JPH01179930A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enable the stable formation of a hard image using a hydrazide compd. by incorporating a specific silver halide compsn. into the title material and providing a specific silver halide emulsion layer thereto. CONSTITUTION:This photosensitive material contains the silver halide compsn. contg. >=50mol.% silver bromide and has the silver halide emulsion layer contg. the compds. expressed by the formulas I-III and contg. at least one kind selected from the compds. expressed by the formulas IV-VI. (R1 and R2 denote an aryl group, etc.; R denotes an org. bond group; n denotes 0-6, m denotes 0 or 1; R21 denotes an aliphat. group, etc.; R22 denotes a hydrogen atom., etc.; Ar denotes an aryl group contg. a diffusion resistant group or silver halide adsorption accelerating group; R31 denotes a substd. alkyl group; A dneotes a phosphorus atom. or nitrogen atom.; R41-R44 denote an alkyl group, etc.; X<-> denotes an acid anion; Y and Z denote a nitrogen atom. or carbon atom.; R51 denotes a hydrogen atom., etc.; R61-R63 denote a hydrogen atom., amino group, etc.). The hard-contrast image is thereby stably formed.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a silver halide photographic material that provides high-contrast images, and more particularly, to an improvement over failures that occur in high-contrast techniques using hydrazine compounds. It is something.

(Prior Art) In recent years, in the field of printing and photolithography, printed matter has become increasingly colored and complex. For this reason, demands for improved and stable quality of silver halide photographic materials for printing (hereinafter referred to as printing materials), which are intermediate media for printing, are increasing year by year. Conventionally, general printing sensitive materials have been given so-called "lith development" processing suitability in order to achieve high quality.

However, in "Lith development," it is mechanically impossible to contain high concentrations of sulfite ions, which are preservatives, in the developing solution, and as a result, the stability of the developing solution is extremely poor. is a well-known fact among those skilled in the art.

As techniques for eliminating the instability of "lithographic development" and obtaining high-contrast images comparable to the "lithographic developing" process, several attempts can be found in patent documents. For example, techniques for obtaining high-contrast images using hydrazine compounds are disclosed in JP-A-53-16623 and JP-A-53-20921.
No. 53-20922, No. 53-49429, No. 53
-66731, 53-66732, 53-77
No. 616, No. 53-84714, No. 53-13713
No. 3, No. 54-37732, No. 54-40629,
55.52050, 55.90940, 56
-67843 etc. In the processing method of the image forming method using these hydrazine compounds,
In order to obtain high-contrast images, it is necessary that the pH value of a developer containing a hydrazine compound or the pH value of a processing developer for photographic light-sensitive materials containing a hydrazine compound be at a relatively high level. However, this high p)(value) has the disadvantage that it reduces the useful life of the developer.

On the other hand, in JP-A-56-106244, a high-contrast image can be formed at a relatively low pH (11-11,5) by containing a hydrazine compound and a development-promoting amount of an amino compound during image formation. It is said that it can be formed.

Image forming methods using these hydrazine compounds can provide very high contrast images. In general, if a developing solution is not replenished with an appropriate developer replenisher, fogging may occur, which is unfavorable for photographic performance.However, with this method using hydrazine, even if the degree of fatigue of the developing solution is not too great, unexposed For example, when shooting with a contact screen on printed photosensitive materials, black dots resembling black sesame seeds (hereinafter referred to as Peraper Fog) can be seen between the halftone dots, which can lead to malfunctions that can be a serious drawback in terms of product value. be. In the above-mentioned JP-A-53-16623 and JP-A-53-20921, silver halide photographic emulsions containing benzotriazole, which is an inhibitor, suppress the occurrence of fog including the permeable fog mentioned above. However, the effect is not sufficient, and furthermore, the contrast may be impaired, so it cannot be said that this is a perfected technique.

As a result of intensive research, the inventors of the present invention were able to develop a silver halide photographic material that does not impair high contrast while suppressing fog, including permeable fog, which is a drawback of high contrast technology using hydrazide compounds. .

(Object of the Invention) The first object of the present invention is to provide a silver halide photographic material that can stably form high-contrast images using a hydrazide compound. The second object is to provide a silver halide photographic light-sensitive material with high contrast and free from capri occurrence including Peraper Fog.

(Structure of the Invention) The object of the present invention is achieved by the following structure of the present invention.

It has a silver halide composition with a silver bromide content of 50 mol% or more, contains at least 111 compounds represented by the following general formulas [1], [2], and [3], and has the following general formula [
A silver halide photographic material comprising at least one silver halide emulsion layer containing at least one compound selected from compounds represented by [4], [5] or [6].

/ General formula [1F (wherein, R1 and R8 represent an aryl group or a heterocyclic group, R represents an organic bonding group, n represents O to 6, m represents 0 or 1, and n represents 2 In the above cases, each R may be the same or different.) General formula [2] (wherein, R21 is an aliphatic group, aromatic group, or heterocyclic group, R22 is a hydrogen atom, Represents an alkoxy group, heterocyclic oxy group, amino group, or aryloxy group that may be substituted, and Pl and R2 represent a hydrogen atom, an acyl group, or a sulfinic acid group.) General formula [3] % Formula % ( (In the formula, Ar represents an aryl group containing at least one diffusion-resistant group or silver halide adsorption promoting group, and Rll represents a substituted alkyl group.) General formula [4] In the formula, A represents a phosphorus atom or a nitrogen atom. show.

