JPH0353619B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a light-sensitive silver halide photographic emulsion,
More specifically, the present invention relates to a method for sensitizing a silver halide emulsion containing silver halide grains mainly composed of silver bromide, and a silver halide photographic emulsion sensitized by the method. In recent years, there has been a demand for silver halide photographic emulsions with increasingly high sensitivity from a variety of perspectives, and in order to develop new sensitization technologies, multifaceted technical fields such as emulsion grain production, chemical sensitization, spectral sensitization, and development are being developed. approach is being taken. In the field of emulsion grain manufacturing technology, traditionally,
(111) Octahedral, dodecahedral, or plate-like crystal grains with faces are usually manufactured under conditions of low silver concentration, so there are few silver nuclei that can become latent image nuclei or fogging nuclei unique to silver halide grains. It is known to have the following advantages. However, in the field of chemical sensitization technology, chemical sensitization reactions are highly crystal habit dependent; for example, in the usual method, more sulfur sensitizing nuclei are formed on the (111) plane than on the (100) plane. Therefore, it is known that latent image formation becomes dispersive and inefficient, and therefore sensitization efficiency is poor, making it disadvantageous to put silver halide grains with the above-mentioned (111) plane into practical use. or has been considered difficult. By the way, hydroxyazaindene compounds have been well known in the industry as stabilizers for photographic emulsions because they have the property of inhibiting chemical ripening caused by sulfur-containing compounds, and they are used to terminate sulfur sensitization reactions. purpose and/or manufacturing process;
It is added to prevent fogging during storage or development. however,
This compound is also known to have the effect of increasing photographic sensitivity. For example, British Patent No. 1315755 describes a method of sensitizing a silver halide emulsion (sulfur + gold) by adding azaindene before sulfur sensitization, and adding a monovalent gold complex compound containing sulfur at the same time or afterwards. It is stated that additional ripening increases the inherent sensitivity of silver halide compared to conventional methods. Furthermore, Japanese Patent Application Laid-Open No. 50-63914 and German Patent Application (OLS) No. 2419798 disclose that after sulfur sensitization of a monodisperse silver halide grain emulsion of cubic grains with a silver bromide content molar ratio of 80% or more, , it is described that the sensitivity increases when a hydroxytetrazaindene compound is included. However, this publication does not contain crystal forms other than cubic, for example, substantially (111)
It is also noted that for octahedral grains and plate-like grains that have a grain shape surrounded by planes, the sensitivity decreases or increases, but only to a small extent.
Furthermore, JP-A-51-77223 states that in a silver halide photographic emulsion subjected to sulfur sensitization, when the average grain size of silver halide grains does not exceed 0.5 μm, certain hydroxyl It is described that sensitivity increases when a tetrazaindene compound is included. However, in the industry, it has been common sense to add a hydroxytetrazaindene compound as a stabilizer after chemical ripening, regardless of whether it has a sensitizing effect or whether it is recognized as such. The methods described in JP-A-50-63914 and JP-A-51-77223 cannot be expected as new sensitization methods. By the way, as a result of repeated research on sensitizing silver halide grains by effectively imparting photosensitive nuclei to the (111) plane, the present inventors have found that hydroxyazaindene is present in an amount that is more than enough to almost completely cover the grain surface. It has been found that when a sulfur sensitizer and a gold sensitizer are added and ripened after adding , the sensitization is markedly sensitized. Moreover, the gold sensitizer does not have to be a monovalent gold complex compound containing sulfur, and the sensitizing effect is significantly greater when sulfur sensitization is combined with total sensitization, and furthermore, the higher the exposure is at high illuminance and short time. I found out. This fact is surprising and unknown until now. Therefore, an object of the present invention is, firstly, to provide a method for significantly sensitizing silver halide having a (111) plane with almost no fogging;
The second object is to provide a highly sensitive silver halide photographic emulsion obtained by such a chemical sensitization method. Further objects and features of the invention will be apparent from the following description. The object of the present invention is to prepare a silver halide emulsion consisting essentially of silver halide grains of octahedral or dodecahedral crystals having (111) faces on a support in the presence of an azaindene compound that forms a complex with silver. A silver halide photographic light-sensitive material comprising at least one light-sensitive silver halide emulsion layer containing a silver halide emulsion which has been subjected to sulfur sensitization or selenium sensitization and gold sensitization, and the above-mentioned halogen This is achieved by a method for producing a silver halide emulsion, which comprises subjecting the silver halide emulsion to the sensitization treatment described above. The present invention will be specifically explained below. The silver halide composition of the octahedral or dodecahedral crystal silver halide grains of the present invention is not particularly limited, but it is preferably composed mainly of silver bromide, containing 50 mol% or more of silver bromide, and containing 50 mol% or more of silver bromide. More preferably, the content ratio of silver oxide is 10 mol% or less,
More preferred are those containing 90 mol% or more of silver bromide. The morphology of the silver halide grains is substantially an octahedron formed by (111) planes, or a dodecahedron formed by (111) planes and (100) planes.
Their particle size is not limited. Although the ratio of the (111) plane to the (100) plane on the surface of the dodecahedral silver halide grains used in the present invention is not limited to a specific one, the larger the ratio of the (111) plane, the The sensitization effect by the method of the present invention is increased. Furthermore, in the emulsion of the present invention, the greater the proportion of the silver halide grains of the present invention among the silver halide grains contained in the emulsion, the greater the effect of the present invention. Emulsions consisting essentially of grains are preferred. The silver halide grains may have compositionally different phases inside and on the surface, or may consist of a uniform phase. The silver halide emulsion of the present invention is described in Chimie et Phyeique Photography by P. Glafkides.
