JPH11231476A - Silver halide photographic sensitive material and its processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material and a method using it for forming a high-contrast negative image and manufacturing a printing plate good in processing stability. SOLUTION: This silver halide photographic sensitive material is exposed and developed and processed in the presence of a contrast-enhancing promoter represented by formula I or II in which each of Z1 and Z2 is an atomic group necessary to form an N-containing 5- or 6-membered hetero ring; each of L1 and L2 is a divalent bonding group; each of R1 and R2 is an alkyl or aryl or heterocyclic group; R1 and R2 or R1 and L1 may combine with each other to form a ring; each of m1 and m2 0 or 1; X<+> is group having a cationic group; and A<-> is a counter ion. The silver halide photographic sensitive material containing a hydrazine compound can form a high-contrast image in the presence of one of these contrast-enhancing promoters selected from the compound of the formula I or II easily by using a developing solution even in a pH lower than the preceding techniques.

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, a technique for obtaining a high contrast image using a hydrazine compound is disclosed in JP-A-53-16623, JP-A-53-20921, and JP-A-53-20922.
No. 53-49429, No. 53-66732, No. 55-90940,
No. 56-67843, No. 57-99635, No. 62-73256, No. 62
-275247, 62-178246, 62-180361, 63-
121838, 63-223744, 63-234244, 63-25
Nos. 3357, 64-90439, JP-A-1-105943, 2-258
No. 43, No. 2-120736, No. 2-37, No. 2-8834, No. 3-
Nos. 125134, 3-184039 and 4-51143. 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,
Stability against air oxidation is not always sufficient, and there is a drawback that the useful life of the developer is short.

[0003] To overcome these drawbacks, lower p is used.
As intensified with H, for example, JP-A-60-1779734,
No. 62-948, U.S. Pat.Nos. 4,385,108, 4,269,929
Nos. 4,988,604, 4,994,365, and 5,104,769 have been attempted to make the hydrazine derivative more active.However, improvement of only the hydrazine derivative makes it harder at a low pH to improve the contrast. There was a limit. Therefore, the development of a high contrast enhancement agent has been conventionally promoted. JP-A-56-106244, JP-A-60-218642, JP-A-61-167939,
As described in JP-A-61-267759, a method of adding an amino compound or an onium compound to a developer, JP-A-60-140340, JP-A-62-222241, JP-A-63-124045, and JP-A-6-140245. No. 4,514,534, US Pat. No. 4,975,354, and a method of adding an amino compound or an onium compound to a light-sensitive material is known.
However, none of them exhibit satisfactory high contrast, must be used in large amounts, cannot achieve high sensitivity, or changes in photographic performance when the composition of the developer changes due to running or air oxidation. However, there are drawbacks such as an increase in size and generation of black spots, and the development of a more effective high-contrast accelerator has been desired.

[0004]

SUMMARY OF THE INVENTION It is a first object of the present invention to provide a method for processing a light-sensitive material capable of obtaining a high contrast and high image density with little black spots by using a stable developer at a low pH. It is in. A second object of the present invention is to provide a light-sensitive material for printing plate making which contains an effective accelerator having a high contrast-increasing action with a small amount of use.

[0005]

The object of the present invention is to provide an exposed silver halide photographic material represented by the following general formula (1):
Alternatively, the present invention has been attained by a method for processing a silver halide photographic light-sensitive material, which comprises developing in the presence of the compound represented by (2).

[0006]

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In the formula, Z ₁ and Z ₂ represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. L ₁ , L ₂
Represents a divalent linking group, R ₁ and R ₂ represent an alkyl group, an aryl group or a heterocyclic ring, and R ₁ and R ₂ , and R ₁ and L ₁ may be linked to form a ring. m ₁ and m ₂ represent 0 or 1, and X ⁺
Represents a group containing a cationic group, and A ⁻ represents a counter ion.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The general formula (1) or (2) will be described in detail below. Z ₁ and Z ₂ each represent an atom group necessary for forming a 5- or 6-membered nitrogen heterocycle, and preferably include a pyridine ring, a thiazole ring, a quinoline ring, etc. No. Further, on the carbon of these heterocycles, a halogen atom (such as chlorine or bromine), an alkyl group (such as a methyl group, an ethyl group, or a t-butyl group), an alkoxy group (such as a methoxy group or an n-propoxy group), or a hydroxy group , A fluorine-substituted alkyl group (such as a trifluoromethyl group), a cyano group, an alkanesulfonyl group (such as a methanesulfonyl group), and a sulfamoyl group (N, N
-Dimethylsulfamoyl group, morpholinosulfamoyl group, etc.), aryl group (phenyl group, p-tolyl group, etc.)
And the like may be substituted. L ₁ and L ₂ are a divalent linking group composed of a combination of a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, and a selenium atom, preferably an alkylene group (ethylene group, propylene group , cyclohexylene group), an arylene group (phenylene group, naphthylene group, _{etc.), - CONR 11 -, -} OC
_{ONR 11 -, - NR 11 CONR} 12 -, - NR 11 CSNR
_{12 -, - NR 11 COCONR 12} -, - COO -, - CO
-, - CS -, - SO 2 NR 11 -, - SO 2 -, - O-,
_{-S -, - NR 11 -,} - PR 11 -, - Se- (R 11, R
₁₂ may be the same or different and represents a hydrogen atom, an alkyl group, an acyl group, an alkylsulfonyl group, etc.)
Etc. alone or in combination. m ₁ and m ₂ are 0
Or represents 1.

