JPS62299839A - Silver halide photographic emulsion - Google Patents

Abstract

PURPOSE:To enhance sensitivity to infrared rays by incorporating a combination of one of specified infrared sensitizing dyes and one of other specified compounds in an emulsion. CONSTITUTION:The emulsion contains a combination of at least one of the infrared sensitizing dyes represented by formula I and at least one of the compounds represented by formulae II and III, preferably in a I/(II or III) weight ratio of 1:1-1:300, especially, 1/2-1/100. In these formulae, each of R1 and R2 is alkyl or the like; each of R3 is H, lower alkyl, or the like; V is substituted alkyl or the like; Z is a nonmetallic atomic group necessary to complete a 5- or 6-membered N-containing hetero ring; X is an acid anion; each of m, n, and p is independently 1 or 2; each of R4 and R5 is H or the like; and R6 is >=5C alkyl or the like.

Description

Detailed Description of the Invention (Field of Industrial Application) 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. This invention relates to a silver halide photographic emulsion used in a silver halide photographic light-sensitive material with improved sensitivity and storage stability.

(Prior art) In the exposure method for photographic light-sensitive materials, an original image is scanned and the silver halide photographic light-sensitive material is exposed to light based on the image signal, thereby creating a negative or positive image corresponding to the image on the original image. An image forming method using a so-called scanner is known.

There are a variety of recording devices that use a scanner-only image forming method, and glow lamps, xenon lamps, mercury lamps, tungsten lamps, light-emitting diodes, etc. have traditionally been used as recording light sources for these scanner-only recording devices. . However, all of these light sources have practical drawbacks of low output and short lifespan. To compensate for these shortcomings, there are scanners that use a coherent laser light source such as N5-t (e laser, argon laser, or He-Cd laser) as a scanner-only light source. being large, expensive, and requiring a modulator;
Furthermore, since visible light is used, the safe light of the photosensitive material is limited, resulting in disadvantages such as poor handling.

On the other hand, semiconductor lasers are small, inexpensive, easy to modulate, have a longer lifespan than the lasers mentioned above, and emit light in the infrared region, so if a photosensitive material sensitive to the infrared region is used, a bright safelight can be produced. Since it can be used, it has the advantage of improving handling workability. However, since there is no photosensitive material that has high photosensitivity in the infrared region and excellent storage stability, it has not been possible to take advantage of the characteristics of semiconductor lasers that have excellent performance as described above.

A commercially available red-sensitized film is, for example, Eastman Kodak's H-E135-20, but it cannot be left at room temperature and must be refrigerated or frozen to preserve the photosensitive material. It is.

As can be seen from this, the sensitivity of conventional infrared sensitized photosensitive materials is unstable, and special consideration is required for storage.

As a manufacturing technology for photographic light-sensitive materials, spectral sensitization technology is applied, which is a technology that expands the sensitive wavelength range to longer wavelengths by adding a certain type of cyanide dye to a silver halide photographic emulsion. It is also known that this spectral sensitization technique can be applied not only to the visible region but also to the infrared region. For spectral sensitization in the infrared region, sensitizing dyes that absorb infrared light are used, such as Mies (Me
es) “The Theory of the Photographic Process”
Photographic Process) 3rd edition” (MacMj, ], ], published by an publisher 1966)
], 98-P, 201. In this case, it is desirable that the spectral sensitivity, that is, the sensitivity to light in the infrared region, be high, and that the change in sensitivity be small even during storage of the emulsion. For this purpose, many sensitizing dyes have been developed.

These include, for example, U.S. Pat. No. 2,095,854;
．． No. 095,856, No. 2,955,939, No. 3,
No. 482,978, No. 3,552,974, No. 3,5
It is described in No. 73,921, No. 3,582,344, etc. However, even if the sensitizing dyes described above are used, the sensitivity and storage stability cannot be said to be sufficient.

On the other hand, in light-sensitive materials, in addition to spectral sensitizing dyes, a second
By adding certain specifically selected organic compounds, the spectral sensitivity can be significantly increased by -1-, an effect known as the supersensitizing effect. Generally the addition of a second organic compound.

Supersensitization can be said to be a unique phenomenon because the sensitivity often decreases by -1-Jl or even decreases. Inorganic materials require extremely high selectivity. Therefore, what seems at first glance to be a slight difference in chemical structure significantly affects this supersensitizing effect, and it is difficult to obtain a supersensitizing combination by predicting from the chemical structural formula m. Second organic compounds for supersensitization known to date include, for example, U.S. Patent No. 2,875,05
8 and 3,695,888, mercapto compounds described in U.S. Pat. No. 3,457,078, U.S. Pat.
There are thiourea compounds described in US Pat. No. 318, pyrimidine derivatives described in US Pat. No. 3,615,632, and US Pat. It has been described that infrared sensitization is carried out using sensitive amounts of infrared sensitizing dyes.

(Problems to be solved by the present invention) However, although the methods described in these patents do indeed increase the infrared sensitivity by 1, and in some cases even slightly improve storage stability, they are still insufficient. Therefore, there is a need for a means of supersensitization that can further increase infrared sensitivity and improve storage stability.

On the other hand, emulsions in a solution state before coating are generally susceptible to changes in sensitivity and fog, particularly changes in sensitivity and fog caused by desorption and decomposition of sensitizing dyes. Such changes in the photographic properties of the emulsion in the solution state before coating pose a very serious problem in the production of light-sensitive materials. However, commonly known stabilizers such as 1-phenyl-5-mercaptotetrazole are not effective for improving the stability of sol-formed emulsions containing infrared sensitizing dyes. Therefore, it has been desired to develop a technique for specifically improving the stability of emulsions containing infrared sensitizing dyes in a solution state before coating.

An object of the present invention is to provide a silver halide photographic emulsion for use in silver halide photographic materials having high sensitivity to infrared light. Another object of the present invention is to provide a silver halide photographic emulsion that exhibits little change in sensitivity in the emulsion in a solution state before coating and has high sensitivity to infrared light. An object of the present invention is to provide a silver halide photographic emulsion for use in silver halide photographic materials that exhibits little change in sensitivity and fog during storage and has high sensitivity to infrared light.