R411R4! l43 and R44 each represent a substituted or unsubstituted alkyl group, aryl group or aralkyl group. X- represents an acid anion.

General formula [5] In the formula, Y and Z represent a nitrogen atom or a carbon atom, and Y
and 2, when either one is a nitrogen atom, the other is a carbon atom. Rll represents a hydrogen atom, a lower alkyl group, a halogen atom or a nitro group.

General Formula [6] In the formula, R81, Ra2 and Ra3 represent a hydrogen atom, an amine group, a hydroxy group, a mercapto group, an alkyl group or an aryl group.

(Specific explanation of the structure of the invention) Hereinafter, the configuration of the present invention will be specifically explained in detail.

Below is a blank space 1 General formulas [1], [2], and [3] will be specifically explained below.

General formula [11 In the formula, R2 and R8 represent an aryl group or a heterocyclic group, R represents a divalent organic group, n is O to 6, and the base is O
or represents l.

Here, examples of the aryl group represented by R1 and R3 include a phenyl group, a naphthyl group, etc., and examples of the heterocyclic group include a pyridyl group, a benzothiazolyl group, a quinolyl group, a thienyl group, etc., but preferred as R1 and R3. is an aryl group.

Various substituents can be introduced into the aryl group or heterocyclic group represented by R and R2. Examples of substituents include halogen atoms (e.g., chlorine, fluorine, etc.), alkyl groups (e.g., methyl, ethyl, dodecyl, etc.), alkoxy groups (e.g., methoxy, ethoxy, isopropoxy, butoxy, octyloxy, dodecyloxy, etc.), and acylamino groups. (e.g. acetylamino, pivalylamino,
Benzoylamino, tetradecanoylamino, α-(2
, 4-di-t-amylphenoxy)butyrylamino, etc.), sulfonylamino groups (e.g., methanesulfonylamino, butanesulfonylamino, dodecanesulfonylamino, benzenesulfonylamino), urea groups (e.g., phenylurea, ethylurea, etc.) , thiourea group (e.g., phenylthiourea, ethylthiourea, etc.), hydroxy group, amine group, alkylamino group (
Examples include methylamino, dimethylamino, etc.), carboxy groups, alkoxycarbonyl groups (eg, ethoxycarbonyl), carbamoyl groups, and sulfo groups. Examples of the divalent organic group represented by R include alkylene groups (e.g., methylene, ethylene, trimethylene, tetramethylene, etc.), arylene groups (e.g., phenylene, naphthylene, etc.), aralkylene groups, etc. may contain an oxy group, thio group, seleno group, carbonyl group, -N- group (R3 represents a hydrogen atom, an alkyl group, or an aryl group), a sulfonyl group, etc. in the bond. Various substituents can be introduced into the group represented by R.

Examples of substituents include -C0NHNI! R, (R represents the same meaning as R1 and R3 described above), an alkyl group, an alkoxy group, a halogen atom, a hydroxy group, a carboxy group, an acyl group, an aryl group, and the like.

R is preferably an alkylene group.

Among the compounds represented by the general formula [11, preferably R1
and R8 is a substituted or unsubstituted phenyl group, and n=
(2)-1 is a metal compound in which R represents an alkylene group.

Representative compounds represented by the above general formula [N are shown below.

The following margin is white) \--~'' Specific compound ■ -12 LCsH++ l -22 ■ -31 ■ -38 ShiH! tC gift H1l ■ -50 l -53 t(4f(++ Next, general formula [2] The aliphatic group represented by R21 preferably has 6 carbon atoms.
Among the above, it is particularly a straight chain, branched or cyclic alkyl group having 8 to 50 carbon atoms. The branched alkyl group herein may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Further, this alkyl group may have a substituent such as an aryl group, an alkoxy group, or a sulfoxy group.

The aromatic group represented by RlI is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group.

Examples include a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrorazole ring, a quinoline ring, an inquinoline ring, a benzimidazole ring, a thiazole ring, and a benzothiazole ring, among which those containing a benzene ring are preferred.

Particularly preferred as R21 is an aryl group.

The aryl group or unsaturated heterocyclic group of R21 may be substituted, and typical substituents include a linear, branched or cyclic alkyl group (preferably a monocyclic alkyl group having 1 to 20 carbon atoms). or two rings), alkoxy groups (
(preferably one having 1 to 20 carbon atoms), substituted amino group (preferably an amino group substituted with an alkyl group having 1 to 20 carbon atoms), acylamino group (preferably one having 2 to 30 carbon atoms), sulfonamide Group (preferably 1 to 1 carbon atoms)
30), a ureido group (preferably a carbon number of 1 to
30).

Among the groups represented by R2□ in general formula [2], the optionally substituted alkoxy group has 1 to 20 carbon atoms, and may be substituted with a halogen atom, an aryl group, or the like.