In the general formula (1), R ₁ and R ₂ represent an alkyl group, an aryl group or a heterocyclic ring. The alkyl group represented by R ₁ and R ₂ is preferably a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and this alkyl group may be linear, branched or cyclic. Examples of the unsubstituted alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-hexyl group, a cyclohexyl group, and an n-decyl group. R ₁ and R ₂ , and R ₁ and L ₁ may be linked to form a ring, and a saturated hetero ring containing a hetero atom (for example, a nitrogen atom, an oxygen atom, a sulfur atom, etc.); For example, a piperidine ring, a 2-methylpiperidine ring, a morpholine ring, a piperazine ring and the like may be formed. Substituents as the substituted alkyl group include an aryl group (eg, phenyl group, naphthyl group, etc.), an alkenyl group (eg, vinyl group, allyl group, butenyl group, etc.), an alkynyl group (eg, ethynyl group, etc.),
Heterocyclic group (pyridyl group, tetrahydropyranyl group, sulfolanyl group, etc.), hydroxy group, alkoxy group (eg, methoxy group, ethoxy group, benzyloxy group, polyethyleneoxy group, etc.), alkoxycarbonyl group (eg, ethoxycarbonyl group, benzyl group) Oxycarbonyl group, etc.), carboxy group, sulfo group, halogen atom (eg, chlorine atom, bromine atom, etc.), cyano group, aryloxy group (eg, phenoxy group, p-tolyloxy group, etc.), acyloxy group (eg, acetyloxy group) Group, propionyloxy group, etc.), acyl group (eg, acetyl group, propionyl group, benzoyl group, mesyl group, etc.), carbamoyl group (eg, carbamoyl group, N, N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidino) Carbonyl group), sulf Moyl group (eg, sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group, etc.), acylamino group (eg, acetylamino group, propionylamino group, mesylamino group, etc.), sulfonamide Groups (ethylsulfonamide group, p-toluenesulfonamide group, etc.), ureido groups (eg, methylureido group, phenylureido group, etc.) and the like. Examples of the aryl group represented by R ₁ and R ₂ include a phenyl group and a naphthyl group, and these may have a substituent (the same as described in the section of the substituted alkyl group). Examples of the heterocyclic group represented by R ₁ and R ₂ include a piperidyl group, a morpholinyl group, a furyl group, a thienyl group, a tetrahydropyranyl group, and a pyridyl group. (Same as described).

X ⁺ in the general formula (2) represents a group containing at least one cationic group, and examples of the cation include ammonium, phosphonium, and sulfonium. A preferred onium for X ⁺ is the following general formula (3):
(4), (5) and (6). A ^- is an anion, Cl ^-, Br -, ^{p-toluenesulfonate,} methyl sulfonate, tetrafluoroborate, and the like.

[0011]