Photographique) (Paul Montel, 1967)
Photographic Emulsion Chemistry (The
Making and Coating Photographic Emulsion (Focal Prese, 1966) Co-authored by VL Zeelikman et al.
Emulsion) (The Focal Press, 1964).
That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any of the injection mixing method, simultaneous mixing method, a combination thereof, etc. good. As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called controlled double jet method can also be used. Examples of the azaindene compound used in the present invention include a diazaindene ring, a triazaindene ring, a tetrazaindene ring, and a pentazaindene ring. More preferred are azaindene compounds having a hydroxy group as a substituent on the azaindene ring, such as hydroxytriazaindene, tetrahydroxyazaindene, hydroxypentaazaindene compounds, and the like. The azaindene ring may have a substituent other than a hydroxy group. Examples of substituents include alkyl groups, substituted alkyl groups, alkylthio groups, amino groups, hydroxyamino groups, alkylamino groups,
It may have a dialkylamino group, an arylamino group, a carboxy group, an alkoxycarbonyl group, a halogen atom, a cyano group, etc. Specific examples are listed below, but the invention is not limited to these. (1) 2,4-dihydroxy-6-methyl-1,
3a,7-triazaindene (2) 2,5-dimethyl-7-hydroxy-1,
4,7a,-triazaindene (3) 5-amino-7-hydroxy-2-methyl-
1,4,7a-triazaindene (4) 4-hydroxy-6-methyl-1,3,3a
-7-tetrazaindene (5) 4-hydroxy-1,3,3a,7-tetrazaindene (6) 4-hydroxy-6-phenyl-1,3,
3a,7-tetrazaindene (7) 4-methyl-6-hydroxy-1,3,3a,
7-tetrazaindene (8) 2,6-dimethyl-4-hydroxy-1,
3,3a,7-tetrazaindene (9) 4-hydroxy-5-ethyl-6-methyl-
1,3,3a,7-tetrazaindene (10) 2,6-dimethyl-4-hydroxy-5-ethyl-1,3,3a,7-tetrazaindene (11) 4-hydroxy-5,6- dimethyl-1,
3,3a,7-tetrazaindene (12) 2,5,6-trimethyl-4-hydroxy-
1,3,3a,7-tetrazaindene (13) 2-methyl-4-hydroxy-6-phenyl-1,3,3a,7-tetrazaindene (14) 4-hydroxy-6-methyl-1, 2,
3a,7-tetraazaindene (15) 4-hydroxy-6-ethyl-1,2,
3a,7-tetraazaindene (16) 4-hydroxy-6-phenyl-1,2,
3a,7-tetraazaindene (17) 4-hydroxy-1,2,3a,7-tetraazaindene (18) 4-methyl-6-hydroxy-1,2,3a
-7-tetraazaindene (19) 7-hydroxy-5-methyl-1,2,
3,4,6-pentazaindene (20) 5-hydroxy-7-methyl-1,2,
3,4,6-pentazaindene (21) 5,7-dihydroxy-1,2,3,4,
6-pentazaindene (22) 7-hydroxy-5-methyl-2-phenyl-1,2,3,4,6-pentazaindene (23) 5-dimethylamino-7-hydroxy-2
-Phenyl-1,2,3,4,6-pentazaindene The amount of the azaindene ring compound added varies over a wide range depending on the emulsion grain size, composition, aging conditions, etc., but preferably halogen It is preferable that the amount added be sufficient to form a monomolecular layer to 10 molecular layers on the surface of the silver oxide grains. The amount added can also be adjusted by controlling the adsorption equilibrium state by changing the pH and/or temperature during ripening. Further, two or more of the above compounds may be added to the emulsion in such a way that the total amount falls within the above range. The compound can be added to the emulsion by dissolving it in a suitable solvent (for example, water or aqueous alkaline solution) that does not have a harmful effect on the photographic emulsion, and then adding it as a solution. The timing of addition is preferably before or at the same time as adding the sulfur sensitizer or selenium sensitizer for chemical ripening. The gold sensitizer may be added during or at the end of ripening for sulfur or selenium sensitization. In the present invention, known sulfur sensitizers can be used. Examples include thiosulfate, allylthiocarbamide thiourea, allyl isothiacyanate, cystine, p-toluenethiosulfonate, and rhodanine. Other U.S. Patents No. 1574944, U.S. Patent No. 2410689, U.S. Patent No. 2278947
No. 2728668, No. 3501313, No.
Sulfur sensitizers described in each specification of No. 3656955, German Patent No. 1422869, Japanese Patent No. 56-24937, Japanese Patent Application Laid-Open No. 55-45016, etc. can also be used.
The amount of sulfur sensitizer added may be sufficient to effectively increase the sensitivity of the emulsion. This amount varies over a considerable range under various conditions such as the amount of hydroxyazaindene added, pH, temperature, and the size of silver halide grains, but as a guide, it should be approximately 1 mole of silver halide. The amount is preferably about 10 ^-7 mol to about 10 ^-1 mol. In the present invention, selenium sensitization can be used instead of sulfur sensitization, and the selenium sensitizers include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, selenamides, Selenocarboxylic acids and esters, selenophosphates, and selenides such as diethylselenide and diethyl diselenide can be used, and specific examples thereof include U.S. Pat. No.