Among the groups represented by R2□ in general formula [21, the optionally substituted aryloxy group or heterocyclic oxy group is preferably a monocyclic group, and the substituents include a halogen atom alkyl group, an alkoxy group, Among the groups represented by R82 that include a cyan group, preferred are an optionally substituted alkoxy group or an amino group.

A may be a cyclic structure containing an optionally substituted alkyl group, an alkoxy group, or a 10-1-S-1-N- group bond. However, R2z is never a hydrazino group.

R21 or R22 of general formula [2] 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 photography, such as an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group,
It can be selected from alkylphenoxy groups, etc.

- RZ+ or R22 in general formula [2] may have a group incorporated therein that enhances adsorption to the silver halide grain surface. Such adsorption groups include thiourea group,
U.S. Pat. No. 4,355 for heterocyclic thioamide groups, mercapto heterocyclic groups, triazole groups, etc.

The group described in No. 105 is exemplified. General formula [2]
Among the compounds represented by the following general formula [2-al], the compound represented by the following general formula [2-al] is particularly preferable.

General formula [2-al In the above general formula [2-al, Ro and R24 are hydrogen atoms, optionally substituted alkyl groups (e.g. methyl group, ethyl group, butyl group, dodecyl group, 2-hydroxypropyl group, -cyanoethyl group,
2-chloroethyl group), an optionally substituted phenyl group,
Naphthyl group, cyclohexyl group, pyridyl group, pyrrolidyl group (e.g. phenyl group, p-methylphenyl group, naphthyl group, α-hydroxynaphthyl group, cyclohexyl group, p-methylcyclohexyl group, pyridyl group, 4-propyl-2-pyridyl group) group, pyrrolidyl group, 4-methyl-2
-pyrrolidyl group), Rls is a hydrogen atom or an optionally substituted benzyl group,
Alkoxy and alkyl groups (e.g. benzyl, p-
methylbenzyl group, methoxy group, ethoxy group, ethyl group, butyl group), R21 and R1 represent a divalent aromatic group (e.g. 7-enylene group or naphthylene group),
Y represents a sulfur atom or an oxygen atom, and L represents a divalent bonding group (e.g. -3OzC1(2cH2NHSO*NIl,
0CHaSOJH1-〇-1-CH-N-), Ro represents -NR'R〃 or -OR, R', R
" and Rzs are a hydrogen atom, an optionally substituted alkyl group (e.g. methyl group, ethyl group, dodecyl group), a phenyl group (e.g. phenyl group, p-methylphenyl group, p-methoxyphenyl group), or a naphthyl group (e.g. a-naphthyl group, β-naphthyl group), m and n are 0 or 1
represents. When R1 represents OR, Y preferably represents a sulfur atom.

Representative compounds represented by the above general formulas [2] and [2-al] are shown below.

Below is Reihaku.

′\　− Mataichi;/ Specific example of general formula [21] F3 C.I.

■ *-NIINHCCOCllzCll*SOxCllx
C) 1go) 1 convex 0 ■ * NHNHCCOClliCHzSC15CLlz
1M1CH.

CIllthl(1 ! I II.

η*-NHNHCCN)lc+sH*sNext, a method for synthesizing the compound 2-45°2-47 from among the above-mentioned specific compounds will be shown as an example.

Synthesis of compound 2-45 Synthesis scheme (A) (B) (E) Compounds 4-nitrophenylhydrazine 1539 and 500
Mix tnf:l of diethyl oxalate and reflux for 1 hour. As the reaction progresses, ethanol is removed,
Finally, it is cooled to precipitate crystals. Filter, wash several times with petroleum ether and recrystallize. Next, 509 of the obtained crystals (A) was dissolved in 10100O methanol, and p
Reduction is carried out under a d/C (palladium on carbon) catalyst in an H2 atmosphere pressurized to 50 Psi to obtain compound CB).

22g of this compound (B) in 200mff of acetonitrile
and pyridine 169 at room temperature.
4 g of acetonitrile solution was added dropwise. After filtering off insoluble matter, the filtrate was concentrated and purified by recrystallization to obtain Compound (D) 319.

Compound (D) 309 was hydrogenated in the same manner as above to obtain compound (
E) 209 was obtained.

Compound (E) 109 was dissolved in 100 mff of acetonitrile, 3.09 g of ethyl inthiocyanate was added, and the mixture was refluxed for 1 hour. After distilling off the solvent, the compound CF)7 was purified by crystallization.
．． Obtained 0g. Compound (F) 5.09 methanol 5
Methylamine (40% aqueous solution 3a+) was dissolved in 0raQ.
ff) was added and stirred. After slightly concentrating methanol, the precipitated solid was taken out, recrystallized and purified to obtain Compound 2-45.

Synthesis of Compound 2-47 Synthesis Scheme (B) (C) (D) (E) Compound 2-47 Compound (B) 229 was dissolved in 200 ml of pyridine, and p-nitrobenzenesulfonyl chloride 229 was added to the stirring vessel. . The reaction mixture was poured with water, and the precipitated solid was taken out to obtain compound (C). Compound 2-47 was obtained by reacting this compound (C) in the same manner as compound 2-45 according to the synthetic scheme.