(Means for Solving the Problems) The object of the present invention is to include at least one infrared sensitizing dye represented by the following general formula (1) in a silver halide photographic emulsion, and the following general formula (Ila) or This was achieved by containing in combination with at least one of the compounds represented by (IIb).

General formula (1) %Formula% In the formula, R2 and R2 may each be the same or different, and each represents an alkyl group or a substituted alkyl group.

R3 is a hydrogen atom, a lower alkyl group, a lower alkoxy group,
Represents a phenyl group or a benzyl group. (2) represents a hydrogen atom, a lower alkyl group, an alkoxy group, a halogen atom or a substituted alkyl group.

Z represents a group of nonmetallic atoms necessary to complete a 5- or 6-membered nitrogen-containing heterocycle. X represents an acid anion. m, n
and p each independently represent 1 or 2.

General formula (Tla) General formula (IIb) In the formula, R4 and R6 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& represents a carbon atom number of 5 to 4 −
alkyl group, aralkyl group, aryl group, alkylthio group, arylthio group, alkoxy group having 3 or more carbon atoms, aryloxy group, alkylamino group having 3 or more carbon atoms, aryl where X□ is a divalent linking group represents,
R7 and R each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, or a heterocyclic group.

Hereinafter, the compounds of general formulas (T), (+la) and (IIb) used in the present invention will be explained in more detail.

General formula (I) In the formula, R0 and R, l may each be the same or different, and each represents an alkyl group (preferably 1 to 1 carbon atoms).
8, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, heptyl group, etc.), or substituted alkyl group (for example, carboxyl group, sulfo group, cyano group, halogen atom (for example, fluorine atom, chlorine atom, etc.) atom,
bromine atom, etc.), hydroxyl group, alkoxycarbonyl group (preferably 8 or less carbon atoms, e.g. methoxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group, etc.), alkoxy group (preferably 7 or less carbon atoms, e.g. methoxy group) , ethoxy group, propoxy group, butoxy group, benzyloxy group, etc.), aryloxy group (e.g. phenoxy group, p-tolyloxy group, etc.), acyloxy group (preferably 3 or less carbon atoms, e.g. acetyloxy group, propionyloxy group) Such),
Acyl group (preferably 8 or less carbon atoms, such as acetyl group, propionyl group, benzoyl group, mesyl group, etc.)
, carbamoyl group (e.g. carbamoyl group, N, N-
dimethylcarbamoyl group, morpholinocarbamoyl group,
piperidinocarbamoyl group, etc.), sulfamoyl group (
For example, a sulfamoyl group, N.

N-dimethylsulfamoyl group, morpholinosulfonyl group, etc.), aryl group (e.g. phenyl group, P-hydroxyphenyl group, P-carboxyphenyl group, P-sulfophenyl group, α-naphthyl group, etc.), etc. an alkyl group (preferably the number of carbon atoms in the alkyl moiety is 6 or less); However, two or more of these substituents may be substituted with an alkyl group. ).

R3 is a hydrogen atom, a lower alkyl group (preferably having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a probyl group, etc.), or a lower alkoxy group (preferably having 1 to 6 carbon atoms).
, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc.), a phenyl group, or a benzyl group.

In particular, lower alkyl groups and benzyl groups are advantageously used.

(2) is a hydrogen atom, a lower alkyl group (preferably 1 to 8 carbon atoms, such as a methyl group, ethyl group, propyl group, etc.)
, alkoxy groups (preferably 1 to 8 carbon atoms, such as methoxy, ethoxy, butoxy), halogen atoms (such as fluorine, chlorine, etc.), substituted alkyl groups (preferably 1 to 8 carbon atoms, For example, it represents a trifluoromethyl group, a carboxymethyl group, etc.).

Z represents a nonmetallic atom group necessary to complete a 5- or 6-membered nitrogen-containing heterocycle, such as a thiazole nucleus (e.g., benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole). ,7
-Chlorbenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-promobenzothiazole, 6-promobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxy Benzothiazole, 6-ethoxybenzothiazole, 5-ethoxybenzothiazole, 5-carboxybenzothiazole, 5-
Ethoxycarbonylbenzothiazole, 5-phenethylbenzothiazole, 5-fluorobenzothiazole, 5
-Trifluoromethylbenzothiazole, 5,6-dimethylbenzothiazole, 5-hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole, 4-
Phenylbenzothiazole, naphtho[2,I-d)thiazole, naphtho(1,2-d)thiazole, naphtho(2-d)thiazole
,3-d) Thiazole, 5-methoxynaphtho(1,2-
d) Thiazole, 7-nitoxynaphtho(2,1-d)thiazole, 8-methoxynaphtho(2,1,-d)thiazole, 5-methoxynaphtho(C2,3-d)thiazole, etc.), selenazole core (e.g. benzoselenium) Zoll, 5
-Chlorbenzoselenazole, 5-methoxybenzoselenazole, 5-methylbenzoselenazole, 5-hydroxybenzoselenazole, naphtho(2,1-d) selenazole, naphtho(1,2-d) selenazole, etc.), oxazole Nucleus (benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5-trifluorobenzoxazole, 5- Hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-ethoxybenzoxazole, 6-hydroxybenzoxazole,
5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5-ethoxybenzoxazole, naphtho(Z,1-d)oxazole, naphtho(1
, 2-d]oxazole, naphtho[2°3-d]oxazole, etc.), quinoline nuclei (e.g. 2-quinoline, 3-
Methyl-2-quinoline, 5-ethyl-2-quinoline, 6
-Methyl-2-quinoline, 8-fluoro-2-quinoline, 6-medoxy-2-quinoline, 6-hydroxy-2-
Quinoline, 8-chloro-2-quinoline, 8-fluoro-
4-quinoline, etc.), 3,3-dialkylindolenine core (e.g., 3,3-dimethylindolenine, 3,3
-diethylindolenine, 3,3-dimethyl-5-cyanoindolenine, 3,3-dimethyl-5-methoxyindolenine, 3,3-dimethyl-5-methylindolenine, 3,3-dimethyl-5-chlor indolenine, etc.),
Imidazole nuclei (e.g. 1-methylbenzimidazole, 1-ethylbenzimidazole, ■-methyl-5-chlorobenzimidazole, 1-ethyl-5-chlorobenzimidazole, 1-methyl-5,6-dichlorobenzimidazole, 1- Ethyl-5,6-dichlorobenzimidazole, ■-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 nuclei (for example, pyridine, 5-methyl-2-pyridine, 3-methyl-4-pyridine, etc.). Among these, thiazole nuclei and oxazole nuclei are preferably used.

