JP3233735B2 - 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 material and a method for forming an ultra-high contrast negative image using the same, and more particularly to a silver halide photographic material used in a photomechanical process. is there.

[0002]

2. Description of the Related Art In recent years, in the field of photolithography, the colorization and complexity of printed matter are rapidly advancing. For this reason, there is an increasing demand for silver halide photosensitive materials for printing (hereinafter referred to as printing photosensitive materials), which are intermediate media for printing, to improve quality and stabilize the quality year by year. Conventionally, general printing photographic materials have been given so-called lith development suitability in order to achieve high quality. However, in lith development, it is mechanically impossible to contain a high concentration of a sulfite ion as a preservative in the developing solution, and it is known to those skilled in the art that the stability of the developing solution is extremely poor. It is a well-known fact. As techniques for eliminating the instability of squirrel development and obtaining a high-contrast image comparable to squirrel development processing, the disclosure of patent literature can be seen for some attempts. For example, a technique for obtaining a high contrast image using a hydrazine compound is disclosed in JP-A-53-16623, JP-A-53-20921, JP-A-53-20922,
53-49429, 53-66732, 55-90940, 56-67843
No. 57-99635, No. 62-73256, No. 62-275247, No.
62-178246, 62-180361, 63-121838, 63
-223744, 63-234244, 63-253357, 64-9
No. 0439, JP-A-1-105943, JP-A-2-25843, JP-A-2-120736,
2-37, 2-8834, 3-125134, 3-84039,
No. 4-51143 and the like. It is necessary for the developer containing these hydrazine compounds to have a relatively high pH value in order to obtain a high contrast image, and the developer having this high pH value removes carbon dioxide from air. There are drawbacks that the pH tends to decrease due to absorption, and that the stability to air oxidation is not always sufficient, and the useful life of the developer is short.

[0003] To overcome these drawbacks, lower p is used.
For example, Japanese Patent Application Laid-Open No.
34, 62-948, U.S. Pat.
8, 4, 269, 929, etc., attempts have been made to make hydrazine derivatives more active.
Further, as a contrast enhancement accelerator, JP-A-61-165752,
Various accelerators are disclosed in Japanese Patent Application No. 61-271113 and JP-A-2-8833. These accelerators accelerate development but have almost no effect of lowering the pH of the developer. Even with these accelerators and highly active hydrazine, there is a limit to lowering the pH. On the other hand, although the accelerator disclosed in JP-A-2-170155 can reduce the pH of the developer by using a highly active hydrazine, another problem is that the photographic performance when the pH of the developer fluctuates is increased. Was that the change in the size became larger. There has been a problem that the dot area fluctuates or the line width of a line image fluctuates even with a slight pH fluctuation.

[0004]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a high-contrast image using a hydrazine compound at a low developing solution pH.
And to provide a silver halide photographic light-sensitive material having a small variation in photographic performance even when the pH varies.

[0005]

In a silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer, wherein at least one of the emulsion layer and another hydrophilic colloid layer contains a hydrazine compound, This is achieved by a silver halide photographic material characterized by containing a water-soluble polymer having a group.

The hydrazine compound used in the present invention includes a compound represented by the following formula 1.

Embedded image Reduction in 1, A _1, A ₂ on the other hand both hydrogen atoms or one is hydrogen atom represents a sulfonyl group, or an acyl group, R ₁ represents an aliphatic group, an aromatic group, or a heterocyclic group, G ₁ Represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group, an oxalyl group or an iminomethylene group, and R ₂ represents a hydrogen atom, an aliphatic group, an aromatic group, an alkoxy group, an aryloxy group, or an amino group.

