JPH08248549A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To provide the silver halide photographic sensitive material for making a printing plate enhanced in rapid processability and processing stability. CONSTITUTION: The photographic sensitive material contains the compound represented by the formula in which each of L1 and L2 is a divalent bonding group; G is a carbonyl, sulfinyl, oxalyl, or phosphoryl group; each of R1 and R2 is, independently, an H atom or an alkyl, aralkyl, alkenyl, or aryl group or each may combine with each other to form an N-containing 5--18-membered ring; R3 is an alkyl, aralkyl, or alkenyl group; R4 is an H atom or an alkyl, alkoxy, aryloxy, aryl, or amino group; and the isothioureido group in the formula may be a salt a protonic acid. The use of this hydrazine compound permits the photosensitive material to maintain a high Dmax by using a developing solution low in pH and a small replenishing rate and to give good dot quality.

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 showing photographic characteristics of super-high contrast (especially gamma of 10 or more) is provided in order to improve reproduction of continuous tone images or halftone images by halftone dot 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,
A method using a hydrazine derivative described in U.S. Pat. No. 4,272,606 is known. According to this method, ultra-high contrast and highly sensitive photographic characteristics can be obtained, and since it is permissible to add a high concentration of sulfite to the developer, the stability of the developer against air oxidation is higher than that of the lith developer. And dramatically improve. 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, an ultrahigh contrast system using a hydrazine compound requires a developer having a relatively high pH, for example, 11.5 or 11.8.
There is a high risk of handling, and when treating waste liquid B
There are problems such as high OD and COD. Also, 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. Further, the reversing sensitive material generally handled in a bright room occupies a large field as one of the sensitive materials for plate making, and in this field, a high quality of blank characters for reproducing thin Mincho characters is required. Therefore, the development of a more active nucleating agent 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 achieved by a silver halide photographic light-sensitive material characterized by containing a compound represented by the chemical formula 1.

In the formula, L ₁ and L ₂ represent a divalent linking group.
Among them, the arylene group is preferable, and the phenylene group is particularly preferable. Further, the carbon atom may have a substituent well known in the art (for example, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a hydroxy group, a halogen atom, an amide group, a sulfonamide group, etc.). G represents a carbonyl group, a sulfonyl group, a sulfinyl group, an oxalyl group, or a phosphoryl group. Of these, a carbonyl group and an oxalyl group are preferable. R ₁ and R ₂
Each independently represent a hydrogen atom, an alkyl group, an aralkyl group, an alkenyl group, or an aryl group, or represent an atomic group necessary for forming a nitrogen-containing 5- to 18-membered ring by linking with each other, and R ₃ is alkyl. Represents a group, an aralkyl group and an alkenyl group. Preferable examples of these alkyl group, aralkyl group and alkenyl group are those having 1 to 30 carbon atoms, and those having 1 to 20 carbon atoms are particularly preferable. The aryl group is preferably monocyclic or bicyclic. Examples of the nitrogen-containing 5- to 18-membered ring formed by R ₁ and R ₂ connected to each other include, for example, pyrrolidine, piperidine, hexamethyleneimine, piperazine, morpholine, thiomorpholine, monoazacrown ether-12,15, There are 18 and so on.
The R _{1 to} R ₃ may be substituted with a substituent well known in the art. Typical examples thereof include an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group,
Aryl group, aryloxy group, sulfamoyl group, ureido group, urethane group, carbamoyl group, alkyl or arylthio group, alkyl or arylsulfonyl group, hydroxy group, halogen atom, cyano group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group , An acyloxy group, an amide group, a sulfonamide group, a carboxy group and the like.

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

Further, R _{1 to} R ₃ 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 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 to} R ₃ 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, for example, heterocyclic thioamide group, mercaptoheterocyclic group, triazole group and the like, US Pat.
9,347, JP-A-59-195233, 59-59.
No. 200231, No. 59-201045, No. 59-2
No. 01046, No. 59-201047, No. 59-20
No. 1049, No. 61-170733, No. 61-270
744, 62-948, 63-234244.
No. 63-234245 and No. 63-234246.

