JPH0477732A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide photographic sensitive material which has high dot quality and lessens the generation of black spots by incorporating a silver halide emulsion consisting of lamination type silver halide particles prepd. in the presence of an iridium salt into silver halide photographic emulsion layers and adding a specific org. compd. thereto. CONSTITUTION:The lamination type silver halide particles are formed in the presence of the iridium salt. The timing for adding the iridium salt is at the time of particle formation, physical maturation or chemical maturation or thereafter. The physical maturation time is more preferable in order to incorporate the more iridium salt into the surface layer of the silver halide particles. The lamination type silver halide particles formed in such a manner are incorporated into the silver halide photographic emulsion layers. Further, at least one kind of the compds. expressed by general formula [1],[2] or [3] are incorporated into the silver halide photographic emulsion layers or other hydrophilic colloidal layers. The silver halide photographic sensitive material which is high in contrast and has the excellent dot quality and high sensitivity is obtd. in such a manner.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and particularly to a silver halide photographic light-sensitive material that provides a photographic image with high contrast.

[Prior Art] In general, high-contrast photographic images are used in the photoengraving process to form characters and separated photographic images, and in the ultra-precision photoengraving process to form fine line images. It is known that when silver halide photographic materials (1) for this purpose are used, photographic images with extremely high contrast and luster can be obtained.

Conventionally, for example, the average particle diameter was 0.2 μm, the particle distribution was narrow, the particle shape was uniform, and the content of silver chloride was high (
A silver halide photographic light-sensitive material having an emulsion consisting of silver chlorobromide grains (at least 50 mol% or more) is processed with an alkaline hydroquinone developer having a low sulfite ion concentration to produce a high-contrast, high-resolution image, such as a halftone image or a fine image. It was used to obtain line images.

This type of silver halide photographic light-sensitive material is known as a lithium-type light-sensitive material.

The photolithography process includes the process of converting a continuous tone original into a halftone image, i.e. converting the continuous tone density changes of the original into a set of halftone dots having an area proportional to the density. It is.

For this purpose, a dot image is formed by using the above-mentioned lithium-type photosensitive material and photographing an original through an intersection screen or a contact screen, followed by development processing.

For this purpose, a silver halide photographic light-sensitive material containing an emulsion consisting of fine grains and silver halide grains with uniform grain size and grain shape is used. However, when processed with a general black and white developer, the formation of halftone images is inferior to when developed with a Lith type developer. Therefore, it is processed with a developer called a Lith type developer, which has an extremely low concentration of sulfite ions and uses single hydroquinone as the developing agent.

However, since the Lith type developer is susceptible to auto-oxidation, its storage stability is extremely poor, and there is a strong need for a control method to maintain constant development quality even during continuous use. Great efforts have been made to improve it.

As an improvement method, in order to maintain the stability of the above-mentioned Lith-type developer, a replenisher that compensates for the deterioration of activity due to development processing (processing fatigue replenishment) and a replenisher that compensates for oxidative deterioration over time (replenisher A so-called two-liquid separation replenishment system, in which the replenisher (fatigue replenisher) and the replenisher (fatigue replenisher) are replenished using separate replenishers, is generally widely adopted in automatic developing machines for photolithography and the like.

However, the above method has the disadvantage that it is necessary to control the replenishment balance of the two liquids, which complicates the equipment and operation.

Further, in the Lith type development, it takes a long time (induction period) until an image appears due to development, so it is not possible to obtain an image quickly.

On the other hand, the above-mentioned Lith type developer can be used quickly and with high contrast.
No. 23 and Japanese Unexamined Patent Publication No. 51-20921. These methods involve incorporating a hydrazine compound into a silver halide photographic light-sensitive material. According to these methods, it is possible to maintain a high concentration of sulfite ions in the developer, and it is possible to process with improved preservability.

However, all of these methods require a developer with a fairly high pH to obtain a high-contrast image, and there is a problem in the stability of the developer as a technique for obtaining images quickly and with high sensitivity. Further, since the pH of the developing solution is high, fog is likely to occur, and as a result of containing various organic inhibitors at high concentrations in order to suppress this fog, sensitivity has been sacrificed.

On the other hand, JP-A No. 61-29837 discloses that silver halide grains prepared in the presence of an iridium salt and having a silver iodide content on the grain surface or a silver iodide content larger than the average silver iodide content of the grains are disclosed. A silver halide photographic light-sensitive material is disclosed which has a silver emulsion layer and contains a hydrazine compound in the emulsion layer or other hydrophilic colloid layer.

However, even with this photosensitive material, the image contrast is still insufficient, the sensitivity is also insufficient, and there is still room for improvement, such as deterioration of image quality due to the occurrence of black spots in non-image areas. there were.

In addition, with conventional silver halide photographic materials of this type, if the film is not handled properly, scratches may occur on the surface, which can lead to blackening pressure, and when large films are transported, nails may break. It was often found that the so-called poor pressure resistance was caused by blackening pressure and deteriorating the quality of the finish.

Accordingly, an object of the present invention is to provide a highly sensitive silver halide photographic material that can obtain photographic images with high contrast using a stable developer.

Another object of the present invention is to provide a silver halide photographic material that has high halftone dot quality and less occurrence of black spots.

Still another object of the present invention is to provide a silver halide photographic material having excellent pressure resistance.

[Means for Solving the Problems] The above-mentioned object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer on a support. Laminated halogenated grains comprising at least two layers prepared in the presence of an iridium salt in one layer, the silver iodide content of the grain surface layer being thicker than the silver iodide content of the grain inner core. It contains a silver halide emulsion consisting of silver particles, and further contains at least one compound represented by the following general formula [1], [2] or [3] in the silver halide photographic emulsion layer or other hydrophilic colloid layer. This is achieved by a silver halide photographic material characterized by containing seeds.

