JPH10213871A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the silver halide photographic sensitive material for printing plate superior in rapid processability and high in processing stability. SOLUTION: This silver halide photographic sensitive material contains an a nucleator a hydrazine compound represented by the formulae in which R1 is a substitutable aromatic group; G is carbonyl, sulfonyl, sulfinyl, oxalyl, or phosphoryl group; R2 is a group having at least one quaternary phosphonium group; X is a counter ion; and (n) is 0 or >=1, thus permitting high Dmax to be maintained by using this hydrazine compound in a small amount and to form high-quality reversed characters and high-dot images.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material and a method for forming an ultra-high contrast negative image using the same, and more particularly to a silver halide photographic light-sensitive material used in a photomechanical process. .

[0002]

2. Description of the Related Art In the field of graphic arts, an image forming system exhibiting photographic characteristics of ultra-high contrast (particularly, gamma of 10 or more) is required in order to improve reproduction of continuous tone images or line images by halftone images. is necessary.
Methods for obtaining high-contrast photographic characteristics using a stable developer are described in U.S. Pat. Nos. 4,166,742, 4,168,977, 4,211,857, and 4,224. No. 4,401, No. 4,311,781,
Nos. 4,272,606 and 4,912,016
No. 4,998,604, JP-A-3-25924
0, JP-A-5-45761, JP-A-6-17525
No. 3, JP-A-7-5610 and the like using a hydrazine derivative are known. According to this method, it is possible to obtain a photographic characteristic having a high contrast and high sensitivity, and furthermore, it is permissible to add a high concentration of sulfite to the developer.
The stability of the developer against air oxidation is dramatically improved as compared with the lith developer. However, conventionally known hydrazine compounds have been found to have several disadvantages. In other words, an attempt was made to make the structure of the hydrazine compound diffusion resistant in order to reduce the adverse effect on other photographic light-sensitive materials caused by the hydrazine compound flowing into the developing solution. These diffusion-resistant hydrazine compounds are required in large amounts for sensitization and high contrast, and have the problems of deteriorating the physical strength of the obtained photosensitive layer and causing the hydrazine compound to precipitate in the coating solution. Further, it has been found that when the photosensitive material is processed in a large amount with a fatigued developer, sufficient contrast cannot be obtained. Conventionally, a super-high contrast system using a hydrazine compound requires a developer having a relatively high pH, for example, 11.5 or 11.8.
Risk of handling increases, and B
It has problems such as high OD and COD. Also, it is necessary to use a large amount of a pH buffer to keep the pH of the developer constant, so that the solid concentration of the developer becomes high, the solution becomes sticky, and the scattered solution is difficult to wipe off. was there. Therefore, development of a hydrazine compound which can be hardened by a developer having a lower pH has been desired. In addition, a returned photographic material generally handled in a light room occupies a large field as one of the photographic materials for plate making, and in this field, there is a demand for a high blank character quality capable of reproducing a thin Mincho character. Therefore, development of a nucleating agent having higher activity has been desired. In particular, in a low-sensitivity bright room light-sensitive material that can be handled even in a bright room, development of a nucleating agent that is less likely to be hardened by a nucleating agent and has higher activity is desired.

[0003]

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

[0004]

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

[0005]

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In the general formula (1), R ₁ represents a substitutable aromatic ring, and G represents a carbonyl group, a sulfonyl group, a sulfinyl group, an oxalyl group or a phosphoryl group. R ₂
Represents a group containing at least one quaternary phosphonium group. X represents a counter ion, and n represents 0 or an integer of 1 or more.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The compound represented by formula (1) will be described in more detail. In the general formula (1), R ₁
Is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic ring. Here, the unsaturated heterocyclic group may be condensed with the aryl group. The aromatic group represented by R ₁ may be substituted. Representative examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, an aryloxy group, a sulfamoyl group, a ureido group, and a urethane group. , A carbamoyl group, an alkyl or arylthio group, an alkyl or arylsulfonyl group, a hydroxy group, 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. No. R ₁ may have incorporated therein a ballast group commonly used in immobile photographic additives such as couplers. The ballast group is a group having a carbon number of 8 or more, which is relatively inert to photographic properties, and can be selected from, for example, an alkyl group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group and the like. . R ₁ may have a group in which a group that enhances adsorption to the surface of silver halide grains is incorporated. Examples of such adsorbing groups include thiourea, heterocyclic thioamide group, mercapto heterocyclic group, triazole group and the like U.S. Pat. Nos. 4,385,108 and 4,459,347, JP-A-59-195233,
Nos. 59-200231, 59-201045, 59-201046, 59-201047, and 5
Nos. 9-201049, 61-170733, 61
-270744, 62-948, 63-234
No. 244, No. 63-234245, No. 63-2342
And the groups described in No. 46.