It is described in the specification of No. 1623499. The amount added varies over a wide range as with the sulfur sensitizer, but as a guide, it is preferably about 10 ^-7 mol to 10 ^-3 mol per mol of silver halide. In the present invention, various gold compounds are used as the gold sensitizer, and the oxidation number of gold may be +1 or +3. Typical examples include chlorauric acid salts, potassium chloroaurate, oleic trichloride, potassium oleic thiocyanate, potassium iodooleate, tetracyano oleic acid, ammonium aurothiocyanate, pyridyl trichlorogold, and the like. The amount of gold sensitizer added varies depending on various conditions, but as a rough guide, it is preferably in the range of about 10 ^-7 mol to 10 ^-1 mol per mol of silver halide. When gold sensitization is used in combination with sulfur sensitization or selenium sensitization, gold nuclei, silver sulfide gold nuclei, or silver selenide nuclei are produced as photosensitive nuclei, but their numbers and especially silver sulfide gold nuclei or selenium The composition of the silver-gold core is greatly influenced by electron trapping properties or developability. Therefore, the ratio of gold sensitizer to sulfur sensitizer or selenium sensitizer greatly affects the sensitizing effect, so it is necessary to determine the amount sufficient to effectively increase the sensitivity of the emulsion depending on the ripening conditions. good. The addition ratio of the sulfur sensitizer or selenium sensitizer to the gold sensitizer depends on the number of sulfur atoms that produce silver sulfide in the sulfur sensitizer or the number of selenium atoms that produce silver selenide in the selenium sensitizer. On the other hand, the number of gold atoms is 1/2
It is preferable to set it to ~1/200. For example, when using sodium thiosulfate as a sulfur sensitizer and sodium chloroaurate as a gold sensitizer, it is recommended to add the latter in a range of about 1/2 to 1/200 (molar ratio) to the former. preferable. The gold sensitizer may be added at the same time as the sulfur or selenium sensitizer, or during or after the sulfur or selenium sensitization step. The pAg of the emulsion subjected to sulfur sensitization, selenium sensitization, and gold sensitization in the present invention is 7.5 to 10.0, and the pH is 5.0 to 5.0.
A range of 9.0 is preferred. The sensitization method of the present invention includes other noble metals, such as platinum,
A sensitization method using metals such as palladium, iridium, and rhodium or their salts can also be used in combination. In the present invention, it is also possible to further use reduction sensitization. The reducing agent is not particularly limited, but includes known stannous chloride, thiourea dioxide, hydrazine derivatives, and silane compounds. It is preferable to perform reduction sensitization during the growth of silver halide grains or after completion of sulfur sensitization and gold sensitization. The sensitization method of the present invention can also be used as a significant spectral sensitization method by using a sensitizing dye. The sensitizing dye used in the silver halide emulsion produced by the production method of the present invention is one that extends the sensitive region of silver halide to an electromagnetic liquid to the wavelength range of its inherent sensitivity. Specifically, the sensitizing dyes useful in the present invention include cyanine-based, merocyanine-based, hemicyanine-based, oxonol-based, hemioxonol-based, and complex merocyanine-based dyes, which are described, for example, in "The Cyanine Dyes" by FM Hamer.・
And Related Compounds” (The
Cyanine Dye and Related Compounds and C.
“The Theory of the Photographic Process Focus Edition” by THJames
Process Forth Edition) pages 194-234, etc. More specifically, preferable sensitizing dyes used in the present invention include compounds represented by the following general formulas [] to [X]. [In the formula, R ₁₂ , R ₁₃ and R ₁₄ are each an alkyl group (e.g. methyl group, ethyl group, propyl group, pentyl group, etc.), a substituted alkyl group (e.g. chloroethyl group, hydroxyethyl group, methoxyethyl group, acetoxyethyl group, Carboxymethyl group, carboxyethyl group, ethoxycarbonylmethyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, β-hydroxy-γ-sulfopropyl group, sulfatepropyl group, allyl group, benzyl group,
phenethyl group, etc.), an aryl group (e.g. phenyl group), or a substituted aryl group (e.g. carboxyphenyl group, sulfophenyl group, etc.), and L ₁ , L ₂ and L ₃ each represent a methine group or a substituted methine group. groups (e.g. -CH= group, -C
(CH ₃ ) = group, -C (C ₂ H ₅ ) = group, -C (CH ₂ COOH)
= group, -C(

[Formula]) = group, -C(C ₆ H ₅ ) = group, -C(C ₆ H ₄ COOH) = group, etc.), Z ₁ ,
Z ₂ and Z ₃ each represent a substituted or unsubstituted 5- or 6-membered heterocyclic nucleus, such as a thiazoline nucleus (e.g., thiazoline, 4-methylthiazoline, 4-phenylthiazoline, etc.), or an oxazoline nucleus (e.g., oxazoline, 4-methyloxazoline). etc.), selenazoline nucleus (selenazoline, 4-methylselenazoline, etc.), thiazole nucleus (e.g. thiazole, 4-methylselenazoline, etc.),
-Methylthiazole, 4-phenylthiazole,