Next, general formula [3] will be explained.

General formula [3].

禦Ar-NIINH-C-R,, In the general formula [3], Ar represents an aryl group containing at least one diffusion-resistant group or silver halide adsorption promoting group,
The diffusion-resistant group is preferably a ballast group commonly used in immobile photographic additives such as couplers. The ballast group is a group having 8 or more carbon atoms and is relatively inert to photography, and may be selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group, etc. Can be done.

Examples of the silver halide adsorption promoting group include groups described in US Pat. No. 4,385,108, such as a thiourea group, a thiourethane group, a heterocyclic thioamide group, a mercapto heterocyclic group, and a triazole group.

R31 represents a substituted alkyl group, and the alkyl group represents a linear, branched, or cyclic alkyl group, such as methyl, ethyl, propyl, butyl, inglovir, pentyl, cyclohexyl, and the like.

Substituents introduced into these alkyl groups include alkoxy (e.g., methoxy, ethoxy, etc.), aryloxy (e.g., phenoxy, p-chlorophenoxy, etc.), heterocyclic oxy (e.g., pyridyloxy, etc.), mercapto, alkylthio (methylthio), etc. , ethylthio, etc.), arylthio (e.g., phenylthio, p-chlorophenylthio, etc.), heterocyclic thio (e.g., pyridylthio, pyrimidylthio, thiadiazolylthio, etc.), alkylsulfonyl (e.g., methanesulfonyl, butanesulfonyl, etc.), arylsulfonyl ( For example, benzenesulfonyl, etc.), heterocyclic sulfonyl (for example, pyridylsulfonyl, morpholinosulfonyl, etc.), acyl (for example, acetyl, benzoyl, etc.), cyano, chloro, bromine, alkoxycarbonyl (for example, ethoxycarbonyl, methoxycarbonyl, etc.), aryloxycarbonyl ( (e.g., phenoxycarbonyl), carboxy, carbamoyl, alkylcarbamoyl (e.g., N-methylcarbamoyl, N,N-
dimethylcarbamoyl, etc.), arylcarbamoyl (e.g., N-phenylcarbamoyl, etc.), amino, alkylamino (e.g., methylamine, N,N-dimethylamino, etc.), arylamino (e.g., phenylamino,
naphthylamino, etc.), acylamino (e.g., acetylamino, benzoylamino, etc.), alkoxycarbonylamino (e.g., ethoxycarbonylamino, etc.), aryloxycarbonylamino (e.g., phenoxycarbonylamino, etc.), acyloxy (e.g., acetyloxy, benzoyloxy), etc.), alkylaminocarbonyloxy (e.g. methylaminocarbonyloxy etc.), arylaminocarbonyloxy (e.g. phenylami7carponyloxy etc.), sulfo, sulfamoyl, alkylsulfamoyl (e.g. methylsulfamoyl etc.), arylsulf Examples include various groups such as famoyl (eg, phenylsulfamoyl, etc.).

Even if the hydrogen atom of hydrazine is substituted with a substituent such as a sulfonyl group (e.g., methanesulfonyl, toluenesulfonyl, etc.), an acyl group (e.g., acetyl, trifluoroacetyl, etc.), an oxalyl group (e.g., ethoxalyl, etc.), good.

Representative compounds represented by the above general formula [3] include:
There are the following.

υ しLILtr 3 *-Kin811CC) 120CIIICH□OCR,C)
1. OHNext, a synthesis example of compound 3-5 will be described.

Synthesis of compound 3-5 Synthesis scheme Compound 3-5 was obtained according to the synthesis method of compound 2-45.

General formula [
The amount of the compounds 1], [2], and [3] is from 5 x 10-' to s x io-' mol per 1 mol of silver halide contained in the silver halide photographic material of the present invention. is preferred, and more preferably in the range of 5 x 10-' to I x 10-'' moles.

The silver halide used in the silver halide emulsion layer of the present invention is silver chlorobromide or silver chloroiodobromide containing 50 mol % or more of silver bromide. When the content of silver bromide is less than 50 mol %, fog including permeable fog occurs significantly on the film after development.

There is no particular restriction on the grain size of this silver halide, but it is preferable that the average grain is smaller than 0.5 μm, and 90% or more of the total grains are so-called monodisperse, within ±40% of the average grain size. Preferably they are particles.

The silver halide grains may have a cubic, tetradecahedral or octahedral crystal habit, and may also be tablet grains as disclosed in JP-A-53-108525.

The method for preparing silver halide grains in the silver halide emulsion layer of the present invention may be a single jet method such as a forward mixing method or a back mixing method, or a double jet method using a simultaneous mixing method, and more preferably a simultaneous mixing method. be. Also, ammonia method,
Any method such as a neutral method, an acid method, or the modified ammonia method disclosed in Japanese Patent Publication No. 58-3232 may be used, and the acid method or the neutral method is more preferred.

In addition, these silver halide grains contain iridium, rhodium, osmium, bismuth, cobalt, nickel,
Metal atoms such as ruthenium, iron, copper, zinc, lead, and cadmium may be contained.