General formula [1co (in the formula, R1 and R2 each represent an aryl group or a heterocyclic group, R represents an organic bonding group, n is O-6, m
represents 0 or 1, and when n is 2 or more, each R may be the same or different. ) General formula [2] General formulas [1], [2], and [3] will be specifically explained below.

General formula [1] (wherein R, 21 represents an aliphatic group, aromatic group or heterocyclic group, R2□ is a hydrogen atom, an optionally substituted alkoxy group, a heterocyclic oxy group, an amino group, or represents an aryloxy group, and Pl and R2 each represent a hydrogen atom, an acyl group, or a sulfinic acid group.) General formula [3] % formula % (In the formula, Ar represents a diffusion-resistant group or a silver halide adsorption-promoting group. represents an aryl group containing at least one, and R31 represents a substituted alkyl group.) The specific structure of the present invention will be described in more detail below.

In the formula, R1 and R2 each represent an aryl group or a heterocyclic group, R represents a divalent organic group, and n is 0 to 6.
, m represents O or 1.

Here, examples of the aryl group represented by Ro and R2 include a phenyl group and a naphthyl group.

Examples of the heterocyclic group include a pyridyl group, a benzothiazolyl group, a quinolyl group, and a thienyl group. Preferably R1 and R2 are aryl groups. R1 and R2
Various substituents can be introduced into the aryl group or heterocyclic group represented by. Examples of substituents include halogen atoms (e.g., chlorine, fluorine, etc.), alkyl groups (e.g., methyl, ethyl, dodecyl, etc.), alkoxy groups (e.g., methoxy, ethyloxy, isopropoquine, butoxy, octyloxy, dodecyloxy, etc.). ), acylamino group (
For example, acetylamino, bivalylamino, benzoylamino, tetradecanoylamino, α-(2,4-sheet
-amylphenoquine) phytyrylamino), sulbonylamino groups (e.g. methanesulfonylamino, butanesulfonylamino, dodecanesulfonylamino, pencenesulfonylamino), urea groups (e.g. phenylurea, ethylurea), Thiourea group (e.g., phenylthiourea, ethylthiourea, etc.), hydroxy group, amino group, alkylamino group (e.g., methylamine, dimethylamino, etc.), carboxyne group, alkoxycarbonyl group (e.g., ethoxycarbonyl),
Examples include carbamoyl group and sulfo group.

Examples of the divalent organic group represented by R include alkylene groups (e.g., methylene, ethylene, l-lyltylene,
Examples include tetramethylene), arylene groups (eg, phenylene, naphthylene, etc.), and aralkylene groups. The aralkylene group has an oquine group, a thio group, a seleno group, and a carbonyl group in the bond.

The group may include a -N- group (R3 represents a hydrogen atom, an alkyl group, or an aryl group), a sulfonyl group, and the like. Various substituents can be introduced into the group represented by R.

Examples of the substituent include -CON If N HR.

(R4 has the same meaning as R1 and R2 mentioned above),
Examples include an alkyl group, an alkoxy group, a halogen atom, a hydroxy group, a carboxy group, an acyl group, and an aryl group.

R is preferably an alkylene group.

Among the compounds represented by the general formula [1], preferably Ri
and R2 is a substituted or unsubstituted phenyl group, and n=
A compound in which m=1 and R represents an alkylene group.

Representative compounds represented by the above general formula [1] are shown below.

Specification 8] L(,511 Next, general formula [2] will be explained for general formula [2]. In the formula, the aliphatic group represented by R2□ preferably has 6 or more carbon atoms, particularly 8 carbon atoms. ~50 linear, branched or cyclic alkyl groups, where the branched alkyl group is cyclized to form a saturated heterocycle containing one or more △, terato atoms therein. This alkyl group may also have a substituent such as an aryl group, an alkoxy group, or a sulfoxy group.

The aromatic group represented by R21 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.

For example, those containing a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a virolazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, a benzothiazole ring, etc. are preferred.

Particularly preferred as R21 is an aryl group.

The aryl group or unsaturated heterocyclic group of R21 may be substituted. Typical substituents include linear, branched or cyclic alkyl groups (preferably monocyclic or bicyclic alkyl moieties having 1 to 20 carbon atoms), alkoxy groups (
(preferably those having 1 to 20 carbon atoms), substituted amino groups (preferably amino groups substituted with alkyl groups having 1 to 20 carbon atoms), anrulamino groups (preferably those having 2 to 30 carbon atoms), sulfonamide F Group (preferably 1 to 1 carbon atoms)
30), a ureido group (preferably a carbon number of 1 to
30).

Among the groups represented by R22 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 [2], the optionally substituted aryloxy group or heterocyclic oxy group is preferably a monocyclic group, and the substituent is a halogen atom, an alkyl group, an alkoxy There are cyano groups, etc.

Among the groups represented by R and 22, preferred are an optionally substituted alkoxy group or an amino group.

A+ / In the case of an amino group, it may be a cyclic structure containing an alkyl group, an alkoxy group, or a 10--8--N- group bond that may be substituted with A and \4゜A2 group. . However, R2□ is never a hydrazino group.

R21 or R22 in the general formula [2] may have a ballast group, which is commonly used in immobile photographic additives such as cuffler, incorporated therein.

The ballast group is a group having 8 or more carbon atoms and relatively inert to photography, such as an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group,
You can choose from alkylphenoquine groups.