5-methylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, etc.), selenazole nucleus (e.g. selenazole, 4-methylselenazole, etc.), oxazole nucleus (e.g. oxazole, 4-methyloxazole, 4,5 -dimethyloxazole, 5-ethyloxazole, 5
-phenyloxazole, etc.), benzothiazole nuclei (e.g. benzothiazole, 4-chlorobenzothiazole, 5-methylbenzothiazole, 6-
Methoxybenzothiazole, 5,6-dimethoxybenzothiazole, 5-hydroxybenzothiazole, 5-carboxyethylbenzothiazole,
6-sulfobenzothiazole, etc.), benzoxazole nuclei (e.g. benzoxazole, 5-chlorobenzoxazole, 6-methylbenzoxazole, 5-hydroxybenzoxazole,
4,5-dimethylbenzoxazole, etc.), benzoselenazole core (e.g. benzoselenazole,
5-chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, tetrahydrobenzoselenazole, etc.),
benzimidazole core (e.g. benzimidazole, 3-ethylbenzimidazole, 1-phenyl-5,6-dichlorobenzimidazole, etc.),
Indolenine nucleus (e.g. 3,3-dimethylindolenine, 3,3-diethylindolenine, 3,
3,7-trimethylindolenine, etc.), naphthothiazole nuclei (e.g. naphtho[2,1-d]thiazole, naphtho[1,2-d]thiazole, 5-methoxynaphtho[2,3-d]thiazole, etc.), Naphthoxazole nucleus (e.g. naphtho[2,1-
d]oxazole, naphtho[1,2-d]oxazole, etc.), naphthoselenazole core (e.g. naphtho[2,1-d]selenazole, naphtho[1,2
-d] selenazole etc.), thienothiazole nucleus,
Pyridine core (e.g. 2-pyridine, 5-methyl-
2-pyridine, 4-pyridine, 3-methyl-4-
pyridine, etc.), quinoline nucleus (e.g. 2-quinoline,
3-Methyl-2-quinoline, 6-chloro-2-quinoline, 8-hydroxy-2-quinoline, 4-quinoline, 6-methoxy-4-quinoline, 1-iso-
quinoline, 3,4-dihydro-1-isoquinoline, 3-isoquinoline, etc.), P and Q represent a cyano group, COOR ₁₅ group, COR ₁₅ group, SO ₂ R, respectively. ₁₅ groups (R ₁₅ is an alkyl group) Q and Q ₁ are each substituted or unsubstituted thioxazolone ring, pyrazolone ring, oxindole ring, parbitur ring, 2
-thioparbituric acid, 2,4-oxazolidinedione, 2,4-thiazolidinedione, 2,4-
imidazolidinedione, 2-thio-2,4-oxazolidinedione, 2-thio-2,4-thiazolidinedione, 2-thio-2,4-selenazolidinedione, 2-thio-2,5-thiazolidinedione, Represents an atomic group necessary to form a 2-thiohydantoin ring, 4-oxazolinone ring, 4-thiazolinone ring, or 4-imidazolinone ring, and Y represents a hydrogen atom, an amino group, an alkylamino group, (e.g. ethylamino group, etc.) ), dialkylamino group (e.g. dimethylamino group, etc.), halogen atom (Cl, Br),
Represents a group selected from an alkoxy group (e.g. ethoxy group etc.) and an alkyl group (e.g. methyl group etc.), m ¹ and m ² represent 0 or 1, n ¹
and n ² represents 0 or 2, and X is an acid anion group (e.g. Cl, Br, I, ClOCl,

[Formula] CH ₃ SO ₄ , C ₂ H ₅ SO _4, etc.), and l represents 1 or 2. However, when the compound forms an inner salt, l represents 1. ] Representative specific examples of the sensitizing dye represented by the above general formula according to the present invention are shown below, but the compounds that can be used in the present invention are not limited to these. In order to add these sensitizing dyes to the silver halide emulsion according to the present invention, they may be added after being dissolved in water or an organic solvent miscible with water such as methanol or ethanol. Alternatively, two or more types may be used in combination. In the present invention, the spectral sensitizer is preferably added before the addition of the hydroxyazaindene compound, but it may be added afterwards. Further, it is preferable to adjust the amount of the azaindene compound added depending on the area covered by the particle surface of the spectral sensitizer. Silver halide photographic emulsions sensitized by the method of the present invention may be used at the end of chemical ripening in order to prevent the occurrence of fog during the manufacturing process, storage or development process, or to stabilize photographic performance. A hydroxyazaindene compound may be added, and various other compounds may be included. For example, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzimidazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles. mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines, mercaptotriazines, thioketo compounds such as oxazolithione, and also benzenethiosulfinic acid, benzenesulfinic acid, benzenesulfinic acid, etc. Many compounds known as antifoggants or stabilizers can be added, such as fonic acid amides, hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives, ascorbic acid derivatives, and the like. These agents are preferably added during chemical ripening or before coating. Various hydrophilic colloids including gelatin are used as the binder for the silver halide photographic emulsion of the present invention. Gelatin includes not only gelatin but also derivative gelatin, and derivative gelatin includes a reaction product of gelatin acid anhydride, a reaction product of gelatin and isocyanate, or a reaction product of gelatin and a compound having an active halogen atom. Things, etc. are included. Examples of acid anhydrides used in the reaction with gelatin include maleic anhydride, phthalic anhydride, benzoic anhydride, acetic anhydride, isatoic anhydride, and succinic anhydride, and examples of isocyanate compounds include phthalic anhydride, succinic anhydride, and the like. Enyl isocyanate, p-bromophenyl isocyanate, p-chlorophenyl isocyanate, p-tolyl isocyanate, p-nitrophenyl isocyanate, naphthylisocyanate, and the like. Furthermore, examples of compounds having active halogen atoms include benzenesulfonyl chloride, p-
