JPH04362931A - Silver halide photographic sensitive material and processing method therefor - Google Patents

Abstract

PURPOSE:To enhance the sensitivity and contrast of a silver halide photographic sensitive material for high illuminance exposure having color sensitivity in an IR region. CONSTITUTION:A silver halide emulsion used contains atoms of a group Va, VIa, VIIa or VIII metal with a nitrosyl or thionitrosyl ligand and has been spectrally sensitized at >=750nm wavelength.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to a silver halide photographic material that is spectrally sensitized in the infrared region.
The present invention relates to a silver halide photographic material having high contrast and excellent suitability for rapid processing, and a developing method thereof.

0002

[Prior Art] 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 creating a negative or positive image corresponding to the image on the original image. An image forming method using a so-called scanner method 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 drawbacks, if a coherent laser light source such as a He-Ne, Ar, or He-Cd laser is used, high output can be obtained, but the device becomes large. It's expensive. A modulator is required. Since visible light is used, the safe light of the photosensitive material is limited, and there are drawbacks such as poor handling. 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 safelight can be produced. It has the advantage of improved handling and workability. However, if a semiconductor laser is used as is without special shaping of the laser beam,
The energy distribution is broad, making it difficult to obtain good halftone dot images or line images. Furthermore, in recent years, there has been a strong desire to improve the efficiency and speed of work in the printing industry, and there is a wide range of needs for faster scanning and shorter processing times for photosensitive materials. In order to meet these needs, photosensitive materials are required to have sufficient sensitivity in the infrared region during high-intensity exposure, high contrast, rapid development, and suitability for rapid processing. In response to such requests, for example, Japanese Patent Laid-Open No. 63-4
9752 contains iridium ions in silver halide grains, and provides a photosensitive material that has high sensitivity and high contrast in high-intensity, short-time exposure in the infrared region, and has excellent developability and development temperature dependence. Although methods have been disclosed, they are still insufficient.

0003

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to have appropriate spectral sensitivity to infrared light, high sensitivity and high contrast in high-intensity short-time exposure, and low processing dependence. An object of the present invention is to provide a silver halide photographic material having suitability for rapid processing.

0004

[Means for Solving the Problems] These objects of the present invention are as follows:
In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the silver halide emulsion has a nitrosyl or thionitrosyl ligand, and is a silver halide emulsion having a nitrosyl or thionitrosyl ligand. This was achieved by a silver halide photographic light-sensitive material comprising silver halide grains containing a transition metal selected from the elements of the above group, and characterized in that the sensitization maximum is spectrally sensitized to a wavelength longer than 750 nm. .

The specific structure of the present invention will be explained in detail below. A preferred transition metal ligand complex that achieves the object of the present invention is a hexacoordination complex represented by the following general formula. [M(MY)L5]m (where M is a transition metal selected from the elements of groups Va to VIIa or VIII of the Periodic Table of the Elements. The period and group of the elements follow the IUPAC nomenclature.L is a bridging ligand and may be substituted with one (NY). Y is oxygen or sulfur. m = 1, -1, -2, -3.) Nitrosyl and thionitrosyl bridging ligands L other than Ishi
Preferred specific examples include halide ligands (fluoride, chloride, bromide and iodide), cyanide ligands, cyanate ligands, thiocyanate ligands, selenocyanate ligands, tellocyanate ligands. Ligands include azide ligands and aco ligands. If an aco ligand is present, it is preferred that it occupies one or two of the ligands. Particularly preferred examples of M are rhodium, ruthenium, rhenium, osmium, and iridium. Specific examples of transition metal coordination complexes are shown below. 1 [Ru(NO)Cl5]-2 2 [Ru(NO)2Cl4]-13 [Ru
(NO)(H2O)Cl4 ]-14 [Rh(N
O)Cl5]-2 5 [Re(NO)Cl5]-2 6 [Re(NO)CN5]-2 7 [Re(NO)ClCN4]-28 [Rh
(NO)2 Cl4 ]-19 [Rh(NO)(H
2 O)Cl4 ]-110 [Ru(NO)CN5
]-211 [Ru(NO)Br5]-212
[Rh(NS)Cl5]-213 [Os(NO
)Cl5]-214 [Cr(NO)Cl5]-
315 [Re(NO)Cl5]-116 [O
s(NS)Cl4 (TeCN)]-217 [Ru
(NS)I5]-2 18 [Re(NS)Cl4 (SeCN)]-21
9 [Os(NS)Cl(SCN)4]-220
[Ir(NO)Cl5]-2