More preferably, a benzothiazole nucleus, a naphthothiazole nucleus, a naphthoxazole nucleus, or a benzoxazole nucleus is advantageously used.

X represents an acid anion. lit n and p each independently represent 1 or 2. When the compound forms betaine, n is 1-.

General formula (TTa) General formula (IIb) In the formula, R4 and R5 are each independently a hydrogen atom, a lower alkyl group (preferably a substituted or unsubstituted group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, methoxyethyl group, hydroxyethyl group, hydroxymethyl group,
phenoxymethyl group, etc.), alkenyl group (preferably substituted or unsubstituted one with 2 to 4 carbon atoms, such as vinyl group, allyl group, etc.), carboxyl group, alkoxy group (preferably substituted or unsubstituted one with 1 carbon number) ~5 (eg, methoxy group, ethoxy group, methoxyethoxy group, hydroxyethoxy group, etc.) or a halogen atom (eg, chlorine atom, bromine atom, fluorine atom, etc.).

R6 is an alkyl group having 5 or more carbon atoms, preferably 6 or more carbon atoms (e.g., pentyl group, heptyl group, octyl group,
dodecyl group, pentadecyl group, heptadecyl group, etc.), aralkyl group (preferably substituted or unsubstituted with 7 to 1 carbon atoms)
2 groups, such as benzyl group, phenethyl group, phenylpropyl group, etc.), aryl group (preferably a substituted or unsubstituted group having 6 to 12 carbon atoms, such as phenyl group, 4-
methylphenyl group, 4-methoxyphenyl group, etc.), alkylthio group (preferably substituted or unsubstituted with 1 to 1 carbon atoms)
0, such as methylthio group, ethylthio group, etc.), arylthio group (preferably substituted or unsubstituted, with 6 to 6 carbon atoms)
12, e.g. phenylthio group), carbon number 3
alkoxy groups (e.g. propoxy group, butoxy group, etc.), aryloxy groups (e.g. phenoxy group, etc.),
Alkylamino groups having 3 or more carbon atoms (e.g. propylamino group, butylamino group, etc.), arylamino groups (e.g. anilino□ represents R, -30□-N-X□-, where xl is an alkylene group ( It preferably represents a linking group having 1 to 5 carbon atoms, such as a methylene group, a propylene group, a 2-hydroxypropylene group, etc. R7 and R8 may be the same or different, and represent a hydrogen atom, an alkyl group, etc. Groups (preferably substituted or unsubstituted ones having 1 to 10 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl 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, such as allyl group, propargyl group, etc.), aralkyl group (preferably substituted or unsubstituted ones with 7 to 12 carbon atoms, such as benzyl group, phenethyl group, vinylbenzyl group, etc.), aryl groups (preferably substituted or unsubstituted ones with 6 to 12 carbon atoms, such as phenyl group, 4-methyl phenyl group, etc.), or heterocyclic group (
For example, 2-pyridyl group, etc.).

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

(I-1) 2O- (I-3) (I-4) C2H5Ie (i-6) (I-10) (I-1, 2) (I-14) C.J.T.

CQ O4'' Specific examples of the compounds represented by the general formulas (na) and (IIb) are shown below. However, the present invention is not limited only to these compounds.

(TI-1) 4-hydroxy-6-pentyl-1,
3,3a,7-tetrazaindene (TI-2) 4-hydroxy-6-hebutyl-1,
3,3a,7-tetrazaindene (II-3) 4-hydroxy-6-nonyl-1,3
, 3a, fuchitrazaindene (II-4) 4-hydroxy-6-hebutadecyl-1,3,3a, 7-tetrazaindene (n-5) 4-hydroxy-6-benzyl-1,3
,3a,7-tetrazaindene (■-6) 6-(N,N-diallylcarbamoylmethyl)-4-hydroxy-1,3,3a,7-tetrazaindene (TI-7) 6-(N- Ethylcarbamoylethyldroxy-2-methyl-1.3,3a,7-tetrazaindene (IT-8) 6-(N-phenylcarbamoylmethyl)-4-hydroxy-1.3,3a,7-tetrazaindene Den(1'l-9) 6-(N-2-pyridylcarbamoylmethyl)-4-hydroxy-1.,3,3a
,7-tetrazaindene (JT-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 (H-13) 4-hydroxy-6-(N-vinylbenzylcarbamoylmethyl)-1.3,3a,7-tetrazaindene (II-14) 6-(N,N-diethylcarbamoyl methyl)-5-ethoxycarbonyl-4-bitroxy-
1,3.

