JPH0731384B2 - Silver halide photographic emulsion - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide photographic emulsion used in a silver halide photographic light-sensitive material spectrally sensitized in the infrared region, and particularly in the infrared spectral region. The present invention relates to a silver halide photographic emulsion used in a silver halide photographic light-sensitive material having improved sensitivity and storability.

(Prior Art) One of the exposure methods of a photographic light-sensitive material is to scan an original image and expose the silver halide photographic light-sensitive material on the basis of the image signal to expose a negative or positive image corresponding to the image of the original image. There is known an image forming method by a so-called scanner method for forming an image.

There are various types of recording apparatuses that use the scanner-type image forming method, and conventionally, glow lamps, xenon lamps, mercury lamps, tungsten lamps, light-emitting diodes, and the like have been used as the recording light sources of these scanner-type recording apparatuses. However, each of these light sources has a practical drawback that the output is weak and the life is short. To compensate for these drawbacks, there is a scanner that uses a coherent laser light source such as a Ne-He laser, an argon laser, or a He-Cd laser as a light source of a scanner system. These are capable of obtaining high output, but are large in size, expensive, require a modulator, and use visible light, which limits safelight of the photosensitive material, resulting in poor handling. There are drawbacks such as.

On the other hand, a semiconductor laser is small, inexpensive, easy to modulate, has a longer life than the above laser, and emits light in the infrared region. Since it can be used, it has an advantage that the handling workability is improved. However, since there is no photosensitive material having high photosensitivity in the infrared region and excellent storage stability, the characteristics of the semiconductor laser having excellent performance as described above cannot be utilized.

As an infrared-sensitized commercial film, there is, for example, HIE135-20 manufactured by Eastman Kodak Company, but it cannot be left at room temperature, and it is necessary to refrigerate or freeze it to store the light-sensitive material. . As can be seen from this, the sensitivity of the conventional infrared-sensitized light-sensitive material is unstable,
Preservation requires special consideration.

As one of the manufacturing techniques of photographic light-sensitive materials, a technique of adding a certain kind of senior dye to a silver halide photographic emulsion to extend its light-sensitive wavelength range to a longer wavelength side, that is, a spectral sensitization technique is applied. It is known that this spectral sensitization technique is applied not only in the visible region but also in the infrared region. For spectral sensitization in the infrared region, sensitizing dyes having absorption for infrared light are used.
es) "The Theory of the Photographic Proces
s), 3rd edition ”(published by MacMillan, 1966), pages 198-201.
It is described in. In this case, it is desirable that the spectral sensitivity, that is, the sensitivity to light in the infrared region is high, and that the change in sensitivity is small even during storage of the emulsion. For this reason, many sensitizing dyes have been developed so far.

These are, for example, U.S. Patent Nos. 2,095,854 and 2,095,856.
No., No. 2,955,939, No. 3,482,978, No. 3,552,974,
It is described in No. 3,573,921 and No. 3,582,344. However, even if the sensitizing dyes described in these are used, it cannot be said that the sensitivity and storability are sufficient.

On the other hand, in the light-sensitive material, in addition to the spectral sensitizing dye, the second,
Spectral sensitivity can be significantly increased by the addition of certain specifically selected organic compounds, an effect known as supersensitization. Generally, the addition of the second organic compound does not increase the sensitivity or decreases the sensitivity on the contrary, so it can be said that supersensitization is a unique phenomenon. Remarkably strict selectivity is required for the dye and the second organic compound or inorganic substance. Therefore, what appears to be a slight difference in chemical structure has a significant effect on this supersensitization action, and it is difficult to obtain a combination of supersensitizations by simply predicting from the chemical structural formula. The second organic compound for supersensitization known to date includes, for example, U.S. Pat.
Triazine derivatives described in 875,058 and 3,695,888, mercapto compounds described in U.S. Pat.No. 3,457,078, thiourea compounds described in U.S. Pat.No. 3,458,318, and U.S. Pat.No.3,615,632. There are pyrimidine derivatives and the like, and US Pat. No. 4,011,083 describes that infrared sensitization is performed by using a desensitizing amount of infrared sensitizing dye by using an azaindene compound.

(Problems to be Solved by the Present Invention) However, the methods described in these patents certainly increase the infrared sensitivity and may slightly improve the storage stability in some cases, but they are still insufficient. However, a means for supersensitization that brings about higher infrared sensitivity and improved storage stability is desired.

On the other hand, emulsions in a solution state before coating are generally susceptible to changes in sensitivity and fog, and in particular, changes in sensitivity and fog due to desorption and decomposition of sensitizing dyes are likely to occur. Such a change in the photographic characteristics of the emulsion in the solution state before coating is a very serious problem for the production of a light-sensitive material. However, in order to improve the stability of a sol-ized emulsion containing an infrared sensitizing dye, a commonly known stabilizer such as 1-phenyl-5-
Mercaptotetrazole is not effective. Therefore, it has been desired to develop a technique for specifically improving the stability of an emulsion containing an infrared sensitizing dye in a solution state before coating.

An object of the present invention is to provide a silver halide photographic emulsion used in a silver halide photographic light-sensitive material having high sensitivity to infrared light. Another object of the present invention is to provide a silver halide photographic emulsion having a small change in sensitivity in a solution state emulsion before coating and a high sensitivity to infrared light. Still another object of the present invention is to provide a silver halide photographic emulsion for use in a silver halide photographic light-sensitive material which has little sensitivity and fogging change during storage and high sensitivity to infrared light. .

(Means for Solving Problems) The object of the present invention is to provide at least one infrared sensitizing dye represented by the following general formula (I) in a silver halide photographic emulsion and the following general formula (IIa) or It was achieved by the combined inclusion of at least one compound of formula (IIb).

General formula (I) In the formula, R ₁ and R ₂ may be the same or different and each represents an alkyl group or a substituted alkyl group.
R ₃ and R ₄ each independently represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group or a benzyl group. R ₅
And R ₆ each represent a hydrogen atom, or R ₅ and R ₆ are linked to form a divalent alkylene group. R ₇ is a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, a benzyl group, or Represents Here, W ₁ and W ₂ each independently represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and W ₁ and W ₂ are linked to each other to form a 5- or 6-membered nitrogen-containing group. It is also possible to form a heterocycle. However, R ₃ and R ₇
It is also possible to combine with to form a divalent alkylene group. Z and Z ₁ each independently represent a nonmetallic atom group necessary for completing a 5- or 6-membered nitrogen-containing heterocycle. X represents an acid anion, and n represents 1 or 2.

