JPH04275541A - Silver halide photographic sensitive material and its processing method - Google Patents

Abstract

PURPOSE:To provide the silver halide photographic sensitive material for making a printing plate high in sensitivity and contrast and superior in storage stability and small in black spots trouble even in the case of rapid processing within a developing time of <=15sec. CONSTITUTION:The silver halide photographic sensitive material is provided on a support with at least one of silver halide emulsion layers, and this layer or another hydrophilic colloidal layer contains a specified hydrazine derivative and this silver halide emulsion is composed of monodispersed silver halide grains containing >=50mol% of silver chloride prepared in the presence of a rhodium salt or its complex salt, and a specified sensitizing dye and a development inhibitor. This photosensitive material is characterized by the black-and- white developing method within a developing time of 15sec using a developing solution having a pH of <=11.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material for printing plate making, and more particularly to a silver halide photographic light-sensitive material that exhibits ultra-high contrast even when rapidly developed and has few failures.

0002

BACKGROUND OF THE INVENTION The photolithography process involves converting a continuous tone original into a halftone image. In this process, contagious development has been used as a photographic technique capable of reproducing ultra-high contrast images.

The lithium-type silver halide photographic material used for infectious development has, for example, an average grain size of about 0.2 μm, a narrow grain distribution and a well-shaped grain, and a high content of silver chloride (at least (50 mol% or more) silver chlorobromide emulsion. By processing this lithium-type silver halide photographic light-sensitive material with an alkaline hydroquinone developer having a low sulfite ion concentration, a so-called lithium-type developer, images with high contrast, high sharpness, and high resolution can be obtained.

[0004] However, these lithium-type developers have extremely poor storage stability because they are susceptible to air oxidation.
It is difficult to maintain constant development quality during continuous use. A method of quickly obtaining a high-contrast image without using the above-mentioned Lith type developer is known. For example, as seen in JP-A-56-106244, a hydrazine derivative is contained in a silver halide photographic light-sensitive material. According to these methods, high-contrast images can be obtained even by processing with a developing solution that has good preservability and can be processed quickly.

[0005] In these techniques, in order to fully exhibit the high contrast properties of hydrazine derivatives, a pH of 11.0 or higher is required.
had to be processed with a developer containing H. pH
In a high pH developer of 11.0 or more, the developing agent is likely to be oxidized when exposed to air. Although it is more stable than Lith developer, due to oxidation of the developing agent, it is often impossible to obtain ultra-high contrast images. In order to compensate for this drawback, JP-A-63-2
No. 9751 and European Patent No. 333,435, 3
No. 45,025, etc., discloses a silver halide photographic light-sensitive material containing a high contrast agent that can achieve high contrast even in a developer having a relatively low pH.

Furthermore, recently LEDs, He
-Ne lasers, semiconductor lasers, etc. have been developed and put into practical use, and panchromatic sensitizing dyes are used to accommodate these. However, when a hydrazine compound and a panchromatic sensitizing dye are included, and the silver chloride content exceeds 50%, failures called black spots are likely to occur, storage stability is deteriorated, and the development time is less than 15 seconds. Such rapid development causes problems such as a decrease in sensitivity and loss of contrast, and there is a need to solve these problems.

[0007]

OBJECTS OF THE INVENTION In order to solve the above-mentioned problems, the first object of the present invention is to provide a silver halide photographic material for printing plate making that has high sensitivity, high contrast, and excellent storage stability. The object of the present invention is to provide a silver halide photographic material with fewer black spot defects. A third object is to provide a silver halide photographic material in which the above object is achieved even in rapid processing with a developing time of 15 seconds or less.

[0008]

[Structure of the Invention] The first and second objects of the present invention are to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support. The layer contains a hydrazine derivative represented by the following general formula [H], and the silver halide emulsion is in the presence of 1 x 10-9 to 1 x 10-5 mol of rhodium salt or rhodium complex salt per mol of silver. consisting of monodisperse silver halide grains with a chlorine content of 50 mol% or more prepared by
And this can be achieved by a silver halide photographic material characterized by containing a sensitizing dye represented by the following general formula [D]. Further, in the above silver halide emulsion, it is preferable that the emulsion layer or other hydrophilic colloid layer further contains a compound that suppresses development.

[0009]

[C6]

[In the formula, A represents an aryl group or a heterocyclic group containing at least one sulfur atom or oxygen atom, and G represents a -(C(O))- group, a sulfonyl group, a sulfoxy group, -
Represents a P(O)(R)- group or an iminomethylene group, and n
represents an integer of 1 or 2, A1 and A2 are both a hydrogen atom, one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted acyl group, R is a hydrogen atom, Represents an alkyl group, aryl group, alkoxy group, aryloxy group, amino group, carbamoyl group, oxycarbonyl group or -O-R3 group, R3
represents an alkyl group or a saturated heterocyclic group. ]

[0011]

[C7]