In the general formula (1), G is a carbonyl group,
Represents a sulfonyl group, a sulfinyl group, an oxalyl group or a phosphoryl group. R ₂ represents a substituted amino group, alkyl group, aryl group, aryloxy group or alkoxy group containing at least one quaternary phosphonium group. Examples of the substituted amino group represented by R ₂ include a 3-triphenylphosphoniopropylamino group, a 2- (3-triphenylphosphoniopropylthio) ethylamino group, and [1- (3-
Triphenylphosphoniopropyl) -3-pyridinio]
Methylamino group, 3- [tris (pentafluorophenyl) phosphonio] propylamino group, N-methyl-2-
[(6-triphenylphosphoniohexyl) diethylammonio] ethylamino group, p- (triphenylphosphoniomethyl) benzylamino group and the like, and the alkyl group is a 3-triphenylphosphoniopropyl group, [3-
(3-triphenylphosphoniopropyl) -1-imidazolio] methyl group and the like, and the aryl group includes p-triphenylphosphoniomethoxyphenyl group, o-triphenylphosphoniomethylphenyl group and the like. Examples of the group include an o-triphenylphosphoniomethylphenoxy group and p- (2-triphenylphosphonioethoxycarbonyl) phenoxy group, and examples of the alkoxy group include a 4-triphenylphosphonioboxy group. A preferred phosphonium group contained in R ₂ is represented by the following general formula (2).

[0009]

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In the general formula (2), R ₃ , R ₄ and R ₅ represent an alkyl group, an aryl group or a heterocyclic group.

The aryl group represented by R ₃ , R ₄ and R ₅ includes a phenyl group, a naphthyl group and the like, and these may have a substituent. The substituent as the substituted aryl group is an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a heterocyclic group, a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, a carboxy group, a sulfo group, a halogen atom, a cyano group, an aryloxy group , An acyloxy group, an acyl group, a carbamoyl group, a sulfamoyl group, an acylamino group, a sulfonamide group, a ureido group, a thioureido group, an amino group, an alkylthio group, and a mercapto group. Examples of the heterocyclic group represented by R ₃ , R ₄ and R ₅ include a piperidyl group, a morpholinyl group, a furyl group, a thienyl group, a tetrahydropyranyl group, a 4-picolyl group, and the like. The same as described in the section of the aryl group). R
_The alkyl group represented by ₃ , R ₄ and R ₅ has 1 carbon atom.
Represents up to 30 alkyl groups, which may be linear, branched or cyclic, and which may have a substituent (as described in the section of the substituted aryl group).
X is a counter ion, and as the anion, Cl ⁻ , Br ⁻ ,
Examples include p-toluenesulfonate and methylsulfonate, and examples of the cation include Na ⁺ , K ⁺ , and triethylammonium, and n represents 0 or an integer of 1 or more. 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.

[0012]

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[0013]

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[0014]

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[0015]

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[0016]

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[0017]

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The synthesis examples of the present invention are described below. Synthesis Example 1 Synthesis of H-2 Synthesis of 3-aminopropyltriphenylphosphonium bromide (intermediate A) 1.67 g of 3-bromopropylamine hydrobromide and 3.00 g of triphenylphosphine
The mixture was heated and stirred at 130 ° C. for 3 hours, allowed to cool, and the reaction solid was recrystallized with 20 ml of ethanol. The obtained crystals were added to 10 ml of a 2N aqueous solution of sodium hydroxide, stirred at room temperature until uniform, extracted with 50 ml of chloroform, dried over magnesium sulfate, and concentrated under reduced pressure to give an intermediate of white crystals. A 1.50 g was obtained. 1- (Ethoxalyl) -2- in 50 ml of methanol
[P- (3-n-octyloxypropanesulfonamido) phenyl] 1.71 g of hydrazine and intermediate A1.5
After adding 0 g and heating under reflux for 1 hour, the reaction solution was concentrated under reduced pressure and purified by silica gel chromatography to obtain 0.96 g of a pale yellow candy-like target product.