General formula (IIa) General formula (IIb) In the formula, R ₈ and R ₉ each independently represent a hydrogen atom, a lower alkyl group, an alkenyl group, a carboxyl group, an alkoxy group or a halogen atom, and R ₁₀ represents an alkyl group having 5 or more carbon atoms, an aralkyl group, an alkylthio group. , An arylthio group, an alkoxy group having 3 or more carbon atoms, an aryloxy group, an alkylamino group having 3 or more carbon atoms, an arylamino group, Represents Here, X ₁ represents a divalent linking group, and R ₁₁
And R ₁₂ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, an aryl group or a heterocyclic group.

Hereinafter, general formulas (I), (IIa) and (II) used in the present invention will be described.
The compound b) will be described in more detail.

General formula (I) In the formula, R ₁ and R ₂ may be the same or different,
An alkyl group (preferably having a carbon number of 1 to 8, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a heptyl group, etc.), or a substituted alkyl group {for example, a carboxyl group as a substituent, a sulfo group, Cyano group, halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), hydroxyl group, alkoxycarbonyl group (preferably having 8 or less carbon atoms, eg, methoxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group, etc.), alkoxy A group (preferably having 7 carbon atoms)
Hereinafter, for example, a methoxy group, an ethoxy group, a propoxy group,
Butoxy group, benzyloxy group, etc.), aryloxy group (eg, phenoxy group, p-tolyloxy group, etc.),
An acyloxy group (preferably having 3 or less carbon atoms, such as an acetyloxy group, a propionyloxy group, etc.), an acyl group (preferably having 8 or less carbon atoms, such as an acetyl group, a propionyl group, a benzoyl group, a mesyl group),
Carbamoyl group (for example, carbamoyl group, N, N-dimethylcarbamoyl group, morpholinocarbamoyl group, piperidinocarbamoyl group, etc.), sulfamoyl group (for example, sulfamoyl group, N, N-dimethylsulfamoyl group,
Morpholinosulfonyl group, etc.), an alkyl group substituted with an aryl group (eg, phenyl group, p-hydroxyphenyl group, p-carboxyphenyl group, p-sulfophenyl group, α-naphthyl group, etc.) (preferably an alkyl moiety 6 or less carbon atoms). However, two or more of these substituents may be combined and substituted with an alkyl group. } Is represented.

R ₃ and R ₄ are each independently a hydrogen atom, a lower alkyl group (preferably having a carbon number of 1 to 6, such as a methyl group, an ethyl group,
A propyl group), a lower alkoxy group (preferably having a carbon number of 1 to 6, such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc.), a phenyl group, or a benzyl group.

R ₅ and R ₆ each represent a hydrogen atom, or R ₅ and R ₆ are linked to each other to form a divalent alkylene group (eg, ethylene or trimethylene). The alkylene group is one, two or more suitable groups such as an alkyl group (preferably having 1 to 4 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, etc.), a halogen atom. (Eg, chlorine atom, bromine atom, etc.), or an alkoxy group (preferably having 1 to 4 carbon atoms, such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group).

R ₇ is a hydrogen atom, a lower alkyl group (preferably having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, etc.), a lower alkoxy group (preferably having 1 to 8 carbon atoms).
8, such as methoxy, ethoxy, propoxy, butoxy), phenyl, benzyl, or Represents Here, W ₁ and W ₂ are each independently a substituted or unsubstituted alkyl group (preferably having 1 to 18 carbon atoms in the alkyl moiety, more preferably 1 to 4, for example, methyl group, ethyl group, propyl group, butyl group). , Benzyl group, phenylethyl group), or a substituted or unsubstituted aryl group (eg, phenyl group, naphthyl group, tolyl group, p-chlorophenyl group, etc.), and W ₁ and W ₂ are linked to each other to form a 5-membered member. Alternatively, a 6-membered nitrogen-containing heterocycle can be formed. However, R ₃ and R ₇ are linked to form a divalent alkylene group (the above R ₅ and
It is also possible to form a divalent alkylene group which is formed by linking with R ₆ ).

Z and Z ₁ each independently represent a non-metal atom group necessary for completing a 5- or 6-membered nitrogen-containing heterocycle, 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-methoxy Naft [1,2-
d] thiazole, 7-ethoxynaphtho [2,1-d] thiazole, 8-methoxynaphtho [2,1-d] thiazole, 5-methoxynaphtho [2,3-d] thiazole, etc.}, selenazole nucleus {eg benzo Selenazole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-methylbenzoselenazole, 5-hydroxybenzoselenazole, naphtho [2,1-d] selenazole, naphtho [1,2-
d] selenazole, etc., oxazoles {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, etc., quinoline nucleus {eg, 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, etc.}, 3,3-dialkylindolenine nucleus {eg, 3,3 -Dimethylindolenine, 3,3-
Diethyl indolenine, 3,3-dimethyl-5-cyanoindolenine, 3,3-dimethyl-5-methoxyindolenine, 3,3-dimethyl-5-methylindolenine, 3,3-dimethyl-5-chloroindolenine Renin, etc., imidazole nucleus {eg 1-methylbenzimidazole, 1-ethylbenzimidazole, 1-methyl-5-chlorobenzimidazole, 1-ethyl-5-chlorobenzimidazole, 1-methyl-5,6-dichloro Benzimidazole,
1-ethyl-5,6-dichlorobenzimidazole, 1-
Methyl-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 Etc., pyridine nucleus {eg, pyridine, 5-methyl-2-pyridine, 3-methyl-4-
Pyridine etc.} etc. can be mentioned. Of these, a thiazole nucleus and an oxazole nucleus are advantageously used. More preferably, a benzothiazole nucleus, a naphthothiazole nucleus, a naphthoxazole nucleus or a benzoxazole nucleus is advantageously used.

X represents an acid anion. n represents 1 or 2. N is 1 when the compound forms betaine.