[0006] In order to incorporate the metal complex into silver halide, it can be added at the time of grain preparation. The content of the transition metal in the silver halide grains of the present invention is at least 10-8 to 1 x 10-6 mol per mol of silver halide, but preferably 10
-7 to 5 x 10-7 mol. In the silver halide grains of the present invention, metals having different ligands can be used in combination with the metal complexes having nitrosyl and thionitrosyl ligands. Compounds containing these metals preferably used in the present invention include iron (II) sulfate FeS
O4 −5H2 O; iron(III) chloride FeCl3
; Hexacyanoferric (II) iron potassium K4 Fe (CN
)6 ・3H2 O; Hexacyanoiron(III) Iron potassium K3 Fe(CN)6 ; Cobalt(II) chloride
CoCl2; Cobalt(II) nitrate Co(NO3)
2 ・6H2 O; hexacyanocobalt (III)
Potassium acid K3 Co(CN)6 ; Nickel chloride (I
I) NiCl2; 6H2O nickel (II) nitrate N
i(NO3)2 ・6H2 O; Ruthenium chloride (I
II) RuCl3; hexachlororuthenium (IV)
Potassium acid K2 RuCl6; Rhodium chloride (II
I) RhCl3 4H2 O; ammonium hexachlororhodium(III) acid (NH)3 RhCl6
; Palladium (II) chloride PdCl2; Palladium (II) nitrate Pd(NO3)2; Palladium bromide (
II) PdBr2; hexachloropalladium (IV)
potassium tetrathiopalladate(II) acid K2 Pd(CNS)4 ; osmium(II) chloride OsCl2 ; iridium(I) chloride
II) IrCl3; Iridium (IV) chloride IrC
l4; Iridium(III) bromide IrBr3 ・4
H2 O; Iridium(IV) bromide IrBr4; Potassium hexachloroiridium(III) acid K3 Ir
Cl6 ; Potassium hexachloroiridate (IV) K2 IrCl6 ; Ammonium hexachloroplatinate (IV) (NH4)2 PtCl6 ; Potassium hexachloroplatinate (IV) K2 PtCl6 ; Ammonium hexabromoplatinate (IV) (NH4)2 PtB
r6 ; etc. These metal compounds may be used alone in an amount corresponding to 10<-9> to 10<-3> moles per mole of silver halide, or two or more kinds of compounds may be used in combination.

There is no particular restriction on the halogen composition of the silver halide emulsion used in the present invention, but from the viewpoint of suitability for rapid processing, silver iodochlorobromide or silver chlorobromide with a silver chloride content of 50 mol% or more is preferred. is preferred. The average grain size of the silver halide emulsion in the present invention is preferably 0.7 μm or less, more preferably 0.2 μm to 0.5 μm. The particle size distribution is preferably monodisperse.

[0008] The monodisperse particles mentioned here have a coefficient of variation of
By this we mean a silver halide emulsion with a grain size distribution of less than 20%, particularly preferably less than 15%. The coefficient of variation (%) is expressed as a value obtained by dividing the standard deviation of the grain size of silver halide grains by the average value of the grain size and multiplying the value by 100. The silver halide grains used in the present invention are preferably cubic grains consisting essentially of (100) planes. Here, "substantially consisting of (100) planes" specifically refers to preferably 50% or more, more preferably 80% or more, particularly preferably 95% or more of the grains contained in the silver halide emulsion. This means that several particles are cubic and/or particles in which (100) planes occupy 60% or more of the surface area of the particles. The photographic emulsion used in the present invention is P.
Chimie et Phys by Glafkides
ique Photographique (Paul
Montel Publishing, 1967), G. F. Duff
inAuthor Photographic Emulsion
Chemistry (The Focal Press
(Published, 1966), V. L. Zelikman et.
Making and Coating P
Photographic Emulsion (The
Focal Press, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the formation of the reaction between the soluble silver salt and the soluble halogen salt may be performed using any of the one-sided mixing method, simultaneous mixing method, and a combination thereof. good. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As one type of simultaneous mixing method, a method in which 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 addition, in order to make the particle size uniform, British patent 1,
No. 535,016, Special Publication No. 48-36890, 52-
As described in No. 16364, a method of changing the addition rate of silver nitrate or alkali halide depending on the grain growth rate, British Patent No. 4,242,445, Japanese Patent Application Laid-open No. 5
It is preferable to use a method of varying the concentration of an aqueous solution as described in Japanese Patent No. 5-158124 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.

The grain formation of the silver halide emulsion of the present invention is as follows:
Preferably, the reaction is carried out in the presence of a silver halide solvent such as a tetrasubstituted thiourea or an organic thioether compound. Preferred tetrasubstituted thiourea silver halide solvents used in the present invention are:
It is a compound represented by the following general formula described in JP-A-53-82408 and JP-A-55-77737.

0010

[Chemical formula 1]

In the formula, R1, R2, R3 and R4
is a substituted or unsubstituted alkyl group, alkenyl group (
(allyl group, etc.), or substituted or unsubstituted aryl, which may be the same or different from each other,
The total number of carbon atoms in R1 to R4 is preferably 30 or less. Also, R1 and R2, R2 and R3, or R3
and R4 to form a 5- to 6-membered heterocyclic imidazolidinethione, piperidine, morpholine, etc. Both straight chain and branched alkyl groups are used as the alkyl group. Examples of substituents for alkyl groups include hydroxy groups (-OH), carboxy groups, sulfonic acid groups, amino groups, alkoxy groups (o-alkyl) in which the alkyl residue has 1 to 5 carbon atoms, phenyl groups, It is a 5- or 6-membered heterocycle (such as furan). The substituent for the aryl group is a hydroxy group, a carboxy group or a sulfonic acid group. Here, particularly preferably R1 to R4
Among them, there are three or more alkyl groups, each alkyl group has 1 to 5 carbon atoms, the aryl group is a phenyl group, and R1
The total number of carbon atoms in ~R4 is 20 or less. Examples of compounds that can be used in the present invention include the following.