R21 or R22 in the general formula [2] may have a group introduced therein to enhance adsorption to the surface of the silver halide powder. Such adsorption groups include thiourea group,
Examples include the groups described in US Pat. No. 4,355.105, such as heterocyclic thioamino).^L, merkaft bicyclic group, and triazole group. Among the compounds represented by the general formula [2], the compound represented by the following general formula "2-a" is particularly preferred.

General formula [2-a] In the above general formula [2-a, R2 and R24 are each a hydrogen atom, an optionally substituted alkyl group (for example, a methyl group, an ethyl group, a butyl group, a Fdenyl group, a 2- hydroxypropyl group, 2-cyanoethyl group, 2-chloroethyl group), optionally substituted phenyl group, naphthyl group, nclohexynyl 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, pyrrolidyl group, 4-
methyl-2-pyrrolidyl group), and R2b represents a hydrogen atom or an optionally substituted benzyl group, alkoxy group, and alkyl group (e.g., benzyl group, p-methylphenyl group, methoxy group, ethoxy group, ethyl group, butyl group) ), R26 and R27 represent a divalent aromatic group (for example, a phenylene group or a naphthylene group), Y represents a sulfur atom or an oxygen atom, and L represents a divalent bonding group (for example, a
2CH2CH2NH-3O2NH.

-OCH2S O2N )(, -C)--CI=N-)
, R28 represents -R'R' or -0R29, R
', R' and R2G are hydrogen atoms, optionally substituted alkyl groups (e.g. methyl group, ethyl group, Fdenyl group), phenyl groups (e.g. phenyl group, pmethylphenyl group, p
-methoxyphenyl group), naphthyl group (e.g. α-naphthyl group, β-naphthyl group) or heterocyclic group (e.g. unsaturated heterocyclic group such as pyridine, thiophene, furan, or tetrahydrofuran, sulfolane). R' and R' may form a ring (eg, piperidine, piperazine, morpholine, etc.) together with the nitrogen atom.

m and n represent O or 1. When R2g or OR29 is represented, it is preferable that Y represents a sulfur atom.

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

Margin below Specific example of general formula (2) F8 (1) May CH.

O○ 2-]6 NtINHCCOC11,Cl128CH,CI(,O
Ho 1111 -NIINHCCOCH.

CH.

OH CH.

○0'-NHNliCCNHC,,H2゜Synthesis of compound 2-45 (A> Next, compound 2-452- of the specific compounds listed in -1x)
Taking No. 47 as an example, its synthesis method will be shown.

C.H.

Compound 2-45 Compound 4-nitrophenylhydrazine 153g and 500g
Mix the diethyl oxalate of d and reflux for 1 hour.

Ethanol is removed as the reaction progresses, and finally it is cooled to precipitate crystals. Filter, wash several times with petroleum ether and recrystallize. Next, 50 of the obtained crystals (A)
Pd/C (
H2 under pressure of 50 Psi under palladium/carbon) catalyst
Compound (B) is obtained by reduction in an atmosphere.

22 g of this compound (B) was dissolved in a solution of 200 g of acetonitrile and 16 g of pyridine, and 24 g of compound (C) was dissolved at room temperature.
An acetonitrile solution of was added dropwise. After filtering off insoluble matter, the filtrate was concentrated and purified by recrystallization to obtain 31 g of Compound (D).

30 g of compound (D) was hydrogenated in the same manner as above to obtain compound (
E) 20g was obtained.

10 g of compound (E) was dissolved in 100 d of acetonitrile, 30 g of ethyl isothiocyanate was added, and the mixture was refluxed for 1 hour. After distilling off the solvent, crystallization was carried out to obtain compound (F) 7.0
I got g. Compound (F) 5.0g in methanol 501
Methylamine (40% aqueous solution 8 i, c) dissolved in g
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 (C) (D) (E) Compound adlJ2-47 22 g of compound (B) was dissolved in 200 d of pyridine, and while stirring, p-21-lovensenesulfonyl chloride 2 was added.
Added 2g. The reaction mixture was poured with water, and the precipitated solid was taken out to obtain compound (C). This compound (C) was subjected to the same reaction as compound 2-45 according to the synthesis scheme to obtain compound 2-47.

Next, general formula [3] will be explained.

General formula [3] % formula % In the general formula [3, Ar represents an aryl group containing at least one diffusion-resistant group or silver halide adsorption promoting group, and the diffusion-resistant group is used for immobile photographs such as couplers. Ballast groups commonly used in additives are preferred. The ballast group is a group having 8 or more carbon atoms and is relatively inert to photography, 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.

As the silver halide adsorption promoting group, thiourea group, thiour
Notane group, heterocyclic thioamide group, mercapto heterocyclic group,
Included are groups described in US Pat. No. 43,851.08, such as triazole groups.

Rs□ represents a substituted argyl group, and the alkyl group represents a linear, branched, or cyclic alkyl group, such as methyl, ethyl, propyl, butyl, isopropyl, pentyl, cyclohexyl, and the like.

Examples of substituents introduced into these alkyl groups include alkoxy (e.g., methoxy, ethoxy, etc.), aryloxy (e.g., phenoxy, p-chlorophenoxy, etc.), heterocyclic oxy (e.g., pyridylthion, etc.), mercapto, alkylthio (methylthio, ethylthio, etc.), arylthio (e.g., phenylthio, p-chlorophenylthio, etc.), peterocyclicthio (e.g., pyridylthio, pyrimidylthio, thiadiazolylthio, etc.), alkylsulfonyl (e.g., methanesulfonyl, butanesulfonyl, etc.), arylsulfonyl (e.g. (pensene sulfonyl, etc.), peterocyclic sulfonyl (e.g., pyridylsulfonyl, morpholinosulfonyl, etc.), acyl (e.g., acetyl, benzoyl, etc.), cyanogen chloro, bromine, alkoxycarbonyl (e.g., ethoxycarbonyl, methoxycarbonyl, etc.)
, aryloxycarbonyl (e.g., phenoxycarbonyl, etc.), carboxy, carbamoyl, alkylcarbamoyl (e.g., N-methylcarbamoyl, N,N-dimethylcarbamoyl, etc.), arylcarbamoyl (e.g., N-phenylcarbamoyl, etc.), amino, alkylamino (e.g., methylamino, 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., phenylaminocarbonyloxy) etc.), sulfo, sulfamoyl, alkylsulfamoyl (eg, methylsulfamoyl, etc.), arylsulfamoyl (eg, phenylsulfamoyl, etc.), and the like.