Methoxybenzenesulfonyl chloride, p-phenoxybenzenesulfonyl chloride, p-bromobenzenesulfonyl chloride, p-toluenesulfonyl chloride, m-nitrobenzenesulfonyl chloride, m-sulfobenzoyl dichloride, naphthalene-β-sulfonyl chloride, p-chlorobenzenesulfonyl chloride,
3-nitro-4-aminobenzenesulfonyl chloride, 2-carboxy-4-bromobenzenesulfonyl chloride, m-carboxybenzenesulfonyl chloride, 2-amino-5-methylbenzenesulfonyl chloride, phthalyl chloride, p-nitrobenzoyl chloride, Included are benzoyl chloride, ethyl chlorocarbonate, furoyl chloride and the like. In addition to the above-mentioned derivative gelatin and ordinary photographic gelatin, as hydrophilic colloids for preparing silver halide photographic emulsions, colloidal albumin, agar, gum albia, dextran, alginic acid, such as acetyl content 19 ~
Cellulose derivatives such as cellulose acetate hydrolyzed to 26%, polyacrylamide,
Imidized polyacrylamide, casein, vinyl alcohol polymers containing urethane carboxylic acid groups or cyanoacetyl groups, such as vinyl alcohol-vinyl cyanoacetate copolymers, polyvinyl alcohol-polyvinylpyrrolidone, hydrolyzed polyvinyl acetate, proteins or saturated acylated proteins and vinyl Polyvinylpyridine, a polymer obtained by polymerization with a monomer having groups,
Polyvinylamine, polyaminoethyl methacrylate, polyethyleneimine, etc. can also be used. The silver halide photographic emulsion of the present invention may contain various known agents for various purposes such as coating aids, antistatic properties, improving slipperiness, emulsification and dispersion, preventing adhesion, and improving photographic properties (for example, accelerating development, increasing contrast, and sensitizing). The surfactant may also be included. Namely, U.S. Patent No. 2240472, U.S. Patent No. 2831766
No. 3158484, No. 3210191, No. 3210191, No. 3158484, No. 3210191, No.
No. 3294540, No. 3507660, British Patent No. 1012495
No. 1022878, No. 1179290, No.
1198450, US Patent No. 2939891, US Patent No. 2823123
No. 1179290, No. 1198450, No. 1198450, No. 1179290, No. 1198450, No.
No. 2739891, No. 2823123, No. 3068101, No. 3415649, No. 3666478, No. 3756828,
British Patent No. 1397218, British Patent No. 3113816, British Patent No.
3411413, 3473174, 3345974, 3726683, 3843368, Belgian patent no.
731126, British Patent No. 1138514, British Patent No. 1159825
No. 1374780, U.S. Patent No. 2271623, U.S. Pat.
2288226, 2944900, 3235919, 3671247, 3772021, 3589906,
No. 3666478, No. 3754924, West German patent application
Specifications of OLS1961683 and JP-A-117414
No. 50-59025, Special Publication No. 40-378, No. 40-
No. 379 and No. 43-13822.
For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl or alkylaryl ether polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl amines or amides, non-ionic materials such as polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, and urethanes or ethers. Surfactants, triterbenoid saponins, alkyl carboxylates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates Anionic surfactants containing acidic groups such as carboxy, sulfo, phospho, sulfate, phosphate groups such as acids, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates, etc. agents, amino acids, aminoalkylsulfonic acids, aminoalkyl sulfates or phosphates, alkylpetaines,
Ampholytic surfactants such as amine imides and amine oxides, alkyl amine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridium and imidazolium, and sulfonium containing aliphatic or heterocyclic rings. Alternatively, cationic surfactants such as sulfonium salts can be used. In addition to the above-mentioned surfactants, the silver halide photographic emulsion of the present invention contains OLS patent applications No. 2002871, OLS No. 2445611, OLS No.
It may contain imidazoles, thioethers, selenoethers, etc., which are described in the specifications of No. 2360878 and British Patent No. 1352196. In addition, in order to apply the emulsion of the present invention to a color photosensitive material, the emulsion of the present invention adjusted to have red sensitivity, edge sensitivity, and blue sensitivity may be incorporated in combination with cyan, magenta, and yellow couplers. The photographic emulsions of this invention contain color image-forming couplers, i.e. aromatic amines (usually primary amines) which react with the oxidation products of developing agents to form dyes. It may also contain a compound (hereinafter abbreviated as a coupler). The coupler is preferably a non-diffusible coupler having a hydrophobic group called a pallast group in its molecule. The coupler may be either 4-equivalent or 2-equivalent to silver ions. It may also contain a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler). The coupler may be one in which the product of the coupling 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. Specific examples of yellow couplers that can be used include US Pat. No. 2,875,057;
Same No. 3265506, No. 3408194, No. 3551155, Same No.