General formula (IIa) General formula (IIb) In the formula, R ₈ and R ₉ are each independently a hydrogen atom, a lower alkyl group (preferably a substituted or unsubstituted one having 1 to 4 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n-butyl group, t-butyl group, methoxyethyl group, hydroxyethyl group, hydroxymethyl group, phenoxymethyl group, etc.), alkenyl group (preferably substituted or unsubstituted one having 2 to 4 carbon atoms, for example, vinyl group) ,
Allyl, etc.), carboxyl group, alkoxy group (preferably substituted or unsubstituted one having 1 to 5 carbon atoms, such as methoxy group, ethoxy group, methoxyethoxy group, hydroxyethoxy group, etc.), or halogen atom (eg chlorine atom). , Bromine atom, fluorine atom, etc.).

R ₁₀ is an alkyl group having 5 or more carbon atoms, preferably 6 or more (eg, pentyl group, heptyl group, octyl group, dodecyl group, pentadecyl group, heptadecyl group, etc.), aralkyl group (preferably substituted or unsubstituted carbon). C. 7-12, such as benzyl, phenethyl, phenylpropyl, etc.), alkylthio groups (preferably substituted or unsubstituted C 1-10, such as methylthio, ethylthio, etc.), arylthio groups (Preferably a substituted or unsubstituted C6 to C12, such as phenylthio group), an alkoxy group having 3 or more carbon atoms (eg, propoxy group, butoxy group, etc.), an aryloxy group (eg, phenoxy group, etc.), Alkylamino groups having 3 or more carbon atoms (eg propylamino group, butylamino group, etc.), arylamino groups (eg Reno group, etc.) Represents Here, X ₁ is an alkylene group (preferably having a carbon number of 1 to 5, for example, methylene group, propylene group, 2-
A hydroxypropylene group, etc.). R ₁₁ and R ₁₂ may be the same or different and each is a hydrogen atom, an alkyl group (preferably a substituted or unsubstituted one having 1 to 10 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group). Group, n-butyl group, t-butyl group, n-octyl group, methoxyethyl group, hydroxyethyl group, etc., alkenyl group (preferably substituted or unsubstituted one having 2 to 10 carbon atoms, for example, allyl group, Propargyl group etc.), aralkyl group (preferably substituted or unsubstituted C 7-12 carbon atoms such as benzyl group, phenethyl group, vinylbenzyl group etc.), aryl group (preferably substituted or unsubstituted C 6 -C 6 group). It represents 12 groups such as phenyl group, 4-methylphenyl group and the like, or heterocyclic group (for example, 2-pyridyl group and the like).

Specific examples of the sensitizing dye represented by formula (I) are shown below. However, the present invention is not limited to these sensitizing dyes.

Specific examples of the compounds represented by formulas (IIa) and (IIb) are shown below. However, the present invention is not limited to only these compounds.

(II-1) 4-Hydroxy-6-pentyl-1,3,3a, 7-tetrazaindene (II-2) 4-Hydroxy-6-heptyl-1,3,3a, 7-tetrazaindene (II -3) 4-Hydroxy-6-nonyl-1,3,3a, 7-tetrazaindene (II-4) 4-Hydroxy-6-heptadecyl-1,3,3a, 7
-Tetrazaindene (II-5) 4-hydroxy-6-benzyl-1,3,3a, 7-tetrazaindene (II-6) 6- (N, N-diallylcarbamoylmethyl)-
4-Hydroxy-1,3,3a, 7-tetrazaindene (II-7) 6- (N-ethylcarbamoylethyl) -4-
Hydroxy-2-methyl-1,3,3a, 7-tetrazaindene (II-8) 6- (N-phenylcarbamoylmethyl) -4
-Hydroxy-1,3,3a, 7-tetrazaindene (II-9) 6- (N-2-pyridylcarbamoylmethyl)
-4-Hydroxy-1,3,3a, 7-tetrazaindene (II-10) 6- (N-allylcarbamoylmethyl) -2
-Allyl-4-hydroxy-1,3,3a, 7-tetrazaindene (II-11) 6- (N-allylcarbamoylmethyl) -4
-Hydroxy-1,3,3a, 7-tetrazaindene (II-12) 4-hydroxy-2-methylthio-6- (N
-Vinylbenzylcarbamoylmethyl) -1,3,3a, 7-tetrazaindene (II-13) 4-hydroxy-6- (N-vinylbenzylcarbamoylmethyl) -1,3,3a, 7-tetrazaindene (II-13) II-14) 6- (N, N-diethylcarbamoylmethyl)-
5-ethoxycarbonyl-4-hydroxy-1,3,3a, 7-
Tetrazaindene (II-15) 4-hydroxy-6- (N-propylcarbamoylpropyl) -2-phenoxy-1,3,3a, 7-tetrazaindene (II-16) 6- (N-benzylcarbamoylmethyl) ) −
4-Hydroxy-1,3,3a, 7-tetrazaindene (II-17) 5-cyano-6- (N, N-diallylcarbamoylmethyl) -4-hydroxy-1,3,3a, 7-tetrazaine Den (II-18) 4-hydroxy-6- (N-octylcarbamoylmethyl) -2-phenyl-1,3,3a, 7-tetrazaindene (II-19) 6- (N-benzylcarbamoylmethyl)-
5-Bromo-4-hydroxy-1,3,3a, 7-tetrazaindene (II-20) 2-benzyl-6- (N, N-diethoxycarbamoylmethyl) -4-hydroxy-1,3,3a , 7-Tetrazaindene (II-21) 6- (N-allylcarbamoylmethyl) -4
-Hydroxy-2-dimethylamino-1,3,3a, 7-tetrazaindene (II-22) 6- (N-benzylcarbamoylmethyl)-
4-Hydroxy-2-phenylthio-1,3,3a, 7-tetrazaindene (II-23) 4-hydroxy-6- (N-methyl-N-phenylcarbamoylmethyl) -1,3,3a, 7- Tetrazaindene (II-24) 4-Hydroxy-6- (N-propylcarbamoylmethyl) -1,3,3a, 7-tetrazaindene (II-25) 6- (N, N-dipropylcarbamoylmethyl)
-4-Hydroxy-1,3,3a, 7-tetrazaindene (II-26) 6- (N-benzyl-N-methylcarbamoylmethyl) -4-hydroxy-1,3,3a, 7-tetrazaindene (II-27) 6- [N- (2-methoxyphenyl) -carbamoylmethyl] -4-hydroxy-1,3,3a, 7-tetrazaindene (II-28) 6- [N- (2-methyl (Phenyl) -carbamoylmethyl] -4-hydroxy-1,3,3a, 7-tetrazaindene (II-29) 6- [N- (2,5-dimethoxyphenyl) -carbamoylmethyl] -4-hydroxy-1 , 3,3a, 7-Tetrazaindene (II-30) 6-acetylaminomethyl-4-hydroxy-1,3,3a, 7-tetrazaindene (II-31) 6- (3-butenoylamino Methyl) -4-
Hydroxy-1,3,3a, 7-tetrazaindene (II-32) 4-hydroxy-6- (α-phenylacetylaminomethyl) -1,3,3a, 7-tetrazaindene (II-33) 6 -(N, N-diallylsulfamoylmethyl)
-4-Hydroxy-1,3,3a, 7-tetrazaindene (II-34) 6- (N-benzylsulfamoylmethyl)
-4-Hydroxy-1,3,3a, 7-tetrazaindene (II-35) 4-Hydroxy-6- (methanesulfonamidomethyl) -1,3,3a, 7-tetrazaindene (II-36) 6-Benzenesulfonamidomethyl-4-hydroxy-1,3,3a, 7-tetrazaindene (II-37) 6- (N, N-diallylcarbamoylmethyl)-
4-Hydroxy-1,2,3a, 7-tetrazaindene (II-38) 6- (N-vinylbenzylcarbamoylmethyl) -4-hydroxy-1,2,3a, 7-tetrazaindene (II-39 ) 6-Acetylaminomethyl-4-hydroxy-1,2,3a, 7-tetrazaindene (II-40) 6- (3-butenoylaminomethyl) -4-
Hydroxy-1,2,3a, 7-tetrazaindene (II-41) 6-benzenesulfonamidomethyl-4-hydroxy-1,2,3a, 7-tetrazaindene (II-42) 6- (N- Arylsulfamoyl) -4-hydroxy-1,2,3a, 7-tetrazaindene A general synthesis method of the infrared sensitizing dye represented by the general formula (I) used in the present invention is described in, for example, JP-A-59-59. -192242 etc.

