JPH09127642A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure very contrasty photographic characteristics and to suppress the occurrence of black spots by incorporating a hydrazine compd. and a specified compd. into an emulsion layer or the other hydrophilic colloidal layer. SOLUTION: At least one kind of compd. represented by formula I or II is incorporated into a silver halide photographic sensitive material having at least one silver halide photographic emulsion layer and contg. a hydrazine compd. in the emulsion layer or at least one of other hydrophilic colloidal layers. In the formula I, R<1> is an optionally substd. arom. group or a heterocyclic group, X<1> is O, S or NH and X<2> is an aliphatic group or NH. In the formula II, each of R<2> -R<6> is H, an optionally substd. aliphatic group, an optionally substd. arom. group, a heterocyclic group, amino or a group represented by formula III (where X<3> is O, S or NH and X<4> is an aliphatic group or NH2 ).

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 superhard tone negative image forming method 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 Ultra-high contrast photographic characteristics having a gamma value of more than 10 include photographic reproduction of a continuous tone image using a dot image useful for printing plate making, whether a negative image or a positive image. Very useful for line drawing reproduction. Therefore, there is a strong demand for obtaining super-high contrast photographic characteristics useful for reproducing halftone images and line images by using a high-sensitivity emulsion and a stable developing solution.

The addition of hydrazine compounds to silver halide photographic emulsions and developers is described in US Pat. No. 3,730,7.
No. 27 (developing solution combining ascorbic acid and hydrazine), No. 3,227,552 (using hydrazine as an auxiliary developing agent for directly obtaining a positive color), No. 3,386,831 (halogenated). Containing β-monophenylhydrazide of aliphatic carboxylic acid as a stabilizer of silver sensitive material), No. 2,419,975, and Mees, "The Theory".
of Photographic process ”3rd edition (1966) 28
It is known as page 1. Among these, especially US Patent 2,
No. 419,975 discloses the addition of a hydrazine compound to obtain a hard negative image. That is, adding a hydrazine compound to a silver chlorobromide sensitive material
It is described that when developed with a developer having a high pH such as 2.8, extremely hard photographic characteristics having a gamma (γ) of more than 10 are obtained. However, since a strong alkaline developer having a pH close to 13 is used, the developer is liable to be air-oxidized, is unstable, and has a problem that it cannot be stored or used for a long time.

As means for solving this, US Pat. Nos. 4,168,977, 4,224,401, 4,243,739, 4,269,929, and 4,272,614 are known. No. 4,323,643 and the like, a surface latent image type silver halide photographic light-sensitive material to which a specific acylhydrazine compound is added has a pH value of 11.0 to 10.
A system has been proposed which forms an extremely hard negative image by treating with a developing solution containing a sulfite preservative of 0.15 mol / l or more at 12.3 and having good storage stability. However, the acylhydrazine compounds used in them are known to generate nitrogen gas during the development process, and this gas may collect in the film to form bubbles, which may impair the photographic image.

Therefore, for the purpose of reducing the generation of air bubbles and at the same time, reducing the cost of producing the light-sensitive material, a sufficient maximum density can be obtained with a high contrast even with a small addition amount, and uneven development and black spots (pepper fog) can be obtained. A silver halide photographic light-sensitive material containing a hydrazine compound which is difficult to generate is disclosed in JP-A-62-17824.
No. 6, No. 62-180361, No. 62-2752
No. 47 and No. 63-253357. However, when this light-sensitive material is processed with a developer whose activity has increased due to fatigue over time, nucleation-infectious development with a hydrazine compound is promoted, resulting in increased sensitivity, sudden thickening of halftone dots, and innumerable black spots. I understood.

Therefore, in order to suppress the generation of such black spots and the thickening of halftone dots, the production method of emulsion grains has been improved, hydrazine and the contrast accelerator have been improved, and various additives have been used.
A number of methods have been disclosed. Of these, the addition of sulfur-containing and nitrogen-containing compounds to the emulsion is described in US Pat. Nos. 5,126,227, 5,196,292 (isothiourea compounds) and 5,232,818 ( Thioether), JP-A-5-197057 (dialkyl thiuronium, a heterocyclic compound having a mercapto group), JP-A-5-289226, JP-A-6-347933 (tetrazaindene), and JP-A-6-266069. No. (Thioamide)
Etc. However, this issue is still not fully resolved.

