JP3325164B2 - Silver halide photographic materials - 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 method for forming an ultra-high contrast negative image using the same, and more particularly to a silver halide photographic light-sensitive material used in a photomechanical process. .

[0002]

2. Description of the Related Art In the field of graphic arts, an image forming system exhibiting photographic characteristics of ultra-high contrast (particularly, gamma of 10 or more) is required in order to improve reproduction of continuous tone images or line images by halftone images. is necessary.
Methods for obtaining high-contrast photographic characteristics using a stable developer are described in U.S. Pat. Nos. 4,166,742, 4,168,977, 4,211,857, and 4,224. No. 4,401, No. 4,311,781,
Nos. 4,272,606 and 4,912,016
No. 4,998,604, JP-A-3-25924
No. 0, JP-A-5-45761, JP-A-7-5610 and the like using a hydrazine derivative are known. According to this method, ultra-high contrast and high-sensitivity photographic characteristics can be obtained, and the addition of a high concentration of sulfite to the developer is allowed. And improve dramatically. However, conventionally known hydrazine compounds have been found to have several disadvantages. In other words, an attempt was made to make the structure of the hydrazine compound diffusion resistant in order to reduce the adverse effect on other photographic light-sensitive materials caused by the hydrazine compound flowing into the developing solution. These diffusion-resistant hydrazine compounds are required in large amounts for sensitization and high contrast, and have the problems of deteriorating the physical strength of the obtained photosensitive layer and causing the hydrazine compound to precipitate in the coating solution. Further, it has been found that when the photosensitive material is processed in a large amount with a fatigued developer, sufficient contrast cannot be obtained. Conventionally, a super-high contrast system using a hydrazine compound requires a developer having a relatively high pH, for example, 11.5 or 11.8, which increases the risk of handling. And high COD. Also, it is necessary to use a large amount of a pH buffer to keep the pH of the developer constant, so that the solid concentration of the developer becomes high, the solution becomes sticky, and the scattered solution is difficult to wipe off. was there. Therefore, development of a hydrazine compound which can be hardened by a developer having a lower pH has been desired. In addition, a returned photographic material generally handled in a light room occupies a large field as one of the photographic materials for plate making, and in this field, there is a demand for a high blank character quality capable of reproducing a thin Mincho character. Therefore, development of a nucleating agent having higher activity has been desired. In particular, in a low-sensitivity light-sensitive material which can be handled even in a light room, hardening by a nucleating agent hardly occurs, and the development of a more active nucleating agent 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 characterized by containing the compounds represented by the following general formulas (1) and (2).

Embedded image In the general formulas (1) and (2), R ¹ represents an aliphatic group or an aromatic group, and R ² represents a divalent aliphatic group or a divalent aromatic group. R ³ represents a hydrogen atom, an aliphatic group or an aromatic group, and R ⁴ represents an aliphatic group. G represents a carbonyl group, a sulfonyl group, a sulfinyl group, an oxalyl group or a phosphoryl group. R ⁵ represents a hydrogen atom, an aliphatic group, an alkoxy group, an aryloxy group, an aromatic group, an amino group or the general formula (3). In the general formula (2), L represents —SO ₂ NR ⁶
-, -NR ⁶ SO ₂ NR ^6- , -CONR ^6- , -NR
⁶ CONR ^6- , -G ¹ P (O) (G ¹ R ⁶ ) NR ^6-
Represents R ⁶ represents a hydrogen atom, an aliphatic group or an aromatic group, and G ¹ represents a single bond, an —O— group, or an —NR ⁶ — group. The isothioureido group in the general formulas (1) and (2) may be a salt of a protonic acid.

Embedded image In the general formula (3), Q ⁺ represents a group containing a cationic group, and A ⁻ represents an anion. However, it is unnecessary when Q ⁺ contains a sulfo group.

