JPH04255840A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain photographic characteristics of a high contrast and sufficiently high sensitivity with IR light by incorporating a specific compd. into the above photosensitive material. CONSTITUTION:The compd. expressed by formula is incorporated into this material. In the formula, R1, R2 denote an alkyl group; R3 denotes a hydrogen atom, lower alkyl group, lower alkoxy group, phenyl group, benzyl group or phenetyl group; R4, R5 denote a lower alkyl group; V denotes a hydrogen atom, lower alkyl group, alkoxy group, halogen atom or substd. alkyl group; Z1 denotes a nonmetal atom group necessary for completing a 5-or 6-membered nitrogenous heterocycle; X1 denotes acid anion: m, p, q denotes 1 or 2 and and q is 1 when a dye forms an intra-molecular salt; i, j denote 0 to 4 integer but there is no case both are simultaneously zero.

Description

Detailed Description of the Invention [0001] The present invention relates to a silver halide photographic material spectrally sensitized in the infrared region, and particularly to a high-contrast silver halide photographic material spectrally sensitized in the infrared region. This invention relates to silver halide photographic materials. [0002] One of the methods of exposing photographic light-sensitive materials is to scan an original image and expose the silver halide photographic light-sensitive material based on the image signal, thereby producing a negative image corresponding to the image of the original image. Alternatively, an image forming method using a so-called scanner method for forming a positive image is known. There are various types of recording apparatuses that utilize a scanner-based image forming method, and glow lamps, xenon lamps, mercury lamps, tungsten lamps, light-emitting diodes, and the like have conventionally been used as recording light sources for these scanner-type recording apparatuses. However, all of these light sources have practical drawbacks of low output and short lifespan. To compensate for these shortcomings,
There are scanners that use a coherent laser light source such as a Ne-He laser, an argon laser, a He-Cd laser, etc. as a light source of the scanner method. Although these devices can provide high output, they are large and expensive, require a modulator, and use visible light, which limits the safety of the photosensitive material and makes them difficult to handle. There are drawbacks such as. On the other hand, semiconductor lasers are small, inexpensive, easy to modulate, have a longer lifespan than the lasers mentioned above, and emit light in the infrared region, so if a photosensitive material sensitive to the infrared region is used, a bright safelant can be created. Since it can be used, it has the advantage of not being easy to handle. However, since the output power of currently available semiconductor lasers is not necessarily high, the sensitivity of conventional photosensitive materials for scanners has been insufficient to scan and expose a large screen in a short time. Therefore, there has been a need for a photosensitive material with improved sensitivity in the infrared region. It is known that ways to increase the sensitivity of photographs include increasing the size of silver halide grains and adding various chemical sensitizers, but these methods often reduce the graininess of silver images. It has undesirable side effects such as deterioration and the appearance of fog, and is not suitable for use as a sensitive material for scanners, which particularly requires sharp image quality. SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic material having photographic properties of high contrast and sufficiently high sensitivity to infrared light. [0005] The above-mentioned problems have been achieved by a silver halide photographic material containing a compound represented by the following general formula (I). General formula (I): ##STR2## In the formula, R1 and R2 may each be the same or different, and each represents an alkyl group. R3
represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, a benzyl group or a phenethyl group. R
4 and R5 may be the same or different and each represents a lower alkyl group. V represents a hydrogen atom, a lower alkyl group, an alkoxy group, a halogen atom or a substituted alkyl group. Z1 represents a group of nonmetallic atoms necessary to complete a 5- or 6-membered nitrogen-containing heterocycle. X1
represents an acid anion. m, p and q each independently represent 1 or 2. However, when the dye forms an inner salt, q is 1. i and j represent integers from 0 to 4, but cannot be 0 at the same time. In the compound represented by the general formula (I), R1 and R2 may each be the same or different, and each represents an alkyl group (including a substituted alkyl group). Preferably 1 to 8 carbon atoms. For example, methyl, ethyl, propyl, butyl,
Pentyl, heptyl, octyl. Examples of substituents include carboxyl group, sulfo group, cyano group, halogen atom (
For example, fluorine atom, chlorine atom, bromine atom), hydroxyl group, alkoxycarbonyl group (preferably 8 or less carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl, etc.), alkoxy group (preferably 7 or less carbon atoms) , such as methoxy, ethoxy, propoxy, butoxy, benzyloxy), aryloxy groups (such as phenoxy, p-tolyloxy,
α-naphthoxy), acyloxy groups (preferably up to 3 carbon atoms, e.g. acetyloxy, propionyloxy), acyl groups (preferably up to 8 carbon atoms, e.g. acetyl, propionyl, benzoyl, mesyl), carbamoyl groups (e.g. carbamoyl , N,N-dimethylcarbamoyl, morpholinocarbamoyl, piperidinocarbamoyl), sulfamoyl groups (e.g. sulfamoyl, N,N-dimethylsulfamoyl, morpholinosulfonyl), aryl groups (e.g. phenyl, p-hydroxyphenyl, p-carboxy Examples include alkyl groups substituted with phenyl, p-sulfophenyl, α-naphthyl, etc. (preferably the alkyl moiety has 6 or less carbon atoms). However, two or more of these substituents may be substituted with an alkyl group in combination. R3 is a hydrogen atom, a lower alkyl group (preferably having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, butyl), or a lower alkoxy group (preferably having 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy ,
butoxy), phenyl group, benzyl group or phenethyl group. In particular, lower alkyl groups and benzyl groups are advantageously used. Among the lower alkyl groups represented by R4 and R5, those having 1 to 8 carbon atoms are preferred, and unsubstituted alkyl groups having 1 to 4 carbon atoms (such as methyl, ethyl, propyl) are particularly preferred. , butyl, isobutyl, cyclopropylmethyl, etc.). V is a hydrogen atom, a lower alkyl group (preferably having 1 to 4 carbon atoms, such as methyl, ethyl, or propyl), an alkoxy group (preferably having 1 to 4 carbon atoms, such as methoxy, ethoxy, butoxy), or halogen. It represents an atom (for example, a fluorine atom, a chlorine atom), a substituted alkyl group (preferably having 1 to 4 carbon atoms, for example, trifluoromethyl, carboxymethyl). Z1 represents a nonmetallic atomic group necessary to complete a 5- or 6-membered nitrogen-containing heterocycle, such as a thiazole nucleus [e.g., benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6
-Chlorbenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenyl Benzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-ethoxybenzothiazole, 5-carboxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-phenethylbenzothiazole, 5-
Fluorobenzothiazole, 5-trifluoromethylbenzothiazole, 5,6-dimethylbenzothiazole,
5-hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole, naphtho[2,1-d]thiazole, naphtho[1,2
-d]thiazole, naphtho[2,3-d]thiazole,
5-methoxynaphtho[1,2-d]thiazole, 7-ethoxynaphtho[2,1-d]thiazole, 8-methoxynaphtho[2,1-d]thiazole, 5-methoxynaphtho[2,3-d] thiazole], selenazole core [e.g. benzoselenazole, 5-chlorobenzoselenazole,
5-methoxybenzoselenazole, 5-methylbenzoselenazole, 5-hydroxybenzoselenazole, naphtho[2,1-d] selenazole, naphtho[1,2-d]
selenazole], oxazole nucleus [benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5-trifluorobenzo Oxazole, 5-hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 5,6-dimethylbenzoxazole, 4,6- Dimethylbenzoxazole, 5-ethoxybenzoxazole, naphtho[2,1-d]oxazole, naphtho[1,2-d]oxazole, naphtho[2
, 3-d] oxazole, quinoline nucleus [e.g. 2-quinoline, 3-methyl-2-quinoline, 5-ethyl-2-quinoline, 6-methyl-2-quinoline, 8-fluoro-2
-quinoline, 6-methoxy-2-quinoline, 6-hydroxy-2-quinoline, 8-chloro-2-quinoline, 8-
fluoro-4-quinoline], 3,3-dialkylindolenine core (e.g., 3,3-dimethylindolenine, 3
, 3-diethylindolenine, 3,3-dimethyl-5-
cyanoindolenine, 3,3-dimethyl-5-methoxyindolenine, 3,3-dimethyl-5-methylindolenine, 3,3-dimethyl-5-chlorindolenine),
Imidazole core (e.g. 1-methylbenzimidazole, 1-ethylbenzimidazole, 1-methyl-5-
Chlorobenzimidazole, 1-ethyl-5-chlorobenzimidazole, 1-methyl-5,6-dichlorobenzimidazole, 1-ethyl-5,6-dichlorobenzimidazole, 1-ethyl-5-methoxybenzimidazole, 1-methyl-5-cyanobenzimidazole,
1-ethyl-5-cyanobenzimidazole, 1-methyl-5-fluorobenzimidazole, 1-ethyl-5
-fluorobenzimidazole, 1-phenyl-5,6
-dichlorobenzimidazole, 1-allyl-5,6-
Dichlorobenzimidazole, 1-allyl-5-chlorobenzimidazole, 1-phenylbenzimidazole, 1-phenyl-5-chlorobenzimidazole, 1-
Methyl-5-trifluoromethylbenzimidazole,
1-ethyl-5-trifluoromethylbenzimidazole, 1-ethylnaphtho[1,2-d]imidazole),
Mention may be made of pyridine nuclei (eg pyridine, 5-methyl-2-pyridine, 3-methyl-4-pyridine). Among these, thiazole nuclei and oxazole nuclei are preferably used. More preferably, a benzothiazole nucleus, a naphthothiazole nucleus, a naphthoxazole nucleus, or a benzoxazole nucleus is advantageously used. m, p and q each independently represent 1 or 2. However, when the dye forms an inner salt, q is 1. X1 is an acid anion (e.g. chloride, bromide, iodide, tetrafluoroborate, hexafluorophosphate, methylsulfate, ethylsulfate, benzenesulfonate, 4-methylbenzenesulfonate, 4-chlorobenzenesulfonate, 4-nitrobenzene sulfonate, trifluoromethanesulfonate, perchlorate, etc.). Specific examples of the compound represented by the above general formula (I) are shown below, but the scope of the present invention is not limited thereto. [Formula 3] [Formula 3] [Formula 4] [Formula 5] [Formula 5] [Formula 6] [Formula 7] [Formula 7] [Formula 8] [Formula 9] ##STR10## The compound represented by the above general formula (I) is disclosed in JP-A-59-192242 and US Pat. No. 4,975.
, No. 362. The average grain size of the silver halide used in the present invention is preferably fine (for example, 0.7 μm or less), particularly preferably 0.5 μm or less. The silver halide grains in the present invention are cubic grains consisting essentially of [100] planes. Here, "substantially consisting of [100] planes" more specifically refers to preferably 50% or more, more preferably 80% or more of the grains contained in the silver halide emulsion.
This means that % or more, particularly preferably 95% or more of the particles are cubic and/or particles in which [100] planes occupy 60% or more of the surface area of the particles. The grain size distribution of the silver halide grains used in the present invention is preferably monodisperse. Monodisperse herein means a silver halide emulsion having a grain size distribution with a coefficient of variation defined below of 40% or less, particularly preferably 20% or less. Here, the coefficient of variation is coefficient of variation (%) =
It is defined as (standard deviation of particle size/average value of particle size) x 100. The photographic emulsion used in the present invention is P. Glafkides
Written by Chimie et Physique Pho
tographique (Paul Montel
Publishing, 1967), G. F. Written by Duffin Pho
tographic Emulsion Chemi
stry (The Focal Press, 1
966), V. L. Zelikman et al.
Author: Making and Coating Ph
otographic Emulsion (The
Focal Press, 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 is as follows:
Any one-sided mixing method, simultaneous mixing method, or a combination thereof may be used. In the present invention, a photographic emulsion comprising cubic monodisperse silver halide grains is more preferred. 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 the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called controlled 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. In order to make the particle size uniform, British Patent No. 1,535,016, Japanese Patent Publication No. 48-368
90, No. 52-16364,
A method of changing the addition rate of silver nitrate or alkali halide depending on the grain growth rate, and US Pat. No. 4,242,44
It is preferable to use a method of changing the concentration of an aqueous solution as described in No. 5, JP-A No. 55-158124, to grow rapidly within a range that does not exceed the critical saturation level. The silver halide grains may have a so-called core/shell type structure in which the interior and surface layers have different halogen compositions. Particularly in the case of silver iodobromide, the silver iodide ratio in the core is preferably higher than the silver iodide ratio in the shell by 0.5 mol% or more, and more preferably by 2 mol% or more. When forming the silver halide grains used in the present invention, it is preferable to use a silver halide solvent. As the silver halide solvent used in the present invention, US Pat. Nos. 3,271,157 and 3,53
(a) Organic thioethers described in No. 1,289, No. 3,574,628, etc., JP-A-53-8240
No. 8, No. 55-77737 (b) Thiourea derivatives, described in JP-A-53-144319 (c) Silver halide solvents having oxygen or carbonyl groups, JP-A-54-100717 (d
) imidazoles (e) sulfites (f) thiocyanates (g) thiones. Among these, thioethers are particularly preferred. Specific compounds are shown below. ##STR12## The silver halide photographic emulsion used in the present invention preferably contains a group VIII metal in the periodic table. Examples of metals include iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium,
Iridium and platinum, and compounds containing these metals preferably used in the present invention include iron sulfate (I
I) FeSO4-5H2O; iron(III) chloride Fe
Cl3; Potassium hexacyanoferrate (II) K4 F
e(CN)6 ・3H2 O; hexacyanoferrous (III
) Potassium acid K3 Fe(CN)6 ; Cobalt(II) chloride CoCl2 ; Cobalt(II) sulfate Co(N
O3)2 ・6H2 O; hexacyanocobalt (II
I) Potassium acid K3 Co(CN)6 ; Nickel (II) chloride NiCl2 ; 6H2 O Nickel nitrate (I
I) Ni(NO3)2 ・6H2 O; Ruthenium (III) chloride RuCl3; Hexachlororuthenium (
IV) Potassium acid K2 RuCl6; rhodium(III) chloride RhCl3 ・4H2 O; ammonium hexachlororhodium(III) acid (NH)3 Rh