3a,7-tetrazaindene (n-15) 4-hydroxy-6-(N-propylcarbamoylprobyl)-2-phenoxy-1.3,3a
,7-tetrazaindene (II-16) 6-(N-benzylcarbamoylmethyl)-4-hydroxy-1,3,3a,7-tetrazaindene (If-17) 5-cyano-6- (N,
N-diallylcarbamoylmethyl)-4-hydroxy-
1.3,3a,7-tetrazaindene (H-18) 4-hydroxy-6- (N-octylcarbamoylmethylzaindene (II-19) 6-(N-benzylcarbamoylmethyl)-5-bromo-4 -Hydroxy-1,3,3a,7
-Tetrazaindene (IT-20) 2-benzyl-6- (N, N-
(jetoxycarbamoylmethyl)-4-hydroxy-1
．． 3,3a,7-tetrazaindene (II-21) 6-(N-allylcarbamoylmethyl)-4-hydroxy-2-dimethylamino-1.3.3
a,7-tetrazaindene (H-22) 6-(N-benzylcarbamoylmethyl)-4-hydroxy-2-phenylthio-t,3,aa
t'7 -tetrazaindene (IT-23) 4-hydroxy-6-(N-methyl-
N-phenylcarbamoylmethyl)-1. ,3,3a,
7-tetrazaindene (IT-24) 4-hydroxy-6-(N-propylcarbamoylmethyl)-1.3,3a,7-tetrazaindene (II-25) 6-(N,N-dipropylcarbamoyl methyl)=4-hydroxy-1.3,3a,7
-Tetrazaindene (IT-26) 6-(N-benzyl-N-methylcarbamoylmethyl)-4-hydroxy-1,3,3a,7
-Tetrazaindene (H-21> 6-(N-(2-methoxyphenyl)-
Rubamoylmethyl]-4-hydroxy-1,3.3a
,7-tetrazaindene (If-28) 6-[N-(2-methylphenyl)-
Rubamoylmethyl]-4-hydroxy-1,3,3a
,7-tetrazaindene (If-29) 6-[N-(2,5-dimethoxyphenyl)-rubamoylmethyl]-4-hydroxy-1
, 3, 3a, 7-tetrazaindene (n-30) 6-acetylaminomethyl-4-hydroxy-1,3,3a, 7-tetrazaindene (n-31) 6-(3-butenoylamino methyl)−
4-hydroxy-1,3,3a,7-tetrazaindene (n-32) 4-hydroxy-6-(α-phenylacetylaminomethyl)-1,3,3a,7-tetrazaindene (IT-33 ) 6-(N,N-diallylsulfamoylmethyl)-4-hydroxy-t,3,3a,7-tetrazaindene (TI-34) 6-(N-benzylsulfamoylmethyl)-4-hydroxy -1,3,3a,? -Tetrazaindene (IT-35) 4-hydroxy-6-(methanesulfonamidomethyl)-1,3,3a,? -Tetrazaindene (IT-36) 6-benzenesulfonamidomethyl-4-hydroxy-1,3,3a,7-tetrazaindene (IT-37) 6-(N,N-diallylcarbamoylmethyl)-4- Hydroxy-1,2,3a,7-chitrazainde (II-38) 6-(N-vinylbenzylcarbamoylmethyl)-4-hydroxy-LL3a,7
-Tetrazaindene (IT-39) 6-acetylaminomethyl-4-hydroxy-1,2,3a,? -Tetrazaindene (IT-40) 6-(3-butenoylaminomethyl)
-4-hydroxy-1,,2,3a,7-tetrazaindene (■-■)6-benzenesulfonamidomethyl-4
-Hydroxy-1,2,3a,7-tetrazaindene (
n-42) 6-(N-allylsulfamoyl)-4-
Hydroxy-1,2,3a,7-tetrazaindene The general synthesis method of the infrared sensitizing dye represented by the general formula (1) used in the present invention is described in, for example, JP-A-59-1922/12. has been done.

The infrared sensitizing dye represented by the general formula (1) used in the present invention is preferably 5 x 10 per mole of silver halide.
-7 mol-5X], O-3 mol, more preferably lX
10-' mol~], X10-' mol, particularly preferably 2
It is contained in the silver halide emulsion in a proportion of x10-6 mol-5X 10-' mol.

The infrared sensitizing dye used in the present invention can be directly dispersed into the emulsion. Alternatively, they can be first dissolved in a suitable solvent such as methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine, or a mixed solvent thereof, and then added to the emulsion in the form of a solution. Ultrasonic waves can also be used for dissolution.

In addition, as a method for adding this infrared sensitizing dye, one dye as described in US Pat. No. 3,469,987 is dissolved in a volatile organic solvent, and the solution is added to a hydrophilic colloid. A method of dispersing water-insoluble dyes in a water-soluble solvent without dissolving them, and adding this dispersion to an emulsion, as described in Japanese Patent Publication No. 46-24185, etc. US Patent No. 3,822
, 135, a method of dissolving a dye in a surfactant and adding the solution to an emulsion;
A method of dissolving a red-shifting compound using a red-shifting compound and adding the solution to an emulsion as described in JP-A No. 74624; a method of dissolving a dye in substantially water-free acid as described in JP-A-50-80826; A method is used in which the solution is added to the emulsion. In addition, U.S. Patent No. 2,912.343, U.S. Pat. No. 3,342,605,
Methods described in Japanese Patent No. 2,996,287 and Japanese Patent 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 -1-, but it can of course be dispersed during any step of the preparation of the silver halide emulsion. be able to.

General formula (IIa) or (IIb) used in the present invention
A general method for synthesizing the compound represented by Rer, 42
4638 (1909), Photo-Rundsch,
, 7j% 414.437.465 (1961,), etc. Synthesis examples of typical compounds are shown below, but compounds represented by other general formulas (Tla) or (Ilb) can also be easily synthesized according to the following synthesis examples.

Synthesis example 6-(N,N-diallylcarbamoylmethyl)
Synthesis of -4=hydroxy-1,3,3a,7-tetrazaindene (n-6) 126 g of aminotriazole, 304 g of diethyl acetonedicarboxylate, and 6 kfl of acetic acid are heated under reflux for 8 hours.

After cooling, 500 mM of ethyl acetate was added and left to stand to precipitate white crystals. The obtained crystals were collected by filtration and washed with ethyl acetate to give 6-nitoxycarponylmethyl-4-hydroxy-
305 g of 1,3,3a,7-chitrazaindene are obtained.

Next, 300 g of crystals obtained, 130 g of sodium hydroxide
, heat 500 mQ of water at 80°C for 3 hours. After the reaction, 340n+Q of concentrated hydrochloric acid is slowly added to precipitate white crystals.

The obtained crystals are collected by filtration and recrystallized from water to obtain 212 g of 6-carpoxymethyl-4-hydroxy-1,3,3a,7-chitrazaindene.

Next, 143 g of crystals obtained, 72 g of diallylamine
, dimethylformamide 1.5Q is stirred at room temperature to dissolve. 152 g of N,N-dicyclohexylcarbodiimide was added dropwise to the mixture, and after the dropwise addition, the mixture was lowered in the room and stirred for 8 hours to precipitate white crystals (N,N-dicyclohexylurea). After filtering off the precipitated crystals, the filtrate is poured into 3Q of water to precipitate white crystals. The precipitated crystals are collected by filtration and recrystallized from acetonitrile to obtain the desired 6-(N,N-diallylcarbamoylmethyl)-4-hydroxy-1,3,3a.
, 171 g of 7-chitrazaindene are obtained.

The target product was confirmed by IR and NMR1 elemental analysis results.