The compounds represented by the general formulas (1) and (2) will be described in more detail. General formulas (1) and (2)
In the above, the aliphatic group represented by R ¹ preferably has 1 to 30 carbon atoms, and particularly preferably has 1 to 20 linear groups,
It is a branched or cyclic alkyl group. The aromatic group represented by 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 aliphatic group or aromatic group of R ¹ may be substituted, and typical substituents include, for example,
Alkyl, alkenyl, alkynyl, alkoxy, aryl, aryloxy, sulfamoyl, ureido, urethane, carbamoyl, alkyl or arylthio, alkyl or arylsulfonyl, hydroxy, halogen, cyano , An aryloxycarbonyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group, an amide group, a sulfonamide group, and a carboxy group. 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 an adsorptive group 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 formulas (1) and (2), the divalent aliphatic group represented by R ² preferably has 1 to 30 carbon atoms.
And especially 1 to 20 linear, branched or cyclic alkylene groups. The aromatic group represented by R ² is a monocyclic or bicyclic arylene group or an unsaturated heterocyclic ring. Here, the unsaturated heterocyclic group may be condensed with the aryl group. Preferred as R ² are an alkylene group, and particularly preferred are an ethylene group and a propylene group. In formulas (1) and (2), the aliphatic group represented by R ³ is an alkyl group having 1 to 5 carbon atoms, and may have a substituent such as an aryl group. Preferably, they are a methyl group, an ethyl group, and a benzyl group. When G is a carbonyl group, preferred among the groups represented by R ⁵ are a hydrogen atom, an alkyl group (for example, a methyl group, a trifluoromethyl group, a 3-hydroxypropyl group, a 3-methanesulfonamidopropyl group, Phenylsulfonylmethyl group, 2
-Hydroxybenzyl group), an aryl group (for example,
A phenyl group, a 3,5-dichlorophenyl group, an o-methanesulfonamidophenyl group, a 4-methanesulfonylphenyl group, a 2-hydroxymethylphenyl group, etc., and a hydrogen atom is particularly preferable. R ⁵ if G is a sulfonyl group, a sulfinyl group and an oxalyl group, Preferred among the groups represented by R ⁵ is an alkoxy group (e.g., methoxy group, an ethoxy group), ant - aryloxy group (e.g., phenoxy Group, 4-chlorophenoxy group, etc.), amino group, especially substituted amino group (for example, methylamino group, 3-hydroxypropylamino group, 2,3-
Dihydroxypropylamino, 2-hydroxymethylanilino, etc.) are preferred. R ⁵ may have incorporated therein a ballast group commonly used in immobile photographic additives such as couplers, or may have incorporated therein a group which enhances adsorption to the surface of silver halide grains. When G is a phosphoryl group, R ⁵ is preferably a methoxy group, an ethoxy group, a butoxy group, a phenoxy group, or a phenyl group. Further, R ⁵ may be such as to rise to cyclization reaction to form a cyclic structure containing -G-R ⁵ moiety of atoms disrupt portions of G-R ⁵ from the remainder molecule, examples See, for example,
No. 29751 and the like. R ⁶ is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group, and particularly preferably a hydrogen atom. When the isothioureido group in the general formulas (1) and (2) forms a salt of a protonic acid, examples of the protonic acid include hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, and the like.
-Toluenesulfonic acid.

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

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

[0009]

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[0012]

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[0013]

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[0014]

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[0015]