No. 3582322, No. 3725072, No. 3891445, West German Patent No. 1547868, West German Patent Application (OLS) 2213461
No. 2219917, No. 2261361, No. 2414006,
This is described in No. 2263875, etc. As the magenta coloring coupler, pyrazolone compounds, indazolone compounds, cyanoacetyl compounds, etc. can be used, and pyrazolone compounds are particularly advantageous. Specific examples of magenta coloring couplers that can be used include U.S. Pat.
No. 3062653, No. 3127269, No. 3311476,
3419391, 3519429, 3558319, 3519391, 3519429, 3558319,
No. 3582322, No. 3615506, No. 3834908, No.
3891445, West German Patent No. 1810464, West German Patent Application (OLS) No. 2408665, OLS No. 2417945, OLS No. 2418959,
It is described in No. 2424467, Special Publication No. 6031, 1973, etc. As the cyan color-forming coupler, a phenol compound, a naphthol compound, etc. can be used. Specific examples are US Patent Nos. 2369929 and 2434272.
No. 2474293, No. 2521908, No. 2895826,
Same No. 3034892, No. 3311476, No. 3458315, Same No.
No. 3476563, No. 3583971, No. 3591383, No. 3591383, No. 3583971, No. 3591383, No.
No. 3767411, West German Patent Application (OLS) No. 2414830,
It is described in No. 2454329 and Japanese Patent Application Laid-Open No. 1983-59838. As a colored coupler, for example, a US patent
No. 3476560, No. 2521908, No. 3034892, Tokko Akira
No. 44-2016, No. 38-22335, No. 42-11304, No. 42-11304, No.
No. 44-32461, specification of patent application No. 49-98469, 50-
Specification No. 118029, West German patent application (OLS) 2418959
You can use those listed in the issue. As a DIR coupler, for example, the US patent
No. 3227554, No. 3617291, No. 3701783, No. 3227554, No. 3617291, No. 3701783, No.
No. 3790384, No. 3632345, West German patent application (OLS)
Those described in No. 2414006, No. 2454301, No. 2454329, British Patent No. 953454, and Japanese Patent Application No. 146570-1988 can be used. In addition to the DIR coupler, the light-sensitive material may also contain a compound that releases a development inhibitor during development; for example, U.S. Pat.
The one described in West German patent application (OLS) No. 2417914 can be used. The above couplers may be contained in two or more layers in the same layer. The same compound may be contained in two or more different layers. In order to introduce the coupler into the silver halide emulsion layer, a known method such as the method described in US Pat. No. 2,322,027 can be used. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate,
tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl lauryl amide), or with a boiling point of about 30°C to Organic solvents such as ethyl acetate at 150°C;
After being dissolved in a lower alkyl acetate such as butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used. When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution. These couplers are generally added in an amount of 2 x 10 ^-3 to 5 x 10 -1 mol, preferably 1 x 10 ^-2 to 5 x ^{10 -1} mol, per mol of silver in the emulsion layer. The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifogging agent, and specific examples thereof include US Pat. No. 2,360,290 and US Pat. , No. 2403721, same
No. 2418613, No. 2675314, No. 2701197, No.
No. 2704713, No. 2728659, No. 2732300, No.
No. 2735765, Japanese Patent Application Publication No. 50-92988, No. 50-92989,
No. 50-93928, No. 50-110337, Special Publication No. 50-
It is described in No. 23813 etc. As antistatic agents, diacetylcellulose, styrene perfluoroalkylridium maleate copolymers, alkali salts of reaction products of styrene-maleic anhydride copolymers and p-aminobenzenesulfonic acid, etc. are effective. Examples of matting agents include polymethyl methacrylate, polystyrene, and alkali-soluble polymers. Furthermore, it is also possible to use colloidal silicon oxide. Further, examples of the latex added to improve the physical properties of the film include copolymers of acrylic esters, vinyl esters, etc. and other monomers having ethylene groups. Examples of gelatin plasticizers include glycerin and glycol compounds, and examples of thickeners include styrene-sodium maleate copolymers, alkyl vinyl ether-maleic acid copolymers, and the like. Supports for photosensitive materials made using the emulsion of the present invention prepared as described above include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass paper, cellulose acetate, cellulose nitrate, polyvinyl acetal,
Supports include polypropylene, polyester films such as polyethylene terephthalate, and polystyrene, and these supports are appropriately selected depending on the purpose of use of each silver halide photographic light-sensitive material. These supports are subjected to undercoat processing if necessary. After exposure, a light-sensitive material prepared using the emulsion of the present invention can be developed by a commonly used known method. The black developer is an alkaline solution containing developing agents such as hydroxybenzenes, aminophenols, and aminobenzenes, and may also contain other alkali metal salts such as sulfites, carbonates, bisulfites, bromides, and iodides. I can do it. Further, when the light-sensitive material is for color use, color development can be carried out by a commonly used color development method. In the reversal method, the image is first developed with a black negative developer and then exposed to white light, or
Alternatively, it is processed in a bath containing a fogging agent, and further color-developed with an alkaline developer containing a color developing agent.
