JPH02140736A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain an emulsion having increased spectral sensitivity without increasing fog by adding a specified sensitizing dyestuff and a specified telluro- ether compd. CONSTITUTION:At least one kind of sensitizing dyestuff represented by formula I and at least one kind of telluro-ether compd. represented by formula II are added to a silver halide photographic sensitive emulsion. In the formula I, each of Z1 and Z2 is a group of atoms forming a 5- or 6-membered hetero ring contg. N, each of R1 and R2 is <=10C alkyl or alkenyl, each of R3 and R7 is H, each of R4-R6 is H, lower alkyl, etc., each of j and k is 0 or 1, l is 0, 1 or 2, m is 0 or 1 and X is a residue of an acid anion. In the formula II, each of L1 and L2 is alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl or a heterocyclic group. The spectral sensitivity of the emulsion can be increased.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material spectrally sensitized using a telluroether compound.

(Prior Art) Efforts have heretofore been made to obtain silver halide photographic materials that have high photographic sensitivity, little fogging, and little change in photographic performance during storage over time.

In addition, silver halide photographic emulsions usually use sensitizing dyes,
Silver halide itself is spectrally sensitized so that it has photographic sensitivity to wavelengths such as green, red, and infrared, where it has no absorption.

In order to increase this spectral sensitivity, it is often done to increase the amount of sensitizing dye used, but at the same time, increasing the amount used also inhibits development by the dye, disperses the latent image, or nullifies photoelectrons due to holes in the dye. Decrease in sensitivity in the characteristic wavelength range, which is thought to be due to image bleaching, etc. The so-called characteristic sensitivity increases, and as a result, the spectral sensitivity reaches a plateau and no longer increases.

To further increase this spectral sensitivity, it was known to use certain thioether compounds, as described, for example, in US Pat. No. 3,506,443.

However, these thioether compounds still had insufficient effects.

In addition, similar to thioether compounds, tellurium ether compounds which act as silver halide solvents or sensitizers are described in JP-A-53-57817, and include sensitizing dyes,
A technique in which 1.1'-diethyl-2゜2'-cyanine chloride is used in combination has been disclosed, but the spectral sensitization of this dye is originally quite low, and as shown in the examples, a large amount of the dye is used. Intrinsic desensitization caused by this phenomenon is also small.

For the dyes of the present invention that have large spectral sensitization but also have large inherent desensitization due to a large amount of dye (the following general (I)), it is necessary to develop a technology to reduce the inherent desensitization and further improve the spectral sensitivity. It was coveted.

(Object of the Invention) A first object of the present invention is to provide an emulsion with increased spectral sensitivity without increasing fog.

A second object is to provide a spectrally sensitized silver halide photographic emulsion with high sensitivity that exhibits little deterioration in photographic performance during storage over time.

A third object is to provide a spectrally sensitized silver halide photographic emulsion that can be subjected to rapid development processing and has high sensitivity and little fogging.

(Means for Solving the Problems) An object of the present invention is to contain at least one kind of sensitizing dye represented by the following general formula (I), and at least a telluroether compound represented by the shell formula (II). This was achieved using a silver halide photographic emulsion containing one type of silver halide.

General formula (RI(X-)a In the formula, Z+ and Zz may be different or the same, and 5
It also represents a group of atoms forming a 6-di nitrogen heterocycle.

R, and R2 may be different or the same, and have 10 carbon atoms
It represents the following alkyl group or alkenyl group.

R1 and R1 represent a hydrogen atom;

and R1 and R may be connected to form a 5- or 6-membered ring.

Ra, Rs and Ra may be different or the same and represent a hydrogen atom, a lower alkyl group, an aryl group or a ketomethylene residue.

Further, R4 and R6 may be connected to form a 5- or 6-shell ring.

X represents an acid anion residue.

j and k are O or 1, l is 0.1 or 2, m is 0
Or represents 1.

Ll and may be different or the same and represent an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, an aralkyl group, or a heterocyclic group.

Also, Z'+, Zx, Rt, Rt, R4, Rs
, R1, Ll and RI may each independently be further substituted with a substituent.

A detailed explanation of the compound of general formula (I) will be given.

In the formula, 2. ．． 2. may be different or the same, and represent a group of atoms forming a 5- or 6-membered nitrogen-containing heterocycle, specifically thiazoline, thiazole, benzothiazole, naphthothiazole, dihydronaphthothiazole, selenazoline, selenazole, benzoselenazole. , naphthoselenazole, dihydronaphthoselenazole, oxazole,
Benzoxazole, naphthoxazole, benzimidazole, naphthoimidazole, pyridine, imidazo(
4,5-b) Heterocyclic nuclei such as quinoxaline, telllazole, penzotelllazole, and 3,3-dialkylindolenine can be mentioned.

The nitrogen-containing heterocyclic nucleus represented by 21 and Z2 may have one or more substituents. Examples of preferred substituents include lower alkyl groups (even if branched, further substituents (e.g., hydroxy group, halogen atom, aryl group, aryloxy group, arylthio group, carboxy group, alkoxy group, alkylthio group, alkoxycarbonyl group) etc.), more preferably an alkyl group having a total carbon number of 10 or less. For example, a methyl group, an ethyl group, a butyl group,
Chloroethyl group, 2.2; 3.3-tetrafluoropropyl group, hydroxy group, benzyl group, tolylethyl group, phenoxyethyl group, phenylthioethyl group, carboxypropyl group, methoxyethyl group, ethylthioethyl group, ethoxycarbonylethyl group Examples include groups. )
, a lower alkoxy group (which may further have a substituent).