Elemental analysis value (C□, Hl, N, 0□) Theoretical value H: 5.53% C: 57.13% N
: 25.62% experimental value H: 5.48% C: 5
7.23% N: 25.58% The compound represented by general formula (IIa) or (IIb) used in the present invention is advantageously used in an amount of about 0.01 to 5 grams per mole of silver halide in the emulsion. used for.

The ratio (weight ratio) of the infrared sensitizing dye of general formula (1) to the compound represented by general formula (TTa) or (IIb) is the dye represented by general formula (I) / - general formula Ha) or (I
The range of the compound represented by Ib) from 1/1 to 1/300 is advantageously used, particularly preferably from 172 to 1/100.

The compound represented by the general formula (lTa) or (IIb) used in the present invention can be directly dispersed in an emulsion, or can be dispersed in a suitable solvent (such as water, methyl alcohol,
It is also possible to dissolve the compound in a mixed solvent using two or more of these solvents (ethyl alcohol, propatool, metricellosolve, acetone, etc.) and add it to the emulsion. In addition, it can be added to the emulsion in the form of a solution or a dispersion in a colloid according to the method of adding sensitizing dyes.

The compound represented by the general formula (rla) or (IIb) may be added to the emulsion before or after the addition of the sensitizing dye represented by the general formula (1). Alternatively, the compound of general formula (]TTa or (IIb) and the sensitizing dye of general formula (1) may be dissolved separately and added to the emulsion at the same time, or they may be mixed and then added to the emulsion. May be added.

The sensitizing dye according to the present invention can be used in combination with other sensitizing dyes. For example, U.S. Patent No. 3.703,3
No. 77, No. 2,688,545, No. 3,397,06
No. 0, No. 3,615,635, No. 3,628,964
British Patent No. 1,242,588, British Patent No. 1,293,
No. 862, Special Publication No. 43-493fi, No. 44-140
No. 30, No. 43-10773, U.S. Patent No. 3,416
, No. 927, Japanese Patent Publication No. 43-4930, U.S. Patent No. 3.
No. 615,613, No. 3,615,632, No. 3,6
Sensitizing dyes described in No. 17,295, No. 3,635,721, etc. can be used.

The silver halide used in the present invention may be, for example, any one of silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide, and the like. In the present invention, among the above-mentioned 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 have coarse grains, fine grains, or mixed grains thereof, and these silver halide grains can be prepared by known methods such as the single jet method.

Formed by double jet method or controlled double jet method.

Furthermore, even if the crystal structure of silver halide grains is uniform throughout the interior, there are also those with a layered structure with different interior and exterior structures, British Patent No. 635,841, and U.S. Patent No. 3,62.
It may also be of a so-called conversion type as described in No. 2,318. Further, it may be either a type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside one particle. These photographic emulsions are Mies (Me
ss), [The Theory of the Photographic Process]
The Photographic Process
s) Published by JMacMH1an, Grafi
[Photograph-icChemistry] J
Published by Fountain Press, etc., Research Disclosure Vol. 1.176 (1978
(December 2013) It is also described in RD-17643, etc., and can be adjusted by various methods such as the generally accepted ammonia method, neutral method, acid method, etc.

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

The average diameter of the silver halide grains (measured, for example, by the projected area method or number average) is preferably about 0.04 μm to 4 μm. Particularly preferred is one having a diameter of 0.7 μm or less.

During the formation of silver halide grains, silver halide solvents such as ammonia, rhodanpotash, rhodanammonium, thioether compounds (e.g., U.S. Pat. No. 3,271..157, U.S. Pat.
No. 574,628, No. 3,704,130, No. 4,2
97,439, 4,216,314, etc.), thione compounds (e.g., JP-A-53-144319, JP-A-53-82408, JP-A-55-77737, etc.); 54-10071.7, etc.) can be used.

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

Silver halide photographic emulsions can be produced by commonly used chemical sensitization methods, such as gold sensitization (U.S. Pat. No. 2,540,085,
U.S. Pat. No. 2,597,876, U.S. Pat. No. 2,597,915, U.S. Pat.
No. 086, No. 2,566.245, No. 2,566.2
No. 63, US Pat. No. 2,598,079, etc.), sulfur sensitization (US Pat. No. 1,574,944, US Pat. No. 2,278,947, etc.)
No. 2,440,206, No. 2.52+, No. 926, No. 3,021,215, No. 3,038,805,
No. 2,410,689, No. 3,1.89,458,
No. 3,415,64 (], No. 3,635,717, etc.), reduction sensitization (U.S. Pat. Nos. 2,518,698, 2,419,974, 2,983,610, etc.) Research Disclosure Vol. 176 (197
RD-17643, Section 2, etc.), sensitization with thioether compounds (e.g.
No. 21,926, No. 3,021,215, No. 3,03
No. 8,805, No. 3,046,129, No. 3,046
, No. 132, No. 3,046,133, No. 3,046,
No. 134, No. 3,046,135, No. 3,057,7
No. 24, No. 3,062,646, No. 3,165,55
No. 2, No. 3,189,458, No. 3,192,046
No. 3,506,443, No. 3,671,260, No. 3,574,709, No. 3,625,697,
No. 3,635,717, No. 4,198,240, etc.), or various sensitization methods combined therewith are applicable.

Furthermore, specific chemical sensitizers include allyl thiocarbamide (allyl thiocarba+1ide),
Sulfur sensitizers such as thiourea, sodium thiosulfate, thioethers and cystine; potassium chlorooleate, aurous thiosulfate and potassium chlorovaladate.

noble metal sensitizers such as palladate; tin chloride;
Examples include reduction sensitizers such as phenylhydrazine and reductone.

Other polyoxyethylene derivatives (British Patent No. 981
, No. 470, Japanese Patent Publication No. 31-6475, U.S. Patent No. 2.
716,062), polyoxypropylene derivatives, and derivatives having a quaternary ammonium group.

Various compounds can be added to the photographic emulsion of the present invention in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the light-sensitive material.