Synthesis Example 2 Synthesis of H-10 1.62 g of 1- (3-picolyloxamoyl) -2- [p- (3-n-hexyloxypropanesulfonamido) phenyl] hydrazine in 5 ml of sulfolane and 3 −
1.53 g of bromopropyltriphenylphosphonium bromide was added, and the mixture was heated at 120 ° C for 12 hours. After allowing to cool, the reaction product was crystallized from ethyl acetate to obtain 2.41 g of the desired product as pale brown crystals. Other exemplified compounds were synthesized by the same method.

The hydrazine derivative of the present invention can be prepared by using a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, etc.), ketones (acetone,
Methyl ethyl ketone), N, N-dimethylformamide, dimethyl sulfoxide, methyl cellosolve, etc. Also, by an already well-known emulsification dispersion method, dimethyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl terephthalate, and dissolved using an auxiliary solvent such as ethyl acetate or cyclohexanone, mechanically emulsified dispersion. It can also be created and used. A colloid mill, a ball mill, or a method known as a solid dispersion method using ultrasonic waves can be used.

The silver halide used in the light-sensitive silver halide emulsion layer of the light-sensitive material of the present invention is not particularly limited, but a surface latent image type silver halide emulsion is preferred. Silver bromide, silver chloroiodobromide, silver iodobromide, silver bromide and the like can be used. When silver iodobromide or silver chloroiodobromide is used, the content of silver iodide is 5%. It is preferably in the range of mol% or less. The form, crystal habit, size distribution and the like of the silver halide grains are not particularly limited, but the grain size is 0.7
Submicron ones are preferred. The silver halide emulsion is
Rhodium, gold compounds such as chloroaurate, gold trichloride, etc.
Sensitivity can be increased without coarsening particles by a sulfur compound which forms silver sulfide by reacting with a salt or silver salt of a noble metal such as iridium, or a stannous salt or an amine. Further, an iron compound such as a salt of a noble metal such as rhodium or iridium, or a red blood salt may be present during physical ripening or nucleation of silver halide grains. Especially,
Addition of a rhodium salt or a complex salt thereof is preferable because the effect of the present invention of achieving ultra-high contrast photographic characteristics in a short development time is further promoted.

In the present invention, the surface latent image type silver halide emulsion is an emulsion composed of silver halide grains having a surface sensitivity higher than the internal sensitivity, and this emulsion is preferably US Pat. It has a difference between the surface sensitivity and the internal sensitivity defined in the specification of Japanese Patent No. 401. The silver halide emulsion is desirably monodispersed, especially in the above-mentioned U.S. Pat.
Emulsions having the monodispersity specified in JP-A-224,401 are preferred. The silver halide emulsion used in the present invention preferably contains a water-soluble rhodium salt (for example, rhodium dichloride, rhodium trichloride, potassium hexachloride (III), ammonium rhodium (III) hexachloride, etc.). It is preferable to add these rhodium salts before the completion of the first ripening at the time of emulsion production. The addition amount of the rhodium salt is preferably from 1 × 10 ⁻⁷ mol to 1 × 10 ⁻⁴ mol per mol of silver halide. The average grain size of the silver halide used in the present invention is preferably 0.5 μm or less, particularly preferably 0.1 to 0.4 μm. The shape of the silver halide grains may be a regular one such as cubic or octahedral, or a mixed crystal, but it is preferably a so-called monodisperse emulsion having a relatively narrow grain size distribution. The term "monodisperse emulsion" as used herein means an emulsion in which 90%, more preferably 95%, of the total number of grains falls within a grain size range of ± 40% of the average grain size. The method of reacting the soluble silver salt with the soluble halide salt for preparing the silver halide emulsion in the present invention may be any method such as a single jet method, a double jet method, or a reverse mixing method in which the silver halide emulsion is formed in excess of silver ions. For the purpose of the present invention, a double jet method in which a soluble silver salt and a soluble halogen salt are simultaneously added in an acidic solution to form grains is particularly preferable. The silver halide emulsion prepared in this manner may or may not be chemically sensitized, and from the viewpoint of improving the handling property in a safelight environment, which can be called a bright room, can be used. It is rather preferable not to sensitize. In the case of chemical sensitization, usual sulfur sensitization, selenium sensitization, reduction sensitization and the like are used.