The infrared sensitizing dye represented by the general formula (I) used in the present invention is preferably 5 × 10 ⁻⁷ mol to 5 × 10 ⁻³ mol, and more preferably 1 × 10 ⁻⁶ mol per mol of silver halide. Mol ~ 1x
It is contained in the silver halide photographic emulsion in a ratio of 10 ^-3 mol, particularly preferably 2 × 10 ^-6 mol to 5 × 10 ^-4 mol.

The infrared sensitizing dye used in the present invention can be directly dispersed in the emulsion. Further, these may be first dissolved in a suitable solvent such as methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine or a mixed solvent thereof, and added to the emulsion in the form of a solution. Ultrasonic waves can also be used for dissolution.
As a method for adding the infrared sensitizing dye, as described in U.S. Pat.No. 3,469,987, the dye is dissolved in a volatile organic solvent, and the solution is dispersed in a hydrophilic colloid. Method of adding dispersion to emulsion, Japanese Patent Publication No. 46-2
No. 4,185, etc., a method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving it, and adding this dispersion to an emulsion; a surfactant as described in US Pat. No. 3,822,135. A method of dissolving the dye in the emulsion and adding the solution to the emulsion; a method of dissolving using a compound for red-shifting and adding the solution to the emulsion as described in JP-A-51-74624; A method in which a dye as described in JP-A-50-80826 is dissolved in an acid containing substantially no water and the solution is added to the emulsion is used. In addition, U.S. Patent Nos. 2,912,343, 3,342,605 and 2,996, for addition to the emulsion.
The methods described in No. 287 and No. 3,429,835 can also be used.
Further, the above infrared sensitizing dye may be uniformly dispersed in the silver halide emulsion before being coated on a suitable support, but of course it may be dispersed at any stage of preparation of the silver halide emulsion. it can.

The general synthetic method of the compound represented by the general formula (IIa) or (IIb) used in the present invention is described in Ber., 42 4638 (1909),
Photo-Rundsch, 26 414, 437, 465 (1961) and the like. Representative synthetic examples of the compounds are shown below, but other compounds represented by the general formula (IIa) or (IIb) can be easily synthesized according to the following synthetic examples.

Synthesis example 6- (N, N-diallylcarbamoylmethyl)-
4-hydroxy-1,3,3a, 7-tetrazaindene (II-6)
Synthesis of Aminotriazole 126 g, diethyl acetonedicarboxylate 304 g, and acetic acid 60 ml are heated under reflux for 8 hours. After allowing to cool, 500 ml of ethyl acetate was added and left standing to precipitate white crystals. The obtained crystals are collected by filtration and washed with ethyl acetate to obtain 6-ethoxycarbonylmethyl-4-hydroxy-1,3,3a, 7-tetrazaindene (305 g). Next, 300 g of the obtained crystals, 130 g of sodium hydroxide and 500 ml of water are heated at 80 ° C. for 3 hours.
After the reaction, 340 ml of concentrated hydrochloric acid is slowly added to precipitate white crystals. The obtained crystals were collected by filtration and recrystallized from water to give 6
212 g of -carboxymethyl-4-hydroxy-1,3,3a, 7-tetrazaindene are obtained.

Next, the obtained crystals (143 g), diallylamine (72 g) and dimethylformamide (1.5 l) are stirred and dissolved at room temperature. to this
152 g of N, N-dicyclohexylcarbodiimide was added dropwise,
After the dropping, white crystals (N, N-dicyclohexylurea) are precipitated by stirring at room temperature for 8 hours. The precipitated crystals are filtered off, and the filtrate is poured into 3 l of water to precipitate white crystals. The precipitated crystals are collected by filtration and recrystallized from acetonitrile to give the desired 6- (N, N-diallylcarbamoylmethyl) -4.
171 g of hydroxy-1,3,3a, 7-tetrazaindene are obtained.

The target product was confirmed by IR, NMR, and elemental analysis results.

Elemental analysis value (C ₁₃ H ₁₅ N ₅ O ₂ ) Theoretical value H: 5.53% C: 57.13% N: 25.62% Experimental value H: 5.48% C: 57.23% N: 25.58% General formula (IIa) used in the present invention ) Or (IIb) is advantageously used in an amount of about 0.01 to 5 grams per mole of silver halide in the emulsion.