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The synthesis examples of the present invention are described below. Synthesis Example 1 Synthesis of H-1 Synthesis of 1-ethoxyl-2- {4- [3- (2-n-hexylthioethyl) thioureido] phenyl} hydrazine (intermediate A) 2- (n-hexylthio) in 80 ml of ethanol ) Ethylamine (4.84 g) was added, and 1-ethoxalyl-2 was added at room temperature.
-(4-isothiocyanatophenyl) hydrazine 7.9
After adding 6 g, the mixture was heated at 90 ° C. for 1 hour. When filtered while hot and allowed to cool, crystals precipitated. The crystals were collected by filtration and washed with ethanol to give 6.93 g of the desired product. Melting point 144.5-146
C. Synthesis of 1-ethoxyl-2- {4- [3- (2-n-hexylthioethyl) -S-methylisothioureido] phenyl} hydrazine-p-toluenesulfonate (Intermediate B) 8 ml of sulfolane was added to 6.91 g of A and 3.47 g of methyl p-toluenesulfonate, and the mixture was heated at 90 ° C. for 1 hour. 30 ml of ethyl acetate and 15 ml of acetone were added, and the mixture was stirred at room temperature for 30 minutes. The precipitated crystals were collected by filtration and washed with acetone and ethyl acetate to obtain 7.35 g of the desired product. Melting point 140-
142 ° C. 1.23 g of the above intermediate B and 0.50 g of sodium hydrogen carbonate were added to a mixed solvent of 13 ml of water and 13 ml of ethyl acetate, and the mixture was stirred at room temperature for 15 minutes. The ethyl acetate layer was taken, dried over magnesium sulfate, concentrated under reduced pressure, and concentrated to 3 residues.
-Diethylaminopropylamine (0.26 g) and methanol (10 ml) were added, and the mixture was heated under reflux for 30 minutes, concentrated under reduced pressure, and then purified by silica gel chromatography to obtain the target compound, H-.
0.58 g of 1 was obtained. 86.5-87 [deg.] C.

Synthesis Example 2 Synthesis of H-4 1.23 g of the above intermediate B and 0.50% of sodium hydrogen carbonate
g was added to a mixed solvent of 13 ml of water and 13 ml of ethyl acetate, and the mixture was stirred at room temperature for 15 minutes. The ethyl acetate layer was collected, dried over magnesium sulfate, concentrated under reduced pressure, and 0.21 g of 3-methylthiopropylamine and 10 ml of methanol were added to the residue. The mixture was heated under reflux for 30 minutes, concentrated under reduced pressure, and purified by silica gel chromatography to obtain the desired product. 0.59 for H-4
g was obtained. 132-133 ° C. Other exemplified compounds were synthesized by the same method.

The hydrazine derivative of the present invention may be prepared from 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. Further, by an already well-known emulsification dispersion method, dimethyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl terephthalate, and dissolved using an auxiliary solvent such as ethyl acetate or cyclohexanone, mechanically emulsified dispersion. It can also be created and used. A colloid mill, a ball mill, or a method known as a solid dispersion method using ultrasonic waves can be used.

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

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

In the light-sensitive material of the present invention, the compounds represented by formulas (1) and (2) are preferably contained in a surface latent image type silver halide emulsion layer. It may be contained in a hydrophilic colloid layer adjacent to the layer. Such a layer prevents the compounds represented by general formulas (1) and (2), such as an undercoat layer, an intermediate layer, a filter layer, a protective layer, and an antihalation layer, from diffusing into silver halide grains. As long as there is no layer, any layer having any function may be used. Since the content of 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. A range of about 1.times.10.sup.- ⁶ to 1.times.10.sup.- ² mole per mole 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 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, J.

Gelatin is advantageously used 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, 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 an ultra-high contrast image using a hydrazine compound, a conventional safelight dye is added to an emulsion layer or another hydrophilic colloid layer in order to enable handling in a bright room. Is also good. The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, mercapto Many compounds conventionally known as antifoggants or stabilizers, such as tetrazoles, mercaptopyrimidines, mercaptotriazines, thioketo compounds and 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-
Hydroxy-S-triazine, etc.) alone or in combination.

