JPH11184031A - Silver halide photographic material and processing method thereof - Google Patents

Abstract

The present invention relates to a silver halide photographic light-sensitive material and a method for forming a high-contrast negative image using the same, and to provide a silver halide light-sensitive material for plate making having good processing stability. The present invention has at least one silver halide emulsion layer on a support, and in the emulsion layer or another hydrophilic colloid layer, at least one compound represented by the following formula (1) and at least one hydrazine derivative: A silver halide photographic light-sensitive material, characterized in that it contains at least one of the following. Embedded image Wherein Y represents O, S, and N-R _3. R ₁ and R ₃ represent an aliphatic group, an aromatic group, or a heterocyclic group. R ₂ represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. According to the present invention, formation of a high-contrast image using a silver halide photographic material containing a hydrazine compound in the presence of a high-contrast accelerator selected from the compounds of the formula (1) is easy even with a developer having a lower pH than in the prior art. Photographic characteristics in which the occurrence of black spots is suppressed can be obtained. By including it in the silver halide photographic light-sensitive material, a low pH of the developing solution can be realized, and a high contrast image with excellent halftone dot quality can be obtained.

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 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 provided with 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, techniques for obtaining a high contrast image using a hydrazine compound are disclosed in JP-A-53-16623 and JP-A-53-20921,
Nos. 53-20922, 53-49429, 53
-66732, 55-90940, 56-67
No. 843, No. 57-99635, No. 62-73256
No. 62-275247, No. 62-178246
No. 62-180361, No. 63-121838
Nos. 63-223744 and 63-234244
No., 63-253357, 64-90439,
JP-A-1-105943, JP-A-2-25843, JP-A-2-25843
-120736, 2-37, 2-8834,
3-125134, 3-184039, 4-
No. 51143, and the like. A relatively high level of the pH of the developer containing these hydrazine compounds is necessary for obtaining a high contrast image, and the developer having a high pH absorbs carbon dioxide in the air. PH tends to decrease, and the stability to air oxidation is not always sufficient, and the effective life of the developer is short.

[0003] To overcome these drawbacks, lower p is used.
For example, Japanese Patent Application Laid-Open No.
No. 34, No. 62-948, U.S. Pat.
No. 108, No. 4,269,929, No. 4,988,6
No. 04, No. 4,994,365, No. 5,104,76
Attempts have been made to make the hydrazine derivative more active as disclosed in, for example, Japanese Patent Application Laid-Open No. 9-209, but there is a limit in improving the hydrazine derivative alone at a low pH to achieve high contrast. Therefore, the development of a high contrast enhancement agent has been conventionally promoted. JP-A-56-106244, JP-A-60-218
As described in JP-A Nos. 642 and 61-267759, a method of adding a secondary or tertiary amino compound to a developer, JP-A-60-140340 and JP-A-62-222.
Nos. 241, 63-124045, U.S. Pat.
There is known a method of adding an amino compound to a light-sensitive material as disclosed in Japanese Patent No. 75,354. However, none of them exhibit satisfactory high contrast, black fog (pepper fog) occurs, or the photographic performance changes greatly when the composition of the developer changes due to running or air oxidation. Because of the disadvantages,
The development of more effective accelerators has been desired.

[0004]

SUMMARY OF THE INVENTION The object of the present invention is to
It is an object of the present invention to provide a light-sensitive material which is hard and has a high image density even when a developing solution which is stable at pH is used, and which hardly generates black spots.

[0005]

The above object is achieved by having at least one silver halide emulsion layer on a support, and represented by the above formula (1) in the emulsion layer or another hydrophilic colloid layer. This has been attained by a silver halide photographic material characterized by containing at least one compound and at least one hydrazine derivative.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The compound of the present invention will be described below. Wherein Y in Formula 1 represents O, S, and N-R _3. R ₁ ,
R ₃ represents an aliphatic group (eg, an alkyl group such as methyl, ethyl, butyl, etc., an alkenyl group such as allyl, butenyl, an alkynyl group such as propargyl, an aralkyl group such as benzyl), an aromatic group (eg, a phenyl, naphthyl group, etc.). ) And a heterocyclic group (such as a 2-pyridyl or 2-thiazolyl group). R ₂ is a hydrogen atom, an aliphatic group (synonymous with R ₁ , R ₃ ), an aromatic group (synonymous with R ₁ , R ₃ ), a heterocyclic group (R ₁ ,
R ₃ ). Among them, preferred are R ₁ , R ₂ ,
At least one of R ₃ is a group represented by Chemical Formula 2 or Chemical Formula 3.