The isothioureido group in the formula may be a salt of a protic acid (for example, hydrochloric acid, hydrobromic acid, hydroiodic acid, perchloric acid, methanesulfonic acid, 4-toluenesulfonic acid, sulfuric acid, etc.). good.

When R ₁ is a hydrogen atom and R ₂ is an aryl group, tautomerism may occur between the following chemical formulas 2 and 3 in the isothioureido group in the molecule.

[0010]

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[0011]

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

[0013]

[Chemical 4]

[0014]

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[0015]

[Chemical 6]

[0016]

[Chemical 7]

[0017]

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[0018]

[Chemical 9]

[0019]

[Chemical 10]

[0020]

[Chemical 11]

[0021]

[Chemical 12]

[0022]

[Chemical 13]

[0023]

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[0024]

[Chemical 15]

[0025]

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[0026]

[Chemical 17]

[0027]

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[0028]

[Chemical 19]

[0029]

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[0030]

[Chemical 21]

[0031]

[Chemical formula 22]

[0032]

[Chemical formula 23]

Next, typical synthesis examples of the hydrazine derivative represented by the above chemical formula 1 and used in the present invention will be shown.

Synthesis Example Synthesis of Chemical Formula 9 8.5 g of piperidine and 75 ml of ethanol were mixed,
13.5 g of phenyl isothiocyanate was added with stirring at room temperature, the temperature was raised, and the mixture was heated under reflux for 15 minutes. Then, the solvent was distilled off, and 24.2 g of methyl-p-toluenesulfonate was added to the residue. After heating at a bath temperature of 100 ° C. for 2 hours, 150 ml of ethyl acetate and 150 m of water were added to the reaction mixture.
and 1 were added, and the mixture was stirred at room temperature for 15 minutes. Then, the aqueous layer was separated and 10.1 g of sodium hydrogen carbonate was added. Then, the organic component was extracted with 150 ml of ethyl acetate, the extract was washed with 150 ml of a 1N aqueous sodium hydrogen carbonate solution, dried (anhydrous sodium sulfate), and the solvent was distilled off to give an oily isothiourea derivative: intermediate A14. 0.5 g was obtained.

Under cooling with an ice-water bath, 15 ml of chlorosulfonic acid was added dropwise to 14.5 g of intermediate A over 30 minutes. Then, the temperature was raised and the mixture was heated and stirred at a bath temperature of 90 ° C. for 2 hours.
After cooling, the reaction mixture was poured into 200 ml of ice water and neutralized with sodium hydrogen carbonate. And ethyl acetate 15
The organic component was extracted with 0 ml, the extract was washed with saturated saline (150 ml × 3 times), dried (anhydrous magnesium sulfate), and the solvent was distilled off to give 10.8 g of sulfonyl chloride derivative: intermediate B. Obtained (melting point 72 ° C-).

6.4 g of 1-ethoxalyl-2- (4-aminophenyl) hydrazine was dissolved in 40 ml of pyridine, and a DMF solution of intermediate B (10.7 g / 40 ml) was added dropwise while stirring at an internal temperature of 0 ° C. or lower. did. After completion of the dropping, the mixture was stirred at the same temperature for 1 hour, and then the reaction mixture was mixed with ice water.
Poured into 0 ml. After removing the ooze by decantation, the residue was dissolved in 200 ml of ethyl acetate, washed with saturated saline (150 ml × 2 times), dried (anhydrous magnesium sulfate), and the solvent was distilled off. 25 ml of ethanol and 25 ml of diisopropyl ether were added to the residue,
The mixture was stirred at room temperature for 1 hour, and then the precipitated crystals were collected by filtration. This solid was washed with diisopropyl ether and then dried to obtain 10.5 g of a sulfonamide derivative: intermediate C (melting point: 115.5 ° C).

Intermediate C 2.50 g, N, N-diethyl-
0.73 g of 1,3-propanediamine, 30 of methanol
It was mixed with ml and heated under reflux for 15 minutes. Then, the solvent was distilled off, and the residue was purified by silica gel column chromatography (developing solvent chloroform / methanol: 8/1) to obtain 2.0 g of Chemical formula 9 (melting point: 145.5-14).
8.5 ° C).