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SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photographic light-sensitive material exhibiting super-high contrast photographic characteristics and having less black spots.

[0008]

A silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer and containing a hydrazine compound in at least one of the emulsion layer and other hydrophilic colloid layers, It is achieved by a silver halide photographic light-sensitive material characterized by containing at least one compound represented by the general formula 1 or the general formula 2.

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In the formula, R ¹ represents a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aromatic group or a heterocyclic group. X ¹ represents any one of O, S and NH, and X ²
Represents an aliphatic group or NH ₂ .

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In the formula, R ^{2 to} R ⁶ are hydrogen atoms, substituted or unsubstituted aliphatic groups, substituted or unsubstituted aromatic groups,
It represents a heterocyclic group, an amino group or a group represented by the general formula 3.

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[Chemical 6]

In the formula, X ³ represents any one of O, S and NH, X ⁴ represents an aliphatic group or NH ₂ , and R
² and R ³ , R ⁵ and R ⁶ , R ² and R ⁵ , and R ³ and R ⁶ may be connected to each other to form a ring.

Next, the general formula 1 will be described in detail.
In the formula, R ¹ represents an aliphatic group (alkyl group, alkenyl group, alkynyl group), aromatic group or heterocyclic group, and the aliphatic group is a straight chain (for example, methyl group, ethyl group, n-
Propyl group, n-butyl group, n-octyl group, allyl group, 3-butenyl group, propargyl group, butynyl group, benzyl group, etc.), branched (for example, i-propyl group, t-octyl group, etc.), or cyclic (For example, a cyclohexyl group or the like) may be used. The aromatic group is a monocyclic or bicyclic ring (phenyl, naphthyl, etc.), and the heterocyclic ring contains S, N, or O in the ring, and is a monocyclic ring (eg, pyridyl group, thiadiazolyl group, etc. Or a condensed ring (for example, a benztriazolyl group, a benzthiazolyl group, a benzimidazolyl group, etc.). Moreover, these groups may further have a substituent. Examples of the substituent include an aliphatic group (eg, methyl group, ethyl group, butenyl group, propargyl group, i-propyl group, etc.), aryl group (eg, phenyl group, naphthyl group, etc.), heterocyclic group ( For example, pyridyl group, furyl group, thienyl group, tetrahydrofuryl group, etc.), carboxy group, sulfo group, cyano group, alkoxy group (for example, methoxy group, ethoxy group,
Benzyloxy group etc.), alkylthio group (eg methylthio group, ethylthio group etc.), hydroxy group, mercapto group, halogen atom (eg chlorine atom, bromine atom etc.), alkoxycarbonyl group having 20 or less carbon atoms (eg methoxy) Carbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group, etc.), aryloxy group having 20 or less carbon atoms (eg, phenoxy group, p-tolyloxy group, etc.), acyloxy group (eg, acetyloxy group, propionyloxy group) Groups), 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 group (eg If, a sulfamoyl group,
N, N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group, etc.), acylamino group (eg, acetylamino group, propionylamino group, mesylamino group, etc.), sulfonamide group (eg,
Ethyl sulfonamide group, p-toluene sulfonamide group, 2,4,6-triisopropylphenyl sulfonamide group, etc.), ureido group (for example, methylureido group,
Phenylureido group, etc.), amino group (eg, diethylamino group, etc.) and the like.