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Wherein R ₂₁ , R ₂₂ , R ₂₃ , R ₃₁ , R ₃₂ , R
₃₃ , R ₄₁ and R ₄₂ represent an alkyl group, an aryl group or a heterocyclic ring. _{R 21, R 22, R 23} , R 31, R 32, R 33, R 41, R 42
Is a substituted or unsubstituted alkyl group having 1 carbon atom
Preferred are alkyl groups of up to 30 alkyl groups which may be linear, branched or cyclic. Also, R ₂₁ and R ₂₂ , R ₃₁ and R
₃₂ , R ₄₁ and R ₄₂ may be linked to form a ring, and a saturated hetero ring containing a hetero atom (eg, a nitrogen atom, an oxygen atom, a sulfur atom, etc.) (eg, a piperidine ring, etc.)
May be formed. Examples of the unsubstituted alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
Examples include an n-hexyl group, a cyclohexyl group, and an n-decyl group. Examples of the substituent as the substituted alkyl group include an aryl group (eg, a phenyl group, a naphthyl group, etc.), an alkenyl group (eg, a vinyl group, an allyl group, a butenyl group, etc.), an alkynyl group (eg, an ethynyl group, etc.), Group, tetrahydropyranyl group, sulfolanyl group, etc.), hydroxy group, alkoxy group (for example, methoxy group, ethoxy group, benzyloxy group, polyethyleneoxy group, etc.),
An alkoxycarbonyl group (for example, an ethoxycarbonyl group, a benzyloxycarbonyl group, etc.), a carboxy group,
Sulfo group, halogen atom (eg, chlorine atom, bromine atom, etc.), cyano group, aryloxy group (eg, phenoxy group, p-tolyloxy group, etc.), acyloxy group (eg, acetyloxy group, propionyloxy group, etc.), acyl Groups (eg, acetyl group, propionyl group, benzoyl group, mesyl group, etc.), carbamoyl groups (eg, carbamoyl group, N, N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, etc.), sulfamoyl groups (eg, , A sulfamoyl group, an N, N-dimethylsulfamoyl group, a morpholinosulfonyl group, a piperidinosulfonyl group, etc.), an acylamino group (for example,
Acetylamino group, propionylamino group, mesylamino group, etc., sulfonamide group (ethylsulfonamide group, p-toluenesulfonamide group, etc.), ureido group (eg, methylureido group, phenylureido group, etc.)
And the like. R ₂₁ , R ₂₂ , R ₂₃ , R ₃₁ , R ₃₂ ,
Examples of the aryl group represented by R ₃₃ , R ₄₁ , and R ₄₂ include a phenyl group and a naphthyl group, and these may have a substituent (the same as described in the section of the substituted alkyl group). Good. R ₂₁ , R ₂₂ , R ₂₃ , R ₃₁ , R ₃₂ , R ₃₃ , R ₄₁ ,
Examples of the heterocyclic group represented by R ₄₂ include a piperidyl group, a morpholinyl group, a furyl group, a thienyl group, a tetrahydropyranyl group, a pyridyl group, and the like, and these are the substituents (as described in the section of the substituted alkyl group). The same).

Y represents a group of atoms necessary to form a 5- or 6-membered nitrogen heterocycle, and is preferably a pyridine ring, a thiazoline ring, a quinoline ring, a benzoxazole ring (for convenience, shown by the name of a starting tertiary base). And the like. Further, on the carbon of these heterocycles, a halogen atom (such as chlorine or bromine), an alkyl group (such as a methyl group, an ethyl group, or a t-butyl group), an alkoxy group (such as a methoxy group or an n-propoxy group), or a hydroxy group , A fluorine-substituted alkyl group (such as a trifluoromethyl group), a cyano group, an alkanesulfonyl group (such as a methanesulfonyl group), and a sulfamoyl group (N, N
-Dimethylsulfamoyl group, morpholinosulfamoyl group, etc.), aryl group (phenyl group, p-tolyl group, etc.)
And the like may be substituted.

The compound represented by the general formula (1) or (2) may form a salt such as hydrochloride, sulfate, p-toluenesulfonate and the like. Specific examples of the compound represented by formula (1) or (2) are shown below, but the present invention is not limited to the following compounds.

[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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The compound represented by the general formula (1) or (2) of the present invention can be synthesized by a general synthesis method such as J. Org. Chem., Vol. 34, 4150 (1969) and US Pat. No. 3,163,655. It can be synthesized according to it. A specific synthesis example is shown below. Synthesis of Compound A-1 Hydrobromide 2- (Dielamino) ethyl bromide 2
3.5 g of sodium hydroxide and 3.8 g of sodium hydroxide
0 ml and stirred at room temperature for 1 hour. Thereafter, 38.4 g of a 35% aqueous solution of 2-mercaptopyridine-N-oxide sodium salt was added, and the mixture was heated under reflux for 1 hour. The reaction solution was concentrated under reduced pressure.
After extraction with ml, the organic layer was dried over anhydrous magnesium sulfate. The filtrate was distilled off under reduced pressure to remove insolubles, thereby obtaining 16.2 g of an oily target product. Other exemplified compounds can be easily synthesized by the same method.