Cl6; Palladium (II) chloride PdCl2; Palladium (II) nitrate Pd(NO3)2; Palladium (II) bromide PdBr2; Hexachloropalladium (I
V) Potassium acid K2 PdCl6; Potassium tetrathiopalladate (II) K2 Pd(CNS)4;
Osmium (II) chloride O3 Cl2; Iridium (III) chloride IrCl3; Iridium (IV) chloride
IrCl4; Iridium(III) bromide IrBr3
・4H2O; Iridium (IV) bromide IrBr4
; Hexachloroiridium(III) acid; Potassium K
3 IrCl6 ; Potassium hexachloroiridate (IV) K2 IrCl6 ; Hexachloroplatinum (IV
) ammonium (NH4)2 PtCl6 ; potassium hexachloroplatinate (IV) K2 PtCl6 ; ammonium hexabromoplatinate (IV) (NH4)2
PtBr6 ; etc. These Group VIII metal compounds contain from 10-9 to 1 mole per mole of silver halide.
It is used alone in an amount corresponding to 0-3 mol, or two or more compounds are used in combination. In particular, a combination of two or three of iridium salts, rhodium salts, and iron salts is advantageously used. These compounds can be added as appropriate during the production of the silver halide emulsion and at each stage before coating the emulsion. Furthermore, in the above-mentioned method for producing silver halide grains, it may be added at any stage of nucleation or growth, and may also be added during chemical ripening of the silver halide emulsion. It is preferable. The silver halide photographic emulsion used in the present invention has the following general formula [II-a], [II-b] or [II
-c] is preferably contained. General formula [II-a] Z-SO2 -S-M [Chemical formula 13] [0028] However, Z: alkyl group (1 to 18 carbon atoms)
, aryl group (6 to 18 carbon atoms), or heterocyclic group, Y: aromatic ring (6 to 18 carbon atoms), or an atom necessary to form a heterocycle M: metal atom, or organic cation n: 2
An integer between ~10. Z and Y in general formulas [II-a] to [II-c]
The alkyl group, aryl group, heterocyclic group, aromatic ring, and heterocyclic ring represented by may be substituted. Examples of substituents include lower alkyl groups such as methyl and ethyl groups;
Examples include aryl groups such as phenyl groups, alkoxyl groups having 1 to 8 carbon atoms, halogen atoms such as chlorine, nitro groups, amino groups, and carboxyl groups. Examples of the heterocycle represented by Z and Y include thiazole, benzthiazole, imidazole, benzimidazole, and oxazole rings. The metal atom represented by M is preferably an alkali metal atom such as a sodium ion or potassium ion, and the organic cation is preferably an ammonium ion or a guanidine group. Examples of the above compounds include the following compounds. ##STR14## The above compounds can generally be synthesized by well-known methods. For example, it can be synthesized by reacting the corresponding sulfonyl fluoride with sodium sulfide, or by reacting the corresponding sodium sulfinate with sulfur. On the other hand, these compounds can also be easily obtained as commercial products. [II-a] in the present invention
, [II-b] or [II-c] is preferably added in an amount of 10-3 to 1 g per mole of silver halide, particularly preferably 10-4 to 10-
It is 2g. Although it may be added at any time during grain formation or chemical ripening of the emulsion, it is particularly preferable to add it before grain formation or just before the start of chemical ripening. The silver halide emulsion of the present invention is preferably gold-sensitized and sulfur-sensitized. Gold sensitizers used in the present invention include various gold salts, such as potassium chlorooleite, potassium auric thiocyanate, potassium chlorooleate, and auric trichloride. Specific examples are U.S. Patent Nos. 2,399,083 and 2,642.
It is described in the specification of No. 361. As the sulfur sensitizer used in the present invention, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines, etc. can be used. Specific examples are U.S. Patent Nos. 1,574,944 and 2.
, No. 278,947, No. 2,410,689, No. 2,
No. 728,668, No. 3,501,313, No. 3,6
No. 56,955. Preferred sulfur compounds are thiosulfates and thiourea compounds. The preferred amount of sulfur sensitizer and gold sensitizer added is 10-2 to 10-7 mol per silver mol, more preferably 1x
It is 10-3 to 1 x 10-5 mol. The molar ratio of the sulfur sensitizer to the gold sensitizer is 1:3 to 3:1, preferably 1:2 to 2:1. In the present invention, a reduction sensitization method can be used. In the present invention, the following general formula (IV
) is preferably used. General formula (IV) ##STR16## In the formula, Z3 represents a nonmetallic atom group necessary to complete a 5- or 6-membered nitrogen-containing heterocycle, and R13 is a hydrogen atom, an alkyl group, an alkenyl group. R14 represents a hydrogen atom or an alkyl group, and X2 represents an anion for neutralizing positive charges. The heterocycle completed by Z3 in the general formula (IV) is, for example, a thiazolium compound {for example, thiazolium, 4-methylthiazolium, benzothiazolium, 5-methylbenzothiazolium, 5-methylbenzothiazolium,
Chlorobenzothiazolium, 5-methoxybenzothiazolium, 6-methylbenzothiazolium, 6-methoxybenzothiazolium, naphtho[1,2-d]thiazolium, naphtho[2,1-d]thiazolium, etc. }, oxazoliums {e.g. oxazolium, 4-methyloxazolium, benzoxazolium, 5-chlorobenzoxazolium, 5-phenylbenzoxazolium, 5
-Methylbenzoxazolium, naphtho[1,2-d]
oxazolium, etc.}, imidazoliums (e.g. 1-
methylbenzimidazolium, 1-propyl-5-chlorobenzimidazolium, 1-ethyl-5,6-dichlorobenzimidazolium, 1-allyl-5-trichloromethyl-6-chlorobenzimidazolium, etc.), selenazoliums [For example, benzoselenazolium, 5-chlorobenzoselenazolium, 5-methylbenzoselenazolium, 5-methoxybenzoselenazolium, naphtho]
1,2-d] selenazolium, etc.]. R1
Preferred examples of 3 include a hydrogen atom, an alkyl group (8 or less carbon atoms, such as a methyl group, an ethyl group, a propyl group,
(butyl group, pentyl group, etc.), alkenyl group (eg, allyl group, etc.). Preferred examples of R14 include a hydrogen atom and a lower alkyl group (eg, methyl group, ethyl group, etc.). Preferred examples of X2 include Cl-, Br-, I-, ClO4-, p
-Toluenesulfonic acid and the like. Among the heterocycles completed by Z3, thiazoliums are particularly preferred. More preferred is substituted or unsubstituted benzothiazolium or naphthothiazolium. Specific examples of the compound represented by Chemical Formula 15 are shown below. However, the present invention is not limited to only these compounds. [Formula 17] [Formula 18] [Formula 19] [Formula 19] [Formula 20] [Formula 21] [Formula 21] The compound represented by the above general formula (IV) is Amounts of about 0.01 to 5 grams per mole of silver halide in the emulsion are advantageously used. The ratio (weight ratio) of the above-mentioned infrared sensitizing dye of the present invention and the compound represented by the general formula (IV) is the infrared sensitizing dye of the present invention/the compound represented by the general formula (IV).
The range of the compound represented by IV) from 1/1 to 1/300 is advantageously used, particularly preferably from 1/2 to 1/50. The compound represented by the general formula (IV) used in the present invention can be directly dispersed in an emulsion, or can be dispersed in a suitable solvent (such as water, methyl alcohol,
Ethyl alcohol, propanol, methyl cellosolve,