The hydrogen atom of hydrazine may be substituted with a substituent such as a sulfonyl group (eg, methanesulfonyl, toluenesulfonyl, etc.), an acyl group (eg, acetyl, trifluoroacetyl, etc.), an oxalyl group (eg, ethoxalyl, etc.).

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

Margin below 3-]1 C21～■.

*-NHNHCOC(,CH,C00C,H.

C, I-1.

*-N)IN)1cc820C11,CI(,0CIL
CH20) 1 Next, a synthesis example of compound 3-5 will be described.

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

The compounds represented by the general formulas [1], [2] and [3] of the present invention are present on a light-sensitive silver halide emulsion layer and/or on a support that can diffuse and migrate into the emulsion layer at least until the time of development. It may be contained in at least one of the other coating layers.

General formula [1], [2].

The addition m of the compound represented by [3] is suitably in the range of 5 x 10-7 to 5 x 10'' moles per 1 mole of silver halide, preferably 5 x 1 mole per 1 mole of silver halide.
The range is from 0-5 to 1X10-2 moles. The appropriate amount can be arbitrarily determined by considering the composition of silver halide, particle size, chemical ripeness, amount of hydrophilic colloid as a binder, and balance with additives such as stabilizers, inhibitors, and accelerators. .

The compounds represented by the general formulas [1, [2], and [3] of the present invention can be prepared by dissolving them in an organic solvent and then adding them to a silver halide emulsion, or by dissolving the compounds in an organic solvent. There is a method in which the solution is added to a gelatin solution or a hydrophilic colloid matrix solution such as a gelatin derivative, and then added to a silver halide emulsion. Various organic solvents can be used for this development, but
Preferred solvents are alcoholic solvents, particularly methanol.

The laminated silver halide grains of the present invention are formed in the presence of an iridium salt. The iridium salt is added at the time of particle formation, physical ripening, chemical ripening, or thereafter. In order to incorporate more iridium salt into the surface layer of silver halide grains, physical ripening is preferred.

The iridium salts used here are water-soluble iridium salts or iridium complex salts, such as iridium trichloride, iridium tetrachloride, potassium hexachloroiridate (III), potassium hexachloroiridate (rV), and ammonium hexachloroiridate (IIT). That is.

The laminated silver halide grains of the present invention include No. 10 Silver Saponide No. 1
It is formed in the presence of 1X10-2 to 1X10-'' mol per mole of iridium salt, particularly preferably from IX10-' to 1X10-' mol. Although it may be present anywhere, it is preferably present in the surface layer.

The laminated silver halide grains of the present invention comprising at least two layers include, for example, an inner core made of silver bromide or silver iodobromide, a first coating layer made of silver iodobromide outside the inner core, and a first coating layer made of silver iodobromide outside the inner core. A second coating layer made of silver iodobromide may be provided on the outside of the first coating layer. In the laminated silver halide grains of the present invention, the iodine content of the first coating layer or the second coating layer or the iodine content of the internal core is 10 mol% or less, more preferably 5 mol% or less. A silver halide emulsion containing grains is used.

In the present invention, the grain surface layer refers to the first coating layer when the grain is composed of an inner core and a first coating layer made of silver iodobromide on the outside thereof, and also refers to the first coating layer. When a second coating layer made of silver iodobromide is further formed on the outside, this second coating layer is referred to.

When using a silver halide grain consisting of an inner core, first and second coating layers, or an inner core and a first coating layer as described above, the inner core and each layer are preferably as follows. That is, as for the halogen composition of the internal core, the average content of iodine is preferably 10 mol% or less,
More preferably 0 to 5 mol%, particularly preferably 0
~3 mol%. The ratio of silver in the inner core to the total silver in the particles is preferably 1.0 mol % or more.

When the inner core and/or the first coating layer and/or the second coating layer consists of silver iodobromide, it is not necessary that it be homogeneous, but it is more preferable that it be a homogeneous silver iodobromide. . Further, in order to sufficiently cover the first coating layer, the average thickness of the second coating layer is preferably 0.02 μm.
m or more, more preferably 0.004 μm or more.

The proportion of silver halide grains contained in the emulsion layer containing the silver halide grains as described above may be arbitrarily selected;
For example, the silver amount is preferably 4
It is 0% or more, particularly preferably 90% or more.

The inner core of the above silver halide grain is shown in the graphic (
P. Glafkides), Chimie et Phys Photographic (Chimie et Phys Photography)
iquePhotographique) (Pau
(Published by Monte 1, 1967), Photographic Emulsion Chemist (Photograph
hic Emulsion Chemistry) (
The Focalpress, 1966), V.L. Zelikman et al.
et al), Making and Collating
Photographic Emulsion (Making a
nd Coating Photographic E
mul5ion) (The Focal Pres.
s, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. good.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method in which pΔg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Particles in which the iodine content on the particle surface is higher than that inside the particle can be obtained by performing halogen conversion with an iodine compound.