X ¹ represents any one of O, S and NH, and X ² represents an aliphatic group (eg, methyl group, ethyl group, butenyl group, propargyl group, i-propyl group, etc.) or NH ₂ . Preferably, X ¹ is NH and X ² is NH _2.
Alternatively, X ¹ is O or S and X ² is an alkyl group (eg, methyl group, ethyl group, etc.). Particularly preferably,
X ¹ is NH and X ² is NH ^2, or X ¹ is O and X ² is a methyl group. Further, the compound of general formula 1 may form a salt with a protonic acid (for example, hydrogen chloride, hydrogen bromide, hydrogen iodide, methanesulfonic acid, p-toluenesulfonic acid, etc.).

Next, the general formula 2 will be described in detail. In the formula, R ^{2 to} R ⁶ are hydrogen atoms, aliphatic groups (alkyl groups, alkenyl groups, alkynyl groups), aromatic groups, heterocyclic groups,
It represents an amino group or a group represented by the general formula 3. As the aliphatic group, straight chain (for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, allyl group, 3-butenyl group, propargyl group, butynyl group, benzyl group, etc.), It may be branched (eg, i-propyl group, t-octyl group, etc.) or cyclic (eg, cyclohexyl group, etc.), and R ² and R ³ , and R ⁵ and R ⁶ are linked to each other to form a ring. (Eg, pyrrolidyl ring, piperidyl ring, morpholyl ring, etc.). The aromatic group is monocyclic or bicyclic (phenyl group, naphthyl group, etc.), and the heterocyclic group is one containing S, N, or O in the ring, and is monocyclic (eg, pyridyl group). , Thiadiazolyl group, etc.)
Or may be condensed with a ring (for example, a benztriazolyl group, a benzthiazolyl group, a benzimidazolyl group, etc.). Further, R ² and R ⁵ , and R ³ and R ⁶ may be linked to each other to form a ring (for example, an imidazolidine ring) so as to contain two nitrogens of a guanidyl group. The amino group is preferably a substituted amino group, and examples thereof include a methylamino group, a butylamino group, a benzylamino group and a 3-amino group.
Examples thereof include a phenylpropylamino group and a phenylamino group. In the general formula 3, X ³ represents any one of O, S and NH, and X ⁴ represents an aliphatic group (eg, methyl group, ethyl group, butenyl group, propargyl group, i-propyl group, etc.) or NH ₂ . Represent Preferably, X ³ is NH and X
⁴ is NH ₂ or X ³ is O or S and X ⁴ is an alkyl group (eg, methyl group, ethyl group, etc.). Particularly preferably, X ³ is NH and X ⁴ is NH _2. Or, X ³ is O and X
⁴ is an aliphatic group. These groups may further have a substituent, and examples of the substituent include the substituents mentioned in the description of R ¹ . Further, the compound of the general formula 2 is a protic acid (for example, hydrogen chloride, hydrogen bromide, hydrogen iodide,
(Methanesulfonic acid, p-toluenesulfonic acid, etc.) may form a salt.

Preferred compounds of the general formula 2 are those in which R ² is a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aromatic group or a heterocyclic group, R ^{3 to} R ⁵ are hydrogen atoms, and R ⁶ is A compound which is a hydrogen atom or a group represented by formula 3. A compound in which at least two of R ^{2 to} R ⁶ are an aliphatic group or an aromatic group, a compound in which R ² is an acyl group or an amino group, and R ^{3 to} R ⁶ are hydrogen atoms. Specific examples of the compounds represented by the general formulas 1 and 2 are shown below, but the present invention is not limited to the following compounds.

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Next, specific synthesis examples of the compound represented by the general formula 1 will be shown. <Synthesis Example 1> Synthesis of Exemplified Compound Chemical Formula 7 1-bromooctane 74 g, guanylthiourea 30 g,
300 ml of ethanol was heated under reflux for 6 hours. The solvent was evaporated under reduced pressure, the obtained white solid was washed with hexane, and then recrystallized from ethyl acetate to obtain 64 g of the HBr salt of Chemical formula 7 as a white solid. <Synthesis Example 2> Exemplified compound Synthesis of Chemical formula 1 1-Bromooctane 74 g, acetylthiourea 30 g,
300 ml of acetonitrile was heated to reflux for 6 hours. The solvent was evaporated under reduced pressure, and the obtained white solid was washed with hexane and recrystallized from ethyl acetate to obtain 62 g of the HBr salt of Chemical formula 8 as a white solid. In the same manner, another general formula 1
The compound can also be easily synthesized.