In the light-sensitive material of the present invention, the compound represented by the formula (1) is preferably contained in a surface latent image type silver halide emulsion layer, but is adjacent to the surface latent image type silver halide emulsion layer. It may be contained in a hydrophilic colloid layer. Such a layer is not particularly limited as long as it does not prevent the compound represented by the general formula (1) from diffusing into the silver halide grains, such as an undercoat layer, an intermediate layer, a filter layer, a protective layer, and an antihalation layer. It may be a layer having a function. In-layer formation 1
Content varies depending on the characteristics of the silver halide emulsion to be used, the chemical structure of the compound and the development conditions. Therefore, the appropriate content may vary over a wide range. About 1 × 10 ^-6 to 1 × per mole
A range of 10 ^-2 moles is practically useful.

The photographic emulsion used in the present invention may be spectrally sensitized with a methine dye or the like. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are
It is a dye belonging to a cyanine dye, a merocyanine dye, and a complex merocyanine dye. These sensitizing dyes may be used alone or in combination.
Combinations of sensitizing dyes are often used, especially for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosure 176, 17643 (1978).
(Issued December 2013), page 23, IV, section J.

As a binder or protective colloid which can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol Polyacetal partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, and various kinds of synthetic hydrophilic polymer materials such as copolymers such as polyvinylimidazole can be used. . As gelatin, in addition to lime-processed gelatin, acid-processed gelatin and Bull.Soc.Sci.Phot.Japan, No.
16, P30 (1966) may be used, and hydrolyzate or enzymatic degradation of gelatin may also be used.

In a method for obtaining a super-high contrast image using a hydrazine compound, a conventional safelight dye is added to an emulsion layer or another hydrophilic colloid layer 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, mercapto Many compounds conventionally known as antifoggants or stabilizers, such as tetrazoles, mercaptopyrimidines, mercaptotriazines, thioketo compounds, azaindenes, can be added. Among these, particularly preferred are benzotriazoles (eg, 5-methylbenzotriazoles) and nitroindazoles (eg, 5-nitroindazole). These compounds may be contained in the processing solution.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers. For example, chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glyoxal, etc.), N-methylol compounds, dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds, active halogen compounds (2,4-dichloro- 6-
Such as hydroxy-s-triazine) can be used alone or in combination.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared by using the present invention may contain coating aids, antistatic agents, improving slipperiness, emulsifying and dispersing, preventing adhesion and improving photographic characteristics (for example, developing Surfactants may be included for various purposes such as acceleration, contrast enhancement, and sensitization. For example, saponins (steroids), alkylene oxide derivatives (polyethylene glycol, polyethylene glycol / polypropylene glycol condensate, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl) Amines or amides, silicone polyethylene oxide adducts, etc.), glycidol derivatives (alkenyl succinic polyglycerides,
Alkylphenol polyglycerides), nonionic surfactants such as fatty acid esters of polyhydric alcohols, alkyl esters of sugars, alkyl carboxylate, alkyl sulfate, alkyl benzene sulfonate,
Carboxy group, sulfo group, phospho group, sulfate group, phosphate group such as alkyl phosphates, sulfosuccinates, sulfoalkylpolyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc. Anionic surfactants containing an acidic group such as an amino group, amphoteric surfactants such as amino acids, aminoalkylsulfonic acids, aminoalkylsulfuric acid or phosphate esters, aliphatic or aromatic quaternary ammonium salts, pyridinium, imidazolium And cationic surfactants such as heterocyclic quaternary ammonium salts.