There are no particular restrictions on the processing method, and any processing method can be applied, but typical examples include a method in which after color development, bleach-fixing is performed, and if necessary, washing with water and stabilization treatment are performed, or after color development. Alternatively, it is possible to apply a method in which bleaching and fixing are carried out separately, and further washing with water and stabilization treatment are carried out as necessary. The silver halide photographic emulsion produced by the method of the present invention has extremely high photographic sensitivity, less high-intensity failure, and less fog, and is therefore preferably applied to many silver halide photographic materials. For example, it can be effectively applied to photosensitive materials for various uses such as general black and white, X-ray, color, infrared, micro, silver dye bleaching, reversal, and diffusion transfer. Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto. Example 1 Average particle size of 0.9μ with a silver iodobromide core containing 2 mol% silver iodide and a silver bromide shell with an average thickness of 0.016μ
An octahedral monodispersed emulsion was prepared by a double jet method in which pAg and PH were controlled in the same manner as described in JP-A-54-48521. After desalting by a conventional method, this emulsion was divided into seven parts, two of which were used as controls for sulfur sensitization and sulfur+gold sensitization, and each of the others was divided into seven parts, each containing a predetermined amount of 4-hydroxy- 6-methyl-1,3,3a,
7-tetrazaindene was added, and the pH was adjusted to a predetermined level with an aqueous potassium hydroxide solution as necessary. The emulsions thus prepared were each subjected to sulfur sensitization or sulfur+gold sensitization, which was deemed optimal. After ripening, the above hydroxytetrazaindene was added, and each emulsion had a constant content (1.4 g/mol AgX).
I made it so that Furthermore, after adding common photographic additives such as spreading agents, thickeners, and hardening agents to each of these emulsions, an amount of Ag of 50
Sample No. ¹ ~
7 was created. Sensitometry of these samples was performed as follows. Exposure was carried out using a tungsten bulb (each temperature 5400㎜) as a light source, 1/50 light through an optical wedge and a xenon flash.
I took an exposure of 10 ^-6 seconds. Develop with the following developer at 20
℃ for 10 minutes. Metol 2.5g Ascorbic acid 10.0 Sodium metaborate dihydrate 44g Potassium bromide 1.0g Add water 1 The results are shown in Table 1. The sensitivity is the sensitivity of sample 1.
Relative sensitivity was expressed as 100.

[Table] As is clear from the above results, the sensitivity of the samples obtained using the method of the present invention increases, and the sensitization effect is particularly remarkable when gold sensitization is used together and during short exposure. Furthermore, it can be seen that fog hardly increases. Example 2 The same original emulsion as in Example 1 was divided into two parts, and these emulsions were treated with the panchromatic sensitizing dye Anhydro 3,3'-
Di-(3-sulfopropyl)-5,5'-dichloro-
9-ethyl-thiacarbocyanine hydroxide
One emulsion contained 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene 210 mg/mol Ag
mg/mol AgX was added and the PH was adjusted to 6.5. Each of these emulsions was subjected to sulfur + gold sensitization, which was thought to be optimal. After ripening, the above hydroxytetrazaindene was added, and each emulsion had a constant content (1.4
g/mol AgX). After adding 1-phenyl-5-mercaptotetrazole, the coupler dispersion described below, and other commonly used photographic additives such as extending agents and hardeners to these emulsions, a silver content of 20 mg was prepared on a triacetate base. /dm ² and dried to prepare samples and 2. Coupler dispersion 1-hydroxy-N-{γ-
80 g of (2,4-di-tert-amylphenoxypropyl)}-2-naphthamide was completely dissolved in a mixture of 100 ml of tricresyl phosphate and 50 ml of ethyl acetate, and then sorbitan monolaurate was added. Added 2g. This solution was added to 1 kg of a 10% by weight aqueous gelatin solution containing 2.5 g of dodecylbenzenesulfonic acid, stirred at high speed, and further subjected to ultrasonic stirring to emulsify and disperse the resulting solution. After the above sample was subjected to wedge exposure in the same manner as in Example 1, it was exposed to light at 38°C using a color developing solution with the following composition.
Color development was carried out for 1 minute. Color developer composition 4-amino-3-methyl-N-ethyl-N-(β
-hydroxyethyl)-aniline sulfate 4.80g Anhydrous sodium sulfite 0.14g Hydroxyamine 1/2 sulfate 1.98g Sulfuric acid 0.74g Anhydrous potassium carbonate 28.85g Anhydrous potassium bicarbonate 3.46g Anhydrous potassium sulfite 5.10g Potassium bromide 1.16g Sodium chloride 0.14g Nitrilotriacetic acid trisodium salt (monohydrate)
1.20g Potassium hydroxide 1.48g Add water to make 1. The results are shown in Table-2. As is clear from Table 2, the samples according to the present invention have extremely high sensitivity.

[Table] Example 3 A silver iodobromide core containing 2 mol% of silver iodide and a silver bromide shell with an average thickness of 0.016 μm were produced by the double-jet method with pAg and PH controlled in the same manner as in Example 1. A monodecahedral monodisperse emulsion with an average grain size of 0.9μ was prepared. After desalting, this emulsion was divided into three parts, one of which was used as a control, and the other part was treated with 4-hydroxy-6-methyl-1,3,3a, in the amount shown in Table 3.
After adding 7-tetrazaindene, the predetermined pH was adjusted. Each of the emulsions thus prepared was subjected to sulfur + gold sensitization, which was considered to be optimal. After completion of ripening, the above-mentioned hydroxytetrazaindene was added so that each emulsion had a constant content (1.4 g/mol AgX). Each of these emulsions was evaluated in the same manner as in Example 1. The results are shown in Table-3.