0012

[Case 2]

[0013]

[Chemical formula 3]

[0014]

[C4]

The organic thioether silver halide solvent preferably used in the present invention is disclosed in Japanese Patent Publication No. 47-11386, for example.
Compounds containing at least one group in which an oxygen atom and a sulfur atom are separated by ethylene (e.g. -O-CH2 CH2 -S-) described in JP-A No. 3,574,628, etc. No. 54-155828 (U.S. Pat. No. 4,276,374), an alkyl group at both ends (each alkyl group has at least two substituents selected from hydroxy, amino, carboxy, amide, or sulfone) ) is a chain-like thioether compound. Specifically, the following examples can be given.

[0016]

[C5]

The amount of silver halide solvent added varies depending on the type of compound used, the intended grain size, halogen composition, etc., but it is 10-5 per mol of silver halide.
~10 −2 mol is preferred. If the grain size exceeds the desired size due to the use of a silver halide solvent, the desired grain size can be achieved by changing the temperature during grain formation, the addition time of the silver salt solution, the halide salt solution, etc.

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. As a reduction sensitizer, stannous salt,
Amines, formamidine sulfinic acid, silane compounds, etc. can be used.

The silver halide emulsion of the present invention is disclosed in Japanese Patent Application Laid-Open No.
A thiosulfonic acid compound may be added by the method shown in No. 264935.

The silver halide emulsion of the present invention has a wavelength of 750 nm.
Infrared sensitization is performed to have a maximum in the above wavelength range. Any sensitizing dye may be used for infrared sensitization, but
From the viewpoint of sensitization performance and stability, it is particularly preferable to use a dye represented by the general formula shown below. The general formulas and specific compound examples thereof are shown below.

[0021]

[C6]

In the formula, R1 and R2 may be the same or different, and each represents an alkyl group (including substituted alkyl groups). Preferably 1 to 1 carbon atom
8. For example, methyl, ethyl, propyl, butyl, pentyl,
Heptyl, octyl. Examples of substituents include carboxyl group, sulfo group, cyano group, halogen atom (e.g. fluorine atom, chlorine atom, bromine atom), hydroxyl group, alkoxycarbonyl group (preferably 8 or less carbon atoms,
(e.g. methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl, etc.), alkoxy groups (preferably 7 or less carbon atoms, e.g. methoxy, ethoxy, propoxy, butoxy, benzyloxy), aryloxy groups (e.g. phenoxy, p-tolyloxy), 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-dimethyl) carbamoyl, morpholinocarbamoyl, piperidinocarbamoyl), sulfamoyl groups (e.g. sulfamoyl, N,N-dimethylsulfamoyl, morpholinosulfonyl), aryl groups (e.g. phenyl, p-hydroxyphenyl, p-carboxyphenyl, 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. V is a hydrogen atom, a lower alkyl group (preferably 1 to 4 carbon atoms, e.g. methyl, ethyl, propyl)
, alkoxy groups (preferably 1 to 4 carbon atoms, e.g. methoxy, ethoxy, butoxy), halogen atoms (e.g. fluorine atoms, chlorine atoms), substituted alkyl groups (preferably 1 to 4 carbon atoms, e.g. trifluoromethyl, carboxymethyl).

Z1 represents a nonmetallic atom 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-chlorobenzothiazole, Chlorbenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6
-Methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 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-trifluorobenzoxazole, 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 nucleus (
For example, 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-chloroindolenine), 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-dichlorobenzo Imidazole, 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), pyridine nuclei (e.g. 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 (for example, chloride, bromide, iodide, tetrafluoroborade, hexafluorophosphate, methylsulfate, ethylsulfate, benzenesulfonate, 4-methylbenzenesulfonate, 4-chlorobenzenesulfonate, 4 −
nitrobenzenesulfonate, trifluoromethanesulfonate, perchlorate).