The photographic light-sensitive material used in the present invention may contain a water-insoluble or hardly soluble synthetic polymer decomposition product in a photographic emulsion layer or other hydrophilic colloid layers for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide,
Vinyl acetate, acrylonitrile, olefins, styrene and the like alone or in combination, or acrylic acid,
A polymer having a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, styrene sulfonic acid and the like as a monomer component can be used.

The light-sensitive material of the present invention may contain an organic desensitizer. Preferred organic desensitizers have at least one water-soluble or alkali-dissociable group. These preferred organic desensitizers are described in U.S. Pat. No. 4,908,293.
No. When an organic desensitizer is used, 1.0 × 10 ^{−8 to} 1.0 × 10 ⁻⁴ mol / mol is added to the silver halide emulsion layer.
It is appropriate that m ² , preferably 1.0 × 10 ^{−7 to} 1.0 × 10 ⁻⁵ mol / m ^{2 is} present.

The light-sensitive material of the present invention may contain a development accelerator. Examples of development accelerators suitable for use in the present invention or accelerators for nucleation transmission development include JP-A-53-7761.
No. 6, No. 53-137133, No. 54-37732.
No., No. 60-140340, No. 61-167939
No. 62-222241, No. 63-1224045
In addition to the compounds disclosed in US Pat. No. 4,975,354, various compounds containing an N or S atom are effective. The optimum amount of these accelerators varies depending on the kind of the compound, but is 1.0 × 10 ^{−3 to} 0.5 g / g.
m ² , preferably in the range of 5.0 × 10 ^{−3 to} 0.1 g / m ² . These accelerators are dissolved in a suitable solvent (water, alcohols such as methanol or ethanol, acetone, N, N-dimethylformamide, methyl cellosolve, etc.) and added to the coating solution. A plurality of these additives may be used in combination. The emulsion layer or other hydrophilic colloid layer of the present invention may contain a water-soluble dye as a filter dye or for various purposes such as prevention of irradiation. As the filter dye, a dye for further lowering the photographic sensitivity, preferably an ultraviolet absorber having a spectral absorption maximum in the intrinsic sensitivity range of silver halide, or safety against safelight light when handled as a light room photosensitive material Dyes having substantial light absorption mainly in the region of 310 nm to 600 nm are used to increase the light absorption. These dyes are added to the emulsion layer depending on the purpose, or added together with the mordant to the upper part of the silver halide emulsion layer, that is, the non-photosensitive hydrophilic colloid layer farther from the silver halide emulsion layer with respect to the support, and fixed. It is preferable to use them. Depending on the molar extinction coefficient of the dye, it is usually added in the range of 10 ^{-3 to 1} g / m ² . Preferably it is 10-500 mg / m < ² >. The dye can be dissolved in a suitable solvent (for example, water, alcohols such as methanol and ethanol, acetone, methyl cellosolve and the like, or a mixed solvent thereof) and added to the coating solution. These dyes can be used in combination of two or more kinds. Specific examples of these dyes are disclosed in Japanese Patent Application No. Sho 61
No. 209169. In addition, U.S. Patent Nos. 3,314,794 and 3,352,681,
No. 3,499,762, No. 3,533,794
No. 3,700,455, No. 3,705,80
No. 5, No. 3,707,375, No. 4,045, 2
No. 29, JP-A-46-2784, and West German Patent Application Publication No. 1,547,863. In addition, US Patent No. 2,274,7
No. 82, JP-A Nos. 62-185755 and 63-204
No. 5, pyrazolone oxonol dyes described in U.S. Pat. No. 2,956,879, diaryl azo dyes described in U.S. Pat. Nos. 3,423,207 and 3,384,48.
No. 7, styryl dyes and butadienyl dyes, US Pat. No. 2,527,583, merocyanine dyes,
U.S. Pat. Nos. 3,486,897 and 3,652,2
No. 84, No. 3,718,472, merocyanine dyes and oxonol dyes described in U.S. Pat.
No. 61, enaminohemioxonol dyes described in British Patent Nos. 584,609 and 1,177,429,
JP-A-48-85130, JP-A-49-99620, JP-A-49-114420, U.S. Pat. No. 2,533,472
No. 3,148,187, No. 3,177,07
No. 8, No. 3,247,127, No. 3,540,8
Nos. 87, 3,575,704 and 3,653
905 and JP-A-62-133453 can also be used.