These compounds include nitrobenzimidazole, ammonium chloroplatinate, 4-hydroxy-6-methyl-1,3,3a, 7-thitraazaindene, 3-methylbenzothiazole, 1-phenyl-5-mercaptotetrazole, and many others. heterocyclic compounds, mercury-containing compounds,
A large number of compounds such as mercapto compounds and metal salts have been known for a long time. An example of a compound that can be used is K
, The Theory of the Photographic Process, by Mess.
of The Photographic Process
ss)" (3rd edition, 1966), pages 344 to 349, citing the original literature. Other compounds include:
For example, U.S. Patent No. 2,131,038 and U.S. Patent No. 2,69
Thiazolium salts described in U.S. Pat. No. 4,716 and others; U.S. Pat. No. 2,886,437 and U.S. Pat.
Azaindenes described in U.S. Patent No. 3, etc.
, 287,135; sulfocatechols described in U.S. Patent No. 3,236,652; oximes described in British Patent No. 623,448; U.S. Patent No. 2,403
, No. 927, No. 3.266.897, No. 3,397,
Mercaptotetrazoles and nitrones described in US Pat. No. 987, nitrones; nitroindazoles; US Pat.
Polyvalent metal salts (p
olyvalont metals) ; thiuronium salts (thiuronium 5 alts) described in U.S. Patent No. 3,220,839 etc.
; U.S. Patent No. 2,566.263, U.S. Patent No. 2,597,
Examples include salts of palladium, platinum, and gold, as described in No. 915.

Silver halide photographic emulsions contain developing agents such as hydroquinones; catechols; aminophenols; 3-pyrazolidones; ascorbic acid and its derivatives; reductones and phenylenediamines, or a combination of developing agents. can be done.

The developing agent is used in the silver halide emulsion layer and/or other photographic layers (
For example, a protective layer, an intermediate layer, a filter layer, an antihalation layer, a backing layer, etc.). The developing agent may be dissolved in a suitable solvent or as described in U.S. Patent No. 2,592,3.
68 and in the form of a dispersion as described in French Patent No. 1,505,778.

As the development accelerator, for example, U.S. Pat. No. 3,288,6
No. 12, No. 3,333,959, No. 3,345,17
No. 5, No. 3,708,303, British Patent No. 1,098
, 748, West German Patent No. 1,141,531, 1. , No. 183,784, etc. can be used.

Hardening of the emulsion can be carried out according to conventional methods. Examples of curing agents include aldehyde compounds such as formaldehyde and glutaraldehyde; ketone compounds such as diacetylcyclopentanedione; bis(2-chloroethyl urea), 2-hydroxy-4; i-4,6-dichloro; -1,3,5-triazine, etc. U.S. Patent Nos. 3,288,775 and 2,732,30
3, British Patent No. 974.723, 1. ,167,
Compounds containing reactive halogens such as those shown in No. 207; divinyl sulfone, 5-acetyl-1,3
-diacryloylhexahydro-1,3,5-1-lyazine, etc. U.S. Pat. No. 3,635,718, No. 3,
Compounds with reactive olefins such as those shown in British Patent No. 232,763 and British Patent No. 994,869;
N-Hydroxymethylphthalimide, other US patents 2
, 732,316, 2,586,168, etc.; U.S. Pat.
Isocyanates such as those shown in US Pat. No. 3,017,280 and US Pat. No. 2.983;
, 61.1, etc.; U.S. Pat. Nos. 2,725,294 and 2,725,2
Acid derivatives such as those shown in US Pat. No. 95, etc.; US Pat.
．． Carbodiimide compounds as shown in US Pat. No. 100,704; Epoxy compounds as shown in US Pat. No. 3,091,537; US Pat. No. 3.32
Isoxazole compounds such as those shown in No. 1,313 and No. 3,543,292; halogenocarboxaldehydes such as mucochloric acid; dioxane derivatives such as dihydroxydioxane and dichlorodioxane;
Alternatively, inorganic hardening agents include chloramypan, zirconium sulfate, and the like. Moreover, instead of the above-mentioned compounds, compounds in the form of precursors such as alkali metal bisulfide 1-aldehyde adducts, methylol derivatives of hydantoin, primary aliphatic di-1-alcohols, etc. may be used.

Surfactants +4 may be added alone or in combination to the photographic emulsion of the present invention.

Although they are used as coating aids, they are sometimes applied for other purposes, such as emulsifying and dispersing, improving sensitized photographic properties, antistatic, antiadhesive, etc.

These surfactants include natural surfactants such as saponins,
Nonionic surfactants such as alkylene oxide, glycerin, and glycidol, higher alkyl amines,
Quaternary ammonium salts, pyridine and other heterocycles,
Cationic surfactants such as phosphonium or sulfoniums, anionic surfactants containing acidic groups such as carboxylic acids, sulfonic acids, phosphoric acids, sulfate ester groups, phosphoric ester groups, amino acids, aminosulfonic acids, and sulfuric or phosphoric acids of amino alcohols. It is divided into amphoteric active agents such as esters.

Some examples of surfactant compounds that can be used include U.S. Pat.
, No. 288, 226, No. 2,739,891, No. 3,
068,1 old issue, 3,158,484, 3,20
No. 1,253, No. 3,210,191, No. 3,294
, No. 540, No. 3,415,649, No. 3,441,
No. 413, No. 3,442,654, No. 3,475,1
No. 74, No. 3,545,974, German patent application 1,
942,665, British Patent No. 1,077.317, British Patent No. 1,198,450, and Japanese Patent Publication No. 56-44411, as well as "Synthesis of Surfactants and Their Applications" by Ryohei Oda et al.
Kai Shoten 1964 edition) and A. W. Perry, Surface Active Agents (Interscience Publications Inc. 1958 edition), J. P. Sisley, Encyclopedia of Surface Active Ages. Kunz Volume 2”
(Chemical Publishing Company, 1964 edition).

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

The present invention preferably includes polyalkylene oxide compounds such as alkylene oxides having 2 to 4 carbon atoms, such as ethylene oxide, propylene-1,2-oxide, butylene-1,2-oxide, preferably at least 10 units of ethylene oxide. and a compound having at least one active hydrogen atom such as water, aliphatic alcohol, aromatic alcohol, fatty acid, organic amine, hexitol derivative, etc. A block copolymer of polyalkylene oxide or the like can be used. That is, as polyalkylene oxide compounds, specifically, polyalkylene gelicols, polyalkylene gelicol alkyl ethers, polyalkylene glycol aryl ethers, polyalkylene glycol alkylaryl ethers, polyalkylene glycol esters, polyalkylene glycol fatty acid amides, polyalkylene Glycolamines, polyalkylene gellicol block copolymers, polyalkylene glycol graft polymers, and the like can be used. The molecular weight needs to be 600 or more.