Examples of the substituent include the same substituents as those listed as examples of the substituent for the alkyl group. More preferably, it is an alkoxy group having a total carbon number of 8 or less, such as a methoxy group, an ethoxy group, a pentyloxy group, an ethoxymethoxy group, a methylthioethoxy group, a phenoxyethoxy group, a hydroxyethoxy group, a chloropropoxy group, etc.), Hydroxy group, halogen atom, cyano group, aryl group (e.g., phenyl group, tolyl group, anisyl group, chlorophenyl group, carboxyphenyl group, etc.), aryloxy group (e.g., tolyloxy group, anisyloxy group,
phenoxy group, chlorophenoxy group), arylthio group (e.g., tolylthio group, chlorophenylthio group, phenylthio group), lower alkylthio group (which may be further substituted). Examples include those listed above. More preferably, alkylthio groups having a total carbon number of 8 or less, such as methylthio group, ethylthio group, hydroxyethylthio group, carboxyethylthio group, chloroethylthio group, benzylthio group, etc.), Acylamino group (more preferably total carbon number 8
The following acylamino groups, such as acetylamino groups, benzoylamino groups, methanesulfonylamino groups, benzenesulfonylamino groups, etc.), carboxyl groups, lower alkoxycarbonyl groups (more preferably alkoxycarbonyl groups with a total carbon number of 6 or less, such as ethoxycarbonyl) group, butoxycarbonyl group, etc.), perfluoroalkyl group (more preferably a perfluoroalkyl group with a total carbon number of 5 or less, such as a trifluoromethyl group, a difluoromethyl group, etc.), and an acyl group (more preferably a total carbon number of 8 or less) (eg, acetyl group, propionyl group, benzoyl group, benzenesulfonyl group, etc.).

Specific examples of nitrogen-containing heterocyclic nuclei represented by Zl and Z2 include:
For example, thiazoline, 4-methylthiazoline, thiazole, 4-methylthiazole, 4,5 dimethylthiazole,
4-phenylthiazole, benzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5
-ethylbenzothiazole, 5,6-dimethylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-butoxybenzothiazole,
5.6-Simethoxybenzothiazole, 5-methoxy-
6-methylbenzothiazole, 5-chlorobenzothiazole, 5-chloro-6-methylbenzothiazole, 5-
Phenylbenzothiazole, 5-acetylaminobenzothiazole, 6-propionylaminobenzothiazole, 5-hydroxybenzothiazole, 5-hydroxy-
6-methylbenzothiazole, 5-ethoxyluponylbenzothiazole, 5-carboxybenzothiazole,
naphtho(I,2-d) thiazole, naphtho(2,1-d
) thiazole, 5-methylnaphtho(I,2-d)thiazole, 8-methoxynaphtho(I,2-d)thiazole,
8,9-dihydronaphtho(I,2-d)thiazole, selenazoline, selenazole, benzoselenazole, 5-
Methylbenzoselenazole, 6-methylbenzoselenazole, 5-methoxybenzoselenazole, 6-methoxybenzoselenazole, 5-chlorobenzoselenazole,
5,6-dimethylbenzoselenazole, 5-hydroxybenzoselenazole, 5-hydroxy-6-methylbenzoselenazole, 5゜6-simethoxybenzoselenazole, 5-ethoxycarbonylbenzoselenazole, naphtho(I2 -dl selenazole, natuto(2,I-d) selenazole, 4-methyloxazole, 4.5-dimethyloxazole, 4-phenyloxazole, benzoxazole, 5-hydroxybenzoxazole, 5-
Methoxybenzoxazole, 5-phenylbenzoxazole, 5-phenethylbenzoxazole, 5-phenoxybenzoxazole, 5-chlorobenzoxazole, 5-chloro-5-methylbenzoxazole,
5-phenylthiobenzoxazole, 6-ethoxy5
-Hydroxybenzoxazole, 6-methoxybenzoxazole, naphtho(I,2-d)oxazole, naphtho(2,1-d)oxazole, naphtho(2,3-d)
) oxazole, l-ethyl-5-cyanobenzimidazole, 1-ethyl-5-chlorobenzimidazole,
l-ethyl-5,6-cyanobenzimidazole, 1-
ethyl-6-chloro-5-cyanobenzimidazole,
1-Ethyl-6-chloro-5-trifluoromethylbenzimidazole, 1-propyl-5-butoxycarbonylbenzimidazole, 1-benzyl-5-methylsulfonylbenzimidazole, 1-allyl-5-chloro-
6-acetylbenzimidazole, 1-ethylnaphtho (
I,2-d) imidazole, 1-ethyl-6-chloronaphtho(2,3-d) imidazole, 2-pyridine, 4-
Examples include pyridine, 3,3-diethylindolenine, 33-dimethylindolenine, 3.3.5-)diethylindolenine, and the like.

