JP2847264B2 - Silver halide photographic material and processing method thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material in which the infrared region is spectrally sensitized.
The present invention relates to a silver halide photographic light-sensitive material having high contrast and rapid processing suitability, and a method for developing the same.

[0002]

2. Description of the Related Art One of the methods for exposing a photographic light-sensitive material is to scan an original drawing and to expose the silver halide photographic light-sensitive material on the basis of an image signal thereof, thereby obtaining a negative image or a positive image corresponding to the image of the original drawing. An image forming method based on a so-called scanner method for forming an image is known. There are various types of recording apparatuses that use a scanner-type image forming method, and a glow lamp, a xenon lamp, a mercury lamp, a tungsten lamp, a light-emitting diode, and the like have been conventionally used as a recording light source of these scanner-type recording apparatuses. However, each of these light sources has a practical disadvantage that the output is small and the life is short. In order to compensate for these drawbacks, when a coherent laser light source such as a He-Ne, Ar, He-Cd laser or the like is used, a high output can be obtained, but the apparatus becomes large. Expensive. A modulator is required. Since visible light is used, there are drawbacks in that safelight of the photosensitive material is limited and handling is inferior. On the other hand, semiconductor lasers are small, inexpensive, easy to modulate, and have a longer life than the above lasers and emit light in the infrared region. There is an advantage that handling operability is improved because it can be used. However, if a semiconductor laser is used without any particular shaping, the energy distribution is broad, and it is difficult to obtain a good halftone image or line image. Furthermore, in recent years, there has been a strong demand in the printing industry for work efficiency and speed-up, and there is a wide range of needs for faster scanning and shorter processing time of photosensitive materials. In order to meet such needs, it is desired that the photosensitive material has sufficient sensitivity in the infrared region, high contrast, rapid development progress, and rapid processing suitability in high illuminance exposure. In response to such a request, for example,
In 3-49752, a photosensitive material which contains iridium ions in silver halide grains, has high sensitivity and high contrast, and is excellent in transitivity and developing temperature dependency in high-intensity short-time exposure in the infrared region. The method of providing has been disclosed but is still inadequate.

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a device having an appropriate spectral sensitivity to infrared light, a high sensitivity, a high contrast and a small processing dependency in short-time exposure with high illuminance, An object of the present invention is to provide a silver halide photographic light-sensitive material having suitability for rapid processing.

[0004]

SUMMARY OF THE INVENTION These objects of the invention are:
In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the silver halide emulsion preferably has a nitrosyl or thionitrosyl ligand, a group Va to VIIa or VIIIa of the periodic table. Consisting of silver halide grains containing a transition metal selected from the group elements,
The silver halide photographic light-sensitive material is characterized in that the sensitization maximum is spectrally sensitized to a wavelength longer than 750 nm.

Hereinafter, a specific configuration of the present invention will be described in detail. A preferred transition metal ligand complex for achieving the object of the present invention is a hexacoordinate complex represented by the following general formula. [M (MY) L ₅ ] ^m , wherein M is Va to VIIa or VIII of the periodic table of the elements.
It is a transition metal selected from group 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. Preferred examples of L other than nitrosyl and thionitrosyl bridging ligands include halide ligands (fluoride, chloride, bromide and iodide), cyanide ligand, cyanate ligand, thiocyanate ligand. Ligands, selenocyanate ligands, tellurocyanate ligands, azide ligands and aquo ligands. If an aquo ligand is present, it preferably occupies one or two of the ligands. M
Particularly preferred embodiments of are rhodium, ruthenium, rhenium, osmium and iridium. Specific examples of the transition metal coordination complex are shown below. 1 [Ru (NO) Cl ₅ ] ^-22 [Ru (NO) ₂ Cl ₄ ] ^-13 [Ru (NO) (H ₂ O) Cl ₄ ] ^-14 [Rh (NO) Cl ₅ ] ^-2 5 [Re (NO) Cl _5] ^-2 6 [Re (NO) CN _5] ^-2 7 [Re (NO) ClCN _4] ^-2 8 [Rh (NO) ₂ Cl _4] ^-1 9 [Rh (NO ) (H ₂ O) Cl _4] ^-1 10 [Ru (NO) CN _5] ^-2 11 [Ru (NO) Br _5] ^-2 12 [Rh (NS) Cl _5] ^-2 13 [Os (NO) Cl _5] ^-2 14 [Cr (NO) Cl _5] ^-3 15 [Re (NO) Cl _5] ^-1 16 _{[Os (NS) Cl 4 (TeCN} ) ] ^-2 17 [Ru (NS) I _5] ^-2 18 [Re (NS) Cl ₄ (SeCN)] ^-2 19 [Os (NS) Cl (SCN) ₄ ] ^-2 20 [Ir (NO) Cl ₅ ] ^-2

In order to incorporate the above metal complex into silver halide, it can be added during grain preparation. The content of the transition metal in the silver halide grains of the present invention is at least 10 ^-8 to 1 × 10 ^-6 mol, preferably 10 ^{-7 to} 5 × 10 ^-7 mol, per mol of silver halide. . In the silver halide grains of the present invention, a metal having a different ligand can be used in addition to the metal complex having a nitrosyl or thionitrosyl ligand. Compounds containing these metals preferably used in the present invention include iron sulfate (I
I) FeSO ₄ -5H ₂ O; iron chloride (III) FeCl _3; hexacyanoferrate (II) iron potassium K4 Fe (CN) ₆ · 3H
₂ O; Hexacyanoiron (III) iron potassium K ₃ Fe (C
N) ₆ ; cobalt (II) chloride CoCl ₂ ; cobalt nitrate (I
_{I) Co (NO 3) 2} · 6H 2 O; hexacyanocobaltate
(III) potassium salt K ₃ Co (CN) ₆ ; nickel chloride (I
I) NiCl ₂ ; 6H ₂ O nickel (II) nitrate Ni (N
_{O 3) 2 · 6H 2 O} ; ruthenium (III) Ruc
l ₃ ; potassium hexachlororuthenate (IV) ・ K ₂ R
uCl ₆ ; rhodium (III) chloride RhCl ₃ .4H ₂ O;
Ammonium hexachlororhodate (III) (NH) ₃
RhCl ₆ ; Palladium (II) chloride PdCl ₂ ; Palladium (II) nitrate Pd (NO ₃ ) ₂ ; Palladium (II) bromide Pd
Br ₂ ; potassium hexachloropalladate (IV) K ₂ P
dCl ₆ ; potassium tetrathiopalladium (II) ・ K ₂
Pd (CNS) ₄ ; Osmium (II) chloride OsCl ₂ ; Iridium (III) chloride IrCl ₃ ; Iridium (IV) chloride I
RCL _4; bromide iridium (III) IrBr ₃ · 4H
₂ O; iridium (IV) bromide IrBr ₄ ; potassium hexachloroiridate (III) K ₃ IrCl ₆ ; potassium hexachloroiridate (IV) K ₂ IrCl ₆ ; ammonium hexachloroplatinate (IV) ammonium (NH ₄ ) ₂ PtCl ₆ ;
Potassium hexachloroplatinate (IV) K ₂ PtCl ₆ ; ammonium hexabromoplatinate (IV) ammonium (NH ₄ ) ₂ PtBr
₆ ; These metal compounds are used alone or in combination of two or more in an amount corresponding to 10 ^-9 mol to 10 ^-3 mol per mol of silver halide.