Acetone, etc.) or a mixed solvent using two or more of these solvents can be added to the emulsion. In addition, it can be added to the emulsion in the form of a solution or a dispersion in a colloid according to the method of adding sensitizing dyes. The compound represented by the general formula (IV) may be added to the emulsion before or after the addition of the infrared sensitizing dye of the invention described above. Alternatively, the compound of general formula (IV) and the infrared sensitizing dye may be dissolved separately and added to the emulsion separately and at the same time, or they may be mixed and then added to the emulsion. The silver halide photographic material of the present invention includes:
Furthermore, it is preferable to add a compound represented by the following general formula (V). General formula (V) ##STR22## Here, A represents a divalent aromatic residue. R
21, R22, R23 and R24 are each a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a heterocyclic nucleus, a heterocyclylthio group,
It represents an arylthio group, an amino group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted aralkylamino group, an aryl group, or a mercapto group. However, A, R21, R22, R23 and R
At least one of 24 has a sulfo group. W
3 and W4 represent -CH= or -N=. However, at least one of W3 and W4 represents -N=. In general formula (V), -A- represents a divalent aromatic residue, preferably a -SO3M group (where M represents a hydrogen atom, an alkali metal, or optionally substituted ammonium).General formula ( -A- in V) is preferably selected from -A1- or -A2-, with the proviso that R21, R22, R23, or R24
When -SO3 M is not included in, -A- is -A1
- selected from the group. [Formula 23] [Formula 24] [Formula 24] [Formula 25] R21, R22, R23 and R24 each represent a hydrogen atom, a hydroxy group, or a lower alkyl group (the number of carbon atoms is 1 to 1). 8 is preferred, such as methyl group, ethyl group, n-propyl group, n-butyl group), alkoxy group (preferably 1 to 8 carbon atoms, such as methoxy group, ethoxy group, propoxy group, butoxy group, etc.) ),
Aryloxy group (e.g. phenoxy group, naphthoxy group,
o-troxy group, p-sulfophenoxy group, etc.), halogen atoms (e.g., chlorine atom, bromine atom, etc.), heterocyclic nuclei (e.g., morpholinyl group, piperidyl group, etc.), alkylthio groups (e.g., methylthio group, ethylthio group, etc.)
, heterocyclylthio groups (e.g. benzothiazolylthio group, benzimidazolylthio group, phenyltetrazolylthio group, etc.), arylthio group (e.g. phenylthio group, tolylthio group), amino group, alkylamino group or substituted alkylamino group (e.g. methylamino group) group, ethylamino group, propylamino group, dimethylamino group, diethylamino group, dodecylamino group, cyclohexylamino group, β-hydroxyethylamino group, di-(β-hydroxyethyl)amino group, β-sulfoethylamino group) , arylamino group, or substituted arylamino group (
For example, anilino group, o-sulfoanilino group, m-sulfoanilino group, p-sulfoanilino group, o-toluidino group, m-toluidino group, p-toluidino group, o-carboxyanilino group, m-carboxyanilino group, p- Carboxyanilino group, o-chloroanilino group, m-chloroanilino group, p-chloroanilino group, p-aminoanilino group, o-anisidino group, m-anisidino group, p-anisidino group, o-acetaminoanilino group, hydroxy Anilino group, disulfophenylamino group, naphthylamino group,
sulfonaphthylamino group, etc.), heterocyclylamino group (e.g., 2-benzothiazolylamino group, 2-pyridyl-amino group, etc.), substituted or unsubstituted aralkylamino group (e.g., benzylamino group, o-anisylamino group, m -anisyl amino group, p-anisyl amino group, etc.)
, an aryl group (such as a phenyl group), or a mercapto group. R21, R22, R23, and R24 may be the same or different from each other. When -A- is selected from the group -A2 -, R21, R22, R23, R24
At least one of them needs to have one or more sulfo groups (which may be free acid groups or may form salts). W3 and W4 represent -CH= or -N=, and at least one of them is -N=. Next, specific examples of compounds included in general formula (V) will be given. However, it is not limited only to these compounds. (V-1) 4,4'-bis[4,6-di(
Benzothiazolyl-2-thio)pyrimidin-2-ylamino]stilbene-2,2'-disulfonic acid sodium salt (V-2) 4,4'-bis[4,6-di(benzothiazolyl-2-amino)pyrimidine-2 -ylamino)] stilbene-2,2'-disulfonic acid sodium salt (V-
3) 4,4'-bis[4,6-di(naphthyl-2-oxy)pyrimidin-2-ylamino]stilbene-2,2
'-Disulfonic acid disodium salt (V-4) 4,4'-
Bis[4,6-di(naphthyl-2-oxy)pyrimidin-2-ylamino]bibenzyl-2,2'-disulfonic acid disodium salt (V-5) 4,4'-bis(4,6-
Dianilinopyrimidin-2-ylamino)stilbene-
2,2'-Disulfonic acid disodium salt (V-6) Sodium 4,4'-bis[4-chloro-6-(2-naphthyloxy)pyrimidin-2-ylamino]biphenyl-2,2'-disulfonate Salt (V-7) 4
,4'-bis[4,6-di(1-phenyltetrazolyl-5-thio)pyrimidin-2-ylamino]stilbene-2,2'-disulfonic acid disodium salt (V-8) 4,4'-bis[4,6-di(benzimidazolyl-2-thio)pyrimidin-2-ylamino]stilbene-2,2'-disulfonic acid disodium salt (V-
9) 4,4'-bis(4,6-diphenoxypyrimidin-2-ylamino)stilbene-2,2'-disulfonic acid disodium salt (V-10) 4,4'-bis(4,6-diphenyl Thiopyrimidin-2-ylamino)stilbene-2,2'-
Disulfonic acid disodium salt (V-11) 4,4'-bis(4,6-dimercaptopyrimidin-2-ylamino)biphenyl-2,2'-disulfonic acid disodium salt (V-12) 4,4'-bis(4,6-dianilino-triazin-2-ylamino)stilbene-2,2'-disulfonic acid disodium salt (V-13) 4,4'-bis(4-anilino-6-hydroxy-triazine-2 -ylamino)stilbene-2
, 2'-disulfonic acid disodium salt (V-14) 4,4'-bis(4-naphthylamino-6
-anilino-triazin-2-ylaminol)stilbene-2,2'-disulfonic acid disodium salt (V-15)
4,4'-bis[2,6-di(2-naphthoxy)pyrimidin-4-ylamino]stilbene-2,2'-disulfonic acid (V-16) 4,4'-bis[2,6-di( 2-naphthylamino)pyrimidin-4-ylamino]stilbene-
2,2'-disulfonic acid disodium salt (V-17) 4
,4'-bis(2,6-dianilinopyrimidin-4-ylamino)stilbene-2,2'-disulfonic acid sodium salt (V-18) 4,4'-bis[2-naphthylamino)-
6-anilinopyrimidin-4-ylamino]stilbene-2,2'-disulfonic acid (V-19) 4,4'-bis[2,6-diphenoxypyrimidin-4-ylamino]stilbene-2,2'- Disulfonic acid ditriethylammonium salt (V-20) 4,4'-bis[2,6-di(benzimidazolyl-2-thio)pyrimidin-4-ylamino]stilbene-2,2'-disulfonic acid disodium salt General formula The compound represented by (V) is known or can be easily produced according to known methods. The compound represented by the general formula (V) used in the present invention may be a mixture of two or more thereof. The compound of general formula (V) is advantageously used in an amount of about 0.01 to 5 grams per mole of silver halide in the emulsion. The ratio (weight ratio) between the infrared sensitizing dye and the compound represented by the general formula (V) is the dye/general formula (V).
The range of the compound represented by V) from 1/1 to 1/200 is advantageously used, particularly preferably from 1/2 to 1/50. The compound represented by the general formula (V) used in the present invention can be directly dispersed in an emulsion, or it can be dispersed in a suitable solvent (for example, methyl alcohol, ethyl alcohol, methyl cellosolve, water, etc.) or a mixed solvent thereof. It can also be dissolved in and added to the emulsion. In addition, it can be added to the emulsion in the form of a solution or a dispersion in a colloid according to the method of adding sensitizing dyes. They can also be dispersed and added into the emulsion by the method described in JP-A-50-80119. General formula of the present invention (