When containing these metal atoms, silver halide 1
The content is preferably in the range of 10-101 moles per mole. Also, the silver halide grains are preferably of surface latent image type.

Next, the compound represented by the general formula [4] of the present invention will be explained.

In general formula [4], the optionally substituted alkyl group represented by R, , R, , R, and R44 is preferably a lower alkyl group having 1 to 8 carbon atoms (for example, methyl substituents for this alkyl group include, for example, a hydroxy group, a sulfone group, a carboxylic acid group, an amino group, and a halogeno group.

R4□IR4! Examples of the aryl group which may have a substituent represented by IR43 and R44 include a 7-enyl group and a naphthyl group, with a phenyl group being preferred. Substituents for this aryl group include alkyl groups (preferably lower alkyl groups having 1 to 8 carbon atoms), alkoxycarbonyl groups, alkylsulfonyl groups, and alkylcarbonyl groups (the alkyl portion of these groups preferably has 1 to 8 carbon atoms). 8), nitro group, cyano group, halogen atom,
-N(CjHi)zHc(2-, etc.).

Examples of the aralkyl group which may have a substituent represented by R411Razi 43 and R44 include benzoyl and phenethyl groups, with benzoyl being preferred. Examples of substituents for this aralkyl group include the groups for the above-mentioned aryl group.

Typical substituents for the electron-withdrawing group of the aryl group or aralkyl group of R411Razi 43 and R44 include a nitro group, a cyano group, a halogeno group, a carbonyl group, a carboxyl group, a sulfonyl group, a quaternary amino group, etc. It is mentioned as.

Examples of anions represented by X- include chloride ion, bromide ion, iodide ion, cyanide ion, hypochlorite ion, p-toluenesulfonate ion,
Examples include benzenesulfonic acid ion and hydroxide ion.

The compound represented by the general formula [4] is
It can be easily synthesized by the method described in No. 5.

As shown in the Examples below, when a compound having a chemical structure similar to the above general formula [4] but consisting of an aryl group or an aralkyl group without an electron-withdrawing substituent is used, the resulting photographic light-sensitive material However, there is no effect on suppressing the occurrence of Pella parts.

Specific examples of the compound represented by the general formula [4] include the following compounds, but the compounds are not limited thereto.

[4] -1 [4] -2 [4] -3 (4) -4 [4] -5 [4] -6 [4] -7 [4] -8 [4] -9 [4] -10 [4] -11 [4] -12 [4] -13 [4] -14 [4] -15 [4] -16 [4] -17 Note that the compound represented by the above general formula [4] is halogenated In order to incorporate silver into the constituent elements of photographic materials, it may be dissolved in water or an organic solvent miscible with water such as methanol or ethanol, and then incorporated into the constituent elements. Although it varies depending on the type of silver, the type of constituent elements contained, the type of compound used, etc., in general, when added to the emulsion layer, it is 1O-7 to 1O-3 mol per mol of silver halide, more preferably 10 −'〜
It can be added in a range of 10-4.

Next, the compound represented by the general formula [5] will be explained.

In the general formula [5], the lower alkyl group represented by R31 may be linear or branched, and has 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a 1so-7' lobil group, a butyl group, etc. It will be done.

Specific representative examples of the compound represented by the general formula [5] are listed below.

[5] -15-nitroindazole [5] -26-nitroindazole [5] -35-methylindazole [5] -46-methylindazole [5] -5 Indazole [5] -65-chlorobenzimidazole [5] ]-7
5-Methylbenzimidazole [5]-85-ethylbenzimidazole [5]-95-nitropenzimidazole [5]-106-nitrobenzimidazole [5]
-115-chloropenzimidazole [5]-12
The compound represented by the general formula [5] of benzimidazole is used in an amount in the range of 1 x 10-' to 1
-” range.The addition method of this compound is the general formula [1
] may be applied.

Next, the compound represented by general formula [6] will be explained.

In general formula [6], R IllR81 and R@3
The alkyl group represented by may be linear or branched, preferably having 1 to 16 carbon atoms, and includes long-chain alkyl groups such as methyl, ethyl, and dodecyl. R,
,R,! and R. Examples of the aryl group represented by , include phenyl group and naphthyl group.

Specific representative examples of the compound represented by the general formula [6] include the following compounds.

(6)-1 6-aminopurine (6)-2 4-amino-6-hydroxypurine (
6)-3 6-Benzylaminopurine (6)-4
6-mercaptopurine (6)-5 4.6-cyhydroxypurine (6)-6 4.6-diamitpurine (6)-7 Tomethyl-6-aminopurine (6)
)-8 4-methyl-6-aminopurine (6)-9
1-hydroxy-6-aminopurine (6)-10
1-Mercapto-4-octylpurine (6)-1
1 4-phenyl-6-aminopurine (6)-12
The compound represented by the general formula [6] of 1.6-diamitpurin has IX 10-' to IXIO per mole of silver halide.
-' molar range, particularly preferably I
The range is from XIO-' to IXIO-' moles. The method for adding this compound may be similar to that for the compound represented by general formula [1].