[In the formula, Y1 and Y2 each represent a sulfur atom or a selenium atom (except that Y1 and Y2 are both selenium atoms). R1 and R2 each represent a lower alkyl group or an alkyl group having a sulfo group, and R3 represents a lower alkyl group. A and B each represent a nonmetallic atomic group necessary to complete the naphthothiazole ring, benzothiazole ring, naphthoselenazole ring, or benzoselenazole ring. X- represents an anion, and m represents 0 or 1. [Furthermore, the third objective is to develop a silver halide photographic material having at least one silver halide emulsion layer on a support with a developer having a pH of 11.0 or less for a period of 1 time after image exposure.
In a black and white image forming method in which processing is performed in 5 seconds or less, the emulsion layer or other hydrophilic colloid layer contains a hydrazine derivative represented by the general formula [H] according to claim 1 and the following general formula [1] or [ contains at least one compound selected from [2] and a compound represented by the general formula [3], and the silver halide emulsion consists of monodisperse silver halide grains having a chlorine content of 50 mol% or more, and General formula described in item 1 [D
] This is achieved by a silver halide photographic material characterized by containing a sensitizing dye represented by the following.

[0013]

[Chemical formula 8]

[In the formula, Y represents a group adsorbed to silver halide. X represents two linking groups consisting of atoms or atomic groups selected from hydrogen atoms, carbon atoms, nitrogen atoms, and oxygen atoms. A represents two linking groups. B represents an amino group, an ammonium group, or a nitrogen-containing heterocycle, and the amino group may be substituted. m represents 1, 2 or 3, and n represents 0 or 1. ]

[0015]

[Chemical formula 9]

[In the formula, R1 and R2 each represent a hydrogen atom or an aliphatic residue. R1 and R2 may be combined with each other to form a ring. R3 represents a divalent aliphatic group. X represents a divalent heterocycle containing nitrogen, oxygen or sulfur atom. n represents 0 or 1, M is a hydrogen atom, an alkali metal,
Represents an alkaline earth metal, a quaternary ammonium salt, a quaternary phosphonium salt, or an amidino group. ]

[0017]

[Chemical formula 10]

[In the formula, Y represents a hydrogen atom or a mercapto group, and R represents a hydrogen atom, a halogen atom, a nitro group, an amino group, a cyano group, a hydroxyl group, a mercapto group, a sulfo group, or a substituted or unsubstituted alkyl group. , substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group,
Represents a substituted or unsubstituted aryl group, substituted or unsubstituted alkoxy group, hydroxycarbonyl group, alkylcarbonyl group or alkoxycarbonyl group. 〕below,
The present invention will be explained in detail.

The hydrazine derivative represented by the general formula [H] used in the present invention will be explained.

In the formula, A represents an aryl group or a heterocyclic group containing at least one sulfur atom or oxygen atom, and G represents -(
C(O))n-, sulfonyl group, sulfoxy group, -P(
O)(R)- group or iminomethylene group, n is 1
or 2, A1 and A2 are both a hydrogen atom, one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted acyl group, and R is a hydrogen atom or an alkyl group. , aryl group, alkoxy group, aryloxy group, amino group, carbamoyl group,
It represents an oxycarbonyl group or an -O-R3 group, and R3 represents an alkyl group or a saturated heterocyclic group.

Further, the following general formulas [A] and [B] are preferred.

[0022]

[Chemical formula 11]

In the formula, A represents an aryl group or a heterocyclic group containing at least one sulfur atom or oxygen atom, and n represents an integer of 1 or 2. When n=1, R1 and R2 are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or a hetero group. Represents a ring oxy group, R1 and R
2 may form a ring together with the nitrogen atom. When n=2,
R1 and R2 are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a saturated or unsaturated heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or a heterocyclic group. represents a group. However, when n=2, R1 and R
At least one of 2 represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or a heterocyclic oxy group. R3 represents an alkynyl group or a saturated heterocyclic group. General formula [A] or [
The compound represented by B] includes those in which at least one H of -NHNH- in the formula is substituted with a substituent.

More specifically, A, R1, and R2 have the same meanings as those described in Japanese Patent Application No. 2-222638. H in -NHNH- in general formulas [A] and [B], that is, the hydrogen atom of hydrazine, is a sulfonyl group (e.g., methanesulfonyl, toluenesulfonyl, etc.), an acyl group (e.g.,
acetyl, trifluoroacetyl, ethoxycarbonyl, etc.), oxalyl group (e.g., ethoxalyl, pyruvoyl, etc.), and the general formula [A
] and [B] also include such compounds.

More preferred compounds in the present invention are compounds of general formula [A] where n=2, and compounds of general formula [B]
It is a compound of

In the compound of general formula [A] where n=2,
R1 and R2 are hydrogen atoms, alkyl groups, alkenyl groups,
Alkynyl group, aryl group, saturated or unsaturated heterocyclic group,
More preferably, the compound is a hydroxy group or an alkoxy group, and at least one of R1 and R2 represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group, or an alkoxy group.

Typical compounds represented by the above general formulas [A] and [B] include, for example, H-1 to H-187 described in JP-A-2-327402, pages 20 to 58; I-1 to I described in No. 2-17054, pages 23 to 32
-45 or the following compounds are preferably used.