[0026]

[C7]

In the formula, R1' and R2' may be the same or different, and each represents an alkyl group (including substituted alkyl groups). 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 (e.g. fluorine atom, chlorine atom, bromine atom), hydroxyl group, alkoxycarbonyl group (preferably 8 or less carbon atoms, e.g. methoxycarbonyl, ethoxycarbonyl) , benzyloxycarbonyl, etc.), alkoxy groups (
Preferably 7 or less carbon atoms, e.g. methoxy, ethoxy, propoxy, butoxy, benzyloxy), aryloxy groups (e.g. phenoxy, p-tolyloxy),
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-carboxyphenyl, p-sulfamoyl), phenyl, α-naphthyl)
Examples include alkyl groups substituted with (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' and R4' are hydrogen atoms, lower alkyl groups (preferably 1 to 4 carbon atoms, such as methyl,
ethyl, propyl, butyl), lower alkoxy groups (preferably 1 to 4 carbon atoms, e.g. methoxy, ethoxy,
propoxy, butoxy), phenyl group, benzyl group or phenethyl group. In particular, lower alkyl groups and benzyl groups are advantageously used. R5' and R6' each represent a hydrogen atom, or R5' and R6' are linked to form a divalent alkylene group (eg, ethylene or trimethylene). The alkylene group may contain one, two or more suitable groups, such as alkyl groups (preferably having 1 to 4 carbon atoms, such as methyl, ethyl, propyl,
isopropyl, butyl), a halogen atom (for example, a chlorine atom, a bromine atom), or an alkoxy group (preferably having 1 to 4 carbon atoms, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy). R7' is a hydrogen atom, a lower alkyl group (preferably having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, etc.), or a lower alkoxy group (preferably having 1 carbon atom).
~4, e.g. methoxy, ethoxy, propoxy, butoxy), phenyl, benzyl group, or -N(W1'
)(W2'). Here, W1' and W2' each independently represent an alkyl group (including substituted alkyl groups. Preferably, the alkyl moiety has 1 to 18 carbon atoms, more preferably 1 to 4 carbon atoms, such as methyl, ethyl, propyl, butyl,
benzyl, phenylethyl), or aryl groups (including substituted phenyl groups, such as phenyl, naphthyl, tolyl,
p-chlorophenyl, etc.), and W1' and W2
' can also be linked to each other to form a 5- or 6-membered nitrogen-containing heterocycle. However, R3' and R7' or R4' and R7' are connected to form a divalent alkylene group (
(synonymous with the divalent alkylene group formed by connecting R5' and R6').

Z' and Z1' represent 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-chlorobenzo Thiazole, 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
-dianoindolenine, 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
-Chlorbenzimidazole, 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)
, a pyridine nucleus (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.

X1' is an acid anion (eg chloride,
Bromide, iodide, tetrafluoroborade, hexafluorophosphate, methyl sulfate, ethyl sulfate, benzene sulfonate, 4-methylbenzenesulfonate, 4-chlorobenzenesulfonate, 4
- nitrobenzenesulfonate, trifluoromethanesulfonate, perchlorate). m' represents 0 or 1, and is 1 when the dye forms an inner salt.

Specific examples of compounds are shown below. However, the present invention is not limited to these.

[0032]

[Chemical formula 8]

[0033]

[Chemical formula 9]

[0034]

[Chemical formula 10]

[0035]

[Chemical formula 11]

[0036]

[Chemical formula 12]

[0037]

[Chemical formula 13]

[0038]

[Chemical formula 14]

[0039]

[Chemical formula 15]

[0040]

[Chemical formula 16]

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. useful sensitizing dyes,
Combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are subject to Research Disclosure.
176 volume 17643 (1978 1
Published in February) Page 23, IV, Section J, or the above-mentioned Japanese Patent Publications No. 49-25500, No. 43-4933, and Japanese Patent Publication No. 59-1
9032, 59-192242, etc. The content of the sensitizing dye of the present invention depends on the grain size of the silver halide emulsion, the halogen composition, the method and degree of chemical sensitization, the relationship between the layer containing the compound and the silver halide emulsion, the type of antifogging compound, etc. It is desirable to select the optimal amount accordingly, and testing methods for this selection are well known to those skilled in the art. Usually, it is preferably used in a range of 10@-7 mol to 1.times.10@-2 mol, particularly 10@-6 to 5.times.10@-3 mol, per mol of silver halide.

[0042] Infrared sensitizing dyes represented by these general formulas can be synthesized by methods such as those disclosed in JP-A-59-192242 or US Pat. Nos. 3,482,978 and 2,756,227. Can be done. The sensitizing dye having the above general formula is preferable because it has excellent sensitizing properties, especially in the infrared region. In the present invention, compounds of the following general formula can be further used in combination.

[0043]

[Chemical formula 17]

In the formula, Z3 represents a nonmetallic atom group necessary to complete a 5- or 6-membered nitrogen-containing heterocycle, such as thiazoliums {such as thiazolium, 4-methylthiazolium, benzothiazolium, -Methylbenzothiazolium, 5-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 (
For example, 1-methylbenzimidazolium, 1-propyl-5-chlorobenzimidazolium, 1-ethyl-5,
6-dichlorobenzimidazolium, 1-allyl-5-
trichloromethyl-6-chloro-benzimidazolium, etc.), selenazoliums [e.g. benzoselenazolium, 5-chlorobenzoselenazolium, 5-methylbenzoselenazolium, 5-methoxybenzoselenazolium, naphtho[1, 2-d] selenazolium, etc.]. R13 represents a hydrogen atom, an alkyl group (having 8 or less carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, etc.), or an alkenyl group (such as an allyl group). R14 represents a hydrogen atom or a lower alkyl group (eg, methyl group, ethyl group, etc.). X2 is an acid anion (e.g. Cl-, Br-, I-, ClO4-, p
-toluenesulfonic acid, etc.), thiazoliums are preferably used among Z3. More preferably, substituted or unsubstituted benzothiazolium or naphthothiazolium is advantageously used. How to show specific examples of compounds. However, the present invention is not limited to only these compounds.