The hydrazine derivatives of the present invention are suitable water-miscible organic solvents such as alcohols (methanol, ethanol, propanol, etc.), ketones (acetone,
Methyl ethyl ketone), N, N-dimethylformamide, dimethyl sulfoxide, methyl cellosolve, etc. Further, by well-known emulsification dispersion method, dimethyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl terephthalate, 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 is selected from silver chloride and salts. 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, etc. of the silver halide grains are not particularly limited, but the grain size is 0.7.
Those of micron or less are preferable. Silver halide emulsion,
Gold compounds such as chloroaurate and gold trichloride, rhodium,
The sensitivity can be increased without coarsening the particles with a sulfur compound that reacts with a salt of a noble metal such as iridium or a silver salt to form silver sulfide, or with a reducing substance such as a stannous salt or amines. 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. 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 ultrahigh contrast photographic characteristics in a short development time.

In the present invention, the surface latent image type silver halide emulsion refers to an emulsion comprising 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 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 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. 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, ordinary sulfur sensitization, selenium sensitization, reduction sensitization, noble metal sensitization (eg gold sensitization) and the like are used.

In the light-sensitive material of the present invention, the compound represented by Chemical formula 1 is preferably contained in the surface latent image type silver halide emulsion layer, but the hydrophilic colloid adjacent to the surface latent image type silver halide emulsion layer is preferable. It may be contained in the layer. Such a layer has any function such as an undercoat layer, an intermediate layer, a filter layer, a protective layer and an antihalation layer, as long as it does not prevent the compound represented by Chemical formula 1 from diffusing into silver halide grains. It may be a layer. Since the content of the chemical formula 1 in the layer depends 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 the surface latent image type halogen A range of about 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol per mol of silver in the silver halide emulsion 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, 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, Vol. 176, 17643 (1978).
Issued December 2012) Page 23, IV, Section J.

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. . As gelatin, 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.

The photographic emulsion used in the present invention contains various compounds such as nitroimidazoles for the purpose of preventing fog during the production process of the light-sensitive material, during storage or photographic processing, or stabilizing photographic performance. Azoles such as nitrobenzimidazoles, chlorobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, mercaptotetrazoles, mercaptopyrimidines, mercaptotriazines, thioketo Compounds conventionally known as antifoggants or stabilizers such as compounds, azaindenes and benzothiazolium salts can be contained. Among these, particularly preferable are benzotriazoles (such as 5-methylbenzotriazole) and nitroindazoles (such as 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 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.

A photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material produced by using the present invention may be coated with a coating aid, an antistatic agent, an improvement in slipperiness, an emulsion dispersion, an adhesion prevention and an improvement in photographic characteristics (for example, 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,
Non-ionic surfactants such as alkylphenol polyglycerides, fatty acid esters of polyhydric alcohols, alkyl esters of sugars, alkyl carboxylates, alkyl sulfates, alkylbenzene sulfonates,
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, 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.

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 preferable organic desensitizers are exemplified in JP-A-63-64039. When using an organic desensitizer, 1.0 × 10 ^-8 ~1.0 × silver halide emulsion layer 10 ^-4 mol / m ^2,
Preferably 1.0 × 10 ^{−7 to} 1.0 × 10 ⁻⁵ mol / m ²
It is appropriate to make it exist.