Next, chemical formula 1 will be described in detail. Of 1 At a, A _1, A ₂ is a hydrogen atom, an alkylsulfonyl group having 20 or less carbon atoms and an arylsulfonyl group (preferably a phenylsulfonyl group or the sum of the Hammett sigma _p -
A phenylsulfonyl group substituted so as to be 0.5 or more, an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or benzoyl substituted so that the sum of Hammett's σ _p becomes -0.5 or more) Group) or a linear, branched or cyclic unsubstituted or substituted aliphatic acyl group (substituents include, for example, halogen atom, ether group, sulfonamide group, amide group, hydroxy group, carboxy group, sulfo group A ₁ and A ₂ are most preferably hydrogen atoms. The aliphatic group represented by R ₁ is a linear, branched or cyclic alkyl group, alkenyl group, or alkynyl group. The aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group, for example, a phenyl group,
And a naphthyl group. As the heterocyclic group for R ₁ ,
A 3- to 10-membered saturated or unsaturated heterocyclic ring containing at least one of N, O and S atoms, which may be a monocyclic ring or a condensed ring with another aromatic or heterocyclic ring May be formed. The heterocyclic ring is preferably a 5- or 6-membered aromatic heterocyclic group, for example, a pyridyl group,
Imidazolyl group, quinolinyl group, benzimidazolyl group, pyrimidyl group, pyrazolyl group, isoquinolinyl group,
Those containing a thiazolyl group or a benzthiazolyl group are preferred. R ₁ may be substituted with a substituent. Examples of the substituent include the following. These groups may be further substituted. For example, alkyl group, aralkyl group, alkoxy group, aryl group, substituted amino group, acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, aryl group, alkylthio group, arylthio group, Examples include a sulfonyl group, a sulfinyl group, a hydroxy group, a halogen atom, a cyano group, a sulfo group, a carboxy group, a pyridinium group, and a thyuronium group. When possible, these groups may be linked to each other to form a ring. Preferred as R ₁ is an aromatic group, more preferably an aryl group. R ₁ may have a ballast group commonly used in immobile photographic additives such as couplers incorporated therein. The ballast group is a photographically inactive group having 8 or more carbon atoms and is selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group, and the like. be able to.

G ₁ represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group, an oxalyl group or an iminomethylene group, and G ₁ is preferably a carbonyl group or an oxalyl group. The aliphatic group represented by R ₂ is preferably an alkyl group having 1 to 5 carbon atoms, and the aromatic group is preferably a monocyclic or bicyclic aryl group (for example, those containing a benzene ring). When G ₁ is a carbonyl group,
Preferred among the groups represented by ₂ are a hydrogen atom, an alkyl group (for example, a methyl group, a trifluoromethyl group,
-Hydroxypropyl group, 3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc., aralkyl group (eg, 2-hydroxybenzyl group, etc.), aryl group (eg, phenyl group, 3,5-dichlorophenyl group, 2- Methanesulfonamidophenyl group, 4-methanesulfonamidophenyl group, 2-hydroxymethylphenyl group) and the like, and a hydrogen atom is particularly preferable. R ₂ may be substituted, and the substituent may be R _2
The substituents listed for ₁ are applicable. When G ₁ is an oxalyl group, R ₂ is preferably an alkoxy group (for example, methoxy group, ethoxy group, isopropoxy group, methoxyethoxy group, etc.), an aryloxy group (for example, phenoxy group, 2-hydroxymethylphenyl). Xy group, 4-chlorophenoxy group), amino group (for example, 3
-Hydroxypropylamino group, 2,3-dihydroxypropylamino group, 2-dimethylaminoethylamino group, 3-diethylaminopropylamino group, etc., and an amino group is particularly preferable. R ₁ and R ₂ may have incorporated therein a group which enhances the adsorption to the surface of the silver halide grains. Examples of such an adsorbing group include thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, triazole groups, and the like, and the groups described in US Pat. No. 4,355,105. R ₂ may also be such as to cause a cyclization reaction that cleaves the G ₁ -R ₂ moiety from the residual molecule to form a cyclic structure containing atoms of the -Gxo-Rxm moiety. For example, see, for example,
29751 and the like. When the compound represented by Chemical Formula 1 contains two or more R ₂ , they may be the same or different. Specific examples of the compound represented by Chemical Formula 1 are shown below, but the present invention is not limited to the following compounds.

[0009]

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[0010]

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[0013]

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[0014]

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[0024]

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[0026]

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[0027]

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The hydrazine compounds of the present invention are described, for example, in JP-A-61-213847, JP-A-62-178246 and JP-A-62-178246.
-180361, 62-260153, 63-25
3357, U.S. Pat. Nos. 4,684,604, 3,
No. 379,529, 4,377,634, 4,332,878, and Japanese Patent Application No. 63-98803.

The hydrazine compound of the present invention can be used in a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethylacetamide, dimethylsulfoxide, and the like.
It can be used by dissolving it in methylcellosolve or the like.
Also, by an already well-known emulsification dispersion method, dimethyl phthalate, tricresyl phosphate, glyceryl triacetate or an oil such as diethyl phthalate is dissolved using an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. Things can be created and used. Alternatively, a hydrazine compound powder can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method and used. The amount of the hydrazine compound to be used in the present invention is preferably 1 × 10 ^-6 to 5 × 10 ^-2 mol per mol of silver halide, and more preferably 1 × 10 ^-6 mol.
The range of 10 ⁻⁵ mol to 2 × 10 ⁻² mol is a preferable addition amount.