The compound represented by the general formula 2 is obtained by reacting an amine compound with cyanamide, dicyandiamide, chloroformamidine, carbodiimide, or the like, MS Bernatowic
z, The Journal of Organic Chemistry, 1992, 57, 2497, and the like can be easily synthesized by the reaction of the amine compound with 1H-pyrazole-1-carboxyamidine hydrochloride.

The compound represented by the general formula 1 or 2 in the light-sensitive material of the present invention is preferably contained in the silver halide emulsion layer, but may be contained in other hydrophilic colloid layers. Since the content of the compound of the general formula 1 or the general formula 2 of the present invention in the layer varies depending on the characteristics of the silver halide emulsion used, the chemical structure of the compound and the development conditions, a suitable content is in a wide range. Varying, but about 5 × 10 ^-6 per mole of silver in the silver halide emulsion
A range of up to 5 × 10 ^-2 mol is preferable. More preferably, 1
A range of × 10 ^-4 to 1 × 10 ^-2 mol is preferable.

Examples of the hydrazine derivative used in the present invention include compounds represented by the following general formula 4.

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In the general formula 4, A ¹ and A ² are both hydrogen atoms or one is a hydrogen atom and the other is a sulfonyl group or an acyl group, and R ⁷ is an aliphatic group, an aromatic group or a heterocyclic group. And G ¹ represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group, an oxalyl group or an iminomethylene group, and R ⁸ represents a hydrogen atom, an aliphatic group, an aromatic group, an alkoxy group, an aryloxy group, an amino group or Represents the general formula 5.

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In the general formula 5, Q ⁺ represents a group containing a cationic group and A ⁻ represents an anion, but it is not necessary when Q ⁺ contains a sulfo group.

Next, general formulas 4 and 5 will be described in detail. In the general formula 4, A ¹ and A ² are hydrogen atoms and have 2 carbon atoms.
0 or less alkylsulfonyl group and arylsulfonyl group (preferably a phenylsulfonyl group or a phenylsulfonyl group substituted such that the sum of Hammett's σ _p is −0.5 or more), an acyl group having 20 or less carbon atoms ( Preferably, the benzoyl group or the sum of Hammett's σ _p is -0.5.
A benzoyl group substituted as described above), or a linear, branched or cyclic unsubstituted and substituted aliphatic acyl group (as a substituent, for example, a halogen atom, an ether group,
Examples include a sulfonamide group, an amide group, a hydroxy group, a carboxy group, and a sulfo group. It is most preferable that A ¹ and A ² are hydrogen atoms. The aliphatic group represented by R ⁷ is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group. The aromatic group represented by R ⁷ is a monocyclic or bicyclic aryl group, for example,
Examples thereof include a phenyl group and a naphthyl group. The heterocyclic group for R ⁷ is a 3- to 10-membered saturated or unsaturated heterocyclic ring containing at least one of N, O and S atoms, and these may be monocyclic or You may form a condensed ring with the aromatic ring or heterocycle of. 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 ⁷ 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, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, carboxy group, Examples include an ammonium group, a pyridinium group, a thyuronium group, an isothioureido group. When possible, these groups may be linked to each other to form a ring. Preferred as R ⁷ is an aromatic group, more preferably an aryl group. R ⁷ may have a ballast group commonly used in immobile photographic additives such as couplers incorporated therein.
The ballast group is a group having 8 or more carbon atoms and is relatively inert to photographic properties, and is selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group. be able to. Q ⁺ in the general formula 5 is a group containing a cationic group having at least one quaternary nitrogen atom, and is bonded to G ¹ through a linear or branched hydrocarbon chain having 1 to 4 carbon atoms. Part or all of this chain may constitute a part of a heterocyclic ring having a quaternary nitrogen atom. 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 ⁷ . Further, when these groups form a ring structure, they may be condensed with another ring.
A ⁻ is a counter anion of Q ⁺ , and a preferred example is C
Examples thereof include l ⁻ , Br ⁻ , p-toluene sulfonate, and methyl sulfonate, but they do not exist when they have a sulfo group as a substituent of Q ⁺ and form an intramolecular salt.