The light-sensitive material of the present invention may contain a development accelerator. 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,
In addition to the compounds disclosed in JP-A-60-140340, JP-A-62-222241, JP-A-63-124045, JP-A-2-294637, US Pat. No. 4,975,354, etc., an N or S atom is contained. Various compounds are effective. The optimum addition amount of these accelerators varies depending on the type of compound, but in the range of 1.0 × 10 ^{−3 to} 0.5 g / m ² , preferably 5.0 × 10 ^{−3 to} 0.1 g / m ² . It is desirable to use. These accelerators are suitable solvents (water, alcohols such as methanol and ethanol, acetone,
(N, N-dimethylformamide, methyl cellosolve, etc.) and added to the coating solution. You may use these additives together in multiple types. The emulsion layer of the present invention, or
In other hydrophilic colloid layers, as a filter dye,
Or for various purposes such as prevention of irradiation,
It may contain a water-soluble dye. As the filter dye, a dye for further reducing the photographic sensitivity, preferably,
A UV absorber having a spectral absorption maximum in the intrinsic sensitivity region of silver halide, and mainly for enhancing the safety against safelight light when it is handled as a bright room light-sensitive material, are mainly used.
A dye having substantial light absorption in the region of 10 nm to 600 nm is used. These dyes may be added to the emulsion layer depending on the purpose, or may be added together with a mordant to the upper portion of the silver halide emulsion layer, that is, to the non-photosensitive hydrophilic colloid layer farther than the silver halide emulsion layer with respect to the support. It is preferable to use it after fixing. Although it depends on the molar extinction coefficient of the dye, it is usually added in the range of 10 ^{−3 to 1} g / m ² . It is preferably 10 to 500 mg / m ² . The above dye can be dissolved in an appropriate solvent (for example, water, alcohols such as methanol and ethanol, acetone, methyl cellosolve, etc., 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 disclosed in JP-A-63-64.
No. 039. Others, US Pat. No. 3,3
No. 14,794, No. 3,352,681, No. 3,
499,762, 3,533,794, 3,700,455, 3,705,805, 3,707,375, 4,045,229.
JP-A-46-2784, West German patent application publication 1,54
Ultraviolet absorbing dyes described in JP-A-7-863 and JP-A-2-293839 are also used. Others, U.S. Pat. No. 2,274,782, JP-A-62-185755
No. 63-2045, pyrazolone oxonol dyes, U.S. Pat. No. 2,956,879, diarylazo dyes, U.S. Pat. Nos. 3,423,207, and 3,384,487. Styryl dyes and butadienyl dyes described, merocyanine dyes described in US Pat. No. 2,527,583, US Pat. No. 3,486,897,
Merocyanine dyes and oxonol dyes described in U.S. Pat. Nos. 3,652,284 and 3,718,472, enaminohemioxonol dyes described in U.S. Pat. No. 3,976,661, and British Patent 584. No. 609, No. 1,
177,429, JP-A-48-85130, 49.
-99620, 49-114420, U.S. Patents 2,533,472, 3,148,187, 3,177,078, 3,247,127,
No. 3,540,887, No. 3,575,704
No. 3,653,905, JP-A-62-1334.
The dye described in No. 53 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 developing solution close to the above, 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 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 for being processed with a developing solution 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 the 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 of 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. The compounds described in JP-A-56-24347 can be used in the developer of the present invention as a silver stain preventing agent. As a solubilizing agent to be added to a developer, JP-A-61-61
The compounds described in -267759 can be used. Further, as a pH buffer agent used in a developing solution, JP-A-60-
The compound described in Japanese Patent No. 93433 or JP-A-62-18
The compounds described in No. 6259 can be used.

[0052]

[Example 1]

1) Preparation of coating sample 5.0 × per mol of silver in gelatin aqueous solution kept at 40 ° C.
An aqueous solution of silver nitrate and an aqueous solution of sodium chloride were simultaneously mixed in the presence of 10 ⁻⁶ mol of (NH ₄ ) ₃ RhCl ₆ , and then soluble salts were removed by a method well known in the art, followed by addition of gelatin, followed by chemical treatment. 2-Methyl-4-hydroxy-1,3,3a, 7-tetraazaindene was added as a stabilizer without aging. This emulsion has an average grain size of 0.2
It was a monodisperse emulsion having a cubic crystal shape of μ. After adding the hydrazine compounds selected from Chemical Formula 1 shown in Tables 1 and 2 and the following Chemical formulas 24, 25, 26 and 27 as comparative compounds to this emulsion in the amounts shown in Tables 1 and 2, Then, 10 mg / m ² of the following chemical formula 28 was added as a nucleation accelerator, and polyethyl acrylate latex was added to gelatin in solid content of 30.
wt% was added, 1,3-divinylsulfonyl-2-propanol was added as a hardening agent, and it was coated on a polyester film so that the Ag amount was 3.8 g / m ² . The gelatin was 1.8 g / m ² . Gelatin 1.5 g / m ² as a protective layer thereon, and applying a layer of polymethyl methacrylate 0.3 g / m ² of particle size 2.5 [mu].