When the compound of the formula (1) or (2) of the present invention is added to a photographic material, it is preferably added to a silver halide emulsion layer. May be contained in a hydrophilic colloid layer (for example, a protective layer, an intermediate layer, a filter layer, an antihalation layer, etc.). Specifically, when the compound to be used is water-soluble, an aqueous solution is used, and when the compound is hardly water-soluble, a water-miscible organic solvent is used.
For example, it may be added to a hydrophilic colloid solution as a solution of an organic solvent such as alcohols (methanol, ethanol, isopropanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylacetamide, dimethylsulfoxide, methylcellosolve and the like. When it is added to the silver halide emulsion layer, it can be added at any time during the preparation of the emulsion, but it is preferably added after completion of chemical ripening and before coating. Particularly preferably, it is added to a coating solution prepared for coating. The addition amount is 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. When the compound is added to the developing solution, the amount is preferably 5 × 10 ^{−3 to} 0.30 mol per liter of the developing solution. The compound represented by the general formula (1) or (2) of the present invention has an effect of promoting high contrast when used in a system for obtaining a so-called high contrast silver image. The compound represented by the general formula (1) or (2) of the present invention has the best effect in a system using a hydrazine derivative as a nucleating agent. The hydrazine derivative used in the present invention includes a compound represented by the following general formula (7).

[0023]

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In the general formula (7), A ₁ and A _{2 each} 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 ₃ 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 ₄ represents a hydrogen atom, an aliphatic group, an aromatic group, an alkoxy group, an aryloxy group, an amino group; Represents a group or a general formula (8).

[0025]

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In the general formula (8), Q ⁺ represents a group containing a cationic group, and B ⁻ represents an anion. However, it is unnecessary when Q ⁺ contains a sulfo group.

Next, the general formula (7) or (8) will be described in detail. Formula At a _{(7), 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 A phenylsulfonyl group which is substituted so as to have the following formula, an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a benzoyl group which is substituted so that the sum of Hammett's σ _p is -0.5 or more), or Straight-chain, branched or cyclic unsubstituted and substituted aliphatic acyl groups (substituents include, for example, halogen atoms, ether groups, sulfonamide groups, amide groups, hydroxy groups, carboxy groups, and sulfo groups); , A ₁ and A ₂ are most preferably hydrogen atoms. The aliphatic group represented by R ₃ is a linear, branched or cyclic alkyl group, alkenyl group, or alkynyl group. The aromatic group represented by R ₃ is a monocyclic or bicyclic aryl group, and examples include a phenyl group and a naphthyl group.
The heterocyclic group represented by R ₃ 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 single 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 ₃ 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 thiouronium group, an isothioureido group, and the like. When possible, these groups may be linked to each other to form a ring. Preferred as R ₃ is an aromatic group, more preferably an aryl group.
R ₃ may have a ballast group incorporated therein 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, such as an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group,
It can be selected from phenoxy groups, alkylphenoxy groups and the like. Q ⁺ in the general formula (8) is a group containing a cationic group having at least one quaternary nitrogen atom, and is represented by G ₁ through a linear or branched hydrocarbon chain having 1 to 4 carbon atoms. And part or all of this chain may form part of a heterocyclic ring having a quaternary nitrogen atom. 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 ₃ . Further, when these groups form a ring structure, they may be condensed with another ring. B ^- 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

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 ₄ 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 R ₄ are a hydrogen atom and an alkyl group (for example, a methyl group, a trifluoromethyl group, a 3-hydroxypropyl group, a 3-methanesulfonamidopropyl group) Phenylsulfonylmethyl group), aralkyl group (eg, 2-hydroxybenzyl group), aryl group (eg, phenyl group, 3,5-dichlorophenyl group, 2-methanesulfonamidophenyl group, 4-methanesulfonamidophenyl) Group, 2-hydroxymethylphenyl group), general formula (8) and the like, and particularly preferably a hydrogen atom and general formula (8). R ₄ may be substituted, and as the substituent, the substituents listed for R ₃ can be applied. When G ₁ is an oxalyl group, R ₄ is preferably an alkoxy group (for example, a methoxy group, an ethoxy group, an isopropoxy group, a methoxyethoxy group, etc.), an aryloxy group (for example, a phenoxy group, 2-
Hydroxymethylphenoxy group, 4-chlorophenoxy group), amino group (for example, 3-hydroxypropylamino group, 2,3-dihydroxypropylamino group, 2-dimethylaminoethylamino group, 3-diethylaminopropylamino group, etc.), Formula (8) and the like are preferable, and an amino group and formula (8) are particularly preferable. R ₃ and R ₄ may have incorporated therein a group that 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 ₄ may also be such as to cause a cyclization reaction that cleaves the G ₁ -R ₄ moiety from the residual molecule to form a cyclic structure containing the atoms of the -G ₁ -R ₄ moiety. Examples thereof include those described in JP-A-63-29751. Specific examples of the compound represented by the general formula (7) are shown below, but the present invention is not limited to the following compounds.