The infrared sensitizing dye of the general formula (I) and the general formula (IIa) or (I
The ratio (weight ratio) with the compound represented by Ib) is preferably in the range of 1/1 to 1/300 of the dye represented by the general formula (I) / the compound represented by the general formula (IIa) or (IIb). The range of 1/2 to 1/100 is preferably used.

The compound represented by formula (IIa) or (IIb) used in the present invention can be directly dispersed in an emulsion,
It is also possible to dissolve in a suitable solvent (for example, water, methyl alcohol, ethyl alcohol, propanol, methyl cellosolve, acetone, etc.) or a mixed solvent containing a plurality of these solvents and add it to the emulsion. Other sensitizing dyes can be added to the emulsion in the form of a solution or a dispersion in a colloid according to the method of addition.

The compound represented by formula (IIa) or (IIb) may be added to the emulsion before or after the addition of the sensitizing dye represented by formula (I). Further, the compound of the general formula (IIa) or (IIb) and the sensitizing dye of the general formula (I) may be separately dissolved, and these may be separately added to the emulsion at the same time, or they may be mixed and then added to the emulsion. You may add.

The sensitizing dye according to the present invention may be used in combination with other sensitizing dyes. For example, U.S. Pat.No. 3,703,377,
2,688,545, 3,397,060, 3,615,635, 3,6
28,964, British Patents 1,242,588, 1,293,862, Japanese Patent Publication Nos. 43-4936, 44-14030, 43-10773, U.S. Patent No. 3,416,927, Japanese Patent Publication No. 43-4930, U.S. Patent No. 3,615,
The sensitizing dyes described in No. 613, No. 3,615,632, No. 3,617,295, No. 3,635,721, etc. can be used.

The silver halide used in the present invention may be any of silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide and the like. In the present invention, of the above silver halides, silver chloroiodobromide, silver chlorobromide and silver iodobromide are preferred. More preferably, silver chlorobromide or silver chloroiodobromide containing 0 to 1 mol% of silver iodide is advantageously used.

These emulsions may be coarse grains, fine grains, or mixed grains thereof, and these silver halide grains can be formed by a known method such as a single jet method, a double jet method, or a control double jet method.

Further, even if the crystal structure of the silver halide grains is uniform to the inside, it has a layered structure in which the inside and the outside are different, and it is described in British Patent No. 635,841 and U.S. Patent No. 3,622,318. Such a so-called conversion type may be used. Further, it may be of a type in which a latent image is mainly formed on the surface or an internal latent image type in which the latent image is formed inside the particles. These photographic emulsions are described by Mees in The Theory of the Photographic Process.
Theory of the Photographic Process ”by MacMillan, by Grafikides,“ Photographic Chemistry ”Faunta
In Press, published in publications, Research Disclosure Vol.176 (December 1978) RD-17643, etc., generally accepted ammonia method, neutral method, acidic method, etc. Can be adjusted in any way.

The grain size distribution of the silver halide emulsion of the present invention is preferably so-called monodisperse.

The average diameter of silver halide grains (measured by the projected area method, number average) is about 0.04 μm to 4 μm.
m is preferred. It is particularly preferably 0.7 μm or less.

In order to control the growth of grains during the formation of the silver halide grains, as a silver halide solvent, for example, ammonia, rodancali, rhodammone, thioether compounds (e.g., U.S. Pat.Nos. 3,271,157, 3,574,628,
3,704,130, 4,297,439, 4,276,374, etc.), thione compounds (for example, JP-A-53-144319, JP-A-53-144319, 5)
3-82408, 55-77737, etc.), amine compounds (for example, JP-A-54-100717, etc.) and the like can be used.

Further, water-soluble rhodium and / or water-soluble iridium can be added during the formation of the silver halide grains or before or after the formation of the grains.

The silver halide photographic emulsion is prepared by a commonly used chemical sensitization method such as gold sensitization (US Pat. Nos. 2,540,085 and 2,597,8).
No. 76, No. 2,597,915, No. 2,399,083, etc.), Sensitization with Group VIII metal ions (US Pat. Nos. 2,448,060, 2,54)
0,086, 2,565,245, 2,566,263, 2,598,079
), Sulfur sensitization (US Pat. Nos. 1,574,944, 2,27)
8,947, 2,440,206, 2,521,926, 3,021,215
No., No. 3,038,805, No. 2,410,689, No. 3,189,458,
No. 3,415,649, No. 3,635,717, etc.), reduction sensitization (US Patent Nos. 2,518,698, 2,419,974, 2,983,610,
Research Disclosure Vol.176 (December 1978) R
D-17643, Item III, etc.), sensitization with thioether compounds (for example, US Pat. Nos. 2,521,926 and 3,021,215,
No. 3,038,805, No. 3,046,129, No. 3,046,132, No. 3,0
46,133, 3,046,134, 3,046,135, 3,057,72
No. 4, No. 3,062,646, No. 3,165,552, No. 3,189,458,
3,192,046, 3,506,443, 3,671,260, 3,5
74,709, 3,625,697, 3,635,717, 4,198,24
No. 0), or various sensitizing methods in which they are combined.

Further, specific chemical sensitizers include allyl thiocarbamide, thiourea, sodium thiosulfate, sulfur sensitizers such as thioether and cystine; potassium chloroaurate, auraththiosulfate and potassium chloroparasate. Dating (potassiu
noble metal sensitizers such as m chloro palladate); tin chloride,
Examples thereof include reduction sensitizers such as phenylhydrazine and reductone.

In addition, polyoxyethylene derivatives (UK Patent 981,47
No. 0, JP-B-31-6475, US Pat. No. 2,716,062, etc.), polyoxypropylene derivatives, quaternary ammonium group-containing derivatives and the like may be included.