[0053]

[Chemical formula 24]

[0054]

[Chemical 25]

[0055]

[Chemical formula 26]

[0056]

[Chemical 27]

[0057]

[Chemical 28]

2) Evaluation of Photographic Property The coated sample thus obtained was imagewise exposed with a bright room printer P-627GA manufactured by Dainippon Screen Co., Ltd., and developed with a developer-1 having the following composition at 35 ° C. for 30 seconds to obtain Mitsubishi. It was fixed with a fixing solution PURCF901 from Paper Manufacturing Co., Ltd., washed with water and dried. Tables 1 and 2 show the results of evaluating Dmax and character image quality of each sample. What is the character quality 5 without dots?
This is an image quality in which a character having a width of 30 μm is reproduced when properly exposed so that a halftone dot area of 0% results in a halftone dot area of 50% on the reversal light-sensitive material, which is a very good blank character image quality. On the other hand, when the proper exposure is applied, which is the same as the blank character image quality 1,
The quality of the extracted characters is such that the image quality is such that only characters with a width of 0 μm or more can be reproduced, and a rank of 4 to 2 is provided between 5 and 1 by sensory evaluation. A level of 3 or more is a practical level. Similarly, Dmax is the maximum density when exposure is performed so that the halftone dot area of 50% of the original becomes the halftone dot area of 50%. 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-1] Hydroquinone 30.0 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-plasmaline 0.3 g Sodium sulfite 75.0 g EDTA.2Na 1.0 g Tripotassium phosphate 80.0 g Potassium bromide 2.0 g Sodium hydroxide 13.0 g 5-Methylbenzotriazole 0.3 g 1-Diethylamino-2,3-diethylpropoxypropanone 17.0 g Sodium p-toluenesulfonate 7.0 g Water was added 1 liter Hydroxyl Adjust to pH 11.0 with potassium.

[0060]

[Table 1]

[0061]

[Table 2]

Example 2 1) Preparation of Coating Sample 4 × 10 ⁻⁷ mol of iridium hexachloride (1 mol per mol of silver)
) 97 mol% AgB in the presence of potassium and ammonia
r average particle size 0.25μ containing 3 mol% AgI
A silver iodobromide emulsion consisting of cubic crystals was prepared by the double jet method. This emulsion was desalted by the flocculation method, and then 40 g of inert gelatin was added per mol of silver. This emulsion was kept at 50 ° C. and used as a sensitizing dye as 5,5′-dichloro-9-ethyl-3,3′-bis (4
-Sulfobutyl) oxacarbocyanine was added and the temperature was lowered for 20 minutes and then lowered. Using this emulsion, Table 3 and Table 4
The compounds of the present invention shown in
5, Chemical formula 26 and Chemical formula 27 are added, and 5-methylbenzothiazole and 2-methyl-4-hydroxy-1,3,3 are further added.
a, 7-Tetraazaindene was added. Further, to each sample, 20 mg / m ² of Compound 28 and 30 mg / m ² of Compound 29 were added as a contrast enhancing agent to obtain 1,3-divinylsulfonyl-2.
-Propanol was added and coated on a polyethylene terephthalate film so that the amount of silver was 3.7 g / m ² . As a protective layer, gelatin was coated thereon to 1.5 g / m ² to obtain a sample.

[0063]

[Chemical 29]

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

[Developer-2] 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-Benzenesulfoneamido-2-mercaptopentimimisosol 0.5 g Water is added to adjust to 1 liter pH 10.5.

[0066]

[Table 3]

[0067]

[Table 4]

[0068]

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

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material containing at least one compound represented by the following chemical formula 1. Embedded image In the formula, L ₁ and L ₂ represent a divalent linking group. G is a carbonyl group, a sulfonyl group, a sulfinyl group, an oxalyl group,
Represents a phosphoryl group. R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an aralkyl group, an alkenyl group, or an aryl group, or represent an atomic group necessary for forming a nitrogen-containing 5- to 18-membered ring by connecting with each other. , R ₃ represents an alkyl group, an aralkyl group or an alkenyl group. R ₄ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an aryl group or an amino group. The isothioureido group in the formula may be a salt of a protonic acid.