R3 and R2 may be the same or different, and represent an optionally substituted alkyl group or alkenyl group having a total carbon number of IO or less. More preferable substituents for the alkyl group and alkenyl group include, for example, a sulfo group, Carboxy group, halogen atom, hydroxy group, alkoxy group having 6 or less carbon atoms, optionally substituted aryl group having 8 or less carbon atoms (e.g., phenyl group, tolyl group, sulfophenyl group, carboxyphenyl group, etc.), hetero cyclic group (for example, furyl group, thienyl group, etc.), optionally substituted aryloxy group having 8 or less carbon atoms (for example, chlorophenoxy group, phenoxy group, sulfophenoxy group, hydroxyphenoxy group), 8 or less carbon atoms acyl group (e.g., benzenesulfonyl group, methanesulfonyl group, acetyl group,
propionyl group, etc.), alkoxycarbonyl group with 6 or less carbon atoms (e.g., ethoxycarbonyl group, phthoxycarbonyl group, etc.), cyano group, alkylthio group with 6 or less carbon atoms (e.g., methylthio group, ethylthio group, etc.), carbon number An optionally substituted arylthio group having 8 or less carbon atoms (e.g., phenylthio group, tolylthio group, etc.), an optionally substituted carbamoyl group having 8 or less carbon atoms (e.g., carbamoyl group, N-ethylcarbamoyl group, etc.), carbon Examples include acylamino groups of number 8 or less (eg, acetylamino group, methanesulfonylamino group, etc.). The substituent is
- You may have more than one.

Specific examples of groups represented by R5 and Rt include, for example, a methyl group, an ethyl group, a propyl group, an allyl group, a pentyl group, a hexyl group, a methoxyethyl group, an ethoxyethyl group, a phenethyl group, a tolylethyl group, a sulfophenethyl group, ，
2.2-trifluoroethyl group, 2.2.3.3-tetrafluoropropyl group, carbamoylethyl group, hydroxyethyl group, 2-(2-hydroxyethoxy)ethyl group, carboxymethyl group, carboxyethyl group, ethoxy carbonylmethyl group, sulfoethyl group, 2-chloro-
3-sulfopropyl group, 3-sulfopropyl group, 2-hydroxy-3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 2(2,3-dihydroxypropyl)ethyl group, N-ethylcarbamoylethyl group , N
-methanesulfonylamine ethyl group and 2- (2-(
R1 and R1, which include a 3-sulfopropyloxy)ethoxy)ethyl group, represent a hydrogen atom. Further, R1 may be linked to R8, and R1 may be linked to R2 to form a 5- or 6-membered ring.

R4, Rs and R4 are a hydrogen atom, a lower alkyl group (which may be substituted, for example, a methyl group, an ethyl group, a propyl group, a methoxyethyl group, a phenethyl group, etc., more preferably an alkyl group having 5 or less carbon atoms) , an optionally substituted aryl group having 8 or less carbon atoms (e.g., phenyl group,
tolyl group, etc.) or negatively charged ketomethylene residues forming allopolar cyanine (e.g. l,3-bis(2-methoxyethyl)-1,2,3,4-tetrahydro-4-oxo-6 -oxide-5-pyrimidinyl group, 1,3-dibutyl-4-oxo6-oxide-1,2
, 3,4-tetrahydro-5-pyrimidinyl group, etc.), and R4 and R4 may be connected to form a 5- or 6-membered ring.

X represents an acid anion residue.

j and k represent 0 or l.

1 represents 0.1 or 2.

m represents 0 or 1, and is 0 in the case of an inner salt.

This was achieved by containing at least one type of sensitizing dye represented by:

Among the sensitizing dyes represented by the general formula (I), more preferable sensitizing dyes are those in which ZI is benzoxazole, naphthoxazole, benzimidazole, naphthimidazole, benzthiazole, naphthothiazole, dihydronaphthothiazole, benzoselenazole. , represents a heterocyclic nucleation group such as naphthoselenazole or dihydronaphthoselenazole, and Z! is thiazole, benzothiazole,
This is the case when representing a heterocyclic nucleation atomic group such as naphthothiazole, dihydronaphthothiazole, selenazole, benzoselenazole, naphthoselenazole, dihydronaphthoselenazole, benzoxazole, naphthoxazole, benzimidazole, or naphthimidazole. The heterocyclic nucleus representing Zl and Z2 may have one or more substituents as described above, but when Zl and Z2 represent a benzimidazole nucleus or a naphthimidazole nucleus, an electron-withdrawing substituent may be present. Preferred (especially preferred examples of electron-withdrawing groups include, for example, fluorine atom, chlorine atom,
Perfluoroalkyl groups having 4 or less carbon atoms such as trifluoromethyl group, alkoxycarbonyl groups having 5 or less total carbon atoms such as butoxycarbonyl group, alkylsulfonyl groups having 4 or less carbon atoms such as cyano group and methanesulfonyl group, etc. It will be done. ).

Furthermore, in the alkyl group or alkenyl group represented by R1 and R2, it is more preferable that at least one of R and R2 is an alkyl group or alkynyl group containing a sulfo group, a carboxy group, or a hydroxy group. .

Specific examples of the compound of general formula (I) include the following compounds.