The iodine compound may be added at any point from the 95% point of grain formation to the end of grain formation, before the start of draft removal, after desalting, before the start of chemical ripening, or after the end of chemical ripening, preferably after the end of desalting. Before, preferably before the start of desalting. The amount added is between 0.1-1.0g/Agmo, p.
Preferably 03-08g/Δgmop, particularly preferably 0.5-0.7g/Agm0! It is.

When developing the silver halide photographic light-sensitive H material of the present invention, a 3-pyrazolidone compound and a di- or trihydroxybenzene compound may be included in the developer.

The 3-pyrazolidone compound contained in the developer is represented by the following formula.

R1 In the formula, R41 represents an optionally substituted aryl group, and R42+ R< 3 and R44 each represent a hydrogen atom or an optionally substituted alkyl group.

Examples of substituents for the aryl group represented by R41 include groups such as a methyl group, a chloro group, an amino group, a methylamino group, an acetylamino group, a metquine group, and a methylsulfonamidoethyl group.

Examples of the aryl group represented by R11 include phenyl group, p-aminophenyl group, p-chlorophenyl group, p-
-acetamidophenyl group, p-methoxyphenyl group, etc.

The alkyl group represented by R42, R, 3 and R44 is
Can be straight chain, branched, or cyclic, preferably with 1 carbon number
~8, and its substituents include, for example, a hydroxy group,
Examples include a carboxy group and a sulfo group, such as a methyl group, a hydroxymethyl group, an ethyl group, and a propyl group.

Typical specific examples of the above 3-pyrazolidone compound are shown below.

[A-1] 1-phenyl-3-pyrazolidone [A-
2 1-phenyl-4,4-dimethyl-3-pyrazolidone [A-3] 1-phenyl-4-methyl-4-hydroxymethyl [A-4 1-phenyl-4,4-di(hydroxymethyl) -3-pyrazolidone [Δ-5] 1-phenyl-5-methyl-3-pyrazolidone [A-6] 1-phenyl-4,4-dimethyl-3-
Pyrazolidone [A-7] 1-P-chlorophenyl-4-methyl-
4-Propyl-3-pyrazolidone [A-8] 1-P-chlorophenyl-4-methyl-
4 [Δ-9] 1-P-acetamidophenyl-4゜4
-diethyl-3-pyrazolidone [8-10] 1-P-methoxyphenyl-4,4
-Diethyl-3-pyrazolidone The 3-pyrazolidone compound has a development lry 1 (0 per 2
, 01g to 20g is added to the developer solution.

The di- or trihydroxybenzene compound contained in the developer of the silver halide photographic film t-:) of the present invention is represented by the following formula.

In the above formula, R511R62 and R53 are each a hydrogen atom, a halogen atom, an alkyl group (including a substituted alkyl group), an aryl group (including a substituted aryl group)
, heterocyclic group (including substituted heterocyclic group), OR5
4 or -S-R, 4. R represents a hydrogen atom, an alkyl group (including substituted alkyl groups), an aryl group (including substituted allyl groups), or a heterocyclic group (including substituted heterocyclic groups). n represents O or 1.

Specific examples of the above di- or trihydroxybenzene compounds are shown below.

[B-1] Hydroquinone [B-2] Chlorohydroquinone [B-3]
Bromohydroquinone [B-4] Methylhydroquinone [B-5] 2,3-Dichlorohydroquinone [B
-6] 2.5-henzoylaminohytroquinone [B-7] Gallic acid butyl ester [B-8]
Ethyl gallic acid ester The dihydroquinbenzene compound contained in the developer used in the silver halide photographic light-sensitive material of the present invention is most preferably hydroquinone, which is a developing agent widely used in photographic processing, and the amount added is usually It is 0.05 to 0.05 mol/f.

Furthermore, as the sulfite contained in the developer used in the silver halide photographic light-sensitive material of the present invention, those commonly used in the developer of silver halide photographic light-sensitive materials can be used, and specific examples thereof include: Examples include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and sodium formaldehyde bisulfite. The concentration may be as long as it can provide a sufficient sulfite ion concentration to protect the developing solution from air oxidation and thereby provide stable photographic performance, and the amount added is 0.005 mol/r.
The amount is preferably 0.15 mol/litre or more.

Furthermore, the developing solution used for the silver halide photographic photosensitive abrasive of the present invention contains an amino compound for the purpose of promoting high contrast, and particularly for the purpose of exhibiting a strong effect even at a relatively low pH level of the developing solution. be able to. Amino compounds useful in this invention include both inorganic and organic amines. Organic amines include aliphatic amines, aromatic amines,
It can be a cyclic amine, a mixed aliphatic-aromatic amine or a heterocyclic amine. 1st. Secondary and tertiary amines and quaternary ammonium compounds have all been found to be effective.

Particularly preferred alkanolamines for the purposes of the present invention are represented by the formula:

In the above formula, R61 is a hydroxyalkyl group having 2 to 10 carbon atoms, and R6□ and R63 are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and 2 to 10 carbon atoms, respectively. a hydroxyalkyl group, a benzyl group, or a group of the following formula having 1 to 1 carbon atoms, n in the above formula is an integer of 1 to 10, and X and Y are each a hydrogen atom, 1 to 10 carbon atoms. or a hydroxyalkyl group having from 2 to 10 carbon atoms.

Another preferred class of amino compounds is the alkylamines, especially those represented by the formula:

In the above formula, R64 is an alkyl group having 1 to 10 carbon atoms, and R65 and R66 are each a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

Among the many amino compounds that can be used in developing the silver halide photographic material of the present invention, representative examples are listed below.