[0028]

[Chemical formula 12]

[0029]

[Chemical formula 13]

[0030]

[Chemical formula 14]

[0031]

[Chemical formula 15]

[0032]

[Chemical formula 16]

Next, the sensitizing dye represented by the general formula [D] will be explained.

Examples of the lower alkyl group represented by R1 and R2 include methyl group, ethyl group, propyl group, butyl group, and examples of the alkyl group having a sulfo group include β-sulfoethyl group and γ-sulfopropyl group. group, γ-sulfobutyl group, δ-sulfobutyl group, sulfoethoxyethyl group, sulfopropoxyethyl group, and the like.

The lower alkyl group represented by R3 is:
Examples include methyl group, ethyl group, and propyl group.

A and B each represent a nonmetallic atomic group necessary to complete the naphthothiazole ring, benzothiazole ring, naphthoselenazole ring, or benzoselenazole ring,
These rings each contain a lower alkyl group (e.g., ethyl group, methyl group, etc.), an alkoxy group (e.g., methoxy group, ethoxy group, etc.), a hydroxyl group, an aryl group (e.g., phenyl group), an alkoxycarbonyl group (e.g., methoxycarbonyl group, etc.). group), halogen atoms (for example, chlorine atoms, bromine atoms, etc.), etc. are included. Note that the lower alkyl group may be substituted. Examples of naphthothiazole rings, benzothiazole rings, naphthoselenazole rings, and benzoselenazole rings completed by nonmetallic atom groups substituting these substituents are [1,2-d], [2,3
-d] and [2,1-d] naphthothiazole, benzothiazole, 5-methylbenzothiazole, 5-chlorobenzothiazole, 5-methoxybenzothiazole, 5-
Bromobenzothiazole, 5,6-dimethylbenzothiazole, 5-cyanobenzothiazole, 5-phenylbenzothiazole, 5-hydroxybenzothiazole, 5
-Hydroxy-6-methylbenzothiazole, 5-ethoxy-6-ethylbenzothiazole, 5-ethoxy-6
-butylbenzothiazole, 5-ethoxy-6-methylbenzothiazole, 5-carboxybenzothiazole,
[1,2-d], [2,3-d] and [2,1-d] naphthoselenazole, benzoselenazole, 5-methylbenzoselenazole, 5-chlorobenzoselenazole, 5
-methoxybenzoselenazole, 5-phenylbenzoselenazole, 5,6-dimethylbenzoselenazole, 5
-Hydroxybenzoselenazole, etc.

X- represents an anion commonly used in cyanine dyes, such as a halogen ion, benzenesulfonate ion, p-toluenesulfonate ion, etc.

m represents 1 or 0, and when R1 or R2 forms an inner salt, m represents 0. Specific examples of the sensitizing dye represented by the general formula [D] include, for example,
No. 14430, pages 9 to 14, No. The sensitizing dyes shown in Nos. 1 to 30 are preferably used. Representative examples are listed below.

[0039]

[Chemical formula 17]

[0040]

[Chemical formula 18]

The compound for suppressing and controlling the development of the present invention may be any compound as long as it can be added to the light-sensitive material to suppress sensitivity or fog, but specifically,

[0042]

[Chemical formula 19]

[0043]

[C20]

[0044] is preferred. The amount added is preferably 1.times.10@-1 to 1.times.10@-4 mol per mol of silver halide. The layer to be added may be either a silver halide emulsion layer or a hydrophilic colloid layer.

The compound represented by the general formula [1] will be explained below.

The group represented by Y which adsorbs to silver halide includes nitrogen-containing heterocyclic compounds.

When Y represents a nitrogen-containing heterocyclic compound, the compound of general formula [1] is represented by the following general formula [1a].

[0048]

[C21]

In the formula, l represents 0 or 1, m represents 1,
2 or 3, and n represents 0 or 1.

[(X)n-A-B]m is the general formula [2
], and Q represents an atomic group necessary to form a 5- or 6-membered heterocycle composed of at least one of carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms. Further, this heterocycle may be fused with a carbon aromatic ring or a heteroaromatic ring.

Examples of the heterocycle formed by Q include substituted or unsubstituted indazoles, benzimidazoles, benzotriazoles, benzoxazoles, benzthiazoles, imidazoles, thiazoles, oxazoles, tritezoles, Examples include tetrazoles, azaindenes, pyrazoles, indoles, triazines, pyrimidines, and quinolines.

M is a hydrogen atom, an alkali metal atom (eg, sodium atom, potassium atom, etc.), an ammonium group (eg, trimethylammonium group, dimethylbenzylammonium group, etc.), and under alkaline conditions, M=H or an alkali metal atom. It represents a diluent group (for example, an acetyl group, a cyanoethyl group, a methanesulfonylethyl group, etc.).