In the formulas (2) and (3), R ₄ is an aliphatic group (R ₁ , R
₃ ), an aromatic group (same as R ₁ and R ₃ ), a heterocyclic group (eg, 2-pyridyl, morpholino, piperazino, 4-
Tetrahydropyranyl, 1,3-dioxan-2-yl group, etc.). R ₅ is a hydrogen atom, an aliphatic group (R ₁ , R ₃
), An aromatic group (same as R ₁ and R ₃ ), a heterocyclic group (R
₄ ), an amino group (eg, dimethylamino, diethylamino, di-n-butylamino group, etc.) and an alkoxy group (eg, methoxy, ethoxy, n-butoxy, n-octyloxy group, etc.). L _{1 to} L _{3 each} represent a divalent linking group (eg, an alkylene, alkenylene, arylene group, etc., which may be used alone or in combination). A represents an alkylene group (for example, a methylene, ethylene, propylene group, etc.). Further, the above-mentioned groups may be substituted by substituents known in the art. m represents 0 or 1, and n represents an integer of 2 or more. Among the above-mentioned compounds, particularly preferable ones are those represented by the following chemical formula 4.

[0008]

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[0009] of 4 wherein R ₆ aliphatic group (synonymous R _1, R _3), an aromatic group (synonymous R _1, R _3), a Hajime Tamaki (R _1,
R ₃ ). Among them, preferred is an alkyl group having 4 or less carbon atoms. R ₇ is a hydrogen atom, an aliphatic group (R ₁ ,
Synonymous R _3), represents an aromatic group (synonymous R _1, R _3), a Hajime Tamaki (R _1, synonymous to R _3). Among them, preferred are a hydrogen atom and an alkyl or alkenyl group having 4 or less carbon atoms. R ₈ is a group represented by the above formula (2) or (3).

Hereinafter, typical compounds used in the present invention will be described, but the present invention is not limited thereto.

[0011]

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[0012]

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[0013]

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[0014]

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The compound of the formula 1 of the present invention is described, for example, in Research Disclosure, Vol. 12, Item 17643 (197)
8 years), Research Disclosure, Vol. 6, 170
29 (1978); Org. Chem. 32, 2245 (1976); Chem. Soc. 37
99 (1959); Am. Chem. Soc. 80
Vol. 1895 (1958); Chem. Soc. P
arcin. Trans. I 633 (1974),
J. Chem. Soc. Parkin. Trans. I
627 (1974); Heterocyclic
c. Chem. 2, 105 (1965); Hete
rocyclic. Chem. Vol. 5 5277 (196
8), Chem. Commun. 1222 (197
1), Tetrahedron. Lett. 5881
(1968), Tetrahedron. Lett. 1
578 (1971), Tetrahedron. Let
t. 2933 (1972), Tetrahedron.
Lett. 1809 (1967); U.S. Pat.
No. 8,424, No. 4,631,253, No. 4,6
No. 75,276 and 4,939,075 can be easily synthesized. Hereinafter, typical synthesis examples will be described.