[C-1] [(,2] [C-3 [C-4] [C-5] [C-6] [C-7] [C-8] [C-9] [C-1, 0] [C-11] [C-12] [C-13] [C-14] [C-+5co[C-16] Triethanolamine jetanolamine ethanolamine 2-diethylamino-1-ethanol 2-methyl Amino-1-ethanol 3-diethylamino-1-propatol 5-amino-1-pentanoldiethylamine triethylamine cyisobrobylamine 2-dibutylaminoethanol 1-4-chlorohexane bis(methylamine) 0-aminobenzoic acid aminobua Nidine sulfite 4-amino-1-butanol 3-Viroline-1,2-propanediol [C-17 3-(dimethylamino)-1,2-propanediol [C,18] 1,4-Piperazino bis(ethanesulfonic acid) ) [C-19] 3-Piperidino-1,2-propanediol The amount of the amino compound used in developing the silver halide photographic material of the present invention is 001 to 10.
Mol/! It is preferably in the range of 001 to 004 mol/.

Furthermore, the developer used in the present invention contains 5 (or 6)
)-nitroindazole is preferably contained.

This is the most effective method for preventing fog, and high sensitivity and high contrast are maintained. The amount added is 0.0 per developer.
A range of 0.001 to 0.01 mol is suitable.

The developer used in the present invention may contain a 3-birazoliton compound or an ortho- or p-aminophenol compound as a developer in addition to the cyclohexene-based compound. The pTI of the developer is preferably 10 to 12, but in order to maintain the pTI of pI-1, an alkali metal hydroxide or carbonate may be added as an alkali agent. Furthermore, in order to suppress the occurrence of fog during development, inorganic inhibitors such as potassium bromide, triazole compounds such as 5-methylbenzotriazole and 5-talolopenzotriazole, and 2-mercaptobenzimidazole, 1
Organic antifoggants such as mercapto compounds such as -phenyl-5-mercaptotetrazole can be used.

Further, in addition to the above-mentioned components, arbitrary additives can be used in the developer used in the present invention depending on the purpose.

Examples include solvents, buffers, sequestering agents, development accelerators, viscosity agents, and emulsion layer swelling inhibitors.

Examples of the development accelerator used in the present invention include compounds represented by the following general formula.

R7,-0(CH2CH20)nT-1 [in the formula R'11
represents a hydrogen atom or an aromatic ring that is unsubstituted or has a substituent, and n represents an integer from 10 to 200. ] More preferable than the compounds represented by the above general formula, specific examples are listed or limited to these (Iv).

D I HO(CH2CH20)nHn=10
D2HO(CH2CH20)nHn=3
0D −3HO(CH2CH20)nHn= 50D
-4HO(CH2CH2O)nHn= 70D 5
HO(CHiCHzO)nHn= 150D
6 HO(CH2CH20)nHn=200 or less Margin D-1 D-13 These compounds are commercially available and can be easily obtained. These compounds are preferably added in an amount of 0.01 to 40 mol per mol of silver halide, and more preferably 0.02 to 2 mol.

Further, two or more types of compounds having different values of n may be included.

Various silver halides can be used in the silver halide emulsion of the silver halide photographic light-sensitive material used in the present invention. Examples include silver chloride, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide. In particular, the effect of the present invention is remarkable for silver bromide and silver iodobromide, with less silver iodide (AgI
(5 mol% or less) is particularly effective for highly sensitive photosensitive materials.

The silver halide emulsion used in the present invention may be prepared by suspending the silver halide emulsion in a hydrophilic colloid by a known method, such as a neutral method, a single jet method using an ammonia method, a double jet method, etc. Emulsion preparation method is used.

The silver halide contained in the silver halide emulsion layer of the light-sensitive material used in the present invention has an average grain size of 0.1-1.
．． 0 μm, particularly preferably 0.1 to 0. '1prn,
and at least 75% of the total number of particles, particularly preferably 80
% or more preferably contains silver halide having a grain size of 0.7 to 1.3 times the average grain size.

In the present invention, particles having substantially no twin planes are defined as
A particle in which all or a majority of its surfaces are (100) planes.

Further, after desalting, the pAg to be adjusted is preferably in the range of 90 to 65, more preferably 90 to 80. For pAg adjustment, either potassium bromide or potassium iodide is used, and potassium iodide is more preferred.

Furthermore, polyvalent metal ions (e.g. iridium, rhodium, etc.)
U.S. Patent Box 3 as an occluded silver halide emulsion
, No. 271.157, No. 3,447,927, No. 35
Emulsions such as those according to No. 31.291 can also be used. Silver halide emulsions can be chemically sensitized using conventional sulfur compounds, gold compounds such as chlorauric acid salts, gold trichloride, and the like.

The silver halide emulsion to which the present invention is applied can be imparted with color sensitivity in a desired wavelength range by using a sensitizing dye.

As the sensitizing dye, commonly used dyes such as cyanine, hemicyanine, rhodacyanine, melonanine, oxanol, hemioxonol, methine dyes and styryl dyes can be used.

The above dyes are disclosed in U.S. Pat. Nos. 2,742,833 and 2,7.
No. 56,148, No. 3,567.458, No. 3.61
No. 5,517, No. 3.615519, No. 3,632,
No. 340, No. 3, 1.55, 519, No. 3.3844
No. 85, No. 4,232,115, No. 3,796,58
Reference may be made to the descriptions in No. 0, No. 4.028110, No. 3,752,673, and Japanese Patent Application Laid-open No. 45015/1983.