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 ⁸ 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, one containing a benzene ring). When G ¹ is a carbonyl group, R
Preferred among the groups represented by ⁸ are a hydrogen atom, an alkyl group (eg, methyl group, trifluoromethyl group, 3
-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, etc.), general formula 5 and the like, with hydrogen atom and general formula 4 being particularly preferred. R ⁸ may be substituted, and as the substituent, the substituents listed for R ⁷ can be applied.
When G ¹ is an oxalyl group, preferred R ⁸ is an alkoxy group (eg, methoxy group, ethoxy group,
Isopropoxy group, methoxyethoxy group, etc.), aryloxy group (eg, phenoxy group, 2-hydroxymethylphenoxy group, 4-chlorophenoxy group, etc.), amino group (eg, 3-hydroxypropylamino group, 2,3)
-Dihydroxypropylamino group, 2-dimethylaminoethylamino group, 3-diethylaminopropylamino group, etc.), general formula 5 and the like, with an amino group being particularly preferred. R
⁷ and R ⁸ may have incorporated therein a group which enhances the adsorption to the surface of the silver halide grains. Examples of the adsorptive group include thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, and triazole groups, which are disclosed in US Pat.
The groups described in No. 55,105 are mentioned. Also, R ⁸
Causes the part of G ¹ -R ⁸ to split from the rest of the molecule, and -G ^1-
It may be one that causes a cyclization reaction to form a cyclic structure containing the atom of the R ⁸ moiety, and examples thereof include those described in JP-A-63-29751. Specific examples of the compound represented by Formula 4 are shown below, but the present invention is not limited to the following compounds.

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The hydrazine compound of the present invention is described in, for example, JP-A-61-213847, JP-A-62-178246, JP-A-62-180361, JP-A-62-260153, and JP-A-62-260153.
No. 3-253357, U.S. Pat. No. 4,684,604
No. 3,379,529 and 4,377,63
No. 4, No. 4,332,878, No. 4,937,1
No. 60, Japanese Patent Application No. 63-98803, and the like.

The hydrazine compound of the present invention is a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethylacetamide, dimethyl sulfoxide,
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.

Further, the photographic emulsion used in the present invention may contain amines, alcohols, pyridines, onium salts and other high-contrast accelerators. Among these, preferred tertiary hardeners are various tertiary amine compounds (eg, US Pat. No. 4,975,354, Japanese Patent Publication No. 6-124).
06, Japanese Patent Publication No. 7-36076, KD2354, KD
2462) and phosphonium salt compounds (for example, compounds described in JP-A-61-167939). The contrast enhancing agent is preferably contained in the surface latent image type silver halide emulsion layer, but may be contained in the hydrophilic colloid layer adjacent to the surface latent image type silver halide emulsion layer. Since the content of the contrast enhancing agent in the layer varies depending on the characteristics of the silver halide emulsion used, the chemical structure of the compound and the developing conditions, the appropriate content may vary over a wide range, but the surface latent image 1 × 10 ⁻⁵ to 1 × 10 ⁻² mol per mol of silver in the silver halide emulsion of the type. Further, a contrast-increasing accelerator may be added to the developing solution, and in that case, 1 × 10 ⁻³ to 1 mol per 1 liter of the developing solution is preferable.