[0045]

[Chemical formula 18]

[0046]

[Chemical formula 19]

[0047]

[C20]

[0048]

[C21]

The above compounds are advantageously used in amounts of about 0.01 to 5 grams per mole of silver halide in the emulsion. The ratio (weight ratio) of the above-mentioned infrared sensitizing dye of the present invention to the above compound is advantageously used in the range of infrared sensitizing dye of the present invention / above compound = 1/1 to 1/300, In particular, a range of 1/2 to 1/50 is advantageously used. The above compounds used in the present invention can be directly dispersed in an emulsion, or can be dispersed in an appropriate solvent (for example, water, methyl alcohol, ethyl alcohol, propanol, methyl cellosolve, acetone, etc.) or a combination of these solvents. It can also be dissolved in a mixed solvent and added to an 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 above compound may be added to the emulsion before or after the addition of the infrared sensitizing dye of the invention described above. Alternatively, the above compound and the infrared sensitizing dye may be dissolved separately and added separately to the emulsion at the same time, or they may be mixed and then added to the emulsion. Compounds having the following general formula can also be added to the combinations of the invention.

[0050]

[C22]

In the formula, -A- represents a divalent aromatic residue, and these are -SO3M groups [where M is a hydrogen atom or a cation imparting water solubility (for example, sodium, potassium, etc.)]
represents. ] may be included. -A- is usefully selected from, for example, the following -A1- or -A2-. However, -SO in R21, R22, R23 or R24
3 When M is not included, -A- is selected from the group -A1 -.

[0052]

[C23]

[0053]

[C24]

[0054]

[C25]

R21, R22, R23, and R24 are each a hydrogen atom, a hydroxy group, or a lower alkyl group (the number of carbon atoms is preferably 1 to 8, such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, etc.) ), an alkoxy group (the number of carbon atoms is preferably 1 to 8; for example, a methoxy group, an ethoxy group, a propoxy group, a 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, R2
At least one of 4 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 the above compounds will be given. However, it is not limited only to these compounds.

(a) 4,4'-bis[4,6-di(benzothiazolyl-2-thio)pyrimidin-2-ylamino]stilbene-2,2'-disulfonic acid sodium salt (
b) 4,4'-bis[4,6-di(benzothiazolyl-
2-amino)pyrimidin-2-ylamino)]stilbene-2,2'-disulfonic acid disodium salt (c) 4,
4'-bis[4,6-di(naphthyl-2-oxy)pyrimidin-2-ylamino]stilbene-2,2'-disulfonic acid disodium salt (di)4,4'-bis[4,6-di (naphthyl-2-oxy)pyrimidin-2-ylamino]bibenzyl-2,
2'-disulfonic acid disodium salt (e) 4,4'-bis(4,6-dianilinopyrimidin-2-ylamino)stilbene-2,2'-disulfonic acid disodium salt (f) 4,4'- Bis[4-chloro-6-(2-naphthyloxy)pyrimidin-2-ylamino]biphenyl-
2,2'-disulfonic acid disodium salt (t)4,4'
-bis[4,6-di(1-phenyltetrazolyl-5-
thio)pyrimidin-2-ylamino]stilbene-2,
2'-disulfonic acid disodium salt

(H)
4,4'-bis[4,6-di(benzimidazolyl-2
-thio)pyrimidin-2-ylamino]stilbene-2
, 2'-disulfonic acid disodium salt (li) 4,4'-bis[4,6-diphenoxypyrimidin-2-ylamino)stilbene-2,2'-disulfonic acid disodium salt (nu) 4,4'-bis[4,6-diphenylthiopyrimidin-2-ylamino)stilbene-2,2'-disulfonic acid disodium salt (ru)4,4'-bis[4,6-dimercaptopyrimidin-2-ylamino)biphenyl -2,2'-disulfonic acid disodium salt (w) 4,4'-bis[4,6-dianilino-triazin-2-ylamino)stilbene-2,2'-disulfonic acid disodium salt (w) 4, 4'-bis(4-anilino-6-hydroxy-triazin-2-ylamino)stilbene-2,2'
-Disulfonic acid disodium salt (f) 4,4'-bis[4-naphthylamino-6-anilino-triazin-2-ylamino)stilbene-2,
2'-Disulfonic acid disodium salt (Yo)4,4'-bis[2,6-di(2-naphthoxy)
pyrimidin-4-ylamino]stilbene-2,2'-
Disulfonic acid (ta)4,4'-bis[2,6-di(2-naphthylamino)pyrimidin-4-ylamino]stilbene-2,2
'-Disulfonic acid disodium salt (l)4,4'-bis[2,6-dianilinopyrimidin-4-ylamino)stilbene-2,2'-disulfonic acid disodium salt (l)4,4'-bis [2-naphthylamino)-6-anilinopyrimidin-4-ylamino]stilbene-2,
2'-Disulfonic acid (2) 4,4'-bis[2,6-diphenoxypyrimidin-4-ylamino]stilbene-2,2'-disulfonic acid ditriethylammonium salt (2)4,4'-bis[ 2,6-di(benzimidazolyl-2-thio)pyrimidin-4-ylamino]stilbene-2,2'-disulfonic acid disodium salt