The number of polyalkylene oxide chains is not limited to one in the molecule, and two or more may be included. In that case, the lateral polyalkylene oxide chains may consist of fewer than 10 alkylene oxide units, but the total number of alkylene oxide units in the molecule must be at least 10. When the molecule has two or more polyalkylene oxide chains, each of them has a different alkylene oxa at position 411,
For example, it may consist of ethylene oxide and propylene oxide. The polyalkylene oxide compound that can be used in the present invention is preferably 14 or more and 1
It contains up to 00 alkylene oxide units.

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

Polyalkylene oxide compound example P-I HO(CH,CH20). HP-2C,H
,0(CH2CT(,O),,HP 3 CxzH
zsO(CHzCHzO)tsHP-4C111H3,
0(CH,CH,O),,HP-5G,,H,0(C
H-CHzO)4nHP-60,H,CH=C)(C,
H,,0(C)T2CH20)1. HP-7C,H,,
-0-0-(CH2CH20)3゜Hp-s CH,
-Q-o-(cH2aH2o)3o■rP-90-〇-
(CH2CH,0)2. HP-10C engineering, H23COO
(CH,CH,O),,HP-11C,1H,,Coo
(CH, CH, O), 40CC, H23P-13C engineering,
H2□C0NH(CH,CH,O)□, HP -15C
L4H,,N(CH□)(CHzCHiO)z4Hb
: a+c=]O: 9 P 18 T(OCH-CHzO(CH2CH2O)
s-f\\-/-CgHls P-20110(C12CH20)8(C12CI□C
112CI et al. 0)b (CIl□C11□0). 1(a+
b=30. b=14 b=8. a+c=50 etc. JP-A-50-156423, JP-A-52-108
The polyalkylene oxide compounds described in No. 130 and JP-A-53-3217 can be used.

These polyalkylene oxide compounds may be used alone or in combination of two or more.

When these polyalkylene oxide compounds are added to a silver halide emulsion, they are dissolved in an aqueous solution of an appropriate concentration or in a low boiling point organic solvent that is miscible with water.
The polyalkylene oxide compound used in the present invention can be added to the emulsion at an appropriate time before coating, preferably after chemical ripening, in an amount of 1 x 10-' mol to I x 10-' mol per mol of silver halide in the emulsion. ``A molar range is desirable.

Also, U.S. Patent No. 3,411,911;
No. 912, No. 3,142,568, No. 3,325,2
No. 86, No. 3,547,650, Special Publication No. 45-533
A polymer latex consisting of a homopolymer or copolymer of alkyl acrylate, alkyl methacrylate, acrylic acid, glycidyl acrylate, etc. described in No. 1 etc. is contained for the purpose of improving the dimensional stability of the photographic material, improving the physical properties of the film, etc. be able to.

Silver halide photographic emulsions may also contain antistatic agents, plasticizers, optical brighteners, air antifoggants, toning agents, and the like.

The silver halide photographic emulsion of the present invention can contain color pigments such as cyan coupler, magenta coupler, yellow coupler, etc.
It can include a coupler and a compound that disperses the coupler.

That is, it may contain a compound that can develop color through oxidative coupling with an aromatic primary amine developer (for example, a phenylene diamine derivative, an aminophenol derivative, etc.) in color development treatment. These couplers are preferably non-diffusive and have a hydrophobic group called a ballast group in the molecule.

The coupler may be either 4-equivalent or 2-equivalent to silver ions. It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called old R coupler).

In addition to the DTR coupler, the coupling reaction product may include a colorless DIR coupling compound which is colorless and releases a development inhibitor.

In addition, a color image can also be formed by developing with a color developer containing a diffusible coupler.

In addition, as an irradiation prevention dye that may be contained depending on the purpose, for example, Japanese Patent Publication No. 41-20389, No. 4
No. 3-3504, No. 43-13168, U.S. Patent No. 2
．． No. 697,037, No. 3,423,207, No. 2,
No. 865,752, British Patent No. 1,030,392;
Those described in 1,100,546 and the like are used.

The present invention can be applied to the sensitization of silver halide emulsions used in various color light-sensitive materials as well as black and white photographic emulsions.

Furthermore, in addition to the emulsion layer of the present invention, an emulsion layer having photosensitivity in other spectral regions may be layered to form a so-called multilayer multicolor photosensitive material.

Exposure to obtain a photographic image may be carried out using a conventional method. i.e. natural light (sunlight), tungsten electric light,
There are many types of known infrared light sources, such as mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, light emitting diodes, and laser lights (e.g. gas lasers, dye lasers, YAG lasers, semiconductor lasers, etc.). Any light source can be used. Alternatively, exposure may be performed using light emitted from a phosphor excited by electron beams, X-rays, γ-rays, α-rays, or the like. Exposure time is 1/1000 second to 1, which is normally used in cameras.
Not only exposure times of seconds, but also exposures shorter than 1/1000 seconds, such as 1/10 using xenon flash lamps or cathode ray tubes.
Exposures of ' to 1/10' seconds can be used, or exposures longer than 1 second can be used.

If necessary, the spectral composition of the light used for exposure can be adjusted using a color filter.

The photographic emulsion of the present invention can be coated on a flexible support such as a plastic film (cellulose nitrate, cellulose acetate, polyethylene terephthalate, etc.), paper, or a rigid support such as glass, which is commonly used in photographic light-sensitive materials. Ru. For details on the support and coating method, see Research Disclosure Vol. 176 Ite+m 17643
XV term (p, 27) X■ (p, 28) (1978 1
February issue).

Any known method can be used for photographic processing of the light-sensitive material produced by applying the present invention.

A known treatment liquid can be used. The processing temperature is usually selected between 18°C and 50°C, but temperatures below 18°C or above 50°C may also be used. Depending on the purpose, either a development process that forms a silver image (black and white photographic process) or a color photographic process that consists of a development process that forms a single dye image can be applied. Furthermore, lithographic development can also be applied.

For details, see Research Disclosure Volume 176,
N1117643, pages 28-29, volume 187 Nα1
8716, page 651, left column, right column.