Further, these heterocycles include a nitro group, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), a mercapto group, a cyano group, a substituted or unsubstituted alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.). , t-butyl group, cyanoethyl group, methoxyethyl group, methylthioethyl group, etc.), aryl group (e.g. phenyl group, 4-
methanesulfonamidophenyl group, 4-methylphenyl group, 3,4-dichlorophenyl group, naphthyl group, etc.),
Alkenyl groups (e.g. allyl groups, etc.), aralkyl groups (
For example, benzyl group, 4-methylbenzyl group, phenethyl group, etc.), alkoxy group (e.g. methoxy group, ethoxy group, etc.), aryloxy group (e.g. phenoxy group, 4-methylbenzyl group, etc.),
-methoxyphenoxy group, etc.), alkylthio group (e.g. methylthio group, ethylthio group, methoxyethylthio group), arylthio group (e.g. phenylthio group), sulfonyl group (e.g. methanesulfonyl group, ethanesulfonyl group, p-toluenesulfonyl group) groups, etc.), carbamoyl groups (e.g., unsubstituted carbamoyl groups, methylcarbamoyl groups, phenylcarbamoyl groups, etc.), sulfamoyl groups (
For example, unsubstituted sulfamoyl group, methylsulfamoyl group, phenylsulfamoyl group, etc.), carbonamide group (for example, acetamide group, benzamide group, etc.), sulfonamide group (for example, methanesulfonamide group, benzenesulfonamide group) , p-toluenesulfonamide group, etc.), acyloxy group (e.g. acetyloxy group, benzoyloxy group, etc.), sulfonyloxy group (e.g. methanesulfonyloxy group, etc.), ureido group (e.g. unsubstituted ureido group, methyl ureido group, ethylureido group, phenylureido group, etc.), thioureido group (e.g., unsubstituted thioureido group, methylthioureido group,
etc.), acyl groups (e.g. acetyl group, benzoyl group, etc.), heterocyclic groups (e.g. 1-morpholino group, 1-piperidino group, 2-pyridyl group, 4-pyridyl group, 2-thienyl group, 1-pyrazolyl group) , 1-imidazolyl group, 2-tetrahydrofuryl group, tetrahydrothienyl group, etc.),
Oxycarbonyl group (e.g. methoxycarbonyl group, phenoxycarbonyl group, etc.), oxycarbonylamino group (e.g. methoxycarbonylamino group, phenoxycarbonylamino group, 2-ethylhexyloxycarbonylamino group, etc.), amino group ( For example, an unsubstituted amino group,
dimethylamino group, methoxyethylamino group, anilino group, etc.), carboxylic acid or its salt, sulfonic acid or its salt, hydroxy group, etc.

Examples of the divalent linking group represented by X include:

[0055]

[C22]

[0056] These linking groups have a straight chain or branched alkylene group (for example, methylene group, ethylene group, propylene group, butylene group, hexylene group, 1-methylethylene group, etc.) between Q and Q. ) may be connected via. R7, R8, R9, R10, R11, R1
2, R13, R14, R15 and R16 are hydrogen atoms,
Substituted or unsubstituted alkyl groups (e.g. methyl group, ethyl group, propyl group, n-butyl group, etc.), substituted or unsubstituted aryl groups (e.g. phenyl group, 2
-methylphenyl group, etc.), substituted or unsubstituted alkenyl group (e.g. propenyl group, 1-methylvinyl group,
etc.), or a substituted or unsubstituted aralkyl group (eg, benzyl group, phenethyl group, etc.).

A represents a divalent linking group, and examples of the divalent linking group include linear or branched alkylene groups (for example, methylene group, ethylene group, propylene group, butylene group, hexylene group, 1-methylethylene group, etc.), linear or branched alkenylene groups (e.g. vinylene group, 1-methylvinylene group, etc.), linear or branched aralkylene groups (e.g. benzylidene group, etc.), arylene groups (e.g. phenylene, naphthylene, etc.), etc. can be mentioned. In the above group represented by A, X and A may be further substituted in any combination.

The substituted or unsubstituted amino group of B is represented by the general formula [1b].

[0059]

[C23]

(In the formula, R11 and R12 may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, an alkenyl group, or an aralkyl group, and these groups is a straight chain (e.g. methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, allyl group, 3-putenyl group, benzyl group, 1-
(eg, naphthylmethyl group, etc.), branched (eg, isopropyl group, t-octyl group, etc.), or cyclic (eg, cyclohexyl group, etc.).