2H5 IhCF3 ■-2 So, II・N (CJs)3 SOs ■-11! -12 ■-13 O3- 8O1-! -7 ■-14 C2H4 1, -15 tHs ■-16 Js ■ zns ■ (CHz)4sOs ■ ■-25 3H SOJ- ■-20 ■-22 SOJ-N (CJs) z SOJ ■-26 ■- 27 C! H5 ■-28 zus ■-29 ■-30 ■-31 ■-35 ■-37 ■-32 ■ Next, a detailed explanation of and L2 of the compound of general formula (II) will be given.

The alkyl group may be linear or branched and has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as methyl, ethyl, propyl, n-butyl, 5ec-butyl, t-butyl, n-hexyl, 2-ethylhexyl,
Examples include n-octyl, t-octyl, n-dodecyl, n-hexadecyl, n-octadecyl, isostearyl group, and eicosyl group.

The alkenyl group may be linear or branched and has 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, and examples thereof include allyl, butynyl, prenyl, octenyl, dodecenyl, and oleyl groups.

The cycloalkyl group is 3 to 12 members, preferably 5
to 7-membered, such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, or cyclododecyl group.The alkynyl group may be linear or branched and has 2 to 30 carbon atoms, preferably 2
-20, such as ethynyl group, propynyl group, butynyl group, indenyl group, etc.

Examples of the aryl group include a phenyl group and a naphthyl group.

Examples of the aralkyl group include benzyl group and phenethyl group.

Examples of the heterocyclic group include pyrrolyl group, furyl group, thienyl group, indolyl group, pyrazolyl group, isoxasilyl group,
isothiazolyl group, indenyl group, benzisoxasilyl group, benzisothiazolyl group, imidazolyl group, oxasilyl group, thiazolyl group, benzimidazolyl group,
Benzoxasilyl group, benzothiazolyl group, pyridyl group, quinolyl group, isoquinolyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, cinnolinyl group, phthalazinyl group, quinazolinyl group, quinoxalinyl group, propynyl group, purinyl group, triazolyl group, tetraazolyl group, Benzotriazolyl group, thiadiazolyl group, tetraazaindenyl group, triazaindenyl group, diazaindenyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group , isoindolinyl group, quinuclidinyl group, morpholinyl group, tetrahydrofuryl group, tetrahydrothienyl group, and the like.

L, , i, and z are preferably an alkyl group, an alkenyl group, or an aryl group, with an alkyl group being particularly preferred.

These LI and Lx may be further substituted with a substituent. Examples of substituents include hydroxyl group, ether group, halogen atom, amino group, substituted amino group, carbonyl group,
carboxyl group, acyloxy group, alkoxycarbonyl group, carbamoyl group, acylamino group, ureido group,
Thiocarbonyl group, thioamide group, thioureido group, sulfo group, sulfino group, sulfonylamine group, sulfamoyl group, sulfonyl group, sulfinyl group, sulfinylamino group, sulfamino group, sulzenamoyl group, sulfeno group, cyan group, mercapto group, thioether group , a selenoether group, an ammonium group, a phosphoric acid group, a phosphino group, a nitro group, a phenyl group, an alkenyl group, an alkynyl group, and a substituted alkyl group substituted with the above substituent, and a heterocyclic group preceded by , LI Examples include the heterocyclic groups listed above.

As the substituents for these LI and Lx, hydroxyl groups, alkoxy groups, carboxyl groups, amino groups, substituted amino groups, carboxyl groups, sulfo groups, thioether groups, and substituted alkyl groups substituted with these are preferable.

Next, specific examples of the compound of general formula (I[) preferably used in the present invention are shown below, but the invention is of course not limited to these.

n I HOCHtCHzTeCHzCHzOHI
I-2HO(Cllz) zTe(CHz) zOH
■-3[0(CJIt)sTecHzcHcHtOHH f-4 t-5 ■-10 ■-11 ■-12 ■-13 ■-14 ■-15 110C11zC)icHzTe-I,C61(I:1
HOCIlzCHzTeCllzCHzOCllxHO
CHzCtlzTeCHzCHzSCtlzHOCHz
CIlzTeCt! zCHzSCIlzCIIJllH
OCHzGHzTe(GHz)JHzHzN(CHz)
:+TeCIItCHJHCHzCIlzSCHi)1
0CthCHzTe(CHz) 3SChHII
1 ■JC (CHz) sTe (CHz) JIICCHz
112HsOZ(CHI)zTe(CHz) 3NHC
ONHCH3110 ((Jig) zTe(CHz)
xSOJllJ(CHz) zTe(Clh) JHC
ONIIClbHJ(CHz)iTe(CHz)JHC
NllCHHz - N n -28HOOCCHzCIItTeCHzCHzC
OOHC1+3 n 30 Na0sS(CHz)sTe(CTo)
ssOJaHOOCCM-CIItTeCHtCHCO
OHH If 21 HOC1bCH=CHCHzT8CH
zCHzCH=CHCHzOHII 22 HOC
HzCH-CITeCH=CIICHzOHn
-23HOCR1CI=CH-T13C)lzcHz
cHzsOJ(I26HOCIIzCLOCLC)Iz
TeCHtCllzOHI[38(CaH* b Te )I H Regarding the synthesis of the compound of general formula (II) used in the present invention, one of the common methods is the reaction of tellurium cyanion and the corresponding alkyl halide. be. As an example using this method, r Inorganic C
he+*1stsry J Vol. 18, pp. 2696-27
00 (I979), and the compounds used in the present invention can be easily synthesized according to this.