The silver halide photographic emulsion of the light-sensitive material used in the present invention contains aldehydes (formaldehyde, glyoxal, glutaraldehyde,
mucochloric acid, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), activated vinyl compounds (1,3,5-1-lyacryloyl-hexahydro-s) - triazine, bis(vinylsulfonyl) methyl ether, etc.), active halokenides (2,4-dichloro-6-human pheasant-5-1-lyascine, etc.), etc. can be used alone or in combination; Commonly used adhesives, matting agents, coating aids, etc. can be used. Further, as the binder, a commonly used hydrophilic binder having protective colloidal properties can be used.

Furthermore, according to the purpose, the photosensitive material 1 may contain commonly used substances such as a fogger, an ultraviolet absorber, a fluorescent whitening agent, an image stabilizer, an antioxidant, a lubricant, a sequestering agent, an emulsifying dispersant, etc. Can be added.

For photosensitive + and <h used in the present invention, layers other than the silver halide emulsion layer include a protective layer, an intermediate layer, a filter layer, an antihalation layer, a subbing layer, an auxiliary layer, a ylang ion prevention layer, and a backing layer. The support to be used may be appropriately selected from baryta paper, polyethylene-coated paper, cellulose acetate, cellulose nitrate, polyethylene terephthalate, etc., depending on the intended use of the photosensitive material.

The dimensional stability of photographic materials can be improved by adding a polymeratex consisting of a homo- or copolymer of alkyl acrylate, alkyl methacrylate, acrylic acid, glycidyl acrylate, etc. to the photosensitive silver halide emulsion layer or other coated layer on the support. , may be included for the purpose of improving the physical properties of the film.

4-Hydroxy-6-methyl-1°3.3a,7- as a stabilizer or antifoggant in the photosensitive silver halide emulsion.
Many compounds such as citrazaindene, 1-phenyl-5-mercaptotetrazole, resorcinol oxime, hydroquinone aldoxime and others can be added in amounts of 10@-4 to 10@-1 mole per mole of silver halide.

[Examples] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example 1 Silver halide emulsion A of the present invention was produced as follows.

First, nitric acid was added to the protected ceratin kept at 46°C to adjust the pH. This liquid was used as a mother liquid and added in a conventional double et method. In this case, pH and pAg were controlled to pl-1 = 2.0 and pAg = 8.17, respectively, to form a pure silver bromide layer. Then pl-1=2.0, I)A
The particles were grown so that the total AgBr/T content was 98/2 mol% by controlling g = 7.92, and when the particle formation was 89% complete, iridium chloride 8 x 10-7
After mop/Ag-mob is added and particle formation is completed, halogen conversion is performed using KI to raise pAg to 839.

This emulsion A was a cubic crystal with an average grain size of 024 μm, and the silver iodide content of the entire grain was about 2 mol % of Il1 dispersed grains. Thereafter, modified seratin (exemplified compound G-8 of Japanese Patent Application No. 1-180787) was added, and the mixture was washed with water and desalted in the same manner as in Example 1 of the same patent application. Further, during redispersion, a mixture of the following compounds [A], [B] and [C] was added.

FA] rB] fc]
(Preparation of silver halide photographic light-sensitive material) Undercoat layer with a thickness of 01 μm on both sides (Japanese Patent Laid-Open No. 59-19941
Second, a silver halide emulsion layer of the following formulation (1) was added to a gelatin amount of
g/m, silver Ji 3.2 g/m, and on top of that, a protective layer of emulsion of the following formulation (2) is applied with a gelatin group or 1
．． It was coated so that it was 0 g/m. Moreover, on the other undercoat layer on the opposite side, a backing layer of the following formulation (3) is coated at a gelatin density of 2.4 g/rn', and on top of that, a backing protective layer of the following formulation (4) is applied. If the amount of gelatin is 1. , painted so that it becomes Og/r&, test 14 No.
1 to 16 were obtained.

Prescription (I) (Silver halide emulsion layer composition) Gelatin
2.0 g/m Silver halide emulsion A of the present invention Silver amount 3.2 g/m Sensitizing dye: 8 mg/rn'
O30 SO9・N(C2H5)3 stabilizer, 4-methyl-6-hy3a,7-te)・razaindene capri inhibitor, adenine surfactant, saponin:S-1 troquine], 3゜30mg/n1 '+omg/bo 0.1g/- 8mg/n? Compound of general formula [1], [2] or [3] of the present invention ■ Latex polymer shown in Table 1 1 g/m-fCJ-1-CIN-v
,, Kano CH2-C Shakushichi TC○○C, I-1,0C
OC11゜Polyethylene glycol molecule m 4000 Hardener H-1
: 0.1g/rr? 60mg/+n Na Length Prescription (3) (Banking layer composition) Prescription (2) (Emulsion protective layer) Gelatin surfactant S 2 : 0.9g/r & 10mg/CH2C○OCH, (C,H,)C, H.

CHCOOCf(2CH(C2Hs)C+fl.

0JNa matting agent, silica hardener with average particle size of 35μm, formalin 3mg/bo 30mg/m Seratin 2.4g/rn' Surfactant: Saponin 01g/S-16m resistance
g/m Prescription (4) (Hasoking protective layer) Gelatin 1g/m2 Matting agent, polymethyl methacrylate with average particle size 30-50μm 50mg/m Surfactant: S -21On+g/rr? Hardener, glyoxal 25mg/H-135mg/rn
' The obtained sample was tightly attached with a step wedge and heated at 3200°C.
After being exposed to K tungsten light for 5 seconds, processing was carried out under the following conditions using an automatic developing machine for rapid processing into which a developer and a fixer having the compositions shown in Table 1 were introduced.