Various compounds can be added to the photographic emulsion of the present invention in order to prevent the deterioration of sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the light-sensitive material. Many of these compounds include nitrobenzimidazole, ammonium chloroplatinate, 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene, 3-methylbenzothiazole, 1-phenyl-5-mercaptotetrazole. Many compounds such as heterocyclic compounds, mercury-containing compounds, mercapto compounds, and metal salts have been known for a long time. An example of a compound that can be used is K. Mees, "The Theory of the Photographic Process (The
Theory of The Photographic Process) "(3rd edition, 19
(66) pp. 344 to 349 with the original references.
Other compounds include, for example, thiazolium salts described in US Pat. Nos. 2,131,038 and 2,694,716; azaindenes described in US Pat. Nos. 2,886,437 and 2,444,605; US Pat. No. 3,287,135, etc. Described in US Pat. No. 3,236,65
Sulfocatechols described in No. 2 and the like; oximes described in British Patent No. 623,448 and the like; Mercaptotetrazoles and nitrones described in US Pat. Nos. 2,403,927, 3,266,897, and 3,397,987. Nitroindazoles; polyvalent metal sals described in US Pat. No. 2,839,405 and the like.
ts); thiuronium salts described in US Pat. No. 3,220,839; US Pat. No. 2,566,
Palladium, platinum and gold salts described in No. 263 and No. 2,597,915, etc.

Silver halide photographic emulsions contain developing agents such as hydroquinones; catechols; aminophenols; 3-pyrazolidones; ascorbic acid and its derivatives; reductones and phenylenediamines, or combinations of developing agents. be able to. The developing agent is a silver halide emulsion layer and / or other photographic layer (eg a protective layer,
Intermediate layer, filter layer, antihalation layer, back layer, etc.). The developing agent may be dissolved in a suitable solvent, or may be used in U.S. Pat.
It may be added in the form of a dispersion as described in 05,778.

As the development accelerator, for example, U.S. Patent No. 3,288,612,
3,333,959, 3,345,175, 3,708,303, British Patent 1,098,748, West German Patent 1,141,531, 1,
The compounds described in, for example, No. 183,784 can be used.

Hardening treatment of the emulsion can be carried out according to a conventional method. Examples of the curing agent include aldehyde compounds such as formaldehyde and glutaraldehyde; ketone compounds such as diacetylcyclopentanedione; bis (2-chloroethylurea), 2-hydroxy-4,6-dichloro-1,3, 5-triazine and other U.S. Pat.Nos. 3,288,775 and 2,732,303
Compounds having reactive halogens as shown in U.S. Pat. No. 5,839,697, and No. 1,167,207; divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine, and others. U.S. Patent 3,635,718
Nos. 3,232,763, and compounds having a reactive olefin as shown in British Patent 994,869; N-hydroxymethylphthalimide and other U.S. Patents 2,732,316.
N-methylol compounds as shown in US Pat. No. 2,586,168; isocyanates as shown in US Pat. No. 3,103,437; US Pat. No. 3,017,280,
Aziridine compounds as shown in 2,983,611 and the like; acid derivatives as shown in US Pat. Nos. 2,725,294 and 2,725,295; carbodiimide compounds as shown in US Pat. No. 3,100,704; US Patent 3,
Epoxy compounds as shown in 091,537 etc .;
Isoxazole compounds as shown in US Pat. Nos. 3,321,313 and 3,543,292; halogenocarboxaldehydes such as mucochloric acid; dioxane derivatives such as dihydroxydioxane and dichlorodioxane; or as an inorganic hardener There are chlor alum and zirconium sulfate. Instead of the above compounds, precursors may be used, for example, alkali metal bisulfite aldehyde adducts, hydantoin methylol derivatives, primary aliphatic nitroalcohols and the like.

A surfactant may be added to the photographic emulsion of the present invention alone or as a mixture.

Although they are used as coating aids, they are sometimes used for other purposes such as emulsion dispersion, improvement of sensitized photographic characteristics, antistatic and adhesion prevention.
These surfactants are natural surfactants such as saponins,
Nonionic surfactants such as alkylene oxide type, glycerin type, glycidol type, higher alkyl amines,
Quaternary ammonium salts, pyridine and other heterocycles,
Cationic surfactant such as phosphonium or sulfonium, anionic surfactant containing an acidic group such as carboxylic acid, sulfonic acid, phosphoric acid, sulfuric acid ester group, phosphoric acid ester group, amino acid, aminosulfonic acid, sulfuric acid or phosphoric acid of aminoalcohol Divided into amphoteric activators such as esters.

Some of these examples of surfactant compounds that can be used are US patents.
2,271,623, 2,240,472, 2,288,226, 2,73
9,891, 3,068,101, 3,158,484, 3,201,253
No. 3,210,191, 3,294,540, 3,415,649,
3,441,413, 3,442,654, 3,475,174, 3,5
45,974, German patent application 1,942,665, British patent 1,07
No. 7,317, No. 1,198,450, Japanese Patent Publication No. 56-44411,
Ryohei Oda et al. "Synthesis of surfactants and their applications" (Maki Shoten
1964) and AW Perry "Surface Active Agents" (Interscience Publications Inc. 1958), JP Sisley "Encyclopedia of Surface Active Agents Vol. 2" (Chemical Publish Company 1964 version) ) And other books.

In the silver halide photographic emulsion used in the present invention, in addition to gelatin as a protective colloid, acylated gelatin such as phthalated gelatin and malonated gelatin, cellulose compound such as hydroxyethyl cellulose and carboxymethyl cellulose; dextrin such as dextrin. Soluble starch; polyvinyl alcohol, polyvinylpyrrolidone, hydrophilic polymers such as polyacrylamide and polystyrene sulphonic acid may be added.

In the present invention, preferably a polyalkylene oxide compound such as an alkylene oxide having 2 to 4 carbon atoms such as ethylene oxide, propylene-1,2-oxide,
Butylene-1,2-oxide and the like, preferably a polyalkylene oxide consisting of at least 10 units of ethylene oxide and at least active hydrogen atoms such as water, aliphatic alcohols, aromatic alcohols, fatty acids, organic amines and hexitol derivatives. A condensate with a compound having one or a block copolymer of two or more polyalkylene oxides can be used. That is, as the polyalkylene oxide compound, specifically, polyalkylene glycols, polyalkylene glycol alkyl ethers, polyalkylene glycol aryl ethers, polyalkylene glycol alkyl aryl ethers, polyalkylene glycol esters, polyalkylene glycol fatty acid amides, polyalkylene glycol amine Polyalkylene glycol / block copolymer Polyalkylene glycol graft polymer and the like can be used. The molecular weight should be 600 or more.