For more detailed synthesis methods, please refer to Japanese Patent Application No. 1734-1983.
No. 74, JP-A No. 53-57817, etc. may be referred to.

The compound of the general formula (I) of the present invention is used at least once during the precipitation of silver halide grains during emulsion production, during subsequent physical ripening, during chemical ripening, and immediately before coating.
It is preferable to add it in the process, especially after the chemical thermal formation.The amount to be added can be selected as desired, but it is 101 to 104 mol per mol of silver halide, preferably 10-h to 5 x 101 moles, more preferably 1
The amount is preferably from 0-s to 2×10-' moles, and corresponds to coverage of 10% or more and 100% or less of the surface of the silver halide grains.

In the present invention, the compound of general formula (It) is used in at least one step selected from the steps of producing a silver halide grain during emulsion production, during the subsequent physical ripening, during chemical ripening, and immediately before coating. It is preferably added, particularly during precipitate formation, physical ripening, or chemical ripening.

The amount added can be arbitrarily selected, but is 0.001 g to 30 g, preferably 0.003 g to 10 g per mole of silver halide.
g, more preferably 0.01 g to 3 g.

In addition, at the same time as the compound of general formula (II) of the present invention, the above-mentioned known thioether compounds, thiocyanates (for example, rhodankali, etc.), and Japanese Patent Publication No. 5B-51252, Japanese Patent Application Laid-Open No. 55-77737, U.S. Patent 4,221,8
It may be used in combination with the compounds described in No. 63, Japanese Patent Publication No. 60-11341, etc.

Furthermore, when the compound of the general formula (I[) of the present invention is used before chemical ripening (for example, during silver halide grain formation), a silver halide solvent may be used by the method described in JP-A-60-136736. It is also possible to deactivate the function.

In the present invention, as a method for forming silver halide grains, general methods well known in the art can be used, but a double dient method is particularly preferred.

The double jet method is a process in which an aqueous solution of silver nitrate and an aqueous solution of one or more halides (e.g. alkali metal halides such as potassium bromide) are simultaneously mixed into a protective colloid of silver halide (e.g. gelatin or gelatin) using two separate jets. derivative) into a stirring solution.

In the present invention, the photographic emulsion is P. gelafchides (P, G.
lafkides) Chimie et Physiqu Photography”/ri (Chimie et Physiqui
e Photographique), published by Paul Montel (1967), Photographic Emulsion Chemistry (Ph.
otographic Emulsion Chemi
stry), The 8 Focal Press (The Fo
Cal Press) (I966), V. L. Zerichman et al. (V.L.).

Zelik Suan et al) Making and
Coating Photographic Emulsion (M
making and coating photogr
aphic Emulsion, published by The Focal Press (1964), etc. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble root salt with the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. .

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

Further, although the grain size distribution of silver halide grains in the photographic emulsion is arbitrary, it is preferable that the grain size be monodisperse. Here, monodisperse means a dispersion system in which 95% of the particles fall within ±60%, preferably within 40%, of the number average particle size.

Here, the number average particle size is the number average diameter of the projected area diameter of halogenated root particles.

Two or more types of silver halide emulsions formed separately may be mixed and used.

In the present invention, any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver iodide, and silver chloride may be used as silver halide in the photographic emulsion.

The particle size distribution may be narrow or wide.

Silver halide grains in photographic emulsions are cubic, octahedral, 1
Regular objects such as tetrahedrons and rhombic dodecahedrons
), or may have irregular crystal shapes such as spherical or plate-like, or a composite of these crystal shapes.

It may also consist of a mixture of particles of various crystalline forms.

Further, a crystal having a high-order index plane may be used.

The silver halide grains may have different phases inside and on the surface, or may consist of a uniform phase.

Particles may have a double structure or a multilayer structure.

In addition, for example, a junction type silver halide crystal in which an oxide crystal such as PbO and a silver halide crystal such as silver chloride are combined, and a silver halide crystal grown epitaxially (for example, silver chloride on silver bromide, (Silver iodobromide, silver iodide, etc. are grown epitaxially.), or a crystal in which crystals such as an orthogonal crystal or a crystal in which a regular hexahedral silver chloride is oriented and overlapped with silver iodide may be used.

Further, tabular silver halide grains having an aspect ratio of 3 or more, preferably 5 to 20 can also be used. For more details, see U.S. Pat. Nos. 4,434,226 and 4,439,5.
No. 20, European Patent No. 84,637A, No. 5, Japanese Patent Publication No. 5
No. 9-99433, “Research Disclosure”
It is described in Volume 225, Nα22534 (January 1983), etc.

Also, Japanese Patent Application No. 63-7851, No. 63-7852,
Silver halide grains may be formed by the method described in No. 63-7853.

pHlPAg during silver halide grain formation in the present invention
There are no particular restrictions on conditions such as temperature, but the pH value is about 1 to about 10. In particular, it is preferably from 2 to 8, and preferably from 15 to about 11, particularly preferably from 7.8 to 10.5.