The infrared sensitizing dye represented by I) can be used in combination with other sensitizing dyes. For example, U.S. Patent No.
No. 703,377, No. 2,688,545, No. 3
, No. 397,060, No. 3,615,635, No. 3,628,964, British Patent No. 1,242,588
No. 1,293,862, Special Publication No. 43-4936
No. 44-14030, No. 43-10773, U.S. Patent No. 3,416,927, Japanese Patent Publication No. 43-4930
No. 3,615,613, U.S. Patent No. 3,615
, No. 632, No. 3,617,295, No. 3,63
Sensitizing dyes described in No. 5,721 and the like can be used. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are listed in Research Disclosure (
Research Disclosure) Volume 176 17643 (Published December 1978) Page 23 IV J
It is described in the section. The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fogging or stabilizing photographic performance during the manufacturing process, storage, or photographic processing of the light-sensitive material. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiazoles, aminotriazoles, benzothiazoles, nitrobenzotriazoles, mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinthione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3,3a,
7) Many compounds known as antifoggants or stabilizers can be added, such as tetrazaindenes), pentaazaindenes, etc. In particular, polyhydroxybenzene compounds are preferred because they improve pressure resistance without impairing sensitivity. The polyhydroxybenzene compound is preferably a compound having one of the following structures. [0052] X and Y each represent -H, -OH, a halogen atom, -OM (M is an alkali metal ion), -alkyl group, phenyl group, amino group, carbonyl group, sulfone group, Sulfonated phenyl group, sulfonated alkyl group, sulfonated amino group, sulfonated carbonyl group, carboxyphenyl group, carboxyalkyl group, carboxyamino group, hydroxyphenyl group, hydroxyalkyl group, alkyl ether group, alkylphenyl group, alkylthioether or phenylthioether group. More preferably, -H, -OH, -Cl, -Br, -CO
OH, -CH2CH2COOH, -CH3, -CH
2 CH3, -CH(CH3)2, -C(CH3)
3, -OCH3, -CHO, -SO3Na, -S
O3H, -SCH3, -C6H5, -C6H4
(m-CH3), -C6H4 (p-CH3), etc. X and Y may be the same or different. Particularly preferable examples include the following compounds. [Chemical 27] [Chemical 28] [Chemical 28] [Chemical 29] [Chemical 30] Even if the polyhydroxybenzene compound is added to the emulsion layer of the sensitive material, It may be added to a layer other than the layer. The amount added is preferably in the range of 10-5 to 1 mol, and particularly effective in the range of 10-3 to 10-1 mol. The photosensitive material made using the present invention includes:
The hydrophilic colloid layer may contain a water-soluble dye as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful. More specifically, water-soluble dyes are described, for example, in JP-A-62-123454, JP-A-63-55544, and US Pat. No. 4,876,181. On the other hand, dyes used for such purposes do not necessarily have to be water-soluble and may be dispersed as solid fine particles. An example of this is JP-A-56-126.
No. 39, No. 55-155350, No. 55-15535
Examples include those described in No. 1, No. 63-27838, No. 63-197943, and European Patent No. 15,601. In the photographic emulsion layer of the photographic light-sensitive material of the present invention, for the purpose of increasing sensitivity, increasing contrast, or promoting development,
For example, polyalkylene oxide or its ether,
Derivatives such as esters and amines, thioether compounds,
It may also contain developing agents such as thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and aminophenols. Among them, 3-pyrazolidones (1-phenyl-
3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, etc.) are preferred,
Usually used at 5g/m2 or less, 0.01-0.2g/
m2 is more preferred. The photographic emulsions and non-photosensitive hydrophilic colloids of the present invention may contain inorganic or organic hardeners. For example, active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis(vinylsulfonyl) methyl ether, N,N-methylenebis-(β-(vinylsulfonyl)propionamide), etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, etc.), N-carbamoylpyridinium salts ((1-morpholy)carbonyl-3-pyridinio)methanesulfonate, etc.), haloamidinium Salts (1-(
1-chloro-1-pyridinomethylene)pyrrolidinium,
2-naphthalenesulfonate, etc.) can be used alone or in combination. Among them, JP-A-53-412
Preferred are the active vinyl compounds described in US Pat. The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced using the present invention contains coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, high contrast , sensitization), etc., for various purposes.
Various surfactants may also be included. For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters,
Non-ionic materials such as polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. surfactant; alkyl carboxylate,
Alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkylpolyoxyethylene alkylphenyl ethers Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, such as polyoxyethylene alkyl phosphates; amino acids, aminoalkyl sulfonic acids , aminoalkyl sulfates or phosphoric acid esters,
Ampholytic surfactants such as alkyl betaines and amine oxides; alkyl amine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and aliphatic or heterocyclic Cationic surfactants such as phosphonium or sulfonium salts can be used. Further, in order to prevent static electricity, it is preferable to use a fluorine-containing surfactant described in JP-A-60-80849. The photographic light-sensitive material of the present invention may contain a matting agent such as silica, magnesium oxide or polymethyl methacrylate in the photographic emulsion layer and other hydrophilic colloid layers for the purpose of preventing adhesion. The light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of dimensional stability. For example alkyl (meta)
Polymers containing as monomer components acrylate, alkoxy acrylic (meth) acrylate, glycidyl (meth) acrylate, etc. alone or in combination, or a combination of these and acrylic acid, methacrylic acid, etc. can be used. Gelatin is advantageously used as a condensing agent or protective colloid in photographic emulsions, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. , polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc., single or copolymers thereof. Can be done. As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin may be used, and gelatin hydrolysates and gelatin enzymatically decomposed products can also be used. The silver halide emulsion layer used in the present invention can contain a polymer latex such as an alkyl acrylate. As the support for the photosensitive material of the present invention, cellulose triacetate, cellulose diacetate, nitrocellulose, polystyrene, polyethylene terephthalate paper, baryta-coated paper, polyolefin-coated paper, etc. can be used. There is no particular restriction on the developing agent used in the developer used in the present invention, but it preferably contains dihydroxybenzenes, and dihydroxybenzenes and 1-phenyl A combination of -3-pyrazolidones or a combination of dihydroxybenzenes and p-aminophenols may also be used. The dihydroxybenzene developing agents used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone,