The water-soluble polymer having an amino group other than the primary amino group used in the present invention is a polymer containing a secondary or tertiary amine.
Can be represented by

[0031]

Embedded image Wherein R ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ , R ₂₂ , R ₂₃ ,
R ₂₄ , R ₃₁ and R ₃₂ each represent a hydrogen atom or a substituted or unsubstituted alkyl group, and R ₁₂ and R ₁₃ and R ₂₃ and R ₂₄
May be the same or different and may be further bonded to each other to form a ring, but R ₂₃ and R ₂₄ are not simultaneously hydrogen atoms. L represents a divalent linking group which may have a substituent.

R ₁₁ , R ₁₂ , R ₂₂ , R ₃₁ and R ₃₂ are preferably a hydrogen atom, a lower alkyl group such as a methyl group or an ethyl group, and particularly preferably a hydrogen atom and a methyl group. R ₁₂ , R
₁₃ , R ₂₃ and R ₂₄ are preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a 2-ethylhexyl group, a methoxyethyl group, an ethoxyethyl group and the like, and L is an ethylene group, a propylene group, Isopropylene and butylene are preferred. x, y, and z represent mol%, x is 20 to 99 mol%, preferably 50 to 95 mol%, y is 1 to 50 mol%, preferably 5 to 40 mol%, and z is 0 to ~ 50 mol%, preferably 0-30
Mol%. n is 3 to 50, preferably 3 to 3
0. Specific examples of the compound represented by Chemical Formula 2 are shown below, but the present invention is not limited to the following compounds.

[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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The production of the water-soluble polymer having an amino group of the present invention can be carried out, for example, according to a conventional vinyl polymerization method. That is, a polymerization initiator is added to a solution of a mixture of two or three kinds of vinyl monomers under a nitrogen atmosphere and heated, or the solution containing the polymerization initiator is kept at a high temperature, and the monomer mixture is added therein. It can be obtained by dropping. Solvents used for polymerization are water, methanol, ethanol, DM
F, DMSO, dioxane and the like are used, and preferably water is used, but a mixed system of these solvents is also used. As the polymerization initiator, generally known potassium persulfate, benzoyl peroxide, azobisisobutyronitrile, cumene hydroperoxide and the like can be used.

The silver halide used in the light-sensitive silver halide emulsion of the light-sensitive material of the present invention is not particularly limited, but a surface latent image type silver halide emulsion is preferred. Silver bromide, silver chloroiodobromide, silver iodobromide, silver bromide and the like can be used. When silver chloroiodobromide or silver iodobromide is used, the content of silver iodide is 5%. It is preferably in the range of mol% or less. The form, crystal habit, size distribution 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 refers to 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. From the viewpoint of improving the handling property 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 the formulas (1) and (21) are preferably contained in the surface latent image type silver halide emulsion layer, but are adjacent to the surface latent image type silver halide emulsion layer. It may be contained in a hydrophilic colloid layer. Such a layer may be any layer, 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 or Chemical Formula 21 from diffusing into the silver halide grains. It may be a layer having a function. Since the content of chemical formulas 1 and 21 in the layer varies depending on the characteristics of the silver halide emulsion used, the chemical structure of the compound and the development conditions, the appropriate content can vary over a wide range. The range of about 1 × 10 ^-6 to 1 × 10 ^-2 mol per mol of silver in the surface latent image type silver halide emulsion is practically useful. About 10 mg to 3 g / m ²
Is preferred.

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.

As a binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, gelatin is advantageously used, 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 (such as chrome alum), aldehydes (such as formaldehyde and glyoxal), N-methylol compounds, dioxane derivatives (such as 2,3-dihydroxydioxane), active vinyl compounds, and active halogen compounds (such as 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, development Surfactants may be included for various purposes such as acceleration, contrast enhancement, and sensitization. For example, nonionics such as saponins (steroids), alkylene oxide derivatives (polyethylene glycol, polyethylene glycol alkyl ethers, etc.), glycidol derivatives (alkenyl succinic acid polyglycerides, etc.), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Surfactants, alkyl carboxylates, alkyl sulfates,
Carboxy groups, such as alkyl phosphates,
Anionic surfactants containing acidic groups such as sulfo groups, phospho groups, sulfate groups, and phosphate groups, amino acids,
Amphoteric surfactants such as aminoalkylsulfonic acids, aminoalkylsulfuric acid or phosphoric acid esters, cationic surfactants such as aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium Can be used.