Silver halide grains can be formed at a temperature between about 30°C and about 90°C, particularly between 35°C and 80°C.
is preferred.

Of course, pH, PAg and temperature may be changed during silver halide grain formation.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present. Further, the amount of these additives may be small or large depending on the intended photosensitive material.

Conditions for the chemical ripening process in the present invention, e.g. p) (, P
There are no particular restrictions on AP, temperature, time, additives, etc., and it can be carried out under conditions commonly used in the industry.

For example, the pH value is 3.0 to 8.5, especially 5°0 to 7.
．． 5 is preferable, and the PAg value is 7°0 to 9.5,
In particular, 8.0 to 9.3 is preferable, and the temperature is 40 to 9.3.
85°C1, especially preferably 45-75°C, and the time is 5-2
00 minutes, especially 10 to 120 minutes is preferred.

In order to remove soluble salts from the emulsion after precipitation or physical ripening, the Tardel water washing method, which involves gelatinization of gelatin, may be used. A precipitation method (flocculation method) using gelatin derivatives (eg, acylated gelatin, carbamoylated gelatin, etc.) may also be used.

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, for example, H Freezer (
I1, Fr1rser) ed.
Die Grundlage 7 (DieGrundlage)
n der PhoLographischen Pr
ozesse muSilberhalogenide
n)” (Akademinsche Verlags) Akad
emische Verlagseellschaft
.

The method described on pages 675-734 (published in 1968) can be used.

That is, a sulfur sensitization method using a compound containing sulfur that can react with silver ions or activated gelatin, a selenium enhancement method (for example, dimethylselenourea), a reduction sensitization method using a reducing substance, and a gold or other noble metal compound. Noble metal aggravation methods and the like can be used alone or in combination. Sulfur exacerbants include thiosulfates (e.g. sodium thiosulfate)
, Thiourea 1! (eg, triethylthiourea, acetylthiourea, diphenylthiourea), thiazoles, rhodanines (eg, 5-benzylidene-3ethyl-rhodanine), and other compounds that release unstable sulfur can be used.

Examples of reduction sensitizers include stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, borane compounds,
A silane compound or the like can be used. For noble metal sensitization, in addition to total complex salts such as chloroauric acid and dithiocyanate gold salt (however, primary gold cyanide is not preferred), metals of group II of the periodic system such as platinum, iridium, and palladium are used. A complex salt of can be used.

In particular, an aggravation method using a noble metal such as a gold compound and a sensitization method using a sulfur compound can be preferably used.

In addition, for the purpose of increasing sensitivity, increasing contrast, or accelerating development, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds,
Urethane derivative, urea reader, imidazole derivative, 3
- May contain pyrazolidones and the like. For example, US patent 2
．． 400.532, 2,423,549, 2゜716.062, 3,617,280, 3.7
Those described in No. 72,0.21, No. 3,808,003, etc. can be used.

In addition, various compounds can be contained for the purpose of preventing fogging or stabilizing photographic performance during the manufacturing process, storage, or photographic processing of the photographic material. That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole)
mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinthione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-6-methyl (I3,3a,7)tetrazain); Many compounds known as antifoggants or stabilizers can be added, such as benzenesulfinic acid, benzenesulfonic acid amide, benzenethiosulfonic acid, etc.;

Binders or protective colloids used in photosensitive materials include:
It is advantageous to use gelatin, but other hydrophilic synthetic polymers can also be used. As the gelatin, lime-treated gelatin, acid-treated gelatin, derivative gelatin, etc. can also be used.

In addition, the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (
For example, various known surfactants may be included for various purposes such as development acceleration, contrast enhancement, and sensitization.

The photographic emulsion of the present invention may be further spectrally sensitized with methine dyes in addition to the dye represented by formula (I). The dyes used include cyanine dyes,
Included are merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes.

Particularly useful pigments are those belonging to the merocyanine pigments and complex merocyanine pigments. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, virol nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of Imidazole nuclei, quinoline nuclei, etc. can be applied. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or complex merocyanine dyes include a core with a ketomethylene structure, such as a birapurin-5-one core, a thiohydantoin core, and a 2-thioxazolidine-2 core.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbic acid nucleus, and the like can be applied.

The photographic emulsion of the present invention may also contain a dye-forming coupler, that is, a compound (hereinafter abbreviated as coupler) that reacts with the oxidation product of an aromatic amine (usually a primary amine) developing agent to form a dye. The coupler is preferably a non-diffusible coupler having a hydrophobic group called a ballast group in its molecule. The coupler may be either 4-equivalent or 2-equivalent to silver ion. It may also contain a colored coupler that has a color correction effect or a coupler that releases a development inhibitor upon development (so-called DIR coupler).The coupler may be a coupler in which the product of the campling reaction is colorless.

As the yellow coloring coupler, a known open-chain ketomethylene coupler can be used. Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous.

As the magenta coupler, pyrazolone compounds, indacylon compounds, cyanoacetyl compounds, etc. can be used, and pyrazolone compounds are particularly advantageous.

As the cyan coupler, phenolic compounds, naphthol compounds, etc. can be used.