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 preferable, and the silver halide is selected from silver chloride and salts. Although silver bromide, silver chloroiodobromide, silver iodobromide, silver bromide or 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 means an emulsion composed of silver halide grains having a surface sensitivity higher than the internal sensitivity, and this emulsion is preferably US Pat. No. 4,224,224. It has a difference between the surface sensitivity and the internal sensitivity specified in No. 401. The silver halide emulsions are preferably monodisperse, especially the above-mentioned US Pat. No. 4,22.
Emulsions having the monodispersity specified in JP-A-4,401 are preferred. The silver halide emulsion used in the present invention includes a water-soluble rhodium salt (for example, rhodium dichloride, rhodium trichloride, potassium hexachloride (III), rhodium hexachloride).
(III) ammonium salt, etc.) is preferable,
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 from 1 × 10 ⁻⁷ mol to 1 mol per mol of silver halide.
× 10 ^-4 mol is preferred. The average grain size of the silver halide used in the present invention is preferably 0.7 μm or less, and 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 monodisperse emulsion referred to herein means an average grain size of ±
It refers to an emulsion in which 90%, more preferably 95%, of the total number of grains falls within the 40% grain size range. The method of reacting the soluble silver salt and the soluble halogen salt for the preparation of the silver halide emulsion in the present invention may be a single jet method, a double jet method, a reverse mixing method of forming in the presence of excess silver ions, or the like. However, 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 particles is particularly preferable. The silver halide emulsion thus prepared may or may not be chemically sensitized. In the case of chemical sensitization, usual sulfur sensitization, selenium sensitization, reduction sensitization and the like are used.

The photographic emulsion used in the present invention may be spectrally sensitized with methine dyes and 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.
A combination of sensitizing dyes is often used especially for the purpose of 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 the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol Polyacetal partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, and various kinds of synthetic hydrophilic polymer materials such as copolymers such as polyvinylimidazole can be used. . As gelatin, in addition to lime-processed gelatin, acid-processed gelatin and Bull.Soc.Sci.Phot.Japan, No.
16, an enzyme-treated gelatin as described in P30 (1966) may be used, or a hydrolyzed product or an enzymatically decomposed product of gelatin may be used.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. . That is, azoles,
For example, benzothiazolium salt, nitroimidazoles,
Nitrobenzimidazoles, chlorobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, mercaptotetrazoles; mercaptopyrimidines, mercaptotriazines, thioketo compounds, azaindenes, etc. Many compounds, more known as antifoggants or stabilizers, can be added. Of 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 (chrome alum etc.), aldehydes (formaldehyde, glyoxal etc.), N-methylol compounds, dioxane derivatives (2,3-dihydroxydioxane etc.), active vinyl compounds, active halogen compounds (2,4-dichloro-6). −
Hydroxy-S-triazine, etc.) or the like can be used alone or in combination. The photosensitive silver halide emulsion layer or an adjacent layer may be provided with a research disclosure (R) for the purpose of increasing sensitivity, increasing contrast, or accelerating development.
The compounds described in Esearch Disclosure) No. 17465, Sections XXI, B to D can be added, and particularly polyethylene glycol or a derivative thereof is preferably added.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced by using the present invention may include a coating aid, an antistatic agent, a slipperiness improving agent, an emulsifying dispersion agent, an adhesion preventing agent and a photographic characteristic improving agent (for example, development). A surfactant may be included for various purposes such as acceleration, contrast enhancement, and sensitization. Nonionics such as saponins (steroids), alkylene oxide derivatives (polyethylene glycol, polyethylene glycol alkyl ethers, etc.), glycidol derivatives (alkenyl succinic acid polyglyceride, etc.), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Surfactants, alkyl carboxylates, alkyl sulfates,
Carboxy group, 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 the photographic emulsion layer and 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 monomer component of a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, styrene sulfonic acid and the like can be used. Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.

[0113]

Example 1 6-Methyl-4-hydroxy-1,3,3a, 7 was added to a monodisperse silver chlorobromide emulsion containing iridium and having an average particle size of 0.25 μm prepared by the control double jet method.
-Tetrazaindene was added at 1 g / mol Ag. Anhydro-5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine hydroxide pyridinium was used as a sensitizing dye at 300 mg / mo.
1Ag, 0.18 g / molAg of the exemplified hydrazine, and 1.1 g / molAg of the following nucleation accelerator were added. This was divided and added with 0.05 mmol / mol Ag of the compound of the present invention or the comparative compound, respectively, and after adding a hardening agent, 3.5 g / m ^{2 of} silver nitrate and gelatin on the polyethylene terephthalate film. Of 2.5 g / m ² was applied. Chemical formulas 7 to 18 and comparative compounds are HBr salts, chemical formula 21 is methanesulfonate, and chemical formulas 23 to 26, chemical formula 37, chemical formula 42, chemical formula 47, and chemical formula 51.
Was added as the HCl salt.