Synthesis of M-1 In 2.6 g of 1-acetyl-1-methylhydrazine dissolved in 30 ml of methanol, 5.3 g of {3- (2-methoxy) ethoxy} propyl isothiocyanate was added.
Further, 0.5 ml of triethylamine was added, and the mixture was heated under reflux for 3 hours. Then, the solvent was distilled off under reduced pressure, 20 ml of ethyl acetate was added to the residue, and the mixture was stirred under ice-water cooling. The precipitated crystals were collected by filtration, washed with ethyl acetate and isopropyl ether in that order, and dried to obtain 2.0 g of M-1.
(Melting point 64-66.5 ° C)

Synthesis of M-12 In 2.1 g of 1-acetyl-1-methylhydrazine dissolved in 30 ml of methanol was added 2- (2-morpholino)
5.5 g of ethylthiodiethylisothiocyanate was added, and 0.4 ml of triethylamine was further added. The mixture was heated under reflux for 3 hours. Then, the solvent was distilled off under reduced pressure, 20 ml of ethyl acetate was added to the residue, and the mixture was stirred under ice-water cooling.
The precipitated crystals were collected by filtration, washed with ethyl acetate and isopropyl ether in that order, and dried to obtain 3.6 g of M-12. (Melting point 122.5-125 ° C)

When the compound represented by Chemical Formula 1 of the present invention is added to a photographic light-sensitive material, it is preferably added to a silver halide emulsion layer, but the other non-light-sensitive hydrophilic colloid layer ( For example, it may be contained in a protective layer, an intermediate layer, a filter layer, an antihalation layer, etc.). Specifically, when the compound to be used is water-soluble, it is used as an aqueous solution, and when the compound is hardly water-soluble, it is a water-miscible organic solvent such as alcohols (methanol, ethanol, isopropanol, fluorinated alcohol), ketones (acetone). , Methyl ethyl ketone), dimethylacetamide, dimethylsulfoxide, methylcellosolve and the like as a solution of an organic solvent may be added to the hydrophilic colloid solution. When added to the silver halide emulsion layer, it can be performed at any time during the preparation of the emulsion,
It is preferable to add it after completion of chemical ripening and before coating. Particularly preferably, it is added to a coating solution prepared for coating. The addition amount thereof is in the range of 1.0 × 10 ^{−4 to} 1.0 × 10 ⁻¹ mol, more preferably 5.0 × 10 ^{−4 to} 5.0 × 10 ⁻² mol, per mol of silver halide. Used. The compound represented by Chemical Formula 1 of the present invention can be contained in the same layer as the hydrazine derivative used and / or in another hydrophilic colloid layer. The hydrazine derivative used in the present invention includes a compound represented by the following general formula (1).

[0019]

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In the general formula (1), A ₁ and A ₂ both represent a hydrogen atom or one of them represents a hydrogen atom and the other represents a sulfonyl group or an acyl group, and 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; R ₂ represents a hydrogen atom, an aliphatic group, an aromatic group, an alkoxy group, an aryloxy group, an amino group; Group or general formula (2)
Represents

[0021]

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In the general formula (2), Q ⁺ represents a group containing a cationic group, and A ⁻ represents an anion. However, it is unnecessary when Q ⁺ contains a sulfo group.

Next, the general formulas (1) and (2) will be described in detail. Formula At a _{(1), 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 a sum of Hammett's sigma _p is -0.5 or more substituted phenylsulfonyl group) such that, of 20 or less acyl group carbons (preferably a benzoyl group, or the sum of the Hammett's sigma _p -0.
A benzoyl group substituted so as to have 5 or more), or a linear, branched or cyclic unsubstituted or substituted aliphatic acyl group (for example, a halogen atom, an ether group, a sulfonamide group, an amide group, A hydroxy group, a carboxy group and a sulfo group), and 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.
Examples include a phenyl group and a naphthyl group. The heterocyclic group represented by R ₁ is 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, May form a condensed ring with an aromatic ring or a heterocyclic ring. The heterocyclic ring is preferably a 5- or 6-membered aromatic heterocyclic group, and includes, for example, a pyridyl group, an imidazolyl group, a quinolyl group, a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, an isoquinolyl group, a thiazolyl group, and a benzothiazolyl 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, an alkyl group,
Aralkyl, alkoxy, aryl, substituted amino, acylamino, sulfonylamino, ureido, urethane, aryloxy, sulfamoyl, carbamoyl, alkylthio, arylthio, sulfonyl, sulfinyl, hydroxy A halogen atom, a cyano group, a sulfo group, a carboxy group, an ammonium group, a pyridinium group, a thiuronium group, an isothioureido group, and the like. When possible, these groups may be linked to each other to form a ring. Preferred as R ₁ is an aromatic group, more preferably an aryl group. or,
R ₁ may have incorporated therein a ballast group commonly used in immobile photographic additives such as couplers. A ballast group is a group having a carbon number of 8 or more, which is relatively inert to photographic properties, such as an alkyl group,
It can be selected from an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group and the like. Q ⁺ in the general formula (2) is a group containing a cationic group having at least one quaternary nitrogen atom,
Bonded to G ₁ through a linear or branched hydrocarbon chain having 1 to 4 carbon atoms, and a part or all of this chain may constitute a part of a heterocyclic ring having a quaternary nitrogen atom. Good.
Preferred examples of Q ⁺ include a trialkylammonioalkyl group, a pyridinium-1-ylalkyl group, a 1-alkylpyridinium-2-yl group, a 1-alkylpyridinium-3-yl group, and a 1-alkylpyridinium-4-yl group.
Examples thereof include an yl group, a thiazolinium-3-ylalkyl group, an oxazolinium-3-ylalkyl group, and a 1-alkylimidazolium-3-ylalkyl group. These groups may be substituted, and 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 ⁺ , and preferred examples include Cl ⁻ , Br ⁻ , p-toluenesulfonate, methanesulfonate, etc., but having a sulfo group as a substituent of Q ⁺ , Is not present when forming