[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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The hydrazine compounds of the present invention are described, for example, in JP-A Nos. 61-213847, 62-178246, 62-180361 and 62-180361.
Nos. 62-260153, 63-253357, U.S. Pat.
No. 3,379,529, No. 4,377,634, No. 4,332,87
No. 8, No. 4,937,160, Japanese Patent Application No. 63-98803, and the like.

The hydrazine compound of the present invention can be used in a suitable water-miscible organic solvent such as 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 is an emulsion composed of silver halide grains having a surface sensitivity higher than the internal sensitivity. 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 which 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 a super-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, conventionally known as antifoggants or stabilizers such as azaindenes,
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, XXI, Sections 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 promoting 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 may contain a coating aid, an antistatic agent, an improvement in slipperiness, an emulsification / dispersion, an adhesion prevention, and an improvement in photographic characteristics (eg, development acceleration, high contrast Surfactants for various purposes such as sensitization 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. 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). In particular, a developer having a developer content of 10 to 11.0 can provide a negative image with a sufficiently high contrast. Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited thereto.

[0046]

EXAMPLES Example 1 A monodisperse 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.

[0047]

Embedded image

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 1 liter of water is added. Parts diluted to pH 1
The developer was 0.5.

[0050]

[Table 1]

[0051]

[Table 2]

Example 2 An average particle diameter of 0.1 × 10 ⁻⁶ mol / Agmol containing rhodium dichloride was obtained by a control double jet method.
A 3 μm monodispersed silver chloride emulsion was prepared. Desalting, washing and re-dissolving the emulsion by the flow curation method,
Exemplary hydrazine compounds and high contrast accelerators were added as shown in Table 3. After adding 5 × 10 ⁻³ mol / Agmol of 5-chlorobenzotriazole, polyethyl acrylate latex, and 2-hydroxy-4,6-dichloro-1,3,5-triazine sodium salt to each, a polyethylene terephthalate film was added. Gelatin was coated thereon so that the amount of gelatin was 3 g / m ² and 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. As a comparative sample of the contrast enhancement accelerator, the same as in Example 1, Comparative Compound (1),
(2) and (3) were used.

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.

[0054]

[Table 3]

[0055]

[Table 4]

Example 3 The same treatment and evaluation were carried out by adding 15 g / l of a contrast enhancement accelerator to a developer without adding the contrast enhancement accelerator of Example 2 to the emulsion. As a result, in all of the terms of sensitivity, contrast, dot quality, and black spots, the results exceeded the comparative sample as in Table-4.

It can be seen that the use of the compound of the general formula (1) or (2) of the present invention shows a high effect of promoting hardening with a small amount of addition, and improves sensitivity, contrast, halftone dot quality, and black spots. Practically preferable photographic characteristics in which a high contrast is maintained as compared with the comparative compound and generation of black spots is suppressed are provided. Further, it is apparent that the use of the compound represented by the general formula (1) or (2) causes the hydrazine compound to exhibit high contrast even in a developer having a low pH.

[0058]

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 general formula (1) or (2) is lower than in the prior art. It is easy even with pH developer,
Practically favorable photographic characteristics in which black spots are suppressed can be provided. Further, the high-contrast accelerator described in the present specification is easy to synthesize, low in cost, and very effective.

Claims (2)

[Claims] 1. A processing of a silver halide photographic light-sensitive material, which comprises developing the exposed silver halide photographic light-sensitive material in the presence of a compound represented by the following general formula (1) or (2). Method. Embedded image In the formula, Z ₁ and Z ₂ represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. L ₁ and L ₂ each represent a divalent linking group; R ₁ and R ₂ each represent an alkyl group, an aryl group, or a heterocyclic ring; R ₁ and R ₂ , and R ₁ and L ₁ are linked to form a ring; May be. m _1, m ₂ represents 0 or 1, X ⁺ is a group comprising a cationic group, A ^- represents a counter ion. 2. A compound having at least one silver halide emulsion layer on a support, wherein the compound represented by the formula (1) or (2) and hydrazine are contained in the emulsion layer or another hydrophilic colloid layer. A silver halide photographic material comprising a derivative.