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

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

The light-sensitive material of the present invention may contain an organic desensitizer. Preferred organic desensitizers have at least one water-soluble or alkali-dissociable group. These preferred organic desensitizers are described in U.S. Pat. No. 4,908,293.
No. When an organic desensitizer is used, 1.0 × 10 ^{−8 to} 1.0 × 10 ⁻⁴ mol / mol is added to the silver halide emulsion layer.
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.
6, No. 53-137133, No. 54-37732.
No. 60-140340, U.S. Pat. No. 4,975,35
In addition to the compounds disclosed in No. 4, etc., various compounds containing an N or S atom are effective. These accelerators
Although the optimum amount varies depending on the type of compound, it is 1.0 × 1
0 ^{−3 to} 0.5 g / m ² , preferably 5.0 × 10 ⁻³ to
It is desirable to use in the range of 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 an appropriate 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 are 2
A combination of two or more species may be used. Specific examples of these dyes are described in Japanese Patent Application No. 61-209169. In addition, U.S. Patent Nos. 3,314,794, 3,352,681, 3,499,762, 3,533,794, 3,700,455,
Nos. 3,705,805 and 3,707,375
No. 4,045,229, JP-A-46-2784.
And ultraviolet absorbing dyes described in West German Patent Application Publication No. 1,547,863. In addition, U.S. Pat. No. 2,274,782, JP-A-62-18755
No. 5, No. 63-2045, pyrazolone oxonol dyes, U.S. Pat. No. 2,956,879, diaryl azo dyes, U.S. Pat. No. 3,423,207,
No. 3,384,487, styryl dyes and butadienyl dyes, U.S. Pat. No. 2,527,583, merocyanine dyes, U.S. Pat. No. 3,486,897.
No. 3,652,284, No. 3,718,47
2, merocyanine dyes and oxonol dyes, U.S. Pat. No. 3,976,661, enaminohemioxonol dyes, and British Patent Nos. 584,609 and 1,177,429; Nos. 48-85130, 49-99620, 49-114420, U.S. Pat. Nos. 2,533,472, 3,148,187, 3,177,078, and 3,247. , 12
No. 7, No. 3,540,887, No. 3,575,7
No. 04, No. 3,653,905, JP-A-62-13
The dyes described in No. 3453 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 and a pH 13 described in US Pat. No. 2,419,975 can be used.
It is not necessary to use a highly alkaline developer close to the above, and a stable developer can be used. That is, the silver halide photographic light-sensitive material of the present invention can use a developer sufficiently containing (especially, 0.15 mol / l or more) a sulfite ion as a preservative, and has a pH of 9.5 or more. Especially 10-11.
With the developing solution of No. 5, a negative image having a sufficiently high contrast can be obtained. There is no particular limitation on the developing agent that can be used in the method of the present invention, and examples thereof include dihydroxybenzenes (for example, hydroquinone) and 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone, 4,4-dimethyl-1). -Phenyl-3-pyrazolidone), aminophenols (eg, N-methyl-p-aminophenol) and the like can be used alone or in combination. The silver halide light-sensitive material of the present invention is particularly suitable to be processed with a developer containing dihydroxybenzenes as a main developing agent and 3-pyrazolidones or aminophenols as an auxiliary developing agent. Preferably, the developer contains 0.05 to 0.5 of dihydroxybenzenes.
The moles / liter, 3-pyrazolidones or aminophenols are used together in the range of 0.06 mol / liter or less.

As described in US Pat. No. 4,269,929, the development speed can be increased by adding amines to the 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.

[0032]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited thereto. [Example 1] 1) Preparation of coating sample 5.0 × / mol of silver was added to an aqueous gelatin solution kept at 40 ° C.
After simultaneously mixing an aqueous solution of silver nitrate and an aqueous solution of sodium chloride in the presence of 10 ^-6 mol of (NH ₄ ) ₃ RhCl ₆ , gelatin was added after removing soluble salts by a method well-known in the art, and then chemically added. 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 formulas (1) and (2) shown in Table 1 and the following A, B, C, and D as comparative compounds were added to the emulsion in the amounts shown in Table 1. 30 mg / m ^{2 of} the nucleation accelerator shown in (1), and polyethyl acrylate latex (30 wt% of solid content based on gelatin), and 2,4-dichloro-6-hydroxy-
2. Add s-triazine and add 3 on polyester film.
The coating was performed so that the Ag amount was 8 g / m ² . Gelatin was 1.8 g / m ² . On this, a layer of 1.5 g / m ² of gelatin and 0.3 g / m ² of polymethyl methacrylate having a particle size of 2.5 μm was applied as a protective layer.