In order to obtain ultra-high contrast photographic characteristics using the silver halide light-sensitive material of the present invention, a conventional lith developer or a pH 13 described in US Pat. No. 2,419,975 can be used.
It is not necessary to use a highly alkaline developer close to the above, and a stable developer can be used. That is, the silver halide photographic light-sensitive material of the present invention can use a developer sufficiently containing (especially, 0.15 mol / l or more) a sulfite ion as a preservative, and has a pH of 9.5 or more. Especially 10-11.
With the developing solution of No. 5, a negative image having a sufficiently high contrast can be obtained. There is no particular limitation on the developing agent that can be used in the method of the present invention, and examples thereof include dihydroxybenzenes (for example, hydroquinone) and 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone, 4,4-dimethyl-1). -Phenyl-3-pyrazolidone), aminophenols (eg, N-methyl-p-aminophenol) and the like can be used alone or in combination. The silver halide light-sensitive material of the present invention is particularly suitable to be processed with a developer containing dihydroxybenzenes as a main developing agent and 3-pyrazolidones or aminophenols as an auxiliary developing agent. Preferably, the developer contains 0.05 to 0.5 of dihydroxybenzenes.
The moles / liter, 3-pyrazolidones or aminophenols are used together in the range of 0.06 mol / liter or less.

Further, as described in US Pat. No. 4,269,929, the development speed can be increased by adding amines to a developer to shorten the development time. Others include pH buffers such as alkali metal sulfites, carbonates, borates and phosphates,
It may contain a development inhibitor such as bromide, iodide and an organic antifoggant (particularly preferably nitroindazoles or benzotriazoles) or an antifoggant. Further, if necessary, a water softener, a dissolution aid, a color tone agent, a development accelerator, a surfactant (particularly preferably the above-mentioned polyalkylene oxides), an antifoaming agent, a hardening agent, a silver stain preventing agent for a film. (For example, 2-mercaptobenzimidazolesulfonic acids). The processing temperature in the process according to the invention is usually chosen between 18 ° C and 50 ° C. It is preferable to use an automatic developing machine for the photographic processing. However, according to the method of the present invention, the total processing time from when the photosensitive material is put into the automatic developing machine to when it comes out is 90 to 12 times.
Even if it is set to 0 second, a photographic characteristic of a sufficiently high contrast negative gradation can be obtained. In the developer of the present invention, compounds described in JP-A-56-24347 can be used as a silver stain inhibitor. Japanese Patent Application Sho 60 as a dissolution aid to be added to the developer
The compounds described in JP-A-109743 can be used. Further, as a pH buffering agent used in a developing solution,
Compounds described in Japanese Patent Application No. 93433 / 61-28
No. 708 can be used.

[0034]

[Example 1]

1) Preparation of coating sample 5.0 × / mol of silver was added to an aqueous gelatin solution kept at 40 ° C.
An aqueous solution of silver nitrate and an aqueous solution of sodium chloride are simultaneously mixed in the presence of 10 ^-6 mol of (NH ₄ ) ₃ RhCl ₆ , and after removing soluble salts by a method well known in the art, gelatin is added thereto, followed by chemical reaction. Without aging, 2-methyl-4-hydroxy-1,3,3a, 7-tetraazaindene was added as a stabilizer. This emulsion had an average grain size of 0.2
This was a monodisperse emulsion having a cubic crystal form of μ. A hydrazine compound selected from the general formula (1) shown in Table 1 and the following A, B, and C as comparative compounds were added to the emulsion in the amounts shown in Table 1, and then the nucleation accelerators shown below were added. 30 mg /
m ² , and further, a polyethyl acrylate latex was added at a solid content of 30 wt% with respect to gelatin.
4-Dichloro-6-hydroxy-s-triazine was added, and the mixture was coated on a polyester film so as to have an Ag amount of 3.8 g / m ² . Gelatin was 1.8 g / m ² . On top of this, 1.5 g / m ² of gelatin and 0.3 g / m ^{2 of} polymethyl methacrylate having a particle size of 2.5 μm as a protective layer.
Layers were applied.