In addition to the DIR coupler, the light-sensitive material may contain a compound that releases a development inhibitor upon development; for example, U.S. Pat. Nos. 3,297,445 and 3,379,529
No. 111 (OLS) No. 2.417,914 can be used.

Two or more of the above couplers can be contained in the same layer.

The same compound may be contained in two or more different layers.

To introduce the coupler into the silver halide emulsion layer, known methods such as those described in US Pat. No. 2,322,027 can be used.

The emulsion used in the present invention is usually one that has been subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are listed in Research Disclosure No. 17.
6, Na17643 (December 1978) and Volume 187, Na1B716 (November 1979), and the relevant parts are summarized in the table below.

Known photographic additives that can be used in combination with the present invention are also listed in the above two Research Disclosures, and the locations listed are shown in the table below.

Additive type Chemical enhancer Sensitivity enhancer Spectral sensitizer Super sensitizer Brightener 7 Coupler 8 Organic solvent Ultraviolet absorber Stain inhibitor Dye Image stabilizer Hardener Binder Plasticizer, lubricant Static inhibitor RD17643 23 Pages 23-24 RD18716 Page 648 Right column Same as above Page 648 Right column - Page 649 Right column Page 24 Page 25 Page 25 Page 25 Right column Page 650 Left - Right column Page 25 Page 26 Page 26 Page 27 Page 651 Page Left column Same as above 650 Page right column, page 27 Same as above The silver halide emulsion of the present invention can be used in black and white silver halide photographic materials (e.g., X-ray photosensitive materials, squirrel type materials, negative films for black and white photography, etc.) and color photographic materials (e.g., It can be used for color negative film, color reversal film, color paper, etc.). Furthermore, photosensitive materials for diffusion transfer (e.g., color diffusion transfer elements, silver salt diffusion transfer elements)
It can also be used in heat-developable photosensitive materials (black and white, color), etc.

The photo tag of the present invention can be produced by dip coating, roller coating, curtain coating, or extrusion on a flexible support such as plastic film or paper, or a rigid support such as glass, which is commonly used in photosensitive materials. It is applied using a coating method. Useful as flexible supports are films of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or alpha-olefin polymers. (For example, paper coated with or laminated with polyethylene, polypropylene, ethylene/butene copolymer), etc.

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 chosen between 18°C and 50°C, but
The temperature may be lower than 50°C or above 50°C. 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 dye image can be applied.

For details, see “Research Disclosure” No. 176.
The development process can be carried out by the method described in the left column and right column of page 651 of Volume 18716, Vol.

The present application will be further explained below with reference to Examples.

Example 1 Aqueous solution containing gelatin and potassium bromide at 75°C
While maintaining the temperature and stirring vigorously, a silver nitrate aqueous solution and a mixed water i8 of potassium bromide and potassium iodide were simultaneously added to obtain a solution containing 2 mol% silver iodide and an average particle size of 0.8.
A monodispersed 14-hedral silver iodobromide emulsion of 0 μm was prepared.

After removing unnecessary salts from this emulsion using the flocculene con method, it was divided into 17 parts with a pH of 6.3 and a PAg of 8.4, and I-6 or a comparative compound was added to each part, followed by triethylthiourea. , chloroauric acid and potassium thiocyanate were added, and then the compound of general formula (II) shown in Table 1 was added, and 1/1
Chemical ripening was carried out at 60°C so as to exhibit optimum sensitivity at 00 seconds exposure.

The following stabilizers, antifoggants, hardeners, and coating aids were added to the emulsion thus obtained, and the mixture was coated with a gelatin surface protective layer on a polyethylene terephthalate film support by a coextrusion method and dried. I got 17.

Stabilizer; 4-hydroxy-6-methyl-1,33a,7
-Titrazaindene antifoggant; 1-phenyl-5-mercaptotetrazole hardener; 2,4-dichloro-6-hydroxy 1.3.5
-1 Sodium riazine salt coating aid; Sodium dodecylbenzenesulfonate The obtained sample was passed through an optical wedge using a sensitometer and a 419 nm interference filter (for sensitivity measurement in the intrinsic range (intrinsic sensitivity range)) or Exposure through Fuji Film Co., Ltd.'s 5C-50 filter (for sensitivity measurement in the spectral range (spectral sensitization range) to 1/100 seconds), RD-I [+
The film was developed with a developer (manufactured by Fuji Photo Film ■) at 35°C for 20 seconds, fixed in a conventional manner, washed with water, and dried, and the photographic sensitivity was measured. Photographic sensitivity is expressed as a relative value of the reciprocal of the exposure amount required to obtain an optical density of fog value + 0.2, and the sensitivity in the intrinsic range is that of sample 1 as 100, and the sensitivity in the spectral range is that of sample 3.
was set as 100.

As is clear from Table 1, the compound (I-6) of the present invention is a good spectral sensitizing dye, but when used in a large amount, the inherent sensitivity decreases, and the spectral sensitivity reaches a plateau at a certain amount added. . However, when compound (II) of the present invention was used in combination, the intrinsic sensitivity was restored, and a remarkable combination effect was observed in which the spectral sensitivity increased more than the restoration.

On the other hand, the dye used in JP-A No. 53-57817 (comparative compound) originally has a small decrease in intrinsic sensitivity, but its spectral sensitivity is significantly lower than that of the general formula (I) of the present invention. Even if the compound of the general formula (II) of the invention is used in combination, the spectral sensitivity can only be increased by the same amount as the increase in the intrinsic sensitivity.