The number of polyalkylene oxide chains is not limited to one in the molecule, and may be two or more. In that case the individual polyalkylene oxide chains may consist of less than 10 alkylene oxide units, but the total number of alkylene oxide units in the molecule must be at least 10. When having more than one polyalkylene oxide chain in the molecule, each of them may consist of different alkylene oxide units, such as ethylene oxide and propylene oxide. The polyalkylene oxide compound that can be used in the present invention preferably contains 14 to 100 alkylene oxide units.

Specific examples of the polyalkylene oxide compound that can be used in the present invention are as follows.

Examples of polyalkylene oxide compounds P-1 HO (CH ₂ CH ₂ O) ₉₀ H P-2 C ₄ H ₉ O (CH ₂ CH ₂ O) ₁₅ H P-3 C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₅ H P-4 C ₁₈ H ₃₇ O (CH ₂ CH ₂ O) ₁₅ H P-5 C ₁₈ H ₃₇ O (CH ₂ CH ₂ O) ₄₀ H P-6 C ₈ H ₁₇ CH = CHC ₈ H ₁₆ O (CH ₂ CH ₂ O) ₁₅ H P-10 C ₁₁ H ₂₃ COO (CH ₂ CH ₂ O) ₈₀ H P-11 C ₁₁ H ₂₃ COO (CH ₂ CH ₂ O) ₂₄ OCC ₁₁ H ₂₃ P-13 C ₁₁ H ₂₃ CONH (CH ₂ CH ₂ O) ₁₅ H P-15 C ₁₄ H ₂₉ N (CH ₃ ) (CH ₂ CH ₂ O) ₂₄ H P-20 HO (CH ₂ CH ₂ O) _a (CH ₂ CH ₂ CH ₂ CH ₂ O) _b (CH ₂ CH ₂ O) _c H a + b = 30, b = 14 The polyalkylene oxide compounds described in JP-A-50-156423, JP-A-52-108130 and JP-A-53-3217 such as P-24 HOCH ₂ CH ₂ O ₃₄ H can be used. These polyalkylene oxide compounds may be used alone or in combination of two or more.

When adding these polyalkylene oxide compounds to the silver halide emulsion, as an aqueous solution of a suitable concentration or dissolved in a low boiling organic solvent miscible with water,
It can be added to the emulsion at a suitable time before coating, preferably after chemical ripening. The polyalkylene oxide compound used in the present invention is preferably in the range of 1 × 10 ^-5 mol to 1 × 10 ^-2 mol per mol of silver halide in the emulsion.

Also, U.S. Patent Nos. 3,411,911, 3,411,912, and 3,142,
No. 568, No. 3,325,286, No. 3,547,650, Japanese Patent Publication No. 45-5331
Incorporate a polymer latex consisting of homo- or copolymer such as alkyl acrylate, alkyl methacrylate, acrylic acid, glycidyl acrylate, etc. described in No. 1, etc. for the purpose of improving dimensional stability of photographic materials and improving film physical properties. You can

The silver halide photographic emulsion may also contain antistatic agents, plasticizers, optical brighteners, air antifoggants, toning agents and the like.

The silver halide photographic emulsion of the present invention is a color coupler such as a cyan coupler, a magenta coupler and a yellow coupler.
A coupler and a compound that disperses the coupler may be included.

That is, it may contain a compound capable of forming a color by oxidative coupling with an aromatic primary amine developing agent (for example, a phenylenediamine derivative or an aminophenol derivative) in the color development processing. These couplers are preferably non-diffusible ones having a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent with respect to silver ion. Further, it may be a colored coupler having a color correcting effect, or a coupler releasing a development inhibitor with development (so-called DIR coupler).

In addition to the DIR coupler, a colorless DIR coupling compound which is colorless in the product of the coupling reaction and releases a development inhibitor may be contained.

In addition, it is also possible to form a color image by developing with a color developing solution containing a diffusible coupler.

Further, as an anti-irradiation dye contained depending on the purpose, for example, Japanese Examined Patent Publication Nos. 41-20389 and 43-3504.
No. 43-13168, U.S. Patent Nos. 2,697,037, 3,423,2
07, 2,865,752, British Patents 1,030,392, 1,10
What is described in 0,546 etc. is used.

The present invention can be applied not only to black and white photographic emulsions but also to sensitization of silver halide emulsions used in various color light-sensitive materials.

In addition to the emulsion layer of the present invention, emulsion layers having photosensitivity in other spectral regions may be laminated to form a so-called multi-layer multi-color light-sensitive material.

The exposure for obtaining a photographic image may be performed using a usual method. That is, natural light (sunlight), tungsten light,
Various known light sources including infrared light such as mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, cathode ray tube flying spot, light emitting diode, laser light (eg gas laser, dye laser, YAG laser, semiconductor laser, etc.) Any of these can be used. Further, it may be exposed by light emitted from a phosphor excited by an electron beam, X-ray, γ-ray, α-ray or the like.
The exposure time is not limited to 1/1000 second to 1 second which is usually used in cameras, but is shorter than 1/1000 second, for example, 1/10 ⁴ to 1/10 ⁶ second exposure using a xenon flash lamp or cathode ray tube. Or an exposure longer than 1 second can be used.

The spectral composition of the light used for exposure can be adjusted with a color filter as needed.

The photographic emulsion of the present invention is applied to a rigid support such as a plastic film (cellulose nitrate, cellulose acetate, polyethylene terephthalate, etc.), a flexible support such as paper or a glass, which is usually used for a photographic light-sensitive material. It See Research Disclosure, Vol. 176, Item 17643, XV (p.27), for details on the support and coating method.
XVII (p.28) (December 1978 issue).

Any known method can be used for photographic processing of a light-sensitive material produced by applying the present invention. A known treatment liquid can be used. The treatment temperature is usually chosen between 18 ° C and 50 ° C, but below 18 ° C or 50 ° C
The temperature may be higher than that. Depending on the purpose, either image processing for forming a silver image (black-and-white photographic processing) or color photographic processing including development processing for forming a dye image can be applied. Lith development can also be applied.

For more information, Research Disclosure Vol. 176, No.
17643, pages 28-29, 187, No. 18716, page 651, left column, right column.

The present invention can also be applied to a light-sensitive material having a low silver content in which the amount of silver halide in the emulsion is several to one-hundredth of that in the case of a normal light-sensitive material.