, 5-dimethylhydroquinone, etc., and hydroquinone is particularly preferred. 1-phenyl-3 used in the present invention
- As a developing agent for pyrazolidone or its derivative, 1-
Phenyl-3-pyrazolidone, 1-phenyl-4,4-
Dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1
-p-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and so on. Examples of the p-aminophenol developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N-
(β-hydroxyethyl)-p-aminophenol, N
-(4-hydroxyphenyl)glycine, 2-methyl-
Among them, p-aminophenol, p-benzylaminophenol and the like are preferred, among which N-methyl-p-aminophenol is preferred. The developing agent is usually 0.05 mol/l to 0.05 mol/l.
Preferably it is used in an amount of 8 mol/l. When using a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-amino-phenols, the former is 0.05 mol/l-0.5 mol/l, and the latter is 0.06 mol/l. It is preferable to use the amount less than /l. Preservatives for sulfite used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
Examples include formaldehyde and sodium bisulfite. The amount of sulfite is preferably at least 0.3 mol/l, particularly preferably at least 0.4 mol/l. The upper limit is up to 2.5 mol/l, especially 1.
It is preferable to set it to 2 or less. Alkaline agents used to set pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, trisodium phosphate,
Contains pH adjusters and buffers such as tribasic potassium phosphate, sodium silicate, and potassium silicate. Additives used in addition to the above ingredients include compounds such as boric acid and borax,
Development inhibitors such as sodium bromide, potassium bromide, potassium iodide: ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol,
Organic solvents such as methanol: mercapto compounds such as 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, indazole compounds such as 5-nitroindazole,
It may contain an antifoggant such as a benztriazole compound such as 5-methylbenztriazole, and may further contain a toning agent, a surfactant, an antifoaming agent, a water softener, a hardening agent, etc. as necessary. . Especially JP-A-56-1062
Amino compound described in No. 44, Japanese Patent Publication No. 48-35493
The imidazole compounds described in the above are preferred from the viewpoint of accelerating development or increasing sensitivity. The developer used in the present invention contains a compound described in JP-A No. 56-24347 as a silver stain preventive agent, and a compound described in JP-A No. 62-21 as a development unevenness preventive agent.
2,651) and the compound described in Japanese Patent Application No. 109743/1983 can be used as a solubilizing agent. The developer used in the present invention includes boric acid as described in JP-A-62-186259 as a buffering agent,
Saccharides (e.g., saccharose), oximes (e.g., acetoxime), phenols (e.g., 5-sulfosalicylic acid), tertiary phosphates (e.g., sodium salts, potassium salts), etc. described in 93433 are used, and preferably Boric acid is used. The fixing solution is an aqueous solution containing, in addition to the fixing agent, a hardening agent (for example, a water-soluble aluminum compound), acetic acid, and a dibasic acid (for example, tartaric acid, citric acid, or a salt thereof) as necessary, and preferably has a pH of 3. 8 or more,
More preferably it has 4.0 to 5.5. Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, with ammonium thiosulfate being particularly preferred from the viewpoint of fixing speed. The amount of fixing agent used can be varied as appropriate, and is generally about 0.1 to about 5 mol/l. The water-soluble aluminum salt which mainly acts as a hardening agent in the fixing solution is a compound generally known as a hardening agent for acidic hardening fixing solutions, and includes, for example, aluminum chloride, aluminum sulfate, and potassium alum. As the aforementioned dibasic acid,
Tartaric acid or its derivatives, citric acid or its derivatives can be used alone or in combination of two or more kinds. It is effective to contain these compounds at 0.005 mol or more per liter of fixer, especially from 0.01 mol/l to 0.03 mol/l.
Mol/l is particularly useful. Specifically, there are tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, ammonium tartrate, ammonium potassium tartrate, and the like. Examples of citric acid or its derivatives that are effective in the present invention include citric acid, sodium citrate, and potassium citrate. The fixer further contains a preservative (e.g. sulfite, bisulfite), p
H buffering agents (eg, acetic acid, boric acid), pH adjusting agents (eg, ammonia, sulfuric acid), image preservation improving agents (eg, potassium iodide), and chelating agents can be included. Here, since the pH of the developer is high, the pH buffer is used in the range of 10 to 40 g/l, more preferably in the range of 18 to 25 g/l. The fixing temperature and time are the same as in the case of development, preferably about 20° C. to about 50° C. and 10 seconds to 1 minute. Also, use anti-mold agents in the washing water (for example, Horiguchi's ``Chemistry of Bacteria and Prevention'', Japanese Patent Application Laid-open No. 1983-1999).
115154), a water washing accelerator (such as sulfite), a chelating agent, and the like. According to the above method, the developed and fixed photographic material is washed with water and dried. Washing with water is carried out to almost completely remove the silver salt dissolved during fixing, and is preferably carried out at about 20° C. to about 50° C. for 10 seconds to 3 minutes. Drying is carried out at a temperature of about 40° C. to about 100° C., and the drying time can be changed as appropriate depending on the surrounding conditions, but usually it is about 5 seconds to 3 minutes and 30 seconds. A roller conveyance type automatic developing machine is described in US Pat. No. 3,025,779, US Pat. Roller-conveyed processors are used for developing,
It consists of four steps: fixing, washing, and drying, and although the method of the present invention does not exclude other steps (for example, a stopping step), it is most preferable to follow these four steps. Here, in the water washing step, water can be saved by using a two to three stage countercurrent washing method. The developer used in the present invention is preferably stored in a packaging material with low oxygen permeability as described in JP-A-61-73147. Further, for the developer used in the present invention, a replenishment system described in JP-A-62-91939 can be preferably used. Since the silver halide photographic light-sensitive material of the present invention provides a high Dmax, it maintains a high density even if the halftone dot area is reduced when subjected to a reduction treatment after image formation. There are no particular restrictions on the reducing fluid used in the present invention.
For example, "The Theory of th
e Photographic Process” 738
~744 pages (1954, Macmillan),
Tetsuo Yano, “Photo Processing Theory and Practice” 166-169
In addition to published works such as Page (1978, Kyoritsu Shuppan),
No. 0-27543, No. 52-68429, No. 55-1
No. 7123, No. 55-79444, No. 57-1014
No. 0, No. 57-142639, JP-A-61-6115