The halogen composition of the silver halide emulsion used in the present invention is not particularly limited, but from the viewpoint of rapid processing suitability, silver iodochlorobromide or silver chlorobromide having 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.

The monodisperse particles referred to here have a coefficient of variation of
It means a silver halide emulsion having a grain size distribution of not more than 20%, particularly preferably not more than 15%. The coefficient of variation (%) is a value obtained by dividing the standard deviation of the grain size of silver halide grains by the average value of the grain sizes and multiplying the result by 100. The silver halide grains in the present invention are preferably cubic grains having substantially (100) faces. Here, “consisting substantially of (100) plane” specifically means that preferably 50% or more, more preferably 80% or more, and particularly preferably 95% or more of the grains contained in the silver halide emulsion. It is meant that the number of particles consists of cubes and / or particles such that the (100) plane occupies more than 60% of the surface area of the particles. The photographic emulsion used in the present invention is P.Gl
afkides, Chimie et Physique Photographique (Paul M
ontel, 1967), Photographic by GFDuffin
Emulsion Chemistry (The Focal Press, 1966
Year), Making and Coating Phot by VLZelikman et al
ographic Emulsion (The Focal Press, 1964)
It can be prepared using the method described in, for example.
That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt with a soluble halide may be any one of a one-sided mixing method, a double-sided mixing method, and a combination thereof. Good. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.
In order to make the particle size uniform, British Patent 1,
No. 535,016, JP-B-48-36890, 52-
No. 16,364, a method in which the addition rate of silver nitrate or an alkali halide is changed in accordance with the grain growth rate, a method disclosed in British Patent No. 4,242,445,
It is preferable to use a method of changing the concentration of the aqueous solution as described in JP-A-5-158124 to grow the solution quickly within a range not exceeding the critical saturation. The silver halide grains may have a so-called core / shell structure in which the inside and the surface have different halogen compositions.

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

[0010]

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In the formula, R ₁ , R ₂ , R ₃ and R ₄ represent a substituted or unsubstituted alkyl group, an alkenyl group (such as an allyl group) or a substituted or unsubstituted aryl, and these are the same as each other. Or different, R _{1 to} R
The total number of carbon atoms in ₄ is preferably 30 or less. And a 5- or 6-membered heterocyclic imidazolidinethione, piperidine, which is bonded by R ₁ and R ₂ , R ₂ and R ₃ , or R ₃ and R ₄ ;
Morpholine can also be made. Both linear and branched alkyl groups are used. Examples of the substituent of the alkyl group include a hydroxy group (—OH), a carboxy group, a sulfonic acid group, an amino group, and an alkyl residue.
It is an alkoxy group (o-alkyl) having up to 5 carbon atoms, a phenyl group or a 5- or 6-membered heterocyclic ring (such as furan). The substituent of the aryl group is a hydroxy group, a carboxy group or a sulfonic group. Here, particularly preferably of R ₁ to R _4, the alkyl group has 3 or more carbon atoms in each alkyl group has from 1 to 5, aryl is a phenyl group, further the R ₁ to R ₄ carbon atoms Total is 2
0 or less. Examples of the compounds that can be used in the present invention include the following.

[0012]

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[0013]

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[0014]

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The organic thioether silver halide solvent preferably used in the present invention is, for example, JP-B-47-11386.
No. (U.S. Patent No. 3,574,628) comprising at least one compound group wherein oxygen atom and a sulfur atom are separated by an ethylene (e.g. -O-CH ₂ CH ₂ -S-) in the like, especially An alkyl group at both ends described in Japanese Unexamined Patent Publication No. 54-155828 (U.S. Pat. No. 4,276,374) wherein each alkyl group is at least two groups selected from hydroxy, amino, carboxy, amide or sulfone
Thioether compound having two substituents). Specifically, the following examples can be given.

[0016]

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The amount of the silver halide solvent to be added varies depending on the kind of the compound used, the intended grain size, the halogen composition, and the like, but is 10 ^-5 to 1 mol per mol of the silver halide.
10 ^-2 mol is preferred. If the grain size exceeds the target by using a silver halide solvent, the temperature during grain formation,
A desired particle size can be obtained by changing the addition time of the silver salt solution or the halogen salt solution.

The silver halide emulsion of the present invention is preferably subjected to gold sensitization and sulfur sensitization. The gold sensitizer used in the present invention is various gold salts such as potassium chloroaulite, potassium auric thiocyanate, potassium chloroaurate, and auric trichloride. Specific examples are described in U.S. Pat.
No. 361. As the sulfur sensitizer used in the present invention, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines and the like can be used in addition to the sulfur compounds contained in gelatin. Specific examples are described in U.S. Pat. Nos. 1,574,944, 2,278,947, 2,410,689, 2,728,668, 3,501,313, and 3,656,955. It is described in the issue. Preferred sulfur compounds are thiosulfates and thiourea compounds.
The added amount of the sulfur sensitizer and the gold sensitizer is preferably 10 ⁻² to 10 ⁻⁷ mol per mol of silver, more preferably 1 × 10 ⁷ mol.
^-3 to 1 × 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.
2: 1. In the present invention, a reduction sensitization method can be used. Stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used as the reduction sensitizer.

The silver halide emulsion of the present invention is disclosed in
A thiosulfonic acid compound may be added by the method described in JP-A-264935.

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

[0021]

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In the formula, R ₁ and R ₂ may be the same or different and each represents an alkyl group (including a substituted alkyl group). Preferably it has 1 to 8 carbon atoms.
For example, methyl, ethyl, propyl, butyl, pentyl,
Heptyl, octyl. Examples of the substituent include a carboxyl group, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom, and a bromine atom), a hydroxyl group, an alkoxycarbonyl group (preferably having 8 or less carbon atoms,
For example, methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl, etc.), an alkoxy group (preferably having 7 or less carbon atoms, for example, methoxy, ethoxy, propoxy, butoxy, benzyloxy), an aryloxy group (eg, phenoxy, p-tolyloxy), acyloxy Groups (preferably having 3 or less carbon atoms, such as acetyloxy, propionyloxy), acyl groups (preferably having 8 or less carbon atoms, such as acetyl, propionyl, benzoyl, mesyl), carbamoyl groups (such as carbamoyl, N, N-dimethyl) Carbamoyl, morpholinocarbamoyl, piperidinocarbamoyl), sulfamoyl group (eg, sulfamoyl, N, N-dimethylsulfamoyl, morpholinosulfonyl), aryl group (eg, phenyl, p-hi) Rokishifeniru, p- carboxyphenyl, p- sulfophenyl, alpha-naphthyl) substituted alkyl groups (preferably having 6 or less carbon atoms in the alkyl moiety) are exemplified by such. However, two or more of these substituents may be substituted with an alkyl group.

R ₃ is a hydrogen atom, a lower alkyl group (preferably having 1 to 4 carbon atoms, for example, methyl, ethyl, propyl, butyl), a lower alkoxy group (preferably having 1 to 4 carbon atoms, for example, methoxy, ethoxy, Propoxy, butoxy), a phenyl group, a benzyl group or a phenethyl group. Particularly, a lower alkyl group and a benzyl group are advantageously used. V is a hydrogen atom, a lower alkyl group (preferably having 1 to 4 carbon atoms, for example, methyl, ethyl, propyl),
An alkoxy group (preferably having 1 to 4 carbon atoms, for example, methoxy, ethoxy, butoxy), a halogen atom (for example, fluorine atom, chlorine atom), a substituted alkyl group (preferably having 1 to 4 carbon atoms, for example, trifluoromethyl, carboxy) Methyl).

Z ₁ represents a group of nonmetallic atoms necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic ring, for example, a thiazole nucleus [for example, benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6 -Chlorobenzothiazole, 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-methoxy Naphtho [1,2-d] thiazole, 7-ethoxynaphtho [2,1-d] thiazole, 8-methoxynaphtho [2,1-d] thiazole, 5-methoxynaphtho [2
3-d] thiazole], selenazole nucleus [for example, 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 [for example, 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], a 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 nucleus (for example, 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), a pyridine nucleus (eg, pyridine, 5-methyl-2)
-Pyridine, 3-methyl-4-pyridine). Of these, thiazole nuclei and oxazole nuclei are preferably used advantageously. 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, q is 1 when the dye forms an inner salt.

X ₁ is an acid anion (for example, chloride, bromide, iodide, tetrafluoroborate, hexafluorophosphate, methyl sulfate, ethyl sulfate, benzenesulfonate, 4-methylbenzenesulfonate, 4-chlorobenzenesulfonate, 4-nitrobenzenesulfonate, trifluoromethanesulfonate, perchlorate).

[0026]

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In the formula, R ₁ ′ and R ₂ ′ may be the same or different and each represents an alkyl group (including a substituted alkyl group). Preferably 1 to 1 carbon atoms
8. For example, methyl, ethyl, propyl, butyl, pentyl, heptyl, octyl. Examples of the substituent include a carboxyl group, a sulfo group, a cyano group, a halogen atom (eg, a fluorine atom, a chlorine atom, and a bromine atom), a hydroxyl group,
Alkoxycarbonyl group (preferably having 8 or less carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl,
Benzyloxycarbonyl, etc.), an alkoxy group (preferably having 7 or less carbon atoms, for example, methoxy, ethoxy,
Propoxy, butoxy, benzyloxy), an aryloxy group (eg, phenoxy, p-tolyloxy), an acyloxy group (preferably having 3 or less carbon atoms, for example, acetyloxy, propionyloxy), an acyl group (preferably having 8 or less carbon atoms, For example, acetyl, propionyl, benzoyl, mesyl), carbamoyl group (for example, carbamoyl, N, N-dimethylcarbamoyl, morpholinocarbamoyl, piperidinocarbamoyl), sulfamoyl group (for example, sulfamoyl, N, N-dimethylsulfamoyl, morpholinosulfonyl) An aryl group (eg, phenyl, p-hydroxyphenyl, p-carboxyphenyl, p-sulfophenyl, α-naphthyl)
And the like (preferably having 6 or less carbon atoms in the alkyl portion). However, two or more of these substituents may be substituted with an alkyl group.

R ₃ ′ and R ₄ ′ are a hydrogen atom, a lower alkyl group (preferably having 1 to 4 carbon atoms, for example, methyl, ethyl, propyl, butyl) and a lower alkoxy group (preferably having 1 to 4 carbon atoms; For example, methoxy, ethoxy, propoxy, butoxy), phenyl, benzyl or phenethyl. Particularly, a lower alkyl group and a benzyl group are advantageously used. R ₅ ′ and R ₆ ′ each represent a hydrogen atom, or R ₅ ′ and R ₆ ′ are linked to form a divalent alkylene group (for example, ethylene or trimethylene). The alkylene group may be one, two or more suitable groups, such as an alkyl group (preferably having 1 carbon atom).
To 4, for example, methyl, ethyl, propyl, isopropyl, butyl), a halogen atom (for example, a chlorine atom or a bromine atom), or an alkoxy group (preferably having 1 carbon atom)
-4, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy) and the like. R
₇ 'is a hydrogen atom, a lower alkyl group (preferably having 1 to 4 carbon atoms, for example, methyl, ethyl, propyl, etc.), a lower alkoxy group (preferably having 1 to 4 carbon atoms, for example, methoxy, ethoxy, propoxy, butoxy, etc.) ), represents phenyl, benzyl, or -N a _{(W 1 ') (W 2} '). Here, W ₁ ′ and W ₂ ′ each independently represent an alkyl group (including a substituted alkyl group. Preferably, the alkyl moiety has 1 to 18 carbon atoms, more preferably 1 to 4 carbon atoms, for example, methyl, ethyl, propyl, butyl, Benzyl, phenylethyl) or an aryl group (including a substituted phenyl group; for example, phenyl, naphthyl, tolyl, p-chlorophenyl, etc.), and W ₁ ′ and W ₂ ′ are linked to each other to form a 5- or 6-membered group. It can also form a nitrogen-containing heterocycle. Provided that R ₃ ′ and R ₇ ′ or R ₄ ′ and R ₇ ′ are linked to each other to form a divalent alkylene group (synonymous with the aforementioned divalent alkylene group formed by linking R ₅ ′ to R ₆ ′) ) Can also be formed.

Z ′ and Z ₁ ′ represent a group of nonmetal atoms necessary to complete a 5- or 6-membered nitrogen-containing heterocyclic ring, for example, a thiazole nucleus [for example, benzothiazole, 4-chlorobenzothiazole, 5-chloro] Benzothiazole, 6-
Chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzo Thiazole, 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], a selenazole nucleus [for example, 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-
Methyl benzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5-trifluorobenzoxazole, 5-hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methyl Benzoxazole, 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 [for example, 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-dianoindolenine, 3,3-
Dimethyl-5-methoxyindolenine, 3,3-dimethyl-5-methylindolenine, 3,3-dimethyl-5-
Chlorindolenine), imidazole nucleus (for example, 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) , A pyridine nucleus (for example, pyridine, 5-methyl-2-pyridine, 3-methyl-4-
Pyridine). Of these, thiazole nuclei and oxazole nuclei are preferably used advantageously. More preferably, a benzothiazole nucleus, a naphthothiazole nucleus, a naphthoxazole nucleus or a benzoxazole nucleus is advantageously used.

X ₁ 'is an acid anion (for example, chloride, bromide, iodide, tetrafluoroborate, hexafluorophosphate, methyl sulfate, ethyl sulfate, benzene sulfonate, 4-methylbenzene sulfonate, 4-chlorobenzene sulfonate , 4-
Nitrobenzenesulfonate, trifluoromethanesulfonate, perchlorate). m 'represents 0 or 1, and is 1 when the dye forms an inner salt.

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

[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Disclosur.
e) Vol. 176, Volume 17643 (December 1978) No. 23
Section IV on page IV, or the aforementioned JP-B-49-25500,
43-4933, JP-A-59-19032, and 59-19032.
192242. 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 antifoggant compound, and the like. It is desirable to select the optimal amount accordingly, and the methods of testing for that selection are well known to those skilled in the art. Usually, it is preferably from 10 ^-7 mol to 1 mol per mol of silver halide.
It is used in the range of ^10-2 mol, especially ^10-6 to 5 ^10-3 mol.

The infrared sensitizing dyes represented by these general formulas can be synthesized by the method described in JP-A-59-192242 or US Pat. Nos. 3,482,978 and 2,756,227. Can be. Sensitizing dyes having the above general formula are preferred because they have particularly good sensitizing properties in the infrared region. In the present invention, compounds of the following general formulas can be used in combination.

[0043]

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In the formula, Z ₃ represents a group of non-metallic atoms necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic ring, for example, thiazoliums such as thiazolium, 4-methylthiazolium, benzothiazolium, 5-methylbenzothiazolium, 5-chlorobenzothiazolium, 5-methoxybenzothiazolium, 6-methylbenzothiazolium, 6-methylbenzothiazolium
Methoxybenzothiazolium, naphtho [1,2-d] thiazolium, naphtho [2,1-d] thiazolium, etc., oxazoliums {eg oxazolium, 4-
Methylimoxazolium, benzoxazolium, 5-chlorobenzoxazolium, 5-phenylbenzoxazolium, 5-methylbenzoxazolium, naphtho [1,2-d] oxazolium, etc., imidazolium ( For example, 1-methylbenzimidazolium, 1-propyl-5-chlorobenzimidazolium, 1-ethyl-
5,6-dichlorobenzimidazolium, 1-allyl-
5-trichloromethyl-6-chloro-benzimidazolium, etc.), selenazoliums [for example, benzoselenazolium, 5-chlorobenzoselenazolium, 5-methylbenzoselenazolium, 5-methoxybenzoselenazolium, naphtho [ 1,2-d] selenazolium etc.]. R ₁₃ is a hydrogen atom, an alkyl group (having 8 or less carbon atoms,
For example, methyl group, ethyl group, propyl group, butyl group, pentyl group, etc., alkenyl group (eg, allyl group)
Represents R ₁₄ represents a hydrogen atom or a lower alkyl group (eg, a methyl group, an ethyl group, etc.). X ₂ is an acid anion (eg, Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , p-toluenesulfonic acid, etc.), and Z ₃ is preferably a thiazolium. More preferably, substituted or unsubstituted benzothiazolium or naphthothiazolium is advantageously used. Specific examples of the compounds are shown below. However, the present invention is not limited to only these compounds.

[0045]

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[0046]

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[0047]

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[0048]

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The above compounds are advantageously used in an amount 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 in the range of the infrared sensitizing dye of the present invention / the above compound = 1/1 to 1/300, In particular, the range of 1/2 to 1/50 is advantageously used. The above compound used in the present invention can be directly dispersed in the emulsion, or a suitable solvent (eg, water, methyl alcohol, ethyl alcohol, propanol, methyl cellosolve, acetone, etc.) or a mixture of these solvents is used. It can be dissolved in a mixed solvent and added to the emulsion. The sensitizing dye can be added to the emulsion in the form of a solution or a dispersion in a colloid according to the method of adding the sensitizing dye. The above compound may be added to the emulsion before the addition of the infrared sensitizing dye of the present invention described above, or may be added later. Further, the above compound and the infrared sensitizing dye may be separately dissolved, and these may be separately and simultaneously added to the emulsion, or may be mixed and then added to the emulsion. Compounds having the following general formula can further be added to the combinations according to the invention.

[0050]

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In the formula, -A- represents a divalent aromatic residue, and these are -SO ₃ M groups, wherein M represents a hydrogen atom or a cation that imparts water solubility (eg, sodium, potassium, etc.). ] May be included. As -A-, for example, those selected from the following -A ₁ -or -A _2- are useful. However R _21, R _22, when the R ₂₃ or R ₂₄ do not contain -SO ₃ M is, -A- is -A ₁ - is selected from the group consisting of.

[0052]

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[0053]

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[0054]

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R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ each represent a hydrogen atom, a hydroxy group or a lower alkyl group (preferably having 1 to 8 carbon atoms, for example, a methyl group, an ethyl group, an n-
A propyl group, an n-butyl group and the like, an alkoxy group (the number of carbon atoms is preferably 1 to 8. For example, a methoxy group,
Ethoxy group, propoxy group, butoxy group, etc., aryloxy group (eg, phenoxy group, naphthoxy group, o-troxy group, p-sulfophenoxy group, etc.), halogen atom (eg, chlorine atom, bromine atom, etc.), heterocyclic nucleus ( For example, morpholinyl group, piperidyl group, etc., alkylthio group (eg, methylthio group, ethylthio group, etc.), heterocyclylthio group (eg, benzothiazolylthio group, benzimidazolylthio group, phenyltetrazolylthio group, etc.), arylthio group (eg, phenylthio group, etc.) , Tolylthio group), amino group, alkylamino group or substituted alkylamino group (for example, methylamino group, ethylamino group, propylamino group, dimethylamino group, diethylamino group, dodecylamino group, cyclohexylamino group, β-hydroxy Chiruamino group, di - (beta-hydroxyethyl) amino group, beta-sulfoethylamino group),
An arylamino group or a substituted arylamino group (for example, an anilino group, an o-sulfoanilino group, an m-sulfoanilino group, a p-sulfoanilino group, an o-toluidino group,
-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, hydroxyanilino group, disulfophenylamino group, naphthylamino group, sulfonaphthylamino group, etc., heterocyclylamino group ( For example, a 2-benzothiazolylamino group, a 2-pyridyl-amino group and the like, a substituted or unsubstituted aralkylamino group (for example, a benzylamino group, an o-anisylamino group,
m-anisylamino group, p-anisylamino group, etc.),
Represents an aryl group (for example, a phenyl group) or a mercapto group. R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ may be the same or different from each other. When -A- is selected from the group of -A _2-, at least one of R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄
One must have one or more sulfo groups (which may be free acid groups or may form salts). W ₃ and W ₄ represents -CH = or -N =, at least one is -N =. Next, specific examples of the above compounds will be given. However, it is not limited only to these compounds.

(A) Sodium 4,4'-bis [4,6-di (benzothiazolyl-2-thio) pyrimidin-2-ylamino] stilbene-2,2'-disulfonate (b) 4,4'- Bis [4,6-di (benzothiazolyl-2-amino) pyrimidin-2-ylamino)] stilbene-2,2′-disulfonate disodium salt (c) 4,4′-bis [4,6-di (naphthyl) -2-oxy) pyrimidin-2-ylamino] stilbene-2,
2′-disulfonate disodium salt (d) 4,4′-bis [4,6-di (naphthyl-2-oxy) pyrimidin-2-ylamino] bibenzyl-2,
Disodium salt of 2'-disulfonate (e) 4,4'-bis (4,6-dianilinopyrimidin-2-ylamino) stilbene-2,2'-disulfonate disodium salt (f) 4,4'- Bis [4-chloro-6- (2-naphthyloxy) pyrimidin-2-ylamino] biphenyl-
Disodium 2,2'-disulfonate (g) 4,4'-bis [4,6-di (1-phenyltetrazolyl-5-thio) pyrimidin-2-ylamino] stilbene-2,2'- Disulfonate disodium salt

(H) 4,4'-bis [4,6-di (benzimidazolyl-2-thio) pyrimidin-2-ylamino] stilbene-2,2'-disulfonate disodium salt -Bis [4,6-diphenoxypyrimidin-2-ylamino) stilbene-2,2'-disulfonic acid disodium salt (nu) 4,4'-bis [4,6-diphenylthiopyrimidin-2-ylamino) stilbene Disodium 2,2'-disulfonate (酸) 4,4'-bis [4,6-dimercaptopyrimidin-2-ylamino) biphenyl-2,2'-disulfonate disodium salt (塩) 4 4'-bis [4,6-dianilino-triazin-2-ylamino) stilbene-2,2'-disulfonate disodium salt (W) 4,4'-bis (4-anilino-6-hydroxy- Triazin-2-ylamino) stilbene-2,2 '
Disodium disulfonate (f) 4,4'-bis [4-naphthylamino-6-anilino-triazin-2-ylamino) stilbene-2,
Disodium salt of 2'-disulfonate (Y) 4,4'-bis [2,6-di (2-naphthoxy)
Pyrimidin-4-ylamino] stilbene-2,2'-
Disulfonic acid (t) 4,4'-bis [2,6-di (2-naphthylamino) pyrimidin-4-ylamino] stilbene-2,
Disodium salt of 2'-disulfonate (レ) 4,4'-bis [2,6-dianilinopyrimidin-4-ylamino) stilbene-2,2'-disulfonate disodium salt (so) 4,4'- Bis [2-naphthylamino) -6-anilinopyrimidin-4-ylamino] stilbene-2,
2'-Disulfonic acid (z) 4,4'-bis [2,6-diphenoxypyrimidin-4-ylamino] stilbene-2,2'-disulfonic acid ditriethylammonium salt (d) 4,4'-bis [ 2,6-di (benzimidazolyl-2-thio) pyrimidin-4-ylamino] stilbene-2,2'-disulfonate disodium salt

The compounds represented by the above general formulas are known or can be easily produced according to known methods.
The above compound used in the present invention may be a mixture of two or more of these compounds. The above compounds are advantageously used in an amount of about 0.01 to 5 grams per mole of silver halide in the emulsion. The ratio (weight ratio) of the infrared sensitizing dye to the compound represented by the above general formula is dye / the above compound = 1.
The range of from 1/1 to 1/200 is advantageously used, especially 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 the emulsion or dissolved in an appropriate solvent (eg, methyl alcohol, ethyl alcohol, methyl cellosolve, water, etc.) or a mixed solvent thereof. Can be added to the emulsion. The sensitizing dye can be added to the emulsion in the form of a solution or a dispersion in a colloid according to the method of adding the sensitizing dye. Further, it can be dispersed in an emulsion by the method described in JP-A-50-80119.

The light-sensitive material of the present invention can contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles,
Mercaptothiadiazoles, aminotriazoles,
Benzothiazoles, nitrobenzotriazoles, etc .; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,
3,3a, 7) tetrazaindenes), pentaazaindenes and the like; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonamide and the like are added. be able to.

In particular, polyhydroxybenzene compounds are preferred in that they improve pressure resistance without impairing sensitivity.
The polyhydroxybenzene compound is preferably a compound having any one of the following structures.

[0061]

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X and Y are each -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. Group, sulfonated amino group, sulfonated carbonyl group, carboxyphenyl group, carboxyalkyl group, carboxyamino group, hydroxyphenyl group, hydroxyalkyl group,
An alkyl ether group, an alkylphenyl group, an alkylthioether group, or a phenylthioether group. More preferably, -H, -OH, -Cl, -Br, -C
_{OOH, -CH 2 CH 2 COOH,} -CH 3, -CH 2
_{CH 3, -CH (CH 3)} 2, -C (CH 3) 3, -O
_{CH 3, -CHO, -SO 3 Na} , -SO 3 H, -SC
H ₃ ,

[0063]

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And so on. X and Y may be the same or different. Particularly preferred representative compounds are shown below.

[0065]

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[0066]

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[0067]

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[0068]

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The polyhydroxybenzene compound may be added to the emulsion layer in the light-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 per mol, and particularly preferably in the range of 10 ^-3 to 10 ^-1 mol.

The light-sensitive material prepared by using the present invention may contain a water-soluble dye as a filter dye in the hydrophilic colloid layer or for various purposes such as prevention of 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,
Developing agents such as thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones and aminophenols may be contained. Among them, 3-pyrazolidones (1-phenyl-
3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone) are preferred,
Usually used at 5 g / m ² or less, 0.01 to 0.2 g / m ²
Is more preferred.

The photographic emulsion and the non-photosensitive hydrophilic colloid of the present invention may contain an inorganic or organic hardener. For example, active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N-methylenebis- [β-
(Vinylsulfonyl) propionamide]), an active halogen compound (2,4-dichloro-6-hydroxy-
s-triazine, etc.) mucohalogenic acids (such as mucochloric acid), N-carbamoylpyridinium salts (such as (1-morpholy) carbonyl-3-pyridinio) methanesulfonate) haloamidinium salts (1- (1-chloro-
1-pyridinomethylene) pyrrolidinium, 2-naphthalene sulfonate, etc.) can be used alone or in combination. In particular, JP-A-53-41220 and JP-A-53-41220
-57257, 59-162546, 60-808
Active vinyl compound described in No. 46 and US Pat.
The active halides described in 5,287 are preferred.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared by using the present invention may have a coating aid, antistatic property, improvement of slipperiness, emulsification / dispersion, prevention of adhesion and improvement of photographic properties (for example, development acceleration). For various purposes such as contrast enhancement, sensitization, and the like, various surfactants may be contained. For example, saponins (steroids), alkylene oxide derivatives (eg, 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 alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives ( For example, nonionic surfactants such as alkenyl succinic acid polyglyceride and alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols and alkyl esters of sugars; alkyl carboxylate, alkyl sulfonate, alkyl benzene sulfonate, alkyl Naphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl Such as taurine, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates, carboxy group, sulfo group, phospho group, sulfate group, phosphate group, etc. Anionic surfactants containing an acidic group; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amine oxides; alkylamine salts, aliphatic or aromatic Quaternary ammonium salts, pyridinium,
Heterocyclic quaternary ammonium salts such as imidazolium,
And cationic surfactants such as phosphonium or sulfonium salts containing aliphatic or heterocyclic rings. In order to prevent charging, Japanese Patent Application Laid-Open No. Sho 60-80849
It is preferable to use the fluorinated surfactant described in the above item.

The photographic light-sensitive material of the present invention may contain a matting agent such as silica, magnesium oxide or polymethyl methacrylate for the purpose of preventing adhesion to a photographic emulsion layer or other hydrophilic colloid layers. The light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or hardly soluble synthetic polymer for the purpose of dimensional stability. For example, alkyl (meth)
A polymer having a monomer component of acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate, or the like alone or in combination, or a combination thereof with acrylic acid, methacrylic acid, or the like can be used. Gelatin is advantageously used as a condensing agent or protective colloid of the photographic emulsion, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other macromolecules, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol Use of various kinds of synthetic hydrophilic high-molecular substances such as mono- or copolymers such as polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole Can be. As gelatin, in addition to lime-processed gelatin, acid-processed gelatin may be used, and gelatin hydrolyzate and gelatin enzyme hydrolyzate can also be used. The silver halide emulsion layer used in the present invention may contain a polymer latex such as an alkyl acrylate. As the support of the light-sensitive material of the present invention, cellulose, triacetate, cellulose diacetate, nitrocellulose,
Polystyrene, polyethylene terephthalate paper, baryta-coated paper, polyolefin-coated paper, and the like can be used.

The developing agent used in the developer used in the present invention is not particularly limited, but preferably contains dihydroxybenzenes from the viewpoint that good halftone dot quality can be easily obtained. A combination of -3-pyrazolidones or a combination of dihydroxybenzenes and p-aminophenols may be used. As the dihydroxybenzene developing agent used in the present invention, hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone,
There are 2,5-dimethylhydroquinone and the like, but hydroquinone is particularly preferred. 1-phenyl- used in the present invention
The developing agent for 3-pyrazolidone or a derivative thereof is 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- And pyrazolidone. Examples of the p-aminophenol-based developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol and N-methylphenol.
-(Β-hydroxyethyl) -p-aminophenol,
There are N- (4-hydroxyphenyl) glycine, 2-methyl-p-aminophenol, p-benzylaminophenol and the like, among which N-methyl-p-aminophenol is preferable. The developing agent is preferably used in an amount of usually 0.05 mol / l to 0.8 mol / l. Also, dihydroxybenzenes and 1-phenyl-3-
When a combination with pyrazolidones or p-amino-phenols is used, the former is used in an amount of 0.05 mol / liter.
It is preferred to use 0.5 mol / l and the latter in an amount of 0.06 mol / l or less. Examples of the sulfite preservative used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite. 0.3 mol of sulfite /
It is preferably at least lintole, especially at least 0.4 mol / l. The upper limit is up to 2.5 mol / l, especially 1.
It is preferably up to 2.

The alkaline agent used for setting the pH includes pH such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium tertiary phosphate, potassium tertiary phosphate, sodium silicate and potassium silicate. Contains regulators and buffers. Additives other than the above components include compounds such as boric acid and borax, and development inhibitors such as sodium bromide, potassium bromide and potassium iodide: ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve , Organic solvents such as hexylene glycol, ethanol and methanol: 1-phenyl-5-mercaptotetrazole,
It may contain an antifoggant such as a mercapto compound such as 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, an indazole compound such as 5-nitroindazole, and a benztriazole compound such as 5-methylbenztriazole. If necessary, a color tone agent, a surfactant, an antifoaming agent, a water softener, a hardener, and the like may be contained. In particular, amino compounds described in JP-A-56-106244 and imidazole compounds described in JP-B-48-35493 are preferred in terms of accelerating development or increasing sensitivity. The developer used in the present invention contains a compound described in JP-A-56-24347 as a silver stain inhibitor, a compound described in JP-A-62-212,651 as a development unevenness inhibitor, and a dissolution aid. JP-A-61-267759 as an agent
Can be used.

The fixing solution is an aqueous solution containing 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), if necessary, in addition to the fixing agent. , PH 3.8 or more, more preferably 4.0 to 5.5. Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The amount of the fixing agent can be appropriately changed, and is generally about 0.1 to
About 5 mol / l. The water-soluble aluminum salt mainly used as a hardening agent in the fixing solution is a compound generally known as a hardening agent for an acidic hardening fixing solution, and examples thereof include aluminum chloride, aluminum sulfate and potassium alum. As the above-mentioned dibasic acid, tartaric acid or a derivative thereof, citric acid or a derivative thereof can be used alone or in combination of two or more. It is effective that these compounds contain 0.005 mol or more per liter of the fixing solution, and particularly 0.01 to 0.03 mol / l is particularly effective. Specifically, there are tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, ammonium tartrate, potassium ammonium tartrate, and the like. Examples of citric acid or a derivative thereof effective in the present invention include citric acid, sodium citrate, potassium citrate, and the like. The fixing solution may further contain a preservative (for example, sulfite or bisulfite), if desired.
pH buffers (eg, acetic acid, boric acid), pH adjusters (eg,
Ammonia, sulfuric acid), an image preserving agent (eg, potassium iodide), and a chelating agent. Here, the pH buffer is used in an amount of 10 to 40 g / liter, more preferably about 18 to 25 g / liter, because the pH of the developer is high.

The photosensitive material of the present invention has a total processing time of 15 seconds to
It shows excellent performance in rapid development processing by an automatic developing machine for 60 seconds. In the rapid development processing of the present invention, the temperature and time for development and fixing are each about 25 ° C. to 50 ° C. for 25 seconds or less, preferably 30 ° C. to 40 ° C. for 4 seconds to 15 seconds. In the present invention, after the photosensitive material is developed and fixed, it is subjected to washing or stabilizing treatment. Here, in the rinsing step, water can be saved by using a two- or three-stage countercurrent rinsing method. When washing with a small amount of washing water, a squeeze roller washing tank is preferably provided. Further, a part or all of the overflow solution from the washing bath or the fixing bath can be used for the fixing solution as described in JP-A-60-235133. By doing so, the amount of waste liquid is reduced, which is more preferable. Also,
The washing water contains a fungicide (for example, a compound described in Horiguchi, "The Chemistry of Bacterial Prevention and Prevention", JP-A-62-115154), a washing accelerator (sulfite, etc.), a chelating agent and the like. May be. The temperature and time of the water washing or stabilizing bath according to the above method are 0 ° C to 50 ° C for 5 seconds to 30 seconds, preferably 15 ° C to 40 ° C for 4 seconds to 20 seconds. In the present invention, the photosensitive material that has been developed, fixed and washed with water is dried through a squeeze roller. Drying at 40 ° C to 80 ° C for 4 seconds to 3
This is done in 0 seconds. The total processing time in the present invention means that after inserting the leading end of the film into the insertion opening of the automatic developing machine, a developing tank, a transfer section, a fixing tank, a transfer section, a washing tank, a transfer section,
This is the total time from the drying section to the end of the film coming out of the drying outlet. Hereinafter, the present invention will be described specifically 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 0.13 M aqueous solution of silver nitrate, an aqueous solution of a halogen salt containing 0.04 M of potassium bromide and 0.1 M of sodium chloride, containing sodium chloride and 1,3-dimethylimidazolidin-2-thione In an aqueous gelatin solution,
While stirring, the mixture was added by a double jet method at 43 ° C. for 12 minutes to give an average particle size of 0.15 μm and a silver chloride content of 7
Nucleation was performed by obtaining 0 mol% of silver chlorobromide grains. Subsequently, a 0.87 M silver nitrate aqueous solution and 0.2
A halogen salt aqueous solution containing 6 M potassium bromide and 0.65 M sodium chloride was added by a double jet method over 20 minutes. Thereafter, the mixture was washed with water by a flocculation method according to a conventional method, and 40 g of gelatin was added thereto.
The 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. for 75 minutes, subjected to a chemical sensitization treatment, and added as a stabilizer. 150 mg of -hydroxy-6-methyl-1,3,3a, 7-tetraazaindene were added. The obtained grains were cubic silver chlorobromide grains having an average grain size of 0.26 μm and a silver chloride content of 70 mol% (coefficient of variation: 10%). [Emulsion B] The same method as in Emulsion A except that (NH ₄ ) ₃ RhCl ₆ and K ₃ IrCl ₆ were further added to the aqueous solution of the halogen salt added at the time of nucleation.
26 μm, silver chloride content 70 mol%, Rh per mol of silver
Silver chlorobromide cubic grains containing 1 × 10 ⁻⁷ mol of the compound and 5 × 10 ⁻⁷ mol of the Ir compound were obtained (coefficient of variation: 10 × 10 ⁻⁷ mol).
%). [Emulsion C] The same method as in Emulsion A except that K ₃ IrCl ₆ and K ₂ Ru (NO) Cl ₅ were further added to the aqueous solution of the halogen salt added at the time of nucleation, and the average grain size was 0.1 mm.
26 μm, silver chloride content 70 mol%, Ir per mol of silver
Silver chlorobromide cubic particles containing 5 × 10 ⁻⁷ mol of the compound and 1 × 10 ⁻⁷ mol of the Ru compound were obtained (coefficient of variation: 10 × 10 ⁻⁷ mol).
%). [Emulsion D] A method similar to Emulsion B except that the amount of K ₃ IrCl ₆ added during nucleation was adjusted, and K ₄ [Fe (CN) ₆ ] was further added to the aqueous halide solution used for grain growth. The average particle size was 0.26 μm, the silver chloride content was 70 mol%, and the Rh compound was 1 × 10 ⁻⁷ per mol of silver.
Mole, 2 × 10 ⁻⁷ mole of Ir compound, 3 × Fe compound
Silver chlorobromide cubic grains containing 10 ^-5 mol were obtained (coefficient of variation: 10%). [Emulsion E] A method similar to Emulsion C, except that the amount of K ₃ IrCl ₆ added during nucleation was adjusted and K ₄ [Fe (CN) ₆ ] was further added to the aqueous halide solution used for grain growth. The average particle size was 0.26 μm, the silver chloride content was 70 mol%, and the Ir compound was 2 × 10 ⁻⁷ per mol of silver.
Mol, 1 × 10 ^-7 mol of Ru compound, 3 × Fe compound
Silver chlorobromide cubic grains containing 10 ^-5 mol were obtained (coefficient of variation: 10%).

Preparation of Coated Samples The following sensitizing dyes were added to the emulsions A to E prepared as described above in silver 1
30 mg was added per mole. Further, for supersensitization and stabilization, disodium salt of 4,4'-bis (4,6-dinaphthoxy-pyrimidin-2-ylamino) -stilbene disulfonic acid and 2,5-dimethyl-3-allyl-benzoate were used. Thiazole iodide salt was added in an amount of 30 moles per mole of silver.
0 mg and 450 mg were added. In addition, hydroquinone 100mg
/ M ² , polyethyl acrylate latex at a gelatin binder ratio of 25%, 2-bis (vinylsulfonylacetamide) ethane as a hardener 86 mg / m ^{2 were} added, and a coated silver amount of 3.4 g / m ² was applied on a polyester support. ^2. Coating was performed so that the coated gelatin amount was 1.6 g / m ² . At this time, 0.5 g / m ^{2 of} gelatin, 20 mg / m ² of a dye represented by the following structural formula, 60 mg / m ^{2 of} polymethyl methacrylate having a particle size of 2.5 μm as a matting agent were formed on the upper side of the emulsion layer as a protective layer.
70 mg / m ² of colloidal silica having a particle diameter of 10 μm, and sodium dodecylbenzenesulfonate as a coating aid and a fluorine-containing surfactant having the following structural formula were coated simultaneously with the emulsion layer.

[0081]

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The base used in this example has a back layer and a back protective layer having the following compositions. [Back layer] Gelatin 2.0 g / m ² Sodium dodecylbenzenesulfonate 80 mg / m ²

[0083]

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1,3-divinylsulfone-2-propanol 60 mg / m ² [Back protective layer] Gelatin 0.5 g / m ² Polymethyl methacrylate (particle size 4.7 μm) 30 mg / m ² Sodium dodecylbenzenesulfonate 20 mg / m ² m ² fluorine-containing surfactant (as described above) 2 mg / m ² silicone oil 100 mg / m ² Dye used in the back layer

Evaluation of photographic performance The obtained sample was exposed to xenon flash light having an emission time of 10 ⁻⁶ sec through an interference filter having a peak at 780 nm and a continuous wedge, and was automatically developed by Fuji Photo Film Co., Ltd. Sensitometry was performed using the FG-710NH machine at the temperature and time indicated below.

Current image 38 ° C. 14 seconds 9 seconds Fixing 37 ° C. 9.7 seconds 6.2 seconds Rinse 26 ° C. 9 seconds 5.8 seconds Squeeze 2.4 seconds 1.5 seconds Dry 55 ° C. 8.3 seconds 5.3 seconds total 43.4 seconds 27.8 seconds The composition of the developer and fixer used was as follows. [Developing solution formulation] Hydroquinone 25.0 g 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone 0.5 g Potassium sulfite 90.0 g Disodium ethylenediaminetetraacetate 2.0 g Potassium bromide 5.0 g 5-methyl Benzotriazole 0.2g 2-Mercaptobenzimidazole-5-sulfonic acid 0.3g Sodium carbonate 20g Water 1 liter (add sodium hydroxide to adjust pH = 10.6) [Fixing solution formulation] Ammonium thiosulfate 210g Sodium sulfite (anhydrous) 20 g Disodium ethylenediaminetetraacetate 0.1 g Glacial acetic acid 15 g Add water 1 liter (Adjust to pH = 4.8 with aqueous ammonia)

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. The characteristic curve shows a density of 0.
The gradient of the straight line connecting the points 1 and 3.0 is defined as the gradation, and
Table 1 also shows the difference in sensitivity between seconds and 9 seconds as development progress. As is clear from Table 1, the samples corresponding to the present invention
It is understood that Nos. 3 and 5 are high-sensitivity and high contrast, and the development progress is fast and the processability is excellent.

[0088]

[Table 1]

[0089]

According to the present invention, there is provided a silver chloroiodobromide emulsion, wherein the emulsion contains an atom belonging to any one of groups Va to VIIa or VIII of the periodic table having a nitrosyl or thionitrosyl ligand. Was spectrally sensitized to a wavelength longer than 750 nm, whereby a photosensitive material for high illuminance exposure having a color sensitivity in the infrared region could have a high sensitivity and a high contrast.

Claims (2)

(57) [Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion has a nitrosyl or thionitrosyl ligand. ~ Group VIIa or VI
A transition metal selected from Group II elements is silver halide 1
A silver halide photographic light-sensitive material comprising silver halide grains containing 10 ^-8 to 1 × 10 ^-6 mol per mol, and having a sensitization maximum spectrally sensitized to a wavelength longer than 750 nm. 2. The method for processing a silver halide photographic material according to claim 1, wherein the processing is carried out by an automatic developing machine having a total processing time of 15 to 60 seconds.