Furthermore, R11 and R12 may be linked to form a ring, in which one or more heteroatoms (
For example, it may be cyclized to form a saturated heterocycle containing an oxygen atom, a sulfur atom, a nitrogen atom, etc.
Examples include pyrrolidyl group, piperidyl group, and morpholino group. In addition, examples of substituents for R11 and R12 include carboxyl group, sulfo group, cyano group,
Halogen atoms (for example, fluorine atoms, chlorine atoms, bromine atoms), hydroxy groups, alkoxycarbonyl groups having 20 or less carbon atoms (for example, methoxycarbonyl groups, ethoxycarbonyl groups, phenoxycarbonyl groups, benzyloxycarbonyl groups, etc.), Alkoxy groups having 20 or less carbon atoms (e.g. methoxy group, ethoxy group, benzyloxy group,
phenethyloxy group, etc.), monocyclic aryloxy group having 20 or less carbon atoms (e.g., phenoxy group, p-tolyloxy group, etc.), acyloxy group having 20 or less carbon atoms (e.g., acetyloxy group, propionyloxy group, etc.), carbon number 20 or less acyl groups (e.g. acetyl group, propionyl group, benzoyl group, mesyl group, etc.), carbamoyl group (e.g. carbamoyl group, N,N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, etc.), sulfamoyl group (e.g. sulfamoyl group, N,N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group, etc.), carbon number 20
The following acylamino groups (e.g. acetylamino group, propionylamino group, benzoylamino group, mesylamino group, etc.), sulfonamide groups (ethylsulfonamide group, p-toluenesulfonamide group, etc.), carbonamide groups having 20 or less carbon atoms ( Examples include methylcarbonamide group, phenylcarbonamide group, etc.), ureido groups having 20 or less carbon atoms (eg, methylureido group, phenylureido group, etc.), and amino groups.

The ammonium group of B is represented by the general formula [1c].

[0063]

[C24]

(In the formula, R13, R14, and R15 are the same groups as R11 and R12 in the above general formula [2-b], and Z- represents an anion, such as a halide ion (for example, Cl-, Br- , I-, etc.), sulfonate ions (e.g. trifluoromethanesulfonate, paratoluenesulfonate, benzenesulfonate, parachlorobenzenesulfonate, etc.), sulfate ions (e.g. ethylsulfate, methylsulfate, etc.), perchlorate, tetra Examples include fluoroborate. p represents 0 or 1, and is 0 when the compound forms an inner salt.) The nitrogen-containing heterocycle of B is
It is a 5- or 6-membered ring containing at least one nitrogen atom, and these rings may have a substituent or be fused with another ring. Examples of the nitrogen-containing heterocycle include an imidazolyl group, a pyridyl group, and a thiazolyl group.

Among general formulas [1], preferred are the following general formulas [1m], [1n], [1o] or [1
p].

[0066]

[C25]

(In the formula, -(X)n-A-B, M, and m have the same meanings as those in the above general formula [1a]. Z1, Z2, and Z3 are -(X) in the above general formula [1a] n-A-
Synonymous with B, or halogen atom, alkoxy group having 20 or less carbon atoms (e.g. methoxy group), hydroxy group,
It represents a hydroxyamino group, a substituted or unsubstituted amino group, and its substituent can be selected from the substituents of R11 and R12 in the general formula [1b]. However, at least one of Z1, Z2 and Z3 is -(X)
It is synonymous with n-A-B.

[0068] These heterocycles may also be substituted with substituents applicable to the heterocycle of general formula [1].

The compound represented by the general formula [1] is described in I of JP-A-2-103536, pages (12) to (13).
Compounds I-1 to II-19 can be used. Representative examples of compounds are listed below.

[0070]

[C26]

[0071]

[C27]

Next, in the general formula [2], the aliphatic residues R1 and R2 are preferably alkyl groups, alkenyl groups and alkynyl groups each having 1 to 12 carbon atoms, each of which may be substituted with an appropriate group. Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, hexyl group, decyl group, dodecyl group, isopropyl group, se
Examples include c-butyl group and cyclohexyl group. Examples of the alkenyl group include allyl group, 2-butenyl group, 2-hexenyl group, and 2-octenyl group. Examples of the alkyl group include propargyl group and 2-pentynyl group. Examples of substituents include phenyl group, substituted phenyl group, alkoxy group, alkylthio group, hydroxy group, and carboxyl group. These include a sulfo group, an alkylamino group, an amide group, and the like.

[0073]

[C28]

Particularly preferred as R1 and R2 is an alkyl group having 1 to 3 carbon atoms, more preferably an ethyl group.

The divalent aliphatic group for R3 is preferably -R4- or -R4S-. Here, R4 is a divalent aliphatic residue, preferably a saturated or unsaturated residue having 1 to 6 carbon atoms, such as -CH2-, -CH2CH2-, -(CH2
)3-, -(CH2)4-, -(CH2)6-, -CH
2CH=CHCH2-, -CH2C≡CCH2-, -C
H2CH(CH3)CH2-, etc.

[0076] R4 preferably has 2 to 4 carbon atoms, and R4 is more preferably -CH2CH2- and -CH2CH2CH2. Note that n of (X)n is 0
R3 in the case represents only -R4-.

The heterocycle of X may be a 5- or 6-membered heterocycle containing nitrogen, oxygen or sulfur, and may be fused to a benzene ring. The heterocycle is preferably aromatic, such as tetrazole, triazole, thiadiazole, oxadiazole, imidazole, thiazole, oxazole, benzimidazole, benzothiazole, benzoxazole, and the like. Among these, tetrazole and thiadiazole are particularly preferred.

[0078] As the alkali metal of M, Na+, K+
, Li+, etc.

[0079] As alkaline earth metals, Ca++, M
g++, etc.