[0035]

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[0036]

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2) Evaluation of Photographic Properties The obtained coated sample was image-exposed with a bright room printer P-627GA manufactured by Dainippon Screen Co., Ltd., developed with a developer having the following composition at 35 ° C. for 30 seconds, and processed by Mitsubishi Paper Mills ( The solution was fixed with a fixing solution PURCF901 of Co., Ltd., washed with water and dried. Table 1 shows the results of evaluating the Dmax and the quality of the blank characters of each sample. The blank character image quality 5 is an image quality at which a character having a width of 30 μm is reproduced when properly exposed so that a halftone dot area of 50% becomes a halftone dot area of 50% on a return photosensitive material using a halftone dot document. Very good character image quality. On the other hand, the blank character image quality 1 is an image quality that can reproduce only characters having a width of 150 μm or more when the same proper exposure is given.
2 ranks were provided. Three or more is a practical level. Dmax is also 50% halftone dot area of the document
Dmax when exposure is performed so as to obtain a halftone dot area. The sample of the present invention has a high Dmax and has excellent character image quality. Also, it works effectively with a smaller amount of addition than the comparative compound.

[Developer] Hydroquinone 30.0 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 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-benzenesulfonamido-2-mercaptobenzimidazole 0.5 g Water is added to adjust 1 liter to pH 10.6.

[0039]

[Table 1]

Example 2 1) Preparation of Coated Sample 4 × 10 ⁻⁷ mol of iridium hexachloride (II) per mol of silver
I) 97 mole% AgB in the presence of potassium and ammonia
r, average particle size 0.25μ with 3 mol% AgI
Was prepared by the double jet method. The emulsion was desalted by flocculation, and 40 g of inert gelatin was added per mole of silver. This emulsion was kept at 50 DEG C., and 5,5'-dichloro-9-ethyl-3,3'-bis (4
(Sulfobutyl) oxacarbocyanine was added, and the mixture was aged for 20 minutes and then cooled. Using this emulsion, the compounds of the present invention shown in Table 2 and D, E, F
Was added, and 5-methylbenzothiazole and 2-methyl-4-hydroxy-1,3,3a, 7-tetraazaindene were further added. Further, the following contrast enhancement accelerator was used in 20
mg / m ² , and 1,3-divinylsulfonyl-2-propanol were added, and the mixture was coated on a polyethylene terephthalate film so that the silver amount 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.

[0041]

Embedded image

[0042]

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2) Evaluation of photographic properties These samples were exposed to tungsten light at 3200 ° K through an optical wedge and a 150-line gray contact screen, developed with the above-mentioned developer at 35 ° C for 30 seconds, fixed, washed and dried. The dot quality and Dma of the obtained sample
x is shown in Table 2. The halftone dot quality is visually evaluated on a five-point scale, where 5 is the best and 1 represents the worst quality. As the halftone dot masters for plate making, 5 and 4 are practically usable, 3 is inferior but can be used just barely, and 2 and 1 are qualities which cannot be practically used. Dmax is the exposure amount (log) that gives 1.5 in terms of the optical density of the sample that was similarly exposed through an optical wedge and developed.
The optical density (Dmax) at a point where exposure (0.5 + logE) was larger than that of E) by 0.5 was shown. It can be seen that when the compound of the present invention is used, a high Dmax is maintained with a small amount of addition, and good dot quality is provided as compared with the comparative compound.

[0044]

[Table 2]

[0045]

As described above, the silver halide photographic light-sensitive material of the present invention can provide good image quality and halftone dot quality and high Dmax with a small amount of addition and using a stable developer.

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 represents a substitutable aromatic ring;
Represents a carbonyl group, a sulfonyl group, a sulfinyl group, an oxalyl group or a phosphoryl group. R ₂ represents a group containing at least one quaternary phosphonium group. X represents a counter ion, and n represents 0 or an integer of 1 or more.