The present invention can also be applied to light-sensitive materials with a low amount of silver, in which the amount of silver halide in the emulsion is several times to one-hundredth of that of ordinary light-sensitive materials.

Next, the present invention will be explained 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 a double jet method,
After physical ripening and desalting treatment, it is chemically ripened to produce silver iodobromide (
An emulsion with an iodine content of 1.2 mol % was obtained. The average diameter of the silver halide grains contained in this emulsion was 0.4 microns. 0.6 mol of silver halide was contained in 1 kg of this emulsion.

Weigh out 1 kg of this emulsion and dissolve it by heating at 40°C. As shown in Table 1, the sensitizing dye contained in the general formula (1) and the sensitizing dye contained in the general formula (Ila) or (Ilb) are combined. Predetermined amounts of a methanol solution of the compound or Comparative Compound A were added, and the mixture was mixed and stirred. Then 1-hydroxy-3,5
- 35 mQ of a 1.0% by weight aqueous solution of sodium dichlorotriazine salt was added, and further 50 mQ of a 1.0% by weight aqueous solution of sodium dodecylbenzenesulfonic acid salt was added and stirred. This completed emulsion was coated on a cellulose triacetate film base to a dry film thickness of 5 microns and dried to obtain a sample of a light-sensitive material. Using a photosensitive needle with a light source with a color temperature of 2854°, this film sample was exposed to a dark red filter (SC-72 manufactured by Fuji Photo Film Co., Ltd.).
) was used for optical wedge exposure. After exposure, development was performed at 20° C. for 3 minutes using a developer having the composition shown below, followed by stopping and fixing, followed by washing with water to obtain strips with a predetermined black and white image. The density was measured using a P-type densitometer manufactured by Fuji Photo Film Co., Ltd. to obtain the sensitivity and fog. The reference point for optical density that determined the sensitivity was the point of [fog +0.3]. Composition of developer: water 500
m12N-methyl-p-aminophenol 2.
2g anhydrous sodium sulfite 96.0g hydroquinone 8.8g sodium carbonate-hydrate 56.0g potassium bromide
Add 5.0g water
1 Ω The results obtained are shown in Table 1 as relative values.

These results show that the combination of the present invention provides an excellent photosensitive material with higher sensitivity and less fog than the dyes A and D and comparative examples.

Compound A (for comparison): 4-hydroxy-6-methyl-1,3,3a,7-titraazaindene Example 2 Aqueous solution 241 containing 70 g of gelatin was adjusted to pH 3.0, and 1 kg of silver nitrate was added thereto. 2 kg containing 2 kg of aqueous solution, 210 g of potassium bromide, and 290 g of sodium chloride
was simultaneously added at a constant rate over 30 minutes.

At this time, rhodium was added at 5 x 10-7 mol/silver mol. First, after removing soluble salts, gelatin was added and chemically ripened to form a silver chlorobromide emulsion (grain size 0.31 μm).
Br, 30 mol%) was obtained. 4-hydroxy-6-methyl-1,3,3a,7-chitrazaindene was added to this emulsion as a stabilizer.

As shown in Table 2, a sensitizing dye contained in general formula (1) and a compound contained in general formula (TI) were further added to this emulsion, and then 1-hydroxy-3, 5-dichlorotriazine sodium salt, with addition of dodecylbenzenesulfonic acid sodium salt as a coating aid, on a polyethylene terephthalate film with an amount of 4.2 silver per lnf.
It was coated to give a weight of g.

The film sample thus prepared was exposed to a light wedge through a dark red filter (manufactured by Fuji Photo Film Co., Ltd., SC-72), developed with the following developer at 20° C. for 3 minutes, stopped, fixed, and washed with water. The density was measured using a P-type densitometer manufactured by Fuji Photo Film Co., Ltd., and the sensitivity and fog values were obtained. The optical density reference point that determined the sensitivity was [fog +0.3
].

The results are shown in Table 2.

In addition, a part of the film sample prepared in this way was stored at high temperature and high humidity (40°C, 75% RH) for 3 days, and for comparison, it was stored in a refrigerator (5°C, 10% R1+) for 3 days. The same exposure, development, stopping, fixing, water washing, and drying as described above were performed together with the sample. The results are shown in Table 3.

Composition of developer Metol 0.31 g Anhydrous sodium sulfite 39.6 g Hydroquinone
6.0g anhydrous sodium carbonate 18
．． 7 g Potassium bromide 0.86 g
Citric acid 0.68 g Potassium metabisulfite 1.5 g Add water
IQ From the results in Table 2, it can be seen that the combination of the present invention provides an excellent photosensitive material with higher sensitivity and less fog than the dye alone or the comparative example. Further, from the results in Table 3, it can be seen that the combination of the present invention not only has high sensitivity, but also shows little decrease in sensitivity and little increase in fog when the photosensitive material is stored under high temperature and high humidity.

(Effects of the Invention) The present invention has the effect that a silver halide photographic emulsion has high sensitivity to infrared light and has little fog. In addition, the silver halide photographic material obtained using the silver halide photographic emulsion of the present invention showed little decrease in sensitivity and little increase in fog under high temperature and high humidity conditions, and had excellent preservability effects.

Claims (1)

[Scope of Claims] A silver halide containing a combination of at least one infrared sensitizing dye represented by the following general formula (I) and at least one compound represented by the following general formula (IIa) or (IIb) Photographic emulsion. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ 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, and R_3 is a hydrogen atom, lower alkyl V represents a hydrogen atom, a lower alkyl group, an alkoxy group, a halogen atom or a substituted alkyl group. Z represents a nonmetallic atomic group necessary to complete a 5- or 6-membered nitrogen-containing heterocycle, and X represents an acid anion. m, n
and p each independently represent 1 or 2. General formula (IIa) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula (IIb) In the formula, R_4 and R_5 each independently represent a hydrogen atom, a lower alkyl group, an alkenyl group, a carboxyl group, an alkoxy group, or a halogen atom. , R_6 is an alkyl group having 5 or more carbon atoms, an aralkyl group, an aryl 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 , ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. However, here, X_1 represents a divalent linking group, and R_7 and R_
8 each independently represents a hydrogen atom, an alkyl group, an alkenyl group,
Represents an aralkyl group, an aryl group, or a heterocyclic group.