The quaternary ammonium salt of M has 4 to 30 carbon atoms, such as (CH3)4N+, (
C2H5)4N+, (C4H9)4N+, C6H5CH
2N+(CH3)3, C16H33N+(CH3)3, etc. As a quaternary phosphonium salt, (C4H9)
4P+, C16H3P+(CH3)3, C6H5CH2
P+(CH3), etc.

Examples of inorganic acid salts of the compound represented by formula [2] include hydrochloride, sulfate, and phosphate, and examples of organic acid salts include acetate, propionate, methanesulfonate, and benzene. Examples include sulfonate and p-toluenesulfonate.

The compound represented by the general formula [2] is described in I of JP-A No. 2-103536, pages (14) to (15).
II-1 to III-22 can be used.

Examples of typical compounds are listed below.

[0084]

[C29]

[0085]

[C30]

Next, typical examples of the compound represented by the general formula [3] will be shown, but the invention is not limited thereto.

(Exemplary Compounds) I-1 Benzotriazole I-2 5-Methylbenzotriazole I-3 5
-chlorobenzotriazole I-4 5-nitrobenzotriazole I-5 5-ethylbenzotriazole I-6 5-carboxybenzotriazole I-7
5-Hydroxybenzotriazole I-8 5-
Aminobenzotriazole I-9 5-Sulfobenzotriazole I-10 5-cyanobenzotriazole I-11 5-Methoxybenzotriazole I-1
2 5-ethoxybenzotriazole I-13 5
-Mercaptobenzotriazole These compounds are known as antifoggants in the photographic field, and can be synthesized by known synthesis methods, and some of the compounds are commercially available as chemical reagents.

The compound represented by the general formula [3] according to the present invention is used in an amount of 10 mg to 5 mg per mole of silver halide.
g, preferably 50 mg to 1 g.

In the present invention, the silver halide includes, for example, silver chlorobromide and a silver halide emulsion such as silver chloride containing 50 mol % or more of silver chloride, with silver chlorobromide being preferred.

Furthermore, the particles are monodisperse particles having a coefficient of variation expressed by (standard deviation of particle size)/(average value of particle size) x 100 of 20% or less. It is important to adjust the silver halide grains so that the monodispersity is 20 or less, and the monodispersity is 20 or less.
If it exceeds 0, it is not preferable because the contrast may be impaired and the sharpness may deteriorate. In particular, such monodisperse emulsions are more preferable as photosensitive materials for semiconductor lasers, LEDs (light emitting diodes), helium-neon lasers, etc., and appropriate halftone dot quality can be obtained.

Here, the term "high contrast" refers to the degree of density difference between bright areas and dark areas in a photographic image. Further, sharpness indicates the degree to which the boundaries of an image are clear and even minute parts are shown.

Further, the emulsion grains of the present invention contain 1 mole of silver per mole of silver.
It is preferably prepared in the presence of 0-9 to 10-5 mol of rhodium salt or rhodium complex and/or 10-8 to 10-5 mol of iridium salt or iridium complex.

In addition, various techniques and additives known to those skilled in the art can be used in the silver halide emulsion of the present invention.

For example, the silver halide photographic emulsion and backing layer used in the present invention contain various chemical sensitizers, toning agents, hardeners, surfactants, thickeners, plasticizers, slip agents, and development inhibitors. Agents, ultraviolet absorbers, irradiation inhibitors, dyes, heavy metals, matting agents, and the like can be further incorporated by various methods. Further, a polymer latex can be contained in the silver halide photographic emulsion and backing layer of the present invention.

Supports that can be used in the silver halide photographic material of the present invention include cellulose acetate, cellulose nitrate, polyesters such as polyethylene terephthalate, polyolefins such as polyethylene, polystyrene, baryta paper, and polyolefin-coated supports. paper,
Examples include glass and metal. These supports are subjected to surface treatment if necessary.

After exposure, the silver halide photographic material according to the present invention can be developed by various methods, such as commonly used methods.

The black and white developer can contain hydroxybenzenes, aminofinols, aminobenzenes, carbonates, bisulfites, bromides, iodides, and the like.

[0098]

[Examples] The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.

Example 1 60 g of gelatin was dissolved in water, and 2.0 g of each of the dyes shown in Table 1 was added thereto. Further, 40 ml of a 1% aqueous solution of 1-decyl-2-(3-isopentyl)succinate-2-sulfonic acid sodium salt as a spreading agent and 45 ml of a 4% aqueous solution of glyoxal as a hardening agent were added to make a total volume of 1.
It was set as l. This gelatin-containing aqueous solution was coated on a polyethylene terephthalate film support with a gelatin content of 3.2 g.
/m2. On the other hand, with the following prescription,
A silver chlorobromide emulsion was prepared. (Preparation of coating solution for emulsion layer) Solution A Water

980ml sodium chloride

2.0g gelatin

20g 0.01% aqueous solution of hexachloroiridate potassium salt
3.5ml 0.001% aqueous solution of potassium hexabromorodate salt Table 1 amount Solution B Water

380ml sodium chloride

38g potassium bromide

42g solution C water

380ml silver nitrate

170g In the above solution kept at 40℃, adjust the pH to 3 and pA.
Add the solutions B and C simultaneously over a period of 80 minutes while maintaining g at 7.7, continue stirring for an additional 5 minutes, and then adjust the pH to 5.6 with an aqueous sodium carbonate solution.
After normal desalination and water washing process, 500ml of water and 30g
gelatin and disperse at 50°C for 30 minutes.