G ₁ represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group, an oxalyl group or an iminomethylene group, and G ₁ is preferably a carbonyl group or an oxalyl group. The aliphatic group represented by R 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, R ₂
Preferred among the groups represented by 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), aryl group (eg, phenyl group, 3,5-dichlorophenyl group, 2-methane) A sulfonamidophenyl group, a 4-methanesulfonamidophenyl group, a 2-hydroxymethylphenyl group), a general formula (2) and the like, and a hydrogen atom and a general formula (2) are particularly preferable. R ₂ may be substituted, and as the substituent, the substituents listed for R ₁ can be applied. When G ₁ is an oxalyl group, R ₂ is preferably an alkoxy group (for example, a methoxy group, an ethoxy group, an isopropoxy group, a methoxyethoxy group, etc.),
Aryloxy group (for example, phenoxy group, 2-hydroxymethylphenoxy group, 4-chlorophenoxy group),
An amino group (for example, a 3-hydroxypropylamino group,
2,3-dihydroxypropylamino group, 2-dimethylaminoethylamino group, 3-diethylaminopropylamino group), the general formula (2) and the like, 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 adsorptive group include groups described in US Pat. No. 4,355,105, such as a thiourea group, a heterocyclic thioamide group, a mercapto heterocyclic group, and a triazole group. R ₂ splits the G ₁ -R ₂ moiety from the residual molecule,
It may be one which causes a cyclization reaction to form a cyclic structure containing an atom of the G ₁ -R ₂ moiety. Examples thereof include those described in JP-A-63-29751. No. 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.

[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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The hydrazine compounds of the present invention are described, for example, in JP-A-61-213847, JP-A-62-178246, JP-A-62-180361, JP-A-62-260153 and JP-A-6-260153.
No. 3-253357, U.S. Pat. No. 4,684,604
No. 3,379,529, No. 4,377,6
No. 34, No. 4,332,878, No. 4,937,
No. 160, Japanese Patent Application No. 63-98803, and the like.

The hydrazine compound of the present invention may be used in a suitable water-miscible organic solvent, for example, alcohols (methanol, ethanol, isopropanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethylacetamide, dimethylsulfoxide, 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 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.
Those having a size of μm or less are preferred. Silver halide emulsions include gold compounds such as chloroaurate and gold trichloride, sulfur compounds which form silver sulfide by reacting with salts of noble metals such as rhodium and iridium and silver salts, stannous salts, Sensitivity can be increased without reducing particles with a reducing substance such as an amine. Also, salts of precious metals such as rhodium and iridium,
An iron compound such as a red blood salt may be present during physical ripening or nucleation of silver halide grains. In particular, the 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 properties in a short development time is further promoted.