Those listed in No. 5 etc. can be used. That is, permanganates, persulfates, ferric salts, cupric salts, ceric salts, red blood salts, dichromates, etc. are used alone or in combination as oxidizing agents, and if necessary, Inorganic acids such as sulfuric acid, reducing fluids containing alcohols, or oxidizing agents such as red blood salt or ferric ethylenediaminetetraacetic acid salt, and halogens such as thiosulfate, rhodan salt, thiourea, or their derivatives. A reducing solution containing a silver oxide solvent and, if necessary, an inorganic acid such as sulfuric acid is used. Typical examples of the reducing liquid used in the present invention include so-called Farmer reducing liquid, ferric salt of ethylenediaminetetraacetic acid, potassium permanganate, and ammonium persulfate reducing liquid (Kodak R-5).
, ceric salt reducing fluid. The conditions for the force reduction treatment are generally 10° C. to 40° C., particularly 15° C. to 30° C., and preferably can be completed within a few seconds to several tens of minutes, particularly within several minutes. By using the photosensitive material for plate making of the present invention, a sufficiently wide reduction width can be obtained within the range of these conditions. The reducing solution acts on the silver image formed in the emulsion layer through the non-photosensitive upper layer containing the compound of the present invention. Specifically, there are various methods, such as immersing the photosensitive material for plate making in a reducing liquid and stirring the liquid, or applying the reducing liquid to the surface of the sensitive material for plate making with a brush, roller, etc. method is available. [Examples] Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited thereto. Example 1 Preparation of Emulsion Emulsion A: A halogen salt aqueous solution containing 0.13M silver nitrate aqueous solution, 0.04M potassium bromide and 0.09M sodium chloride was mixed with sodium chloride and 1,8-dihydroxy-3,6 -Nucleation by adding to an aqueous gelatin solution containing dithiaoctane using a double jet method at 45°C for 12 minutes with stirring to obtain silver chlorobromide particles with an average particle size of 0.15 μm and a silver chloride content of 70 mol%. I did it. Then, in the same manner, 0.87M silver nitrate aqueous solution and 0.87M silver nitrate aqueous solution were added.
A halogen salt aqueous solution containing 26M potassium bromide and 0.65M sodium chloride was mixed with 20
It was added over a period of minutes. After that, it was washed with water by the flocculation method according to the usual method, 40 g of gelatin was added, and the pH was adjusted to 6.
．． 5. Adjust the pAg to 7.5, add 5 mg of sodium thiosulfate and 8 mg of chloroauric acid per mole of silver, and add 6.
The mixture was heated at 0° C. for 75 minutes to undergo chemical sensitization treatment, and 150 mg of 1,3,3a,7-tetrazaindene was added as a stabilizer. The obtained particles had an average particle size of 0.28 μm.
, silver chlorobromide cubic grains with a silver chloride content of 70 mol%. (Coefficient of variation 10%). Emulsion B: Sodium chloride and 1,8-dihydroxy-3,
Emulsion A was prepared in the same manner as Emulsion A, except that 10 mg of compound a contained in general formula [II-a] was further added to the aqueous gelatin solution containing 6-dithiaoctane, and the average grain size was 0.
Silver chlorobromide cubic particles having a diameter of 28 μm and a silver chloride content of 70 mol % were obtained. (Coefficient of variation 10%). Emulsion C: After grain formation, water washing and dispersion in the same manner as in Emulsion A, 20 mg of compound a contained in general formula [II-a] per mole of silver was added, and chemical amplification was carried out in the same manner as in Emulsion A. Sensitivity treatment is carried out, and the final average particle size is 0.
Silver chlorobromide cubic particles having a diameter of 28 μm and a silver chloride content of 70 mol % were obtained. (Coefficient of variation 10%). Emulsion D: Further, ammonium hexachlororhodium(III) acid was added to the halogen salt aqueous solution used during nucleation, and then 0.26M potassium bromide and 0.65M potassium bromide were added.
Emulsion A was prepared in exactly the same manner as Emulsion A, except that an aqueous solution of potassium hexachloroiridate (III) was added to an aqueous solution of a halogen salt containing sodium chloride. Mol, Ir
containing 6.0 x 10-7 moles, average particle size 0.
Silver chlorobromide cubic grains having a diameter of 28 μm and a silver chloride content of 70 mol % were obtained (coefficient of variation 10%). Emulsion E: Add ammonium hexachlororhodium(III) to the halogen salt aqueous solution used for nucleation, and add hexachloroiridium(III) to the halogen salt aqueous solution containing 0.26M potassium bromide and 0.65M sodium chloride. The procedure was exactly the same as Emulsion B, except that an aqueous solution containing potassium acid was added, and 1.0 x 10-7 mol of Rh and 6 mol of Ir were used per mol of silver.
．． Containing 0x10-7 moles, average particle size 0.28
Cubic silver chlorobromide grains with a diameter of 70 mol % and a silver chloride content of 70 mol % were obtained (coefficient of variation 10%). Emulsion F: Add ammonium hexachlororhodium(III) to the halogen salt aqueous solution used during nucleation, and add hexachloroiridium(III) to the halogen salt aqueous solution containing 0.26M potassium bromide and 0.65M sodium chloride. ) The procedure was exactly the same as Emulsion C except that an aqueous solution containing potassium acid was used.
1.0 x 10-7 mol of Rh and 6 mol of Ir per mol of silver
．． Containing 0x10-7 moles, average particle size 0.28
Cubic silver chlorobromide grains with a diameter of 70 mol % and a silver chloride content of 70 mol % were obtained (coefficient of variation 10%). Preparation of coating sample 60 ml of a 0.05% solution of the sensitizing dye shown in Table 1 was added to 1 kg of the above emulsion to carry out sensitization in the infrared region. This emulsion was given 4,4'-bis-(4
,6-dinaphthoxy-pyrimidin-2-ylamino)-
70 ml of 0.5% methanol solution of stilbene disulfonic acid disodium salt and 2,5-dimethyl-3-allyl-
0.5% methanol solution of benzothiazole iodo salt 9
Added 0ml. In addition, hydroquinone 100mg/m
2. Polyethyl acrylate latex was used as a plasticizer at a gelatin binder ratio of 25%, and 2-bis(
86.2 mg of vinylsulfonylacetamido)ethane
/m2 added 3.7 g/m2 of silver on polyester support
It was applied so that Gelatin was 2.5 g/m2. On top of this, gelatin 0.6g/m2 and polymethyl methacrylate with a particle size of 3 to 4μ as a matting agent 60mg/
m2, colloidal silica 70mg with particle size 10-20mμ
/m2, silicone oil 10mg/m2, dodecylbenzenesulfonic acid sodium salt as a coating aid, a protective layer upper layer to which a fluorine surfactant of the following structural formula (■) was added, gelatin 0.7g/m2, polyethyl acrylate. Latex 225mg/m2, dye represented by ■20mg/m2, dye represented by ■10mg/m2
2 and a lower protective layer to which sodium dodecylbenzenesulfonate was added as a coating aid were simultaneously coated to prepare a sample. ##STR31## The base used in this example has a back layer and a back protective layer having the following compositions. (back layer,
The swelling rate is 110%. ) (Back layer) Gelatin