Developer prescription Developer solution Ethyleneaminetetraacetic acid sulfur/lium salt 1g Sodium sulfite 60g Trisodium phosphate (1decahydrate) 75g Hydroquinone hydroxide sulfur/lium 3-(dimethylamino)-1,2 propanediol NN- Diethylethanolamisodium bromide 5-methylbenzotriazole l-phenyl-5-mercap) 25g g 15g g 25g) Rasol 08g 1-phenyl-44-dimethyl 3-pyrazolidone 0.2g phenylpicolinium bromine Add mite water to 12p HI
1, 7 Fixer formulation (8Jl composition Δ) Ammonium thiosulfate (725% ■TsuV aqueous solution) Sodium sulfite 40d 7g Sodium acetate trihydrate Boric acid Sodium citrate dihydrate (composition) Pure water (ion Exchange water) Sulfuric acid (50% W/V aqueous solution) Aluminum sulfate 6.5 g g g 7 mg 4.7 g (Aqueous solution with 81% W/V content calculated on Hari 203) 65 g When using the fixer, add the above in 500 d of water. They were melted in the order of composition A and composition 12 and used. This fixer p
H was adjusted to 48 with acetic acid.

(Development processing conditions) (Process) (Temperature) (Time) Development
Fixing at 40°C for 5 seconds Washing at 35°C for 15 seconds Drying at 30°C for 10 seconds
The developed sample obtained at 50°C for 10 seconds was transferred to a Konica digital densitometer P.
It was measured with DA-65, and the sensitivity at the concentration 30 of sample No. 1-1 was set as 100, and the phase and J sensitivity were expressed, and the gamma was expressed as the tangent between the concentrations 03 and 30.

Further, the obtained sample was subjected to a halftone quality test using the method described below.

(Testing method for halftone dot quality) A halftone screen (150 lines/inch) with a halftone dot area of 50% is attached to a step wedge, and the sample is placed in close contact with this screen and exposed for 5 seconds to a xenon light source. The sample was developed under the above conditions in an automatic developing machine for rapid processing into which the developer and fixer were charged, and the halftone dot quality of the sample was reduced to 1.
Observe with 00x Roubaix and rate the one with high halftone quality as "5"
The following five ranks were given: [4], [3], [2], and [1]. Note that ranks "1" and "2" are levels that are not preferred in practice.

The black spots in the halftone dots are evaluated in the same way, and the highest rank is "5" when there are no black spots in the halftone dots, and the rank is "5" depending on the degree of occurrence of black spots in the halftone dots. 4", "
3", "2", and rlJ, and their ranks were sequentially lowered for evaluation. In addition, in ranks "1" and "2", the black spots are also large and are at a level that is not desirable for practical use.

The following compounds (a) to (c) were used as comparative compounds added to the silver halide emulsion layer in formulation (1).

(a) A 5-level evaluation was performed, with the largest change being ranked 1 and the no density change being ranked 5.

Rank 4 is a level that poses a problem in practice.

The results of Example 2 are shown in Table 1.

As is clear from Table 1, Sample 1-1N according to the present invention.

1-6 to 1-15 are comparative samples 1-1 to 1-5 and 1-1
It can be seen that the sensitivity is high for 6, the contrast is high, the quality of vertical dots and black edges are good, and the pressure resistance is also good.

Regarding the margin pressure resistance below, for these test E+, 95% J
After IWJ photography was performed, the exposed sample was bent under a constant pressure and developed. Concentration by Pressure Example 2 The same procedure as in Example 1 was carried out except that the sample used in Example 1 was treated with a developer having the following formulation.

The results are shown in Table 2.

Disaster syndrome Biho Hydroquinone 22.5 g Mel 025 g Ethylenediaminetetraacetic acid 10 g Sodium sulfite
750g sodium hydroxide
7.9 g trisodium phosphate (decahydrate)
75.0g5-methylbenzotriazole
025gN, N-ethylethanolamine 125-
Add water and 1! and the pH was adjusted to 11.6.

The results of the above examples are shown in Table 2.

As is clear from the results in Table 2, the samples according to the present invention, similar to Example 1, have higher sensitivity, higher contrast, and better halftone dot quality and black shading than Comparative Sample 1.

Example 3 The physically ripened emulsion used in Examples 1 and 2 was sulfur sensitized according to a conventional method. Then, as a stabilizer, 6-methyl-4-
Hydroxy-1,3,3a,7-titrazaindene was added, the mixture was divided as shown in Table 3, a hydrazine compound was added, and the same formulation as in Example 1 was applied. The resulting sample was given a 10-' second exposure and processed according to Example 1. The results are shown in Table 3.

As is clear from the results in Table 3, the samples of the present invention also exhibit excellent performance in terms of high illumination characteristics.

[Effects of the Invention] According to the present invention, it was possible to provide a silver halide photographic material that has high contrast, excellent halftone dot quality, and high sensitivity even through rapid processing. Further, the silver halide photographic light-sensitive material of the present invention had less black spots and was excellent in pressure resistance.

Claims (1)

[Scope of Claims] A silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer on a support, wherein at least one of the silver halide photographic emulsion layers is prepared in the presence of an iridium salt. The grains contain a silver halide emulsion consisting of laminated silver halide grains consisting of at least two layers in which the silver iodide content of the grain coating layer is higher than the silver iodide content of the grain inner core. , and further the following general formula [1] in the silver halide photographic emulsion layer or other hydrophilic colloid layer:
A silver halide photographic material containing at least one compound represented by [2] or [3]. General formula [1] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 and R_2 each represent an aryl group or a heterocyclic group, R represents an organic bonding group, and n is 0 to 6
, m represents 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 a ring oxy group, an amino group, or an aryloxy group, and P_1 and P_2 each represent a hydrogen atom, an acyl group, or a sulfinic acid group.) General formula [3] ▲ Contains numerical 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.)