0058
] The compounds represented by the above general formula are known or can be easily produced according to known methods. The above compounds used in the present invention may be a mixture of two or more thereof. The above compounds are advantageously used in amounts of about 0.01 to 5 grams per mole of silver halide in the emulsion. The ratio (weight ratio) of the infrared sensitizing dye and the compound represented by the above general formula is dye/the above compound = 1
/1 to 1/200 is advantageously used, in particular 1/1 to 1/200.
A range of 2 to 1/50 is advantageously used. The compound represented by the above general formula used in the present invention can be directly dispersed in an emulsion, or can be dissolved in a suitable solvent (for example, methyl alcohol, ethyl alcohol, methyl cellosolve, water, etc.) or a mixed solvent thereof. It can also 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. They can also be dispersed and added into the emulsion by the method described in JP-A-50-80119.

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,
Mercaptothiadiazoles, aminotriazoles,
benzothiazoles, nitrobenzotriazoles, etc.; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinthione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1, 3,
3a, 7) tetrazaindenes), pentaazaindenes, etc.; many compounds known as antifoggants or stabilizers can be added, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. can.

[0060] 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.

[0061]

[C26]

X and Y are respectively -H, -OH, 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, -COO
H, -CH2 CH2 COOH, -CH3, -CH
2 CH3, -CH(CH3)2, -C(CH3
)3, -OCH3, -CHO, -SO3Na,
-SO3H, -SCH3,

[0063]

[C27]

[0064] etc. X and Y may be the same or different. Particularly preferred representative compound examples are shown below.

[0065]

[C28]

[0066]

[C29]

[0067]

[C30]

[0068]

[Chemical formula 31]

The polyhydroxybenzene compound may be added to the emulsion layer of the sensitive material, or may be added to a layer other than the emulsion 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 produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer 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.

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], 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-53-41220, JP-A-53
-57257, 59-162546, 60-808
46 and U.S. Pat. No. 3,32
The active halides described in No. 5,287 are preferred.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced using the present invention may contain coating aids, antistatic agents, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (for example, development acceleration). Various surfactants may be included for various purposes such as increasing contrast, increasing contrast, and increasing sensitization. For example, saponin (
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, polyalkylene glycol alkyl amines, amides, polyethylene oxide adducts of silicone),
Nonionic surfactants such as glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonic acids salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc. such as esters; amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphate esters amphoteric surfactants such as alkyl betaines, amine oxides; alkyl amine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and aliphatic or hetero Cationic surfactants such as ring-containing 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 or other hydrophilic colloid layer 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 preferably used in an amount of usually 0.05 mol/liter to 0.8 mol/liter. Further, when using a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-amino-phenols, the former should be mixed at 0.05 mol/liter - 0.05 mol/liter.
5 mol/l, the latter preferably in an amount of up to 0.06 mol/l. Sulfite preservatives used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and sodium formaldehyde bisulfite. The amount of sulfite is preferably 0.3 mol/liter or more, particularly 0.4 mol/liter or more. Further, the upper limit is preferably up to 2.5 mol/liter, particularly up to 1.2 mol/liter.

[0076] Alkaline agents used for setting pH include sodium hydroxide, potassium hydroxide, sodium carbonate,
Contains pH adjusters and buffers such as potassium carbonate, tribasic sodium phosphate, 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, and potassium iodide; ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, and methyl cellosolve. , organic solvents such as hexylene glycol, ethanol, and methanol; mercapto compounds such as 1-phenyl-5-mercaptotetrazole and 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. . In particular, the amino compounds described in JP-A-56-106244 and the imidazole compounds described in JP-B-48-35493 are preferred from the standpoint 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. 62-212,651 as an agent for preventing uneven development.
The compound described in JP-A-61-2677 as a solubilizing agent
Compounds described in No. 59 can be 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. , has a pH of 3.8 or more, more preferably 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 changed as appropriate, and is generally about 0.1
~about 5 mol/liter. The water-soluble aluminum salt used mainly as a hardening agent in the fixing solution is a compound generally known as a hardening agent for acidic hardening fixing solutions, such as aluminum chloride, aluminum sulfate, and potassium alum. As the above-mentioned dibasic acid, tartaric acid or its derivative, citric acid or its derivative can be used alone or in combination of two or more kinds. It is effective to use these compounds in an amount of 0.005 mol or more per liter of the fixing solution, particularly 0.01 mol/liter to 0.03 mol/liter. Specifically, tartaric acid,
Potassium tartrate, sodium tartrate, potassium sodium tartrate, ammonium tartrate, ammonium potassium tartrate, etc. 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) if desired.
, a pH buffering agent (eg, acetic acid, boric acid), a pH adjusting agent (eg, ammonia, sulfuric acid), an image preservation improving agent (eg, potassium iodide), and a chelating agent. Here the pH
Since the pH of the developing solution is high, the buffering agent is used in an amount of about 10 to 40 g/liter, more preferably about 18 to 25 g/liter.