The photographic light-sensitive material used in the present invention may contain a water-insoluble or 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.

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. Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited thereto.

[0060]

【Example】

Example 1 Iridium-containing monodisperse silver chlorobromide emulsion having an average particle size of 0.25 µm prepared by a control double jet method was treated with 6-methyl-4-hydroxy-1,3,3a, 7.
-1 g / Ag 1 mol of tetrazaindene was added. 300 mg / A of anhydro-5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine hydroxidepyridinium as sensitizing dye
g1mol and polyethylene glycol 250m
g / Ag of 1 mol, a hydrazine compound exemplified, and a water-soluble polymer having an amino group as a high contrast accelerator were added as shown in Table 1. 2 g / m ² of a dispersion of polyethylene acrylate and 2.5 g of gelatin were added to the emulsion thus obtained.
/ M ² and a coated silver amount of 3.5 g / m ² on a polyethylene terephthalate film. The following chemical formulas (38), (39) and (40) were similarly used as comparative samples of the high contrast accelerator.

[0061]

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[0063]

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The thus obtained sample was exposed through a light wedge by a printer using a tungsten lamp as a light source, developed with a developer having the following composition at 38 ° C. for 20 seconds, stopped, fixed, washed with water and dried. The relative photographic sensitivity and contrast (optical density: 0.1 to 2.50) were evaluated.
Contrast is the slope of the linear portion of the characteristic curve (optical density 0.
(Tan θ of 1 to 2.50), and the density of the shoulder on the characteristic curve was determined. The dot quality is a subjective measure, with 1 being rated very poor and 5 being rated very good. Three or more were practically usable. The results are shown in Table 2.

<Developer (concentrate)> Hydroquinone 65 g 4-Human-peroxymethyl-4-methyl-1-phenyl-3-perazodritone 2.9 g Sodium pyrosulfite 145 g Diethylenetriaminepentaacetic acid pentasodium salt 6.0 g Boric acid 6.9 g Sodium bromide 12 g 1-Phenyl-5-mercaptotetrasole 0.05 g Sodium hydroxide 23 g Benzotriazole 0.4 g Potassium hydroxide 80 g Potassium carbonate 80 g Diethylene glycol 120 g Add water 1 liter Add 4 parts of the above concentrate to 4 parts of water Diluted in parts
The developer was 10.4.

[0066]

[Table 1]

[0067]

[Table 2]

Example 2 The pH of the developing solution used in Example 1 was adjusted to the value shown in Table 3 with an aqueous sodium hydroxide solution and sulfuric acid, and the developing time was set at 35 ° C. for 1 minute. One similar item and pepper fog were evaluated. Pepper fog is
According to the visual judgment, 1 was extremely poor, and 5 was ranked in 5 levels in a favorable state where almost no pepper was observed. The obtained results are shown in Tables 3 and 4.

[Table 3]

[0069]

[Table 4]

It can be seen that the combination of the hydrazine compound of the present invention and a water-soluble polymer having an amino group other than the primary amino group significantly increases sensitivity, contrast and shoulder density and improves halftone dot quality. Also, the change in pH of the developer is small compared to the comparison, and the generation of pepper fog is suppressed, thereby giving practically preferable photographic characteristics. It is also apparent that the use of the polymer of the present invention causes the hydrazine to exhibit high contrast even in a developer having a low pH.

[0071]

According to the present invention, it is necessary to use an amino compound in a developing solution in forming a high contrast image with a silver halide photographic material using a hydrazine compound of the present invention and a water-soluble polymer having an amino group other than a primary amino group. Not,
A high-contrast image can be obtained without being greatly affected by a pH change due to running. In addition, the polymer having an amino group described in this specification is easy to synthesize, has low cost, and is very effective.

Claims (1)

(57) [Claims] A silver halide photographic emulsion layer comprising at least one
A water-soluble polymer having an amino group other than a primary amino group as a high contrast accelerator in a silver halide photographic material containing a hydrazine compound in at least one of the emulsion layer and another hydrophilic colloid layer A silver halide photographic light-sensitive material comprising: