JP2724635B2 - Silver halide photographic material - 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 having a spectral sensitization in the infrared region, and more particularly to a high contrast silver halide photographic material having a spectral sensitization in the infrared region. .

[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. There is known an image forming method using a so-called scanner method for forming an image. 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 used as a light source for recording in these scanner-type recording apparatuses. However, each of these light sources has a practical disadvantage that the output is weak and the life is short. To compensate for these shortcomings,
There is a scanner that uses a coherent laser light source such as a Ne-He laser, an argon laser, and a He-Cd laser as a light source of a scanner system. These can provide high output, but the equipment is large, expensive, requires a modulator, and uses visible light, which limits the saferant of the photosensitive material, resulting in poor handling. There are drawbacks such as. On the other hand, semiconductor lasers are small, inexpensive, easy to modulate, have a longer life than the above lasers, and emit light in the infrared region. Since it can be used, there is an advantage that handling workability is not good.

However, since the output of currently available semiconductor lasers is not always high, the sensitivity of conventional photosensitive materials for scanners was insufficient to perform large-screen scanning exposure in a short time. Therefore, there has been a demand for a photosensitive material having improved sensitivity in the infrared region. As a method of increasing the sensitivity of a photograph, it is known to increase the size of silver halide grains or to add various chemical sensitizers, but these methods are often used to improve the granularity of a silver image. It has undesirable side effects such as deterioration and appearance of fog, and is not particularly suitable for a photographic material for a scanner which requires sharp image quality.

[0004]

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a silver halide photographic material having high contrast and photographic characteristics sufficiently high in sensitivity to infrared light.

[0005]

The above object is achieved by the following general formula:
This has been attained by a silver halide photographic material containing the compound represented by formula (I). General formula (I)

[0006]

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In the formula, R ₁ and R ₂ may be the same or different and each represents an alkyl group. R ₃ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, a benzyl group or a phenethyl group. R ₄ and R ₅ may be the same or different and each represents a lower alkyl group. V represents a hydrogen atom, a lower alkyl group, an alkoxy group, a halogen atom or a substituted alkyl group. Z ₁ represents a group of nonmetallic atoms necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic ring. X ₁ represents an acid anion. m, p and q each independently represent 1 or 2. However, q is 1 when the dye forms an inner salt. i and j each represent an integer of 0 to 4;
Will not be. In the compound represented by the general formula (I), R ₁ and R ₂ may be the same or different and each represents an alkyl group (including a substituted alkyl group).
Represents 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, and 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 (for example, phenoxy, p-tolyloxy, α-naphthoxy), an acyloxy group ( Preferably it has 3 or less carbon atoms, for example, acetyloxy, propionyloxy), an acyl group (preferably has 8 or less carbon atoms, for example, acetyl, propionyl, benzoyl, mesyl), a carbamoyl group (for example, carbamoyl, N, N-dimethyl). Carbamoyl, morpholinocarbamoyl, piperidinocarbamoyl), sulfamoyl group (eg, sulfamoyl, N, N-dimethylsulfamoyl, morpholinosulfonyl), 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 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.

Among the lower alkyl groups represented by R ₄ and R ₅ , preferred are those having 1 to 8 carbon atoms, and particularly preferred are unsubstituted alkyl groups having 1 to 4 carbon atoms (eg, methyl and ethyl). , Propyl, butyl, isobutyl, cyclopropylmethyl, etc.).

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), halogen Atom (for example, fluorine atom, chlorine atom), substituted alkyl group (preferably having 1 to 4 carbon atoms, for example, trifluoromethyl,
Carboxymethyl). Z ₁ represents a nonmetallic atom group necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic ring,
For example, a thiazole nucleus (eg, 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-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-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- Ethyl naphtho [1,2-
d] Imidazole), pyridine nucleus (for example, pyridine, 5
-Methyl-2-pyridine, 3-methyl-4-pyridine)
Can be mentioned. 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 (eg, chloride, bromide,
Iodide, tetrafluoroborate, hexafluorophosphate, methylsulfate, ethylsulfate, benzenesulfonate, 4-methylbenzenesulfonate, 4-chlorobenzenesulfonate, 4-nitrobenzenesulfonate, trifluoromethanesulfonate, perchlorate, etc. ).

Specific examples of the compound represented by the above general formula (I) are shown below, but the scope of the present invention is not limited only to these.

[0012]

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[0013]

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[0014]

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[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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The compound represented by the above general formula (I) is disclosed in JP-A-59-192242 and US Pat.
The compound can be synthesized with reference to the method described in No. 62.

The average grain size of the silver halide used in the present invention is preferably fine grains (for example, 0.7 μm or less), particularly preferably 0.5 μm or less. The silver halide grains in the present invention are cubic grains having substantially [100] faces. Here, "consisting substantially of [100] planes" means, more specifically, preferably 50% or more, more preferably 8%, of the grains contained in the silver halide emulsion.
0% or more, particularly preferably 95% or more of the particles form a cubic and / or 60% or more of the surface area of the particles [100]
It is meant to consist of particles as occupied by faces. The particle size distribution of the silver halide grains used in the present invention is preferably monodispersed. The term "monodisperse" as used herein means a silver halide emulsion having a grain size distribution having a coefficient of variation defined below of 40% or less, particularly preferably 20% or less. Here, the coefficient of variation is: coefficient of variation (%) = (standard deviation of particle size / average value of particle size) ×
100. The photographic emulsion used in the present invention is P.I. By Chif by Glafkides
e et Physique Photographique (Paul Montel, 1
967); F. Photographic Emulsio by Duffin
n Chemistry (The Focal Press, 1966),
V. L. Making and Coating Pho by Zelikman et al
tographic Emulsion (The FocalPress, 1964
Year)). 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 and a soluble halide may be any of a one-sided mixing method, a double-sided mixing method, a combination thereof and the like. Good. In the present invention, a photographic emulsion comprising cubic monodispersed silver halide grains is more preferred. 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 grain size uniform, as described in British Patent No. 1,535,016, JP-B-48-36890 and JP-B-52-16364, the addition rate of silver nitrate or alkali halide is controlled. The critical saturation is not exceeded by using a method of changing the concentration according to the growth rate or a method of changing the concentration of the aqueous solution as described in US Pat. No. 4,242,445 and JP-A-55-158124. It is preferable to grow quickly in the range. The silver halide grains may have a so-called core / shell structure in which the inside and the surface have different halogen compositions. In particular, in the case of silver iodobromide, the silver iodide ratio of the core is preferably higher than the silver iodide ratio of the shell by 0.5 mol% or more, more preferably higher by 2 mol% or more. The silver halide grains used in the present invention preferably use a silver halide solvent during grain formation.

Examples of the silver halide solvent used in the present invention include US Pat. Nos. 3,271,157 and 3,53.
(A) Organic thioethers described in JP-A Nos. 1,289 and 3,574,628;
(B) Thiourea derivatives described in JP-A-55-77737, (c) Silver halide solvents having an oxygen or carbonyl group described in JP-A-53-144319, JP-A-54-100717 (D) imidazoles, (e) sulfites, (f) thiocyanates, and (g) thiones. Of these, thioethers are particularly preferred. The specific compounds are shown below.

[0024]

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The silver halide photographic emulsion used in the present invention preferably contains a metal of Group VIII in the periodic table. Examples of the metal include iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, and platinum. The compound containing these metals preferably used in the present invention is iron (II) sulfate FeSO ₄ -5H ₂ O: iron (III) chloride Fe
Cl ₃ ; potassium hexacyanoferrate (II) K ₄ Fe
_{(CN) 6 · 3H 2 O} ; potassium hexacyanoferrate (III) _K 3 Fe _{(CN) 6;} cobalt chloride (II) Co
Cl _2; cobalt sulfate _{(II) Co (NO 3)} 2 · 6H
₂ O; potassium hexacyanocobaltate (III) K ₃
Co (CN) ₆ ; nickel (II) chloride NiCl ₂ ; 6
H ₂ O nickel nitrate _{(II) Ni (NO 3)} 2 · 6H 2
O; ruthenium (III) chloride RuCl ₃ ; potassium hexachlororuthenate (IV) · K ₂ RuCl ₆ ; rhodium (III) chloride RhCl ₃ · 4H ₂ O; ammonium hexachlororhodate (III) ₃ Rh
Cl ₆ ; Palladium (II) chloride PdCl ₂ ; Palladium (II) nitrate Pd (NO ₃ ) ₂ ; Palladium bromide (I
I) PdBr ₂ ; potassium hexachloropalladium (IV) K ₂ PdCl ₆ ; tetrathiopalladium (II)
Potassium acid salt K ₂ Pd (CNS) ₄ ; Osmium (II) chloride OsCl ₂ ; Iridium (III) chloride IrC
l _3; iridium chloride (IV) IrCl _4; bromide iridium _{(III) IrBr 3 · 4H 2} O; bromide iridium (IV) IrBr _4; hexachloroiridate (II
I) acid; potassium K ₃ IrCl ₆ ; potassium hexachloroiridate (IV) K ₂ IrCl ₆ ; ammonium hexachloroplatinate (IV) (NH ₄ ) ₂ PtCl ₆ ;
Potassium hexachloroplatinate (IV) K ₂ PtCl ₆ ;
Ammonium hexabromoplatinate (IV) (NH ₄ ) ₂
PtBr ₆ ; These Group VIII metal compounds are present in an amount of from 10 ₋₉ mol to 10 mol per mol of silver halide.
_-3 mol alone or in combination of two or more compounds. In particular, two or three kinds of iridium salts, rhodium salts, and iron salts are advantageously used in combination. These compounds can be appropriately added during the production of a silver halide emulsion and at each stage before coating the emulsion. Further, in the above-mentioned method for producing silver halide grains, it may be added at any stage of nucleation or growth, and may be added at the time of chemical ripening of silver halide emulsion. Is preferred.

The silver halide photographic emulsion used in the present invention has the following general formula [II-a], [II-b] or [II-c]
It is preferable to include a compound represented by the formula: General formula [II-a] Z-SO ₂ -SM

[0027]

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Wherein Z is an alkyl group (having 1 to 1 carbon atoms)
8) an aryl group (having 6 to 18 carbon atoms) or a heterocyclic group; Y: an atom necessary for forming an aromatic ring (having 6 to 18 carbon atoms) or a hetero ring M: a metal atom or an organic cation n: An integer from 2 to 10. Z and Y in the general formulas [II-a] to [II-c]
The alkyl group, the aryl group, the heterocyclic group, the aromatic ring, and the heterocyclic ring represented by may be substituted. Examples of the substituent include a lower alkyl group such as a methyl group and an ethyl group,
Examples include an aryl group such as a phenyl group, an alkoxyl group having 1 to 8 carbon atoms, a halogen atom such as chlorine, a nitro group, an amino group, and a carboxyl group. Examples of the hetero ring represented by Z and Y include a thiazole, benzthiazole, imidazole, benzimidazole, oxazole ring and the like. The metal atom represented by M is preferably an alkali metal atom such as a sodium ion or a potassium ion, and the organic cation is preferably an ammonium ion or a guanidine group. Examples of the above compounds include the following compounds.

[0029]

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[0030]

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The compounds described above can generally be synthesized by well-known methods. For example, it can be synthesized by reacting the corresponding sulfonyl fluoride with sodium sulfide or reacting the corresponding sodium sulfinate with sulfur. On the other hand, these compounds can be easily obtained as commercial products. [II-
a), [II-b] or [II-c] is added in an amount of 10 _-6 to 1 per mol of silver halide.
g is preferable, and _10-4 to 1 is particularly preferable.
Is 0 _-2 g. The timing of addition may be at any time during grain formation or during chemical ripening of the emulsion, but it is particularly preferable to add before grain formation or immediately before the start of chemical ripening.

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.

In the present invention, it is preferable to use a compound represented by the following general formula (IV). General formula (IV)

[0034]

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In the formula, Z ₃ represents a group of nonmetallic atoms necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic ring, R ₁₃ represents a hydrogen atom, an alkyl group or an alkenyl group, and R ₁₄ represents a hydrogen atom. Or X ₂ represents an alkyl group, and X ₂ represents an anion for neutralizing a positive charge. Heterocyclic rings completed by Z ₃ in the general formula (IV), for example, thiazolium compounds {e.g. thiazolium, 4-methyl-thiazolium, benzothiazolium, 5-methyl benzothiazolium, 5-chloro-benzothiazolium , 5-methoxybenzothiazolium, 6-
Methylbenzothiazolium, 6-methoxybenzothiazolium, naphtho [1,2-d] thiazolium, naphtho [2,1-d] thiazolium and the like, oxazoliums such as oxazolium, 4-methyloxazolium,
Benzoxazolium, 5-chlorobenzoxazolium, 5-phenylbenzoxazolium, 5-methylbenzoxazolium, naphtho [1,2-d] oxazolium, etc., imidazoliums (for example, 1-methylbenz Imidazolium, 1-propyl-5-chlorobenzimidazolium, 1-ethyl-5,6-dichlorobenzimidazolium, 1-allyl-5-trichloromethyl-6
-Chloro-benzimidazolium, etc.), selenazoliums [eg benzoselenazolium, 5-chlorobenzoselenazolium, 5-methylbenzoselenazolium, 5
-Methoxybenzoselenazolium, naphtho [1,2-
d] selenazolium etc.]. Preferred examples of R ₁₃ include 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, and a pentyl group), and an alkenyl group (such as an allyl group). Preferred examples of R ₁₄ include a hydrogen atom and a lower alkyl group (eg, a methyl group, an ethyl group, etc.).
Is mentioned. Preferred examples of X ₂ include, for example, C
^{l -, Br -, I -} , ClO 4 -, p- toluenesulfonic acid, and the like. Particularly preferred among the heterocyclic rings completed by Z ₃ is thiazolium compounds. More preferred is a substituted or unsubstituted benzothiazolium or naphthothiazolium. Specific examples of the compound represented by Chemical formula 15 are shown below. However, the present invention is not limited to only these compounds.

[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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The compound represented by the above general formula (IV) is used in an amount of about 0.01 g to 5 mol / mol of silver halide in the emulsion.
It is advantageously used in gram quantities. The ratio (weight ratio) of the aforementioned infrared sensitizing dye of the present invention to the compound represented by the general formula (IV) is such that the ratio of the infrared sensitizing dye of the present invention / the compound represented by the general formula (IV) = 1 The range of / 1 to 1/300 is advantageously used, especially the range of 1/2 to 1/50. The compound represented by the general formula (IV) 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.)
Alternatively, these solvents can be dissolved in a mixed solvent using a plurality of solvents 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 compound represented by the general formula (IV) may be added to the emulsion before or before the addition of the infrared sensitizing dye of the present invention described above. Further, the compound of the formula (IV) 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.

The silver halide photographic light-sensitive material of the present invention includes:
Further, it is preferable to add a compound represented by the following general formula (V). General formula (V)

[0043]

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Here, A represents a divalent aromatic residue. R
₂₁ , R ₂₂ , R ₂₃ and R ₂₄ each represent a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a heterocyclic nucleus, a heterocyclylthio group, an arylthio group, an amino group, a substituted or unsubstituted alkyl It represents an amino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted aralkylamino group, an aryl group, or a mercapto group. However, at least one of A, R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ has a sulfo group. W ₃ and W ₄ is -
Represents CH = or -N =. However at least either W ₃ and W ₄ represents -N =. In -A- represents the general formula (V) represents a divalent aromatic residue, preferably -SO ₃ M group (wherein M represents a hydrogen atom, ammonium which may be an alkali metal, or substituted. General Formula (V)
Is preferably selected from, for example, -A ₁ -or -A _2- . However _{R 21, R 22, R 23} , or when the R ₂₄ does not contain -SO ₃ M is, -A- is -A ₁
Selected from the group of-.

[0045]

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[0046]

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[0047]

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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 (e.g., 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, 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 has at least one sulfo group (which may be a free acid group and forms a salt. May be required). W ₃ and W
₄ represents -CH = or -N =, at least one of which is -N =. Next, specific examples of the compound included in the general formula (V) will be described. However, it is not limited only to these compounds.

(V-1) 4,4'-bis [4,6-di (benzothiazolyl-2-thio) pyrimidin-2-ylamino] stilbene-2,2'-disulfonate sodium salt (V-2) 4 , 4'-bis [4,6-di (benzothiazolyl-2-amino) pyrimidin-2-ylamino)] stilbene-2,2'-disulfonic acid sodium salt (V-3) 4,4'-bis [4 6-di (naphthyl-2
-Oxy) pyrimidin-2-ylamino] stilbene-
Disodium 2,2'-disulfonate (V-4) 4,4'-bis [4,6-di (naphthyl-2
-Oxy) pyrimidin-2-ylamino] bibenzyl-
Disodium 2,2'-disulfonate (V-5) 4,4'-bis (4,6-dianilinopyrimidin-2-ylamino) stilbene-2,2'-disulfonate disodium salt (V-6 ) 4,4'-Bis [4-chloro-6- (2-naphthyloxy) pyrimidin-2-ylamino] biphenyl-2,2'-disulfonic acid sodium salt (V-7) 4,4'-bis [4 , 6-Di (1-phenyltetrazolyl-5-thio) pyrimidin-2-ylamino] stilbene-2,2'-disulfonic acid disodium salt (V-8) 4,4'-bis [4,6- Di (benzimidazolyl-2-thio) pyrimidin-2-ylamino] stilbene-2,2'-disulfonic acid disodium salt (V-9) 4,4'-bis (4,6-diphenoxypyrimidin-2-ylamino) Disodium salt of tilben-2,2'-disulfonate (V-10) Disodium salt of 4,4'-bis (4,6-diphenylthiopyrimidin-2-ylamino) stilbene-2,2'-disulfonate (V -11) 4,4'-bis (4,6-dimercaptopyrimidin-2-ylamino) biphenyl-2,2'-disulfonate disodium salt (V-12) 4,4'-bis (4,6- Dianilino-triazin-2-ylamino) stilbene-2,2'-disulfonate disodium salt (V-13) 4,4'-bis (4-anilino-6-hydroxy-triazin-2-ylamino) stilbene-2,
Disodium salt of 2'-disulfonate (V-14) 4,4'-bis (4-naphthylamino-6-
Anilino-triazin-2-ylaminol) stilbene-2,2'-disulfonic acid dinatriu salt (V-15) 4,4'-bis [2,6-di (2-naphthoxy) pyrimidin-4-ylamino] stilbene-2 ,
2'-Disulfonic acid (V-16) 4,4'-bis [2,6-di (2-naphthylamino) pyrimidin-4-ylamino] stilbene-
Disodium 2,2'-disulfonate (V-17) 4,4'-Bis (2,6-dianilinopyrimidin-4-ylamino) stilbene-2,2'-disulfonate sodium salt (V-18) 4,4'-bis [2-naphthylamino) -6
-Anilinopyrimidin-4-ylamino] stilbene-
2,2'-disulfonic acid (V-19) 4,4'-bis [2,6-diphenoxypyrimidin-4-ylamino] stilbene-2,2'-disulfonic acid ditriethylammonium salt (V-20) 4 4,4'-Bis [2,6-di (benzimidazolyl-2-thio) pyrimidin-4-ylamino] stilbene-2,2'-disulfonate disodium salt Is the compound represented by the general formula (V) known? Alternatively, it can be easily produced according to a known method.

The compound represented by formula (V) used in the present invention may be a mixture of two or more of these.
The compound represented by formula (V) is advantageously used in an amount of about 0.01 to 5 grams per mole of silver halide in the emulsion. The ratio (weight ratio) of the infrared sensitizing dye to the compound represented by formula (V) is preferably in the range of dye / compound represented by formula (V) = 1/1 to 1/200. In particular, the range of 1/2 to 1/50 is advantageously used. The compound represented by the formula (V) used in the present invention can be directly dispersed in the emulsion, or can be dispersed in an appropriate solvent (eg, methyl alcohol, ethyl alcohol, methyl cellosolve, water, etc.) or a mixed solvent thereof. 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. Japanese Patent Laid-Open No. 50
It can also be dispersed and added to the emulsion by the method described in JP-A-80119. The infrared sensitizing dye represented by formula (I) of the present invention can be used in combination with another sensitizing dye. For example, U.S. Patent Nos. 3,703,377, 2,688,545, and 3,397,060,
No. 3,615,635, No. 3,628,964
No. 1,242,588, UK Patent No. 1,29
3,862, JP-B-43-4936, 44-14
No. 030, No. 43-10773, U.S. Pat.
No. 6,927, JP-B-43-4930, U.S. Pat. Nos. 3,615,613, 3,615,632, 3,617,295, and 3,635,721. The sensitizing dyes described can be used. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Discl.
osure) 176 Volume 17643 (Issued December 1978)
It is described in section J on page 23 IV.

The light-sensitive material of the present invention may 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, mercaptothiazoles, aminotriazoles, benzothiazoles, nitrobenzotriazoles, Mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes and tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a,
7) Many compounds known as antifoggants or stabilizers, such as tetrazaindenes, pentaazaindenes and the like can be added. Particularly, a polyhydroxybenzene compound is preferable in that pressure resistance is improved without impairing sensitivity. The polyhydroxybenzene compound is preferably a compound having any one of the following structures.

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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 group. Alkyl 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, -CO
_{OH, -CH 2 CH 2 COOH,} -CH 3, -CH 2 CH 3, -CH
_{(CH 3) 2, -C (} CH 3) 3, -OCH 3, -CHO,
_{-SO 3 Na, -SO 3 H,} -SCH 3, -C 6 H 5,
_{-C 6 H 4 (m-CH} 3), - C 6 H 4 (p-CH 3) , and the like. X
And Y may be the same or different. Particularly preferred examples of the compounds include the following compounds.

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[0057]

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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 are included. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful. More specifically, it is a water-soluble dye described in, for example, JP-A-62-123454, JP-A-63-55544, and U.S. Pat. No. 4,876,181. On the other hand, the dye used for such a purpose is not necessarily water-soluble, and may be dispersed as solid fine particles. Such an example is disclosed in JP-A-56-12639.
No. 55-155350, No. 55-155351
No. 63-27838, No. 63-197943,
There is an example described in European Patent No. 15,601 and the like.

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), active halogen compounds (such as 2,4-dichloro-6-hydroxy-s-triazine), mucohalic acids (such as mucochloric acid), and N-carbamoylpyridinium salts ((1 -Morpholy) carbonyl-3-pyridinio)
Methanesulfonate, etc.), haloamidinium salts (1
-(1-chloro-1-pyridinomethylene) pyrrolidinium, 2-naphthalenesulfonate or the like can be used alone or in combination. Above all, JP-A-53-4
1220, 53-57257, 59-16254
6, active vinyl compounds described in JP-A-60-80846 and active halides described in U.S. Pat. No. 3,325,287 are preferred. The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared by using the present invention may have coating aids, antistatic, slipperiness improvement, emulsification / dispersion, adhesion prevention and photographic property improvement (eg, development acceleration, high contrast For various purposes such as sensitization), various surfactants may be contained. For example, saponins (steroids), alkylene oxide derivatives (eg, polyethylene glycol, polyethylene glycol / polypropylene glycol condensate, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol) Nonionic surfactants such as alkylamines or amides, polyethylene oxide adducts of silicone, glycidol derivatives (eg, alkenyl succinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, and alkyl esters of sugars. Agent: alkyl carboxylate, alkyl sulfonate, alkyl benzene sulfo Acid salts, alkyl naphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphorus Anionic surfactants containing an acidic group such as a carboxy group, a sulfo group, a phospho group, a sulfate group or a phosphate group, such as acid esters; amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfate or phosphoric acid Amphoteric surfactants such as esters, alkyl betaines and 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 the 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 polymers, 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 of polyvinyl alcohol, partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. 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 a 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 developing solution used in the present invention is not particularly limited, but preferably contains dihydroxybenzenes in 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 usually 0.05 mol / l or more.
It is preferably used in an amount of 0.8 mol / l. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenol is used, the former is 0.05 mol / l-0.5 mol / l and the latter is 0.06 mol / l. It is preferably used in an amount of not more than / l.
As a sulfite preservative used in the present invention, sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
Examples include formaldehyde sodium bisulfite. The sulfite is preferably at least 0.3 mol / l, particularly preferably at least 0.4 mol / l. The upper limit is up to 2.5 mol / l, especially 1.
It is preferably up to 2. Alkali agents used for setting the pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate tribasic,
PH adjusters and buffers such as potassium tertiary phosphate, sodium silicate and potassium silicate are included. Compounds such as boric acid and borax as additives used in addition to the above components,
Development inhibitors such as sodium bromide, potassium bromide and potassium iodide: ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide,
Organic solvents such as methyl cellosolve, hexylene glycol, ethanol and methanol: mercapto compounds such as 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, and indazole compounds such as 5-nitroindazole The compound may contain an antifoggant such as a benztriazole-based compound such as 5-methylbenztriazole, and further contains a color tone agent, a surfactant, an antifoaming agent, a water softener, a hardening agent, and the like, if necessary. May be. In particular, JP-A-56-1
No. 06244, Amino compounds described in JP-B-48-35
The imidazole compound described in No. 493 is preferred in terms of accelerating development or increasing sensitivity. In the developer used in the present invention, a silver stain inhibitor is disclosed in JP-A-56-24347.
Described in Japanese Patent Application Laid-open No. Sho 62 (1994)
Compounds described in Japanese Patent Application No. 60-109743 can be used as dissolution aids. In the developer used in the present invention, boric acid described in JP-A-62-186259, saccharides (eg, saccharose), oximes (eg, acetoxime), phenol described in JP-A-60-93433 may be used as a buffer. (For example, 5-sulfosalicylic acid) and tertiary phosphate (for example, sodium salt and potassium salt), and preferably boric acid. 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) as necessary in addition to the fixing agent.
It has 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 to be used can be appropriately changed, and is generally about 0.1 to about 5 mol / l. The water-soluble aluminum salt which mainly acts as a hardening agent in the fixing solution is a compound generally known as a hardening agent for an acidic hardening fixing solution, and examples thereof include aluminum chloride, aluminum sulfate and potassium alum. As the aforementioned dibasic acid,
Tartaric acid or a derivative thereof and citric acid or a derivative thereof can be used alone or in combination of two or more. It is effective that these compounds contain not less than 0.005 mol per liter of the fixing solution, particularly from 0.01 mol / l to 0.0 mol / l.
3 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.
It may contain a pH buffer (eg, acetic acid, boric acid), a pH adjuster (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 / l, more preferably about 18 to 25 g / l, since the pH of the developer is high. The fixing temperature and time are the same as in the case of development, and are about 20 ° C. to about 50 ° C.
For 10 seconds to 1 minute. Further, the washing water may contain a fungicide (for example, Horiguchi's "Bacterial Prevention and Prevention Chemistry",
-115154), a washing accelerator (such as a sulfite), a chelating agent and the like. According to the above method, the developed and fixed photographic material is washed with water and dried. The water washing is performed to almost completely remove the silver salt dissolved by the fixing, and is carried out at about 20 ° C. to about 50 ° C. for 10 minutes.
Seconds to 3 minutes are preferred. Drying is performed at about 40 ° C. to about 100 ° C., and the drying time may be appropriately changed depending on the surrounding conditions, but usually about 5 seconds to 3 minutes and 30 seconds. The roller transport type automatic developing machine is described in U.S. Pat. Nos. 3,025,779 and 3,545,971 and the like, and is simply referred to as a roller transport type processor in this specification. The roller transport type processor has four steps of development, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, a stop step), but most preferably follows these four steps. . Here, in the rinsing step, water can be saved by using a two- or three-stage countercurrent rinsing method. The developer used in the present invention is preferably stored in a packaging material having low oxygen permeability described in JP-A-61-73147. As the developer used in the present invention, a replenishing system described in JP-A-62-91939 can be preferably used.

Since the silver halide photographic light-sensitive material of the present invention provides a high Dmax, when subjected to a power-reducing treatment after image formation, a high density is maintained even if the dot area is reduced.
There is no particular limitation on the reducing fluid used in the present invention,
For example, Mees, The Theory of the PhotographicPr
ocess, pp. 738-744 (1954, Macmilla
n), Tetsuo Yano, Photo Processing Theory and Practice, 166-1
69 pages (1978, Kyoritsu Shuppan), and JP-A-50-27543, JP-A-52-68429, and JP-A-55-68429
Nos. -17123, 55-79444, and 57-10
No. 140, No. 57-142639, JP-A-61-61
No. 155 or the like can be used. That is, as an oxidizing agent, permanganate, persulfate, ferric salt, cupric salt, ceric salt, red blood salt, dichromate, or the like alone or in combination, and further if necessary A reducing solution containing an inorganic acid such as sulfuric acid or an alcohol, or an oxidizing agent such as red blood salt or ferric ethylenediaminetetraacetate, and a halogen such as thiosulfate, rodane salt, thiourea or a derivative thereof. A reducing solution containing a silver halide solvent and, if necessary, an inorganic acid such as sulfuric acid is used. Typical examples of the reducer used in the present invention include so-called Farmer reducer, ferric ethylenediaminetetraacetate, potassium permanganate, and ammonium persulfate reducer (Kodak R).
-5), cerium salt reducer. The conditions of the reduction treatment are generally 10 ° C to 40 ° C, particularly 15 ° C to 30 ° C.
It is preferable that the process can be completed at a temperature of several seconds to several tens of minutes, especially within a few minutes. If the photosensitive material for plate making of the present invention is used, a sufficiently wide reduction range can be obtained within the range of these conditions. The reducer acts on the silver image formed in the emulsion layer via the non-photosensitive upper layer containing the compound of the present invention. Specifically, there are various methods, for example, immersing the plate-making photosensitive material in a reducing fluid, stirring the liquid, or applying the reducing fluid to the surface of the plate-making photosensitive material with a brush, a roller, or the like. Method is available.