3.0g/m2 Sodium dodecylbenzenesulfonate
80mg dye a

80mg
〃b

30mg〃c

100mg
1,3-divinylsulfonyl-2-propanol
60mg/m2 Potassium polyvinyl-benzenesulfonate
30g/m2 (back protective layer) gelatin

0.75g/m2 polymethyl methacrylate (particle size 4.7μ)
30mg/m2 Sodium dodecylbenzenesulfonate
20mg/m2 Fluorine surfactant (above compound ■)
2mg/m2 silicone oil

100mg/m2 00
69] [Chemical 34] [Chemical 34] [Chemical 35] [Chemical 36] [Chemical 36] [Chemical 36] Developing solution formulation Water

720ml Ethylenediaminetetraacetic acid disodium salt
4g sodium hydroxide

44g Sodium sulfite

45g 2-methylimidazole

2g carbonated soda

26.4g boric acid


1.6g potassium bromide

1g hydroquinone

36g diethylene glycol

39g 5-methyl-benzotriazole
0.2g Pyrazone


Add 0.7g water

1l fixer formulation ammonium thiosulfate

170g sodium sulfite (anhydrous)

15g nitric acid


7g glacial acetic acid

15ml
potash alum

20g ethylenediaminetetraacetic acid
0.1g tartaric acid

Add 3.5g water

1
l Evaluation of photographic performance The obtained sample was passed through an interference filter having a peak at 780 nm and a continuous wedge for a light emission time of 10-6 seconds.
Exposure to xenon flash light of Then, sensitometry was performed.The reciprocal of the exposure amount that gives a density of 3.0 was taken as the sensitivity, and the relative sensitivity is shown in Table 1.The characteristic curve also shows the density of 0.1 and 3.0.
Table 1 also shows the gradient of the straight line connecting the points. As is clear from Table 1, the samples of the present invention have high sensitivity without sacrificing high contrast. [Table 1] [0075]

Claims (2)

[Claims] 1. A silver halide photographic material containing a compound represented by the following general formula (I). General formula (I) [Image Omitted] In the formula, R1 and R2 may each be the same or different, and each represents an alkyl group. R3 is a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group,
Represents a benzyl group or a phenethyl group. R4 and R
5 may be the same or different and each represents a lower alkyl group. V represents a hydrogen atom, a lower alkyl group, an alkoxy group, a halogen atom or a substituted alkyl group. Z1 represents a group of nonmetallic atoms necessary to complete a 5- or 6-membered nitrogen-containing heterocycle. X1 represents an acid anion. m, p and q each independently represent 1 or 2. However, when the dye forms an inner salt, q is 1. i and j represent integers from 0 to 4, but cannot be 0 at the same time. 2. The silver halide photographic light-sensitive material according to claim 1, which has at least one silver halide photographic emulsion layer on a support, and the silver halide grains in the silver halide emulsion are monolithic. 2. The silver halide photographic material according to claim 1, which comprises dispersed particles.