The silver halide photographic emulsion of the silver halide emulsion layer according to the present invention (hereinafter referred to as the silver halide photographic emulsion of the present invention) can be chemically sensitized. Chemical sensitization methods include sulfur sensitization,
Although reduction sensitization and noble metal sensitization are included, in the present invention, chemical sensitization is preferably carried out using sulfur sensitization alone.

As the sulfur sensitizer, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, and rhodanines can be used. Specifically, US Pat. No. 1,574,944 No. 241
No. 0689, No. 2728668, Special Publication No. 11/1982
Sulfur sensitizers described in No. 892 and the like can be used.

The silver halide photographic emulsion of the present invention can be provided with photosensitivity in a desired wavelength range.

Here, optical sensitization may be performed using one or more types of sensitizing dyes. Various sensitizing dyes can be used, but optical sensitizing dyes that can be advantageously used in the present invention include cyanines, carbocyanines, merocyanines, and trinuclear or tetranuclear merocyanines. , trinuclear or tetranuclear cyanines, styryls, holopolar cyanines, hemin cyanines, oxonols, hemioxonols, etc. These optical sensitizing dyes have a structure as a nitrogen-containing heterocyclic nucleus. Preferably, one part contains a basic group such as thiazoline or thiazole, or a nucleus such as rhodanine, thiohydantoin, oxazolidinedione, barbylic acid, thiobarbylic acid, or pyrazolone. Alkoxy can be substituted,
Further, these optical sensitizing dyes may be fused with a carbocyclic ring or a heterocyclic ring.

The silver halide photographic emulsion of the present invention includes stabilizers such as tetrazaindenes, anti-capri agents such as triazoles and tetrazoles, covering power improvers, and anti-irradiation agents such as oxanol dyes and dialkylaminobenzylidene dyes. It is possible to add, for example, polymer latexes as wetting agents, and other additives used in general photographic emulsions, such as spreading agents and hardening agents.

As the support for the silver halide photographic material of the present invention, commonly used supports such as polyester base, TAc base, baryta paper, laminated paper, glass plate, etc. are used.

As the developer used in the silver halide photographic light-sensitive material of the present invention, either a developer used in a general silver halide photographic light-sensitive material or a lithium developer can be used. The developing agents of these developers include dihydroxybenzenes such as hydroquinone, chlorohydroquinone, and catechol, l-phenyl-3-pyrazolidone, l-7enyl-4,4-dimethyl-3-pyrazolidone, and l-phenyl-4. -Methyl-3-pyrazolidone, l-
Examples include 3-pyrazolidones such as phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, and also N-methyl-p-aminophenol, N-(4-
Examples include para-aminophenols such as (hydroxyphenyl)glycine, β-methanesulfonamide ester, ethylaminotoluidine, p-7z nylene diamines such as N,N-diethyl-p-7 di-2-diamine, and ascorbic acids. , used as an aqueous solution containing one or more such developing agents.

In addition, the developer contains preservatives such as sodium sulfite, potassium sulfite, formaldehyde sodium bisulfite, hydroxylamine, ethylene urea, and inorganic salts such as sodium bromide, potassium bromide 1, potassium iodide, etc. to inhibit development. agent, l-phenyl-5-mercaptotetrazole, 5
- 1 such as nitropenzimidazole, 5-nitrobenzotriazole, 5-nitroindazole, 5-methyl-benzotriazole, 4-thiazoline-2-thione, etc.
organic inhibitors, alkaline agents such as sodium hydroxide, potassium hydroxide, jetanolamine, triethanolamine, 3-diethylamine-1-propertool, 2
-methylamino-1-ethanol, 3-diethylamino-1,2-propanediol, diisopropylamine,
Alkanolamines having a development accelerating effect such as 5-amino-1-pentanol and 6-amino-1-hexanol, sodium carbonate, sodium phosphate, aqueous carbonate solution,
Buffers that have a buffering effect in developing solutions such as phosphoric acid aqueous solutions, salts such as sodium sulfate, sodium acetate, and sodium citrate, and chelating effects such as sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, and sodium hydroxydiaminetriacetate. Water softeners, developer hardeners such as glutaraldehyde, solvents and organic inhibitors such as diethylene glycol, dimethyl formaldehyde, ethyl alcohol, benzyl alcohol, methyl imidacillin, methyl imidazole, polyethylene glycol, It can be constituted by adding a development regulator such as dodecylpyridinium bromide.

The pH of the developer is not particularly limited, but is preferably in the range of 9 to 13.

An example of the composition of a preferable developer for developing the silver halide photographic material of the present invention is as follows. As a developing agent, hydroquinone 20-609# and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 0.1-29/Q or l-phenyl-4,4-dimethyl-3-pyrazolidone 0.1- 2gIQ, as a developer preservative, sodium sulfite 10-200g/Q or potassium sulfite 10-2009/(2, as an inorganic salt development inhibitor, sodium bromide or potassium bromide 1" 1o9I
Q. Alkanolamines 1 to 50 that have a development accelerating effect
9/Q, organic inhibitors such as 5-methylbenzotriazole 0.05-2 g/(11 or 5-nitroindazole 0,01-2 g/Qs buffer agents such as sodium carbonate 1-509#! or phosphoric acid aqueous solution (1 mo
g#l) 1010-8O0/Q.