The total processing time of the photosensitive material of the present invention is 15 seconds or more.
It exhibits excellent performance in rapid development processing using an automatic processor in 60 seconds. In the rapid development process of the present invention, the temperature and time of development and fixing are each about 25 DEG C. to 50 DEG C. and 25 seconds or less, preferably 30 DEG C. to 40 DEG C. and 4 seconds to 15 seconds. In the present invention, the photosensitive material is subjected to water washing or stabilization treatment after being developed and fixed. Here, in the water washing step, water can be saved by using a two to three stage countercurrent washing method. Further, when washing with a small amount of washing water, it is preferable to provide a squeeze roller washing tank. Further, part or all of the overflow liquid from the washing bath or the fixing bath can be used as a fixing liquid as described in JP-A-60-235133. By doing so, the amount of waste liquid is also reduced, which is more preferable. In addition, in the washing water, mold inhibitors (for example, the compounds described in Horiguchi's "Chemistry of Bacteria and Prevention", Japanese Patent Application Laid-open No. 115154/1983), washing accelerators (sulfites, etc.), chelating agents, etc. May contain. The temperature and time of the water washing or stabilization bath in the above method are 0°C to 50°C for 5 seconds to 30 seconds, preferably 4 seconds to 20 seconds at 15°C to 40°C. In the present invention, the developed, fixed, and water-washed photosensitive material is dried using a squeeze roller. Drying at 40°C to 80°C for 4 seconds to 30 minutes
Done in seconds. The total processing time in the present invention is defined as the time from when the leading edge of the film is inserted into the insertion slot of the automatic processor, to the developer tank,
This is the total time it takes for the film to pass through the transfer section, fixing tank, transfer section, washing tank, transfer section, and drying section until the leading edge of the film emerges from the drying outlet. EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto.

[0079]

【Example】

Example 1 Emulsions [A] to [E] were prepared by the following method. [Emulsion A] A 0.13M silver nitrate aqueous solution, a halogen salt aqueous solution containing 0.04M potassium bromide and 0.1M sodium chloride, and a halogen salt aqueous solution containing sodium chloride and 1,3-dimethylimidazolidine-2-thione. In gelatin aqueous solution,
It was added by double jet method for 12 minutes at 43°C with stirring, and the average particle size was 0.15 μm, and the silver chloride content was 7.
Nucleation was performed by obtaining 0 mol% silver chlorobromide grains. Subsequently, in the same manner, 0.87M silver nitrate aqueous solution and 0.2
A halogen salt aqueous solution containing 6M potassium bromide and 0.65M sodium chloride was added over 20 minutes by a double jet method. 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.
, pAg was adjusted to 7.5, and 20 mg of sodium benzenethiosulfonate, 5 mg of sodium thiosulfate, and 8 mg of chloroauric acid were added per mole of silver, and the mixture was heated at 60 °C to 75 °C.
The mixture was heated for 1 minute, subjected to chemical sensitization treatment, and 150 mg of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene was added as a stabilizer. The obtained particles were cubic silver chlorobromide particles with an average particle size of 0.26 μm and a silver chloride content of 70 mol% (coefficient of variation 10%). [Emulsion B] (NH4)3RhCl6 and K3IrCl6 are added to the halogen salt aqueous solution added during nucleation.
The average grain size was 0.26 μm, the silver chloride content was 70 mol%, the Rh compound was 1×10 −7 mol, and the Ir compound was 5 mol % per mol of silver.
Silver chlorobromide cubic grains containing x10-7 moles were obtained (coefficient of variation 10%). [Emulsion C] K3 IrCl6 and K2 Ru(NO)Cl5 are added to the halogen salt aqueous solution added during nucleation.
An average grain size of 0.26 μm, a silver chloride content of 70 mol%, an Ir compound of 5×10 −7 mol and a Ru compound of 1× per mol of silver were prepared in the same manner as in Emulsion A except that
Silver chlorobromide cubic grains containing 10 −7 mol were obtained (coefficient of variation 10%). [Emulsion D] An average of Particle size 0.26μm,
Silver chloride content 70 mol%, Rh compound 1 per mol silver
x 10-7 mol, Ir compound 2 x 10-7 mol, Fe
Silver chlorobromide cubic particles containing 3×10 −5 mol of the compound were obtained (coefficient of variation 10%). [Emulsion E] An average of Particle size 0.26μm,
Silver chloride content 70 mol%, 2 Ir compounds per mol silver
x 10-7 mol, Ru compound 1 x 10-7 mol, Fe
Silver chlorobromide cubic particles containing 3×10 −5 mol of the compound were obtained (coefficient of variation 10%).