[0114]

Embedded image

[0115]

Embedded image

The sample thus obtained was exposed and developed to evaluate relative sensitivity, gamma and black spot. The development was performed with a developer having the following composition at 35 ° C. for 30 seconds, fixing, washing with water, and drying. For black spots, the sample was magnified 100 times with a microscope and visually evaluated in 5 stages. 5 is best, 1
Represents the worst quality. 5 and 4 are practical, 3 is poor but practically practical, and 2 and 1 are impractical. Gamma is represented by tan θ in the linear portion where the optical density is 1.0 to 2.5. Table 1 shows the results.

<Developer (concentrate)> Hydroquinone 65.0 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 2.9 g Sodium pyrosulfite 145.0 g Diethylenetriaminepentaacetic acid pentasodium salt 6.0 g Boric acid 6.9 g sodium bromide 12.0 g 1-phenyl-5-mercaptotetrazole 0.05 g sodium hydroxide 23.0 g benzotriazole 0.4 g potassium hydroxide 80.0 g potassium carbonate 80.0 g diethylene glycol 120.0 g water was added. 1 l Dilute the above concentrate at a ratio of 1 part with respect to 4 parts of water to adjust the pH.
The developing solution was 10.5.

[0118]

[Table 1]

From the results shown in Table 1, the comparative compounds suppress the generation of black spots, but the relative sensitivity and the degree of contrast decrease, whereas the compounds of the present invention suppress the black spots, and It can be seen that the influence on the sensitivity and the degree of high contrast is small.

[0120]

By incorporating the compound of the present invention into a photographic light-sensitive material, black spots can be suppressed without lowering sensitivity and hardness, and black spots are small.
A high-sensitivity, ultra-high contrast photographic light-sensitive material can be obtained.

Claims (5)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer on a support, wherein the emulsion layer or other hydrophilic colloid layer contains at least one selected from hydrazine compounds. A silver halide photographic light-sensitive material comprising at least one compound represented by the general formula 1. Embedded image In the formula, R ¹ represents a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aromatic group or a heterocyclic group. X
¹ represents any one of O, S and NH, and X ² represents an aliphatic group or NH ₂ . 2. A silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer on a support, wherein the emulsion layer or other hydrophilic colloid layer contains at least one selected from hydrazine compounds. A silver halide photographic light-sensitive material comprising at least one compound represented by the general formula 2. Embedded image In the formula, R ^{2 to} R ⁶ are a hydrogen atom, a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aromatic group, a heterocyclic group,
It represents an amino group or a group represented by formula 3. Note that R ²
And R ³ , R ⁵ and R ⁶ , R ² and R ⁵ , and R ³ and R ⁶ may be connected to each other to form a ring. Embedded image In the formula, X ³ represents any one of O, S and NH, and X ⁴
Represents an aliphatic group or NH ₂ . 3. R ^{3 of the} compound represented by the general formula 2 is a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aromatic group or a heterocyclic group, and R ^{3 to} R ⁵ are hydrogen atoms. , R ⁶ is a hydrogen atom or a group represented by the general formula 3 above, and the silver halide photographic light-sensitive material according to claim 2. 4. A compound represented by the general formula 2 wherein R ^2-
The silver halide photographic material as claimed in claim 2, wherein the at least two is characterized by an aliphatic group or an aromatic group of R ^6. 5. The silver halide photographic light-sensitive material according to claim 2, wherein R ^{2 of the} compound represented by the general formula 2 is an acyl group or an amino group, and R ^{3 to} R ⁶ are hydrogen atoms. material.