Add ethylenediaminetetraacetic acid disodium salt 0.1 = 109/<+ as a chelating agent, and use a suitable alkaline agent (e.g. potassium hydroxide) to convert pi (11.Q
It is a developer adjusted to ~12.5.

The silver halide photographic light-sensitive material of the present invention is developed with the above-mentioned developer, and then undergoes a process of rinsing, washing with water, and drying to fix the image. At this time, there are no particular restrictions on the development temperature and development time in the development process, but the development temperature is preferably in the range of 20 to 45°C and the development time is in the range of 15 seconds to 200 seconds.

EXAMPLES The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto.

Example 1 Silver nitrate aqueous solution and halide aqueous solution (KBr 98 moffi%, KI 2so
Q%) was added at the same time for 50 minutes, and during that time pAg 7
．． 5, a monodisperse silver iodobromide emulsion with an average grain size of 0.25 μi was prepared. This emulsion was desalted by a conventional method.
After washing with water, 15119 sodium thiosulfate was added per mole of silver iodobromide, and chemical ripening was performed at 60° C. for 60 minutes.

Next, this emulsion was added to 6-methyl-4-hydroxy-1,3
3a, 1 g of 7-chitrazaindene/1 mole of AsX was added. Anhydro-5,5°-dichloro-9-ethyl-3,3'-bis(3-sulfopropyl)oxacarbocyanine hydroxide sodium salt was used as a sensitizing dye.
00 carbonate 9/A9X 1 mol, polyethylene glycol 250 mg/A9X 1 mol, and an exemplary hydrazide compound 1. 1 mol of Og/A9X was added, and the compounds of general formulas [4], [5], and [6] according to the present invention were added as shown in Table 1.

The emulsion thus obtained contains ethyl acrylate latex poly? -29/II", gelatin at 2.5 s/m",
AgX particles were coated on a PET base using a saponin solution as a spreading agent so that the silver content was 3.59/II2.

This emulsion layer was protected by a hard overcoat layer containing a saponin solution and mucochloric acid as a hardening agent so that the gelatin concentration was 1.5 g/m''.

Below is 1 white thread.

Table 1 The following compounds (a) to (C) were used as comparative compounds added to the silver halide emulsion layer.

a) After applying stepwise exposure to the sample No. 1"13 using a tungsten light source through a film wedge according to a conventional method,
After developing for 30 seconds at 38° C. with the developer shown in Table 2 below, fixing, washing with water and drying, sensitivity, contrast and perforation lag were evaluated.

Contrast is the slope of the straight line part of the characteristic curve (tana value)
Expressed as , the degree of occurrence of pericarp is ranked in four stages: (5) not occurring at all, (4) 1 to 2 spots in the visual field, (3) few but low quality, and (2) markedly occurring. I attached it.

//- Thread below (white) Table-2 Composition of developer (Developer 1 (2) Hydroquinone 349N.
Methyl-p-aminophenol 0.239 Ethylenediaminetetraacetic acid disodium salt 193-diethylamino-1,2-propanediol 1595.Methylpenztriazole 0.49 NatS
Ox76sNa
Br 39Na
CQl, 3
91moff, l phosphoric acid solution
400mff The pH was adjusted to 112 by adding NaOH necessary to bring the pH to 11.5.

Fixer formulation> Ammonium thiosulfate (72.5% W/V aqueous solution) 2
40mQ Sodium Sulfite 1
79 Sodium acetate trihydrate 6.5
9 Boric acid 6g Sodium citrate dihydrate 29 (composition) Pure water (ion exchange water) 171Q
Sulfuric acid (50% W/V (7) aqueous solution) 4.79 Aluminum sulfate (aqueous solution with Aff203 equivalent content of 8.1% W/V)
When using the 26.59 fixer, it was dissolved in 500 u+ffi of water in the order of the above composition A1 and finished to 1a. The pH of this fixer was adjusted to 6 with acetic acid.

The results are shown in Table-3.

As is clear from the results in Table 3, it can be seen that the samples obtained according to the present invention significantly suppressed the occurrence of permeable fog without impairing sensitivity and contrast.

In Table 3, sensitivity is expressed as relative sensitivity.

Example 2 A silver nitrate aqueous solution and a halide aqueous solution (98 mol% KBr, 1 to 1
2 mol%) to I) 50 at the same time while keeping Ag at 7.5.
Added in minutes. This emulsion was desalted and washed with water in a conventional manner, then gelatin was added to redisperse it, and the average particle size was 0.2.
A monodisperse silver iodobromide emulsion Em-1 of 5 .mu.m was prepared.

Next, water-soluble iridium compound potassium hexachloroiridate (IV) IX 10-' mol/AgX1
A monodispersed silver iodobromide emulsion Em-2 having an average grain size of 0.25 .mu.m was prepared in the same manner as Em-1 except that mol was added to the aqueous halide solution.