Example 2 Same as Example 1, except that the general formula (
Regarding the intrinsic sensitivity and spectral sensitivity when using only compound I), compound ■-1 (addition amount 0°12g 1 mol Ag
) was further expressed as the relative ratio of the intrinsic sensitivity and spectral sensitivity (sensitization ratio).

Sensitization ratio of intrinsic sensitivity = Sensitization ratio of spectral sensitivity = As is clear from Table 2, when the compound of general formula (■) of the present invention is used in combination with the compound of general formula (■), the increase rate of intrinsic sensitivity is It is clear that the spectral sensitivity increases as described above.

Example 3 When forming particles for the core part, 3,6-cythia-18-octanediol was used, then hydrogen peroxide was added, and then a silver nitrate aqueous solution for the shell part and a mixed aqueous solution of potassium bromide and potassium iodide were added. Added by jet method, it has an internal high iodine double structure with an average iodine content of 8 mol%, a core-shell ratio of 1:3, an equivalent sphere diameter of 0.7 μm, and a diameter/thickness ratio of 5.0. A silver iodobromide emulsion consisting of plate-shaped twin crystal grains was prepared, and chloroauric acid, sodium thiosulfate, and sodium thiosulfate were added thereto, and the emulsion was heated at 60°C for 45 minutes to perform total sulfur sensitization.

The obtained emulsion was divided into four parts, and the spectral sensitizing dye of the present invention (I
-311-20, 1-22) were added in mols of 1X10-' and 3X1O-'1X10-' per 1 mole of halogenated i, respectively, and then the compounds shown in Table 3 were added. Furthermore, coupler dispersions (Cp-1, Cp2, Cp-3, Cp-4,
0il-LOil-2), anti-capri agent (I-(m-sulfophenyl-5-mercaptotetrazole mono
Na salt), stabilizer (4-hydroxy-6-methyl-1°3.3a, 7-chitrazaindene), hardener (H-1)
, and coating aids (sodium p-dodecylbenzenesulfonate and sodium p-nonylphenoxypoly(ethyleneoxy)propanesulfonate) were added, and the mixture was coated on a cellulose or triacetate film support along with a gelatin surface protective layer, and dried. Samples 27 to 30 were obtained.

The sample was exposed to light at 1/100 through a 419 nm interference filter (for measuring intrinsic sensitivity) or a 5C-52 filter (for measuring spectral sensitivity) made by Fuji Film ■.
Sec.) After carrying out the following color development treatment, photographic properties were measured and the results shown in Table 3 were obtained.

Note that the intrinsic sensitivity and spectral sensitivity in Table 3 are based on Example 1.
Similarly, each sample 27 was set as 100, and the others were expressed relatively.

1. Color development 2 minutes 45 seconds (38°C) 2. Bleaching 6 minutes 30 seconds 3. Washing 3 minutes 15 seconds 4. Fixing 6 minutes 30 seconds 5. Washing 3 minutes 15 seconds 6. Stability 3. The processing eMi composition used in each step is as follows.

(Color development fi) Sodium nitrilotriacetate 1.0g Sodium sulfite 4.0g Sodium carbonate 30.0g Potassium bromide
1.4g hydroxylamine sulfate 2,4g 4-(N-ethyl-N-β hydroxyethylamino) 2-methyl-aniline sulfate 4.5g Add water 1! (Bleach solution) Ammonium bromide 160.0g Aqueous ammonia (28%) 25.0m Sodium iron salt of ethylenediamine-tetraacetic acid 130.0g Add glacial acetic acid water (Fixer) Sodium tetrapolyphosphate Sodium sulfite Ammonium thiosulfate ( 70χ) Add sodium bisulfite water (stable solution) Add Polmarine water and P-1 0■ 14゜〇- 8,0g ■! ! .

p-2 p-3 H (t)CsH++ p As is clear from Table 3, the combined use of compound (I) and compound (II) of the present invention can significantly increase the sensitivity in the spectral range. Ta.

(Oil-1) (Of tricresyl phosphate dibutyl phthalate (H

Claims (1)

[Scope of Claims] A silver halide photographic material containing at least one compound represented by the following general formula (I) and at least one compound represented by the general formula (II). . General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula (II) L_1-Te-L_2 In the formula, Z_1 and Z_2 may be different or the same,
Represents a group of atoms forming a 5- or 6-membered nitrogen-containing heterocycle. R_1 and R_2 may be different or the same and represent an alkyl group or alkenyl group having 10 or less carbon atoms. R_3 and R_7 represent hydrogen atoms, and R_2 and R_
1, R_7 and R_2 may be connected to form a 5- or 6-membered ring. R_4, R_5 and R_6 may be different or the same and represent a hydrogen atom, a lower alkyl group, an aryl group or a ketomethylene residue. Furthermore, R_4 and R_6 may be connected to form a 5- or 6-membered ring. X represents an acid anion residue. j and k are 0 or 1, l is 0, 1 or 2, m is 0
Or represents 1. L_1 and L_2 may be different or the same and represent an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, an aralkyl group, or a heterocyclic group.