In the present invention, the surface latent image type silver halide emulsion refers to an emulsion comprising silver halide grains having a surface sensitivity higher than the internal sensitivity, and this emulsion is preferably a US Pat.
It has a difference between surface sensitivity and internal sensitivity defined in the specification of 4,224,401. The silver halide emulsion is desirably monodispersed, and in particular, an emulsion having the monodispersity specified in the above-mentioned US Pat. No. 4,224,401 is 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 0.7 μm or less, particularly preferably in the range of 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. Alternatively, for the purposes of the present invention,
The double jet method in which a soluble silver salt and a soluble halogen salt are added simultaneously in an acidic solution to form grains is particularly preferable. The silver halide emulsion prepared in this way may or may not be chemically sensitized, and so-called light-room photographic materials handled in a safelight environment, which can be called a bright room, have good handleability. It is rather preferable that the chemical sensitization is not performed from the viewpoint of improving. In the case of chemical sensitization, usual sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization and the like are used.

In the light-sensitive material of the present invention, the hydrazine compound is preferably contained in a silver halide emulsion layer.
It may be contained in a hydrophilic colloid layer adjacent to the surface latent image type silver halide emulsion layer. Such a layer may have any function, such as an undercoat layer, an intermediate layer, a filter layer, a protective layer, an antihalation layer, as long as it does not prevent the hydrazine compound from diffusing into the silver halide grains. Is also good. Since the content of the hydrazine compound 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. Approximately 1 × 10 per mole of silver in the latent image type silver halide emulsion
A range of ^-6 to 1 x ^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.

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. . Examples of gelatin include lime-processed gelatin, acid-processed gelatin, and Bull.Soc.Sci.Phot.Japan, No.
16, p.30 (1966) may be used, and a hydrolyzate or an enzymatic degradation product 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, mercaptotetrazole Mercaptopyrimidines, mercaptotriazines, thioketo compounds, azaindenes and the like, which have been conventionally known as antifoggants or stabilizers;
Many compounds can be added. Among these, particularly preferred are benzotriazoles (eg, 5-methylbenzotriazoles) and nitroindazoles (eg, 5-nitroindazole). These compounds may be contained in the 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 (2,4-dichloro-6) −
Such as hydroxy-s-triazine) can be used alone or in combination. The compounds described in Research Disclosure No. 17465, Sections XXI B to D are added to the photosensitive silver halide emulsion layer or an adjacent layer for the purpose of increasing sensitivity, increasing contrast, or accelerating development. In particular, it is preferable to add polyethylene glycol or a derivative thereof. The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared by using the present invention has a coating aid, an antistatic,
A surfactant may be contained for various purposes such as improving slipperiness, emulsifying and dispersing, preventing adhesion, and improving photographic properties (eg, development acceleration, high contrast, 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 sparingly 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 or a high alkali developer close to pH 13 described in US Pat. No. 2,419,975 is used. There is no need to use a stable developer. That is, the silver halide photographic light-sensitive material of the present invention can use a developer containing a sufficient amount of sulfite ion as a preservative (particularly, 0.15 mol / l or more). Particularly, a developer having a developer content of 10 to 11.0 can sufficiently provide a negative image having a super-high contrast.
Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited thereto.

[0042]

Example 1 Monodispersed silver chlorobromide emulsion containing iridium and having an average particle size of 0.25 .mu.m, prepared by the control double jet method, was treated with 6-methyl-4-hydroxy-1,3,3a, 7. −
1 g / Agmol of tetrazaindene was added. Anhydro-5,5'-dichloro-9-ethyl-3,
300 mg / Agmol of 3'-di- (3-sulfopropyl) oxacarbocyanine hydroxidepyridinium, and the hydrazine compound exemplified and a contrast enhancement accelerator were added as shown in Table 1. The emulsion thus obtained was coated on a polyethylene terephthalate film such that a dispersion of polyethylene acrylate was 2 g / m ² , gelatin was 2.5 g / m ² , and a coated silver amount was 3.5 g / m ² . Comparative compounds (1), (2), and (3) were similarly used as comparative samples of the high contrast accelerator.