Subsequently, monodispersed iodine with an average particle size of 0.24 μm was prepared in the same manner as in Eml except that rhodium trichloride trihydrate, which is a water-soluble rhodium salt, 2-28X 10-' mol/Agx 1 mol was added to the halide aqueous solution. Silver bromide emulsion Em-3 was prepared.

These Em-1, Em-2 and Em-3 emulsions were subjected to the same operations as in Example 1, from chemical ripening to protection with an overcoat layer, to obtain Samples No. 13 to No. 18.

Thereafter, exposure, development and evaluation were also carried out according to the method of Example 1. Table 4 shows the contents of the compounds of the present invention used in the experiment and the evaluation results.

Table 4 As is clear from Table 4, samples Nos. 16 to 18 using the compounds of the present invention have a remarkable pepper fog suppressing effect even in emulsions doped with metals such as iridium and rhodium. It could be confirmed.

Example 3 Silver chloroiodobromide emulsions Em-4 to Em-8 were prepared using the following solutions of liquid A, liquid B, and liquid C.

The amounts of sodium chloride, potassium bromide and potassium iodide used in Solution C are shown in Table 5 together with the silver halide grain composition of the prepared emulsion.

[Solution A]

Ossein gelatin 17i (both ion exchange treatment agent, jelly strength 250) polyisopropylene-polyethylene oxydisuccinate sodium salt lθ% ethanol solution 5
mQ distilled water 1280
Matome Q [Solution B] Silver nitrate 170 g Distilled water 410 sff [Solution C] Sodium chloride Table-5 Amount of potassium bromide Table-5 Amount of potassium iodide
Table-5 Listed amount ossein gelatin
119 Polyisopropylene polyethylene oxydisuccinate sodium salt 10% ethanol solution 3w, Q distilled water
Solution B and solution C were added to 412 Otori Q solution A by a simultaneous mixing method. Table-6
The insulating temperature at the time of addition and the addition time of solution B and solution C are shown. At this time, p and Ag in the system were controlled at the values shown in Table 6, and the pH was all controlled to pH-3.

After addition of solution B and solution C, stir-wide ripening was performed for 10 minutes at the insulated temperature, followed by desalting and washing with water using a conventional method, followed by a 600i* aqueous solution of ossein gelatin.
Add Q (containing ossein gelatin 309) and incubate at 55℃ for 3 minutes.
Emulsions Em-4 to Em-8 dispersed by stirring for 0 minutes
I got it.

Observation using an electron microscope revealed that these emulsions were monodisperse emulsions with an average grain size of 0.22 to 0.27 μm and more than 90% of the total grains falling within ±0.1 μl.

Each of the emulsions Em-4 to Em-8 thus obtained was subjected to operations from chemical ripening to protection with an overcoat layer in the same manner as in Example 1 to obtain samples No. 19 to No. 23.

Subsequent exposure, development and evaluation were also carried out according to the method of Example 1.

Table 7 shows the contents of the compounds of the present invention used in the experiment and the evaluation results.

Table 7 As is clear from Table 7, in samples No. 22 and No. 23 using emulsions containing less than 50 mol% AgBr, compounds [11-1 and [2]-16 of the present invention were added. However, it was not possible to suppress Peraper Fog, and sample No. 19~ using an emulsion containing silver bromide of 50 mol% or more
Only in No. 20, there is a permeability lag suppressing effect.

(Effects of the Invention) In the formation of high contrast images using a silver halide photographic material using a hydrazide compound, the occurrence of perforation lag is improved without impairing high contrast.

Claims (1)

[Scope of Claims] A silver halide composition having a silver bromide content of 50 mol % or more, and containing at least one compound represented by the following general formulas [1], [2], and [3] and the following general formula [
A silver halide photographic material comprising at least one silver halide emulsion layer containing at least one compound selected from compounds represented by [4], [5] or [6]. General formula [1] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 and R_2 represent an aryl group or a heterocyclic group, R represents an organic bonding group, n is 0 to 6, m is 0
or 1, and when n is 2 or more, each R may be the same or different. ) General formula [2] ▲ Numerical formulas, chemical formulas, tables, etc. Represents an oxy group, an amino group, or an aryloxy group, and P_1 and P_2 represent a hydrogen atom, an acyl group, or a sulfinic acid group.) General formula [3] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Ar represents an aryl group containing at least one diffusion-resistant group or silver halide adsorption promoting group, and R_3_1 represents a substituted alkyl group.) General formula [4] ▲ Contains numerical formulas, chemical formulas, tables, etc. ▼ [In the formula, A represents a phosphorus atom or a nitrogen atom. R_4_1, R_4_2, R_4_3 and R_4_4
each represents a substituted or unsubstituted alkyl group, aryl group or aralkyl group. X^- represents an acid anion. ] General formula [5] ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, Y and Z represent nitrogen atoms or carbon atoms,
When one of Y and Z is a nitrogen atom, the other is a carbon atom. R_5_1 represents a hydrogen atom, a lower alkyl group, a halogen atom, or a nitro group. [In the formula, R_6_1, R_6_2 and R_6_3 represent a hydrogen atom, an amino group, a hydroxy group, a mercapto group, an alkyl group, or an aryl group. ]