Preparation of coating samples The following sensitizing dyes were added to the emulsions A to E prepared in this manner by silver 1.
Added 30 mg per mole. Furthermore, for supersensitization and stabilization, 4,4'-bis(4,6-dinaphthoxy-
pyrimidin-2-ylamino)-stilbendisulfonic acid disodium salt and 2,5-dimethyl-3-allyl-benzothiazole iodo salt for each mole of silver.
00mg and 450mg were added. In addition, hydroquinone 1
00mg/m2, polyethyl acrylate latex with a gelatin binder ratio of 25%, and 2-bis(
86mg/m of vinylsulfonylacetamido)ethane
2 and coated silver amount 3.4g on the polyester support.
/m2, and the applied gelatin amount was 1.6 g/m2. At this time, as a protective layer, 0.5 g/m2 of gelatin was added to the upper side of the emulsion layer, 20 mg/m2 of a dye having the following structural formula,
As a matting agent, 60 mg/m2 of polymethyl methacrylate with a particle size of 2.5 μm, and 70 mg/m2 of colloidal silica with a particle size of 10 μm, and as coating aids, dodecylbenzenesulfonic acid sodium salt and a fluorine-containing surfactant with the following structural formula. was coated simultaneously with the emulsion layer.

[0081]

[C32]

The base used in this example has a back layer and a back protective layer having the following compositions. [Back layer] Gelatin

2.0g/m2 Sodium dodecylbenzenesulfonate
80mg/m2

[0083]

[Chemical formula 33]

1,3-divinylsulfone-2-propanol
60mg/m2 [Back protective layer] Gelatin

0.5g/m2 Polymethyl methacrylate (particle size 4.7μm) 30m
g/m2 Sodium dodecylbenzenesulfonate
20mg
/m2 Fluorine-containing surfactant (above)

2mg/m2 silicone oil

100mg/m2 Dye used in the back layer

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.
The film was exposed to xenon flash light, and sensitometry was performed at the temperature and time shown below using an automatic processor FG-710NH manufactured by Fuji Photo Film Co., Ltd.

Developing at 38°C
14 seconds
9 seconds fixation 37℃
9.7 seconds 6.2
seconds water wash
26℃ 9 seconds
5.8 seconds
squeeze
2.4 seconds 1.5 seconds
Drying
55℃ 8.3 seconds
5.3 seconds
Total 43
．． 4 seconds 27.8 seconds
The compositions of the developer and fixer used are as follows. [Developer prescription] Hydroquinone

25.0g 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone

0.5g potassium sulfite
90.0g
Ethylenediaminetetraacetic acid disodium
2.0g
potassium bromide

5.0g 5-methylbenzotriazole
0.2g 2-mercaptobenzimidazole-5-sulfonic acid 0
．． 3g sodium carbonate

Add 20g water

1 liter
(Add sodium hydroxide to adjust pH to 10.6) [Fixer formulation] Ammonium thiosulfate

210g sodium sulfite (anhydrous)

20g ethylenediaminetetraacetic acid 2
sodium
0.1g glacial acetic acid

15g
add water

1 liter (pH=4.8 with ammonia water)
)

The logarithm of the exposure amount giving a density of 3.0 was defined as the sensitivity, and the relative sensitivity is shown in Table 1. Further, the slope of the straight line connecting the points of density 0.1 and 3.0 on the characteristic curve is defined as the gradation, and the sensitivity difference between 14 seconds of development and 9 seconds of development is also shown in Table 1 as development progress. As is clear from Table 1, sample No. 1 corresponds to the present invention. It is understood that samples Nos. 3 and 5 have high sensitivity and high contrast, and the development progresses quickly, making them excellent in rapid processing suitability.

[0088]

[Table 1]

[0089]

Effects of the Invention The present invention provides a silver chloroiodobromide emulsion in which the emulsion contains atoms of Groups Va to VIIa or Group VIII of the periodic table having a nitrosyl or thionitrosyl ligand, and further has a sensitization maximum By spectrally sensitizing the material to a wavelength longer than 750 nm, it was possible to make a photosensitive material for high-intensity exposure, which has color sensitivity in the infrared region, high sensitivity and high contrast.

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion has a nitrosyl or thionitrosyl ligand. ~A silver halide photographic photosensitive material comprising silver halide grains containing a transition metal selected from elements of group VIIa or group VIII, and characterized in that the sensitization maximum is spectrally sensitized to a wavelength longer than 750 nm. material. 2. The method for processing a silver halide photographic material according to claim 1, wherein the processing is carried out using an automatic processor for a total processing time of 15 to 60 seconds.