[0043]

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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 35 ° C. for 30 seconds, stopped, fixed, washed with water and dried. The relative photographic speed, contrast and halftone quality were evaluated. Contrast is the slope of the linear portion of the characteristic curve (ta at an optical density of 0.1 to 2.50).
When n is less than 10, it is not practical because the degree of high contrast is insufficient. 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 black spots in the unexposed areas were evaluated on a 5-point scale using a 100-fold loupe, and those having no black spots were rated 5, and 3 or more were practically usable. The results are shown in Table 2.

<Developer (Concentrate)> Hydroquinone 65 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 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-mercaptotetrazole 0.05 g sodium hydroxide 23 g benzotriazole 0.4 g potassium hydroxide 80 g potassium carbonate 80 g diethylene glycol 120 g water 1 liter Parts diluted to pH 1
The developer was 0.5.

[0046]

[Table 1]

[0047]

[Table 2]

Example 2 A monodisperse silver chloride emulsion containing 8.0 × 10 ⁻⁶ mol / Agmol of rhodium dichloride and having an average particle size of 0.13 μm was prepared by a control double jet method. The emulsion which had been desalted, washed with water and re-dissolved was divided by a flow curation method, and the hydrazine compound exemplified and a high contrast accelerator were added as shown in Table 3. 5 × 10 ⁻³ mol / Agmol of 5-chlorobenzotriazole, polyethyl acrylate latex, 2-hydroxy-4,6-dichloro-1,
After addition of 3,5-triazine sodium salt, 3 g / m ^{2 of} gelatin was applied on the polyethylene terephthalate film,
Coating was performed so that the coated silver amount was 5 g / m ² . As a protective layer, 80 mg / m ² of a yellow dye having a maximum absorption wavelength at 400 to 450 nm (eg, Oxonol Yellow of Hoechst), a surfactant, and a hardener are added thereto as a protective layer of 1 g / m ^{2 of} gelatin. Then, the samples shown in Table 3 were prepared. Comparative compounds (1), (2), and (3) were used as comparative samples of the contrast enhancement accelerator in the same manner as in Example 1.

These films were used as a light room printer (P-627FM, manufactured by Dainippon Screen Mfg. Co., Ltd.).
After image exposure at 35 ° C. with the developing solution shown in Example 1,
For 30 seconds, and stopped, fixed, washed with water and dried. In this processing, an automatic developing machine (LD-221QT, Dainippon Screen Mfg. Co., Ltd.) was used. And Example-1
The same items were evaluated. The results are shown in Table 4.

[0050]

[Table 3]

[0051]

[Table 4]

It can be seen that the use of the compound of the formula (1) of the present invention makes it possible to obtain practically preferable photographic characteristics with high contrast, good halftone dot quality and little black spots.

[0053]

According to the present invention, the formation of a high-contrast image with a silver halide photographic material containing a hydrazine compound in the presence of a high-contrast accelerator selected from the compounds of the formula (1) is easy even with a developer having a lower pH than in the prior art. Yes, it is possible to give practically preferable photographic characteristics in which generation of black spots is suppressed.

Claims (2)

[Claims] 1. A support having at least one silver halide emulsion layer on a support, wherein at least one compound represented by the following formula (1) and a hydrazine derivative are contained in the emulsion layer or another hydrophilic colloid layer. A silver halide photographic light-sensitive material characterized by containing at least one of the following. Embedded image Wherein Y represents O, S, and N-R _3. R ₁ and R ₃ represent an aliphatic group, an aromatic group, or a heterocyclic group. R ₂ represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. 2. The method according to claim 1, wherein R ₁ , R ₂ , and R ₃
Wherein at least one of the groups is a group represented by Chemical Formula 2 or Chemical Formula 3. Embedded image Embedded image In the formula, R ₄ represents an aliphatic group, an aromatic group, or a heterocyclic group. R ₅ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amino group,
Represents an alkoxy group. L _{1 to} L ₃ represent a divalent linking group.
A represents an alkylene group. m represents 0 or 1, and n represents an integer of 2 or more.