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[0034]

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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., and developed at 35 ° C. for 30 seconds with a developer 1 having the following composition. The image was fixed with a fixing solution PURCF901 from Paper Manufacturing 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 50 using a halftone original.
%, Which 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 becomes 50% halftone dot area on the return photosensitive material. on the other hand,
150μ when the same proper exposure is given as the character image quality 1
The image quality is such that the image quality is such that only characters with a width of m or more can be reproduced. This is a poor character quality, and a rank of 4 or 2 is provided between 5 and 1 in the sensory evaluation. Three or more is a practical level. Dmax is also 50% of the original and the halftone dot area is 50%.
% When exposed to a halftone dot area.
The sample of the present invention has high Dmax and excellent character image quality. Also, it works effectively with a smaller amount of addition than the comparative compound.

[Developer-1] hydroquinone 30.0 g 4-human peroxymethyl-4-methyl-1-phenyl-3-hydroxyperitoneone 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-diethylhydroxyfluoropropane 17.0 g sodium p-toluenesulfonate 7.0 g Adjust to pH 11.5 with potassium.

[0037]

[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 E, F, and G shown below for comparison were prepared.
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 , 1,3-divinylsulfonyl-2-propanol was added, and the mixture was coated on a polyethylene terephthalate film so as to have a silver amount of 3.7 g / m ² . A gelatin was applied thereon as a protective layer so as to be 1.5 g / m ² to obtain a sample.

[0039]

Embedded image

[0040]

Embedded image 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 following developer-2 at 35 ° C for 30 seconds, fixed, washed and dried. Table 2 shows the dot quality and Dmax of the obtained sample. 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 optical density (Dmax) at the point where 0.5 (log + E) was more exposed than the exposure amount (logE) that gave a 1.5 as the optical density of a sample which was similarly exposed through an optical wedge and developed. Was. 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 halftone dot quality is provided as compared with the comparative compound.

[Developer-2] hydroquinone 30.0 g 4-human peroxymethyl-4-methyl-1-phenyl-3-perazodritone 0.3 g potassium hydroxide 20.0 g sodium hydroxide 18.0 g sodium sulfite 30.0 g EDTA -2Na 1.0 g Potassium bromide 10.0 g 5-Methylbenzotriazole 0.4 g 5-Phensene sulfonamito-2-mercaphate benzoimidazole 0.5 g Water is added to adjust 1 liter to pH 10.6.

[0042]

[Table 2]

[0043]

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.

──────────────────────────────────────────────────続 き Continued on the front page (58) Investigated field (Int. Cl. ⁷ , DB name) G03C 1/06 501 CAPPLUS (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support,
A silver halide photographic light-sensitive material characterized in that the emulsion layer or another hydrophilic colloid layer contains at least one compound represented by the following general formulas (1) and (2). Embedded image In the general formulas (1) and (2), R ¹ represents an aliphatic group or an aromatic group, and R ² represents a divalent aliphatic group or a divalent aromatic group. R ³ represents a hydrogen atom, an aliphatic group or an aromatic group, and R ⁴ represents an aliphatic group. G represents a carbonyl group, a sulfonyl group, a sulfinyl group, an oxalyl group or a phosphoryl group. R ⁵ represents a hydrogen atom, an aliphatic group, an alkoxy group, an aryloxy group, an aromatic group, an amino group or the general formula (3). In the general formula (2), L represents —SO ₂ NR ⁶
-, -NR ⁶ SO ₂ NR ^6- , -CONR ^6- , -NR
⁶ CONR ^6- , -G ¹ P (O) (G ¹ R ⁶ ) NR ^6-
Represents R ⁶ represents a hydrogen atom, an aliphatic group or an aromatic group, and G ¹ represents a single bond, an —O— group, or an —NR ⁶ — group. The isothioureido group in the general formulas (1) and (2) may be a salt of a protonic acid. Embedded image In the general formula (3), Q ⁺ represents a group containing a cationic group, and A ⁻ represents an anion. However, it is unnecessary when Q ⁺ contains a sulfo group.