N (CSNR ¹¹ R ¹² )-, -NR ¹³ CSNR.
¹⁴ represents. R ^{11 to} R ¹⁴ represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and R ¹¹ and R ¹² may combine to form a ring. 2. A support having at least one silver halide emulsion layer, and the emulsion layer or another hydrophilic colloid layer containing a compound represented by the general formula (1) and a hydrazine derivative. A silver halide photographic light-sensitive material characterized by the above.