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EXAMPLES Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. Example 1 Preparation of Emulsion Emulsion A: A 0.13 M aqueous silver nitrate solution and an aqueous halide solution containing 0.04 M potassium bromide and 0.09 M sodium chloride were mixed with sodium chloride and 1,8-dihydroxy-3,6 -Addition to a gelatin solution containing dithiaoctane by a double jet method at 45 ° C for 12 minutes with stirring to obtain silver chlorobromide particles having an average particle size of 0.15 µm and a silver chloride content of 70 mol%, thereby forming nuclei. Was performed. Subsequently, similarly, a 0.87 M aqueous solution of silver nitrate, an aqueous solution of a halogen salt containing 0.26 M of potassium bromide and 0.65 M of sodium chloride were subjected to the double jet method.
Added over 20 minutes. Thereafter, it was washed with flocculation according to a conventional method, and 40 g of gelatin was added.
H6.5 and pAg7.5, and 5 mg of sodium thiosulfate and 8 mg of chloroauric acid per mole of silver were added.
The mixture was heated at 0 ° C. for 75 minutes, subjected to a chemical sensitization treatment, and 150 mg of 1,3,3a, 7-tetrazaindene was added as a stabilizer. The resulting particles have an average particle size of 0.28 μm,
The particles were silver chlorobromide cubic grains having a silver chloride content of 70 mol%.
(Coefficient of variation 10%). Emulsion B: sodium chloride and 1,8-dihydroxy-3,
The average grain size was 0.28 in the same manner as in Emulsion A except that 10 mg of the compound a contained in the general formula [II-a] was further added to the aqueous gelatin solution containing 6-dithiaoctane.
Cubic silver chlorobromide grains having a particle size of 70 μm and a silver chloride content of 70 μm were obtained. (Coefficient of variation 10%). Emulsion C: After grain formation, washing and dispersion were carried out in the same manner as Emulsion A, 20 mg of Compound a contained in the general formula [II-a] was added per 1 mol of silver, and then the emulsion was chemically sensitized in the same manner as Emulsion A. Sensation processing, and finally an average particle size of 0.28
Cubic silver chlorobromide particles having a particle size of 70 μm and a silver chloride content of 70 μm were obtained. (Coefficient of variation 10%). Emulsion D: Ammonium hexachlororhodate (III) was further added to the aqueous solution of a halogen salt used for nucleation, and hexachloroiridium (A) was added to an aqueous solution of a halogen salt containing 0.26 M of potassium bromide and 0.65 M of sodium chloride. III) Except for using an aqueous solution to which potassium acid was added, respectively, in the same manner as in Emulsion A, for each mol of Rh, 1.0 × 10 ⁻⁷ mol of Rh and 6.0 × 10 mol of Ir.
Silver chlorobromide cubic grains containing 10 ^-7 mol and having an average grain size of 0.28 μm and a silver chloride content of 70 mol% were obtained (coefficient of variation: 10%). Emulsion E: Ammonium hexachlororhodate (III) is further added to an aqueous solution of a halogen salt used for nucleation, and hexachloroiridium (III) is added to an aqueous solution of a halogen salt containing 0.26 M of potassium bromide and 0.65 M of sodium chloride. In the same manner as in Emulsion B, except that potassium acid was added and the aqueous solution was used, Rh was 1.0 × 10 ⁻⁷ mol and Ir was 6.0 × 10 ⁻⁷ per mol of silver.
Silver chlorobromide cubic grains having an average grain size of 0.28 μm and a silver chloride content of 70 mol% were obtained.
0%). Emulsion F: Ammonium hexachlororhodate (III) was further added to the aqueous solution of a halogen salt used for nucleation, and hexachloroiridium (III) was added to an aqueous solution of a halogen salt containing 0.26 M of potassium bromide and 0.65 M of sodium chloride. In the same manner as in Emulsion C except that an aqueous solution to which potassium acid was added was used, containing 1.0 × 10 ⁻⁷ mol of Rh and 6.0 × 10 ⁻⁷ mol of Ir per 1 mol of silver. Silver chlorobromide cubic grains having an average grain size of 0.28 μm and a silver chloride content of 70 mol% were obtained (coefficient of variation: 10).
%).