[0100] As a result, 62 mol% of silver chloride, 3% of silver bromide
An emulsion of 8 mol %, cubic crystal grains with an average grain size of 0.26 μm was obtained. Add citric acid and potassium bromide to this emulsion to adjust the pH.
5.4, pAg 7.6, gold sensitization and sulfur sensitization at 55°C, 1 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene per mol of silver halide. Add 0.5 g of 1-phenyl-5-mercaptotetrazole and 0.2 g of the mixture, lower the temperature to 50°C, and prepare a 0.1% methanol solution of the sensitizing dye represented by the general formula [D] shown in Table 1. Add 50 ml per mole of silver halide, 60
After stagnation for a minute, the temperature was raised to 36°C, a compound represented by the general formula [H] was added as shown in Table 1, and 50ml of a 10% methanol solution of hydroquinone was added as an antifoggant.
19 ml of a 20% aqueous solution of saponin as a spreading agent, 50 ml of a 4% aqueous solution of styrene-maleic acid copolymer as a thickener, 30 g of a polymer latex of ethyl acrylate, and 1-hydroxy as a hardening agent. -3
,5-dichlorotriazine sodium salt 1% aqueous solution 20
ml and 10 ml of formalin 4% aqueous solution and stir.
It was coated on the opposite side of the film from the gelatin coated side. Furthermore, an aqueous solution containing gelatin and 1-decyl-2-(3-isopentyl)succinate-2-sulfonic acid sodium salt was applied thereon as a protective layer. The sample thus prepared was processed using the following processing solution in an automatic developing machine for rapid processing under the following conditions.

(Processing conditions) Process Temperature (°C)
Time (seconds) Development 3
8 15 established
35
15 water washing
30 10 drying
50
10 Developer prescription Pure water (ion exchange water)

Approximately 800ml potassium sulfite

60g Ethylenediaminetetraacetic acid disodium salt
2g potassium hydroxide

10.5g 5-methylbenzotriazole
300mg
diethylene glycol

25g 1-phenyl-4,4-dimethyl-3-pyrazolidinone 30
0mg 1-phenyl-5-mercaptotetrazole 6
0mg potassium bromide

3.5g hydroquinone

20g potassium carbonate
Add 15g pure water (ion exchange water) to 1,000ml
Finish it. The pH of the developer was approximately 10.8.

Fixer formulation (composition A) Ammonium thiosulfate (72.5% w/v aqueous solution) 240 ml
sodium sulfite

17g Sodium acetate trihydrate

6.5g boric acid

6g Sodium citrate dihydrate
2g acetic acid (90%
w/w aqueous solution)
13.6ml (composition B) Pure water (ion exchange water)

17ml acetic acid (50% w/w aqueous solution)
4.7g aluminum sulfate (A
l2O3 equivalent content is 8.1% w/w)
26.5 g When used, the above composition A and composition B were dissolved in 500 ml of water in that order to make up to 1 liter. The pH of this fixer was about 4.3.

The photographic properties were evaluated after the above processing. However, the evaluation of stability over time was performed using the following method. That is, one half of the halves was conditioned at 23°C relative humidity 48%, sealed and packaged with a moisture-proof material laminated with polyvinyl acetate (thickness 100 μm), and kept at a constant temperature of 55°C relative humidity 50% as a substitute for shelf life over time. The mixture was heat-treated in a pot for 72 hours. After exposing the same-day and aged samples to a xenon flash for 10-5 seconds through an optical wedge and a 680 nm interference filter, a Konica Automatic Processor GR-26 (manufactured by Konica Corporation) was used as an automatic developer, and the above-mentioned developer was used as a developer. Perform development processing using liquid and fixer,
evaluated. In addition, unexposed samples were also treated in the same manner for evaluation of black spots.

The results are shown in Table 1. However, the photographic sensitivity is expressed as a relative sensitivity when sample 1 is taken as 100. In addition, for samples processed without exposure, black spots were visually evaluated using a 40-eye magnifying glass, and the state of black spots was evaluated on a five-point scale, with "5" indicating no occurrence and "1" indicating strong occurrence. Ta. "3
” black spots below are at a level that cannot withstand general use.

As shown in Table 1, the samples of the present invention have sensitivity,
It can be seen that both black spots are good and there is little deterioration in performance over time.

[0106]

[Table 1]

[0107]

[Chemical formula 31]

Example 2 No. 1 of Example 1. In emulsions 1 and 10, the sensitizing dye,
Evaluation was carried out in the same manner as in Example 1, except that the hydrazine compounds shown in Table 2 were added, the compounds that inhibit development were added as shown in Table 2, and the development time was changed to 13 seconds.