Next, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

Example 1 Silver halide grains were precipitated by the double jet method,
After physical ripening and desalting, chemical ripening was performed to obtain a silver iodobromide (iodine content 1.0 mol%) emulsion. The silver halide grains contained in this emulsion had an average diameter of 0.4 micron. 0.6 kg of silver halide was contained in 1 kg of this emulsion.

1 kg of this emulsion was weighed and dissolved by heating at 40 ° C., and as shown in Table 1, the sensitizing dye contained in the general formula (I) and the sensitizing dye contained in the general formula (IIa) or (IIb). Add a predetermined amount of a compound methanol solution or comparative compound A,
Mix and stir. Next, 35 ml of a 1.0 wt% aqueous solution of 1-hydroxy-3,5-dichlorotriazine sodium salt was added,
Further, 50 ml of a 1.0 wt% aqueous solution of dodecylbenzenesulfonic acid sodium salt was added and stirred. This finished emulsion was coated and dried on a cellulose triacetate film base so that the dry film thickness was 5 μm, and a sample of a light-sensitive material was obtained. This film sample was subjected to optical wedge exposure using a sensitometer having a light source with a color temperature of 2854 ° K and a dark red filter (SC-72) manufactured by Fuji Photo Film Co., Ltd. attached to the light source. After exposure, develop with a developer of the following composition at 20 ° C for 3 minutes, stop,
After fixing and washing with water, strips having a predetermined black and white image were obtained. The density was measured using a P-type densitometer manufactured by Fuji Photo Film Co., Ltd. to obtain sensitivity and fog. The reference point of the optical density at which the sensitivity was determined was [fog + 0.3].

Composition of developer 500 ml N-methyl-p-aminophenol 2.2 g anhydrous sodium sulfite 96.0 g Hydroquinone 8.8 g Sodium carbonate monohydrate 56.0 g Potassium bromide 5.0 g Water added 1 The values are shown in Table 1. From these results, it is understood that the combination of the present invention gives an excellent light-sensitive material having high sensitivity and less fog as compared with the dye alone or the comparative example.

Compound A (for comparison): 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene Example 2 2 l of an aqueous solution containing 70 g of gelatin was adjusted to pH 3.0, and 2 kg of an aqueous solution containing 1 kg of silver nitrate and 2 g of an aqueous solution containing 210 g of potassium bromide and 290 g of sodium chloride were simultaneously added thereto at a constant rate of 30. Added in minutes. At this time, 5 × 10 ⁻⁷ mol / silver mol of rhodium was also added. Next, soluble salts were removed, gelatin was added, and chemical ripening was performed to obtain a silver chlorobromide emulsion (grain size 0.31 μm, Br 30 mol%).

To this emulsion, as shown in Table 2, a sensitizing dye contained in the general formula (I) and a compound contained in the general formula (IIa) or (IIb) were added, and then as a hardener 1- Hydroxy-
3,5-dichlorotriazine sodium salt and dodecylbenzenesulfonic acid sodium salt as a coating aid were added, and the amount of silver per 1 m ² was on the polyethylene terephthalate film.
It was applied so as to be 3.9 g.

The film sample thus prepared was subjected to optical wedge exposure through a dark red filter (Fuji Photo Film Co., SC-72), developed with the following developer at 20 ° C. for 3 minutes, stopped, and fixed.
I washed it with water. The density was measured using a P-type densitometer manufactured by Fuji Photo Film Co., Ltd. to obtain sensitivity and fog value. The reference point of the optical density at which the sensitivity was determined was [fog + 0.3]. The results are shown in Table 2.

A part of the film sample thus prepared was stored at high temperature and high humidity (40 ° C., 75% RH) for 3 days, and stored at refrigeration (5 degrees, 10% RH) for 3 days for comparison. The same exposure, development, stopping, fixing, washing with water and drying as described above were performed together with the sample. The results are shown in Table 3.

Composition of developer 0.31 g anhydrous sodium sulfite 39.6 g hydroquinone 6.0 g anhydrous sodium carbonate 18.7 g potassium bromide 0.86 g citric acid 0.68 g potassium metabisulfite 1.5 g Add water 1 From the results shown in Table 2, it can be seen that the combination of the present invention gives an excellent light-sensitive material having high sensitivity and less fog as compared with the dye alone or the comparative example. Further, the results in Table 3 show that not only the combination of the present invention has high sensitivity, but also there is little decrease in sensitivity and increase in fog when the light-sensitive material is stored under high temperature and high humidity.

(Effect of the Invention) According to the present invention, the effect that the silver halide photographic emulsion has high sensitivity to infrared light and less fog is obtained. Further, the silver halide photographic light-sensitive material obtained by using the silver halide photographic emulsion of the present invention showed little deterioration in sensitivity and increase in fog under high temperature and high humidity, and an excellent storability effect was obtained.

Claims (1)

[Claims] 1. At least one infrared sensitizing dye represented by the following general formula (I) and the following general formula (IIa) or (IIb)
A silver halide photographic emulsion containing a combination of at least one compound represented by General formula (I) In the formula, R ₁ and R ₂ may be the same or different and each represents an alkyl group or a substituted alkyl group.
R ₃ and R ₄ each independently represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group or a benzyl group. R ₅
And R ₆ each represent a hydrogen atom, or R ₅ and R ₆ are linked to form a divalent alkylene group. R ₇ is a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, a benzyl group, or Represents Here, W ₁ and W ₂ each independently represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and W ₁ and W ₂ are linked to each other to form a 5- or 6-membered nitrogen-containing group. It is also possible to form a heterocycle. However, R ₃ and R ₇
It is also possible to combine with to form a divalent alkylene group. Z and Z ₁ each independently represent a nonmetallic atom group necessary for completing a 5- or 6-membered nitrogen-containing heterocycle. X represents an acid anion, and n represents 1 or 2. General formula (IIa) General formula (IIb) In the formula, R ₈ and R ₉ each independently represent a hydrogen atom, a lower alkyl group, an alkenyl group, a carboxyl group, an alkoxy group or a halogen atom, and R ₁₀ represents an alkyl group having 5 or more carbon atoms, an aralkyl group, an alkylthio group. , An arylthio group, an alkoxy group having 3 or more carbon atoms, an aryloxy group, an alkylamino group having 3 or more carbon atoms, an arylamino group, Represents Here, X ₁ represents a divalent linking group, and R ₁₁
And R ₁₂ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, an aryl group or a heterocyclic group.