Preparation of Coated Samples To 1 kg of the above emulsion, 60 ml of a 0.05% solution of a sensitizing dye shown in Table 1 was added to perform sensitization in the infrared region. This emulsion was treated with 4,4'-bis- (4,6
-Dinaphthoxy-pyrimidin-2-ylamino) -stilbene disulfonic acid disodium salt in 70% 0.5% methanol and 90 ml of 2,5-dimethyl-3-allyl-benzothiazole iodide in 0.5% methanol were added. . Further hydroquinone 100 mg / m ^2, silver 3 polyethyl acrylate latex as a plasticizer gelatin binder ratio of 25% of 2-bis (vinylsulfonyl acetamide) ethane as a hardening agent 86.2 mg / m ² were added on a polyester support 0.7 g / m ² . Gelatin was 2.5 g / m ² . 0.6 g / m ² of gelatin, 60 mg / m ^{2 of} polymethyl methacrylate having a particle size of 3 to 4 μm as a matting agent, 70 mg / m ² of colloidal silica having a particle size of 10 to 20 μm, and 10 mg of silicone oil
/ M ² , sodium dodecylbenzenesulfonate as a coating aid, an upper protective layer to which a fluorine-based surfactant having the following structural formula was added, and gelatin 0.7 g / m ² ,
Polyethyl acrylate latex 225 mg / m ^2, in the dye 20 mg / m ² expressed, in dyes represented 10mg
/ M ² and the lower layer of the protective layer to which sodium dodecylbenzenesulfonate was added as a coating aid were simultaneously applied to prepare a sample.

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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,
Has a swelling ratio of 110%. (Back layer) Gelatin 3.0 g / m ² Sodium dodecylbenzenesulfonate 80 mg Dye a 80 mg ｂb 30 mg ｃc 100 mg 1,3-divinylsulfonyl-2-propanol 60 mg / m ² Potassium polyvinyl benzenesulfonate 30 g / m 2 ² (Back protective layer) Gelatin 0.75 g / m ² Polymethyl methacrylate (particle size 4.7 μ) 30 mg / m ² Sodium dodecylbenzenesulfonate 20 mg / m ² Fluorinated surfactant (the above compound) 2 mg / m ² silicone Oil 100mg / m ²

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Developer Formulation Water 720 ml Ethylenediaminetetraacetic acid disodium salt 4 g Sodium hydroxide 44 g Sodium sulfite 45 g 2-methylimidazole 2 g Sodium carbonate 26.4 g Boric acid 1.6 g Potassium bromide 1 g Hydroquinone 36 g Diethylene glycol 39 g 5-methyl-benzo Triazole 0.2 g Pyrazone 0.7 g Add water 1 l Fixer formulation Ammonium thiosulfate 170 g Sodium sulfite (anhydrous) 15 g Nitric acid 7 g Glacial acetic acid 15 ml Potassium alum 20 g Ethylenediaminetetraacetic acid 0.1 g Tartaric acid 3.5 g Add water 1 l

Evaluation of photographic performance The obtained sample was exposed to xenon flash light having a light emission time of 10 ⁻⁶ sec through an interference filter having a peak at 780 nm and a continuous wedge, and a developing solution and a fixing solution having the following compositions were used. , Fuji Photo Film Co., Ltd. automatic developing machine FG-
Developed, fixed, washed with water, dried and subjected to sensitometry at 360 ° F (washing tank capacity 6 liters) at 38 ° C. The reciprocal of the exposure amount giving a density of 3.0 was defined as the sensitivity, and the relative sensitivity is shown in Table 1. Also, the gradient of the straight line connecting the points of density 0.1 and 3.0 in the characteristic curve is similarly shown in Table 1. As is clear from Table 1, the sample of the present invention loses high contrast. It can be seen that the sensitivity is high without any change.

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──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location G03C 1/035 G03C 1/035 G

Claims (2)

(57) [Claims] 1. A silver halide photographic light-sensitive material containing a compound represented by the following general formula (I). General formula (I) In the formula, R ₁ and R ₂ may be the same or different and each represents an alkyl group. R ₃ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, a benzyl group or a phenethyl group. R ₄ and R ₅ may be the same or different and each represents a lower alkyl group. V represents a hydrogen atom, a lower alkyl group, an alkoxy group, a halogen atom or a substituted alkyl group. Z ₁ represents a group of nonmetallic atoms necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic ring. X ₁ represents an acid anion. m, p and q each independently represent 1 or 2. However, q is 1 when the dye forms an inner salt. i and j represent an integer of 0 to 4, but are not 0 at the same time. 2. The silver halide photographic light-sensitive material according to claim 1, further comprising at least one silver halide photographic emulsion layer on a support, wherein the silver halide grains in the silver halide emulsion are cubic single grains. 2. The silver halide photographic light-sensitive material according to claim 1, which is a dispersion particle.