The results are shown in Table 2.

[0110]

[Table 2]

From the results in Table 2, it can be seen that, as in Example 1, the samples of the present invention had good sensitivity and black spots, and showed little deterioration in performance over time.

Example 3 No. 2 of Example 2. The emulsion was prepared in the same manner as in Example 1, and the general formulas [1], [2], and [3] were added as shown in Table 3.

In this case, the same evaluation as in Example 1 was performed except that the development time was 13 seconds.

The results are shown in Table 3.

From the results in Table 3, it can be seen that even with ultra-quick processing with a developing time of 15 seconds or less, high contrast, less black spots, and good storage stability can be achieved.

[0116]

[Table 3]

[0117]

Effects of the Invention The present invention provides a silver halide photosensitive material for printing plate making that has high sensitivity, high contrast, excellent storage stability, and fewer black spot failures, and a halogen compound that achieves the above effects even through rapid processing with a developing time of 15 seconds or less. We were able to provide a silver oxide photographic material.

Claims (5)

[Claims] Claim 1: A silver halide photographic material having at least one silver halide emulsion layer on a support, in which the emulsion layer or other hydrophilic colloid layer is represented by the following general formula [H]. containing a hydrazine derivative, and the silver halide emulsion is 1×10 −9 to 1×1 per mole of silver.
A sensitizing dye consisting of monodisperse silver halide grains having a silver chloride content of 50 mol% or more prepared in the presence of 0-5 mol of rhodium salt or rhodium complex salt and represented by the following general formula [D]. A silver halide photographic material comprising: [Formula, A represents an aryl group or a heterocyclic group containing at least one sulfur atom or oxygen atom, and G represents -(C(O)
)- group, sulfonyl group, sulfoxy group, -P(O)(R
)- group or iminomethylene group, n represents an integer of 1 or 2, A1 and A2 are both hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted alkylsulfonyl group. Represents a substituted acyl group, R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a carbamoyl group, an oxycarbonyl group, or an -O-R3 group, and R3 represents an alkyl group or a saturated hetero group. Represents a ring group. ] [Formula, Y1 and Y2 each represent a sulfur atom or a selenium atom (except that Y1 and Y2 are selenium atoms at the same time). R4 and R5 each represent a lower alkyl group or an alkyl group having a sulfo group, and R6 represents a lower alkyl group. A and B each represent a nonmetallic atomic group necessary to complete the naphthothiazole ring, benzothiazole ring, naphthoselenazole ring, or benzoselenazole ring. X-
represents an anion, and m represents 0 or 1. ] 2. A silver halide photographic material having at least one silver halide emulsion layer on a support, in which the emulsion layer or other hydrophilic colloid layer has the general formula [H] according to claim 1. The silver halide emulsion contains monodisperse silver halide grains having a silver chloride content of 50 mol % or more, and contains a hydrazine derivative represented by the formula [D ] A silver halide photographic material characterized by containing a sensitizing dye represented by the following. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the emulsion layer or other hydrophilic colloid layer further contains a compound that inhibits development. 4. A method for processing a silver halide photographic material, which comprises developing the silver halide photographic material according to claim 1, 2 or 3 in a developing time of 15 seconds or less. 5. Forming a black and white image by processing a silver halide photographic material having at least one silver halide emulsion layer on a support with a developer having a pH of 11.0 or less for a development time of 15 seconds or less after image exposure. In the method, the emulsion layer or other hydrophilic colloid layer contains a hydrazine derivative represented by the general formula [H] according to claim 1 and the following general formula [1].
or containing at least one compound selected from [2] and a compound represented by the general formula [3], the silver halide emulsion consisting of monodisperse silver halide grains having a chlorine content of 50 mol% or more, A silver halide photographic material comprising a sensitizing dye represented by the general formula [D] according to claim 1. embedded image [In the formula, Y represents a group that adsorbs to silver halide. X represents two linking groups consisting of atoms or atomic groups selected from hydrogen atoms, carbon atoms, nitrogen atoms, and oxygen atoms. A is 2
represents a number of linking groups. B represents an amino group, an ammonium group, or a nitrogen-containing heterocycle, and the amino group may be substituted. m represents 1, 2 or 3, and n represents 0 or 1. ] [In the formula, R1 and R2 each represent a hydrogen atom or an aliphatic residue. R1 and R2 may be combined with each other to form a ring. R3 represents a divalent aliphatic group. X represents a divalent heterocycle containing nitrogen, oxygen or sulfur atom. n represents 0 or 1, and M represents a hydrogen atom, an alkali metal, an alkaline earth metal, a quaternary ammonium salt, a quaternary phosphonium salt, or an amidino group. [Formula 5] [In the formula, Y represents a hydrogen atom or a mercapto group, and R represents a hydrogen atom, a halogen atom, a nitro group, an amino group, a cyano group, a hydroxyl group, a mercapto group, a sulfo group, a substituted or unsubstituted Alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkoxy group,
Represents a hydroxycarbonyl group, an alkylcarbonyl group, or an alkoxycarbonyl group. ]