[Table] From Table 3, it can be seen that the samples according to the present invention have extremely high sensitivity even in the case of octahedral crystal silver halide grains. Reference Example Instead of the emulsion consisting of octahedral grains in Example 1, core/shell type silver iodobromide cubic crystal grains (core...iodide) with an average grain size of 0.65μ (approximately the same volume as the octahedral grains) were used. An emulsion consisting of silver iodobromide containing 2 mol% silver, shell...silver bromide with an average thickness of 0.02 μm, and an irregularly shaped twinned silver iodobromide commonly used in conventional products. Chemical sensitization similar to that described above was attempted using an emulsion consisting of grains (containing 2 mol % of silver iodide). The results are shown in Table 4.

【table】

[Table] However, in the case of the above reference example, the sensitization rate is very poor if only sodium thiosulfate and chloroauric acid are used as sensitizers, so ammonium thiocyanate is used at 10 to 50%.
mg/AgX mole was added. As is clear from Table 4, in the case of an emulsion consisting of cubic grains and irregularly shaped twin grains, chemical ripening in the presence of a hydroxytetrazaindene compound results in desensitization.

Claims (1)

[Claims] 1. A silver halide emulsion consisting essentially of silver halide grains of octahedral or 14-sided crystals having (111) planes is sulfur-enriched in the presence of an azaindene compound that forms a complex with silver. 1. A method for producing a silver halide emulsion, which comprises performing sensitization or selenium sensitization, and gold sensitization. 2. The method for producing a silver halide emulsion according to claim 1, wherein the azaindene compound is a hydroxyazaindene compound having 3 to 5 nitrogen atoms in the azaindene ring. 3. The method for producing a silver halide emulsion according to claims 1 and 2, wherein the silver halide of the silver halide grains is mainly composed of silver bromide. 4 Silver halide of the above silver halide grains is 50
Contains more than mol% of silver bromide, and the content ratio of silver iodide is
A method for producing a silver halide emulsion according to claims 1 to 3, wherein the content is 10 mol % or less. 5. The method for producing a silver halide emulsion according to claims 1 to 4, wherein the silver halide grains contain 90 mol% or more of silver bromide. 6 The addition ratio of the sulfur sensitizer or selenium sensitizer to the gold sensitizer depends on the number of sulfur atoms that produce silver sulfide in the sulfur sensitizer or the number of selenium atoms that produce silver selenide in the selenium sensitizer. The number of gold atoms is 1/
A method for producing a silver halide emulsion according to claims 1 to 5, wherein the silver halide emulsion is 2 to 1/200. 7. Claim 1, wherein the amount of the azaindene compound is the amount necessary to coat the surface of the silver halide grains with a thickness of monomolecular layer to 10 molecular layers.
A method for producing a silver halide emulsion according to items 6 to 6. 8. Production of a silver halide emulsion according to any one of claims 1 to 7, characterized in that the silver halide emulsion contains at least one sensitizing dye represented by the following general formula: Method. [In the formula, R ₁₂ , R ₁₃ and R ₁₄ each represent a group selected from an alkyl group, a substituted alkyl group, an aryl group and a substituted aryl group, and L ₁ , L ₂ and
L ₃ each represents a methine group or a substituted methine group, Z ₁ , Z ₂ and Z ₃ each represent an atom or atomic group necessary to complete a substituted or unsubstituted 5- or 6-membered heterocyclic nucleus, and P and Q are respectively cyano group, COOR ₁₅ group, COR ₁₅ group, SO ₂ R ₁₅
The group (R ₁₅ is an alkyl group) Q ₂ and Q ₁ are each substituted or unsubstituted thioxazolone ring, pyrazolone ring, oxindole ring, barbiturate ring,
2-thiobarbituric acid, 2,4-oxazolidinedione, 2,4-thiazolidinedione, 2,4
-Imidazolidinedione, 2-thio-2,4-oxazolidinedione, 2-thio-2,4-thiazolidinedione, 2-thio-2,4-selenazolidinedione, 2-thio-2,5-thiazolidinedione , 2-thiohydantoin ring, 4-oxazolinone ring, 4-thiazolinone ring, and 4-imidazolinone ring, and Y represents a hydrogen atom, an amino group, an alkylamino group, a dialkylamino group, or a halogen. Represents a group selected from atoms, alkoxy groups and alkyl groups, m ¹ and m ²
represents 0 or 1, n ¹ and n ² are 0 or 2
, X represents an acid anion group, and l represents 1 or 2. However, when the compound forms an inner salt, l represents 1. 9. The method for producing a silver halide emulsion according to claims 1 to 8, wherein the sulfur sensitization or selenium sensitization and gold sensitization are performed at pAg 7.5 to 10.0 and pH 5.0 to 9.0. 10 A silver halide emulsion consisting essentially of silver halide grains of octahedral or tetradecahedral crystals having (111) faces is sulfur-sensitized or sensitized on a support in the presence of an azaindene compound that forms a complex with silver. 1. A silver halide photographic material comprising at least one light-sensitive silver halide emulsion layer containing a silver halide emulsion subjected to selenium sensitization and gold sensitization. 11. The silver halide photographic light-sensitive material according to claim 10, wherein the azaindene compound is a hydroxyazaindene compound having 3 to 5 nitrogen atoms in the azaindene ring. 12. The silver halide photographic light-sensitive material according to claim 10 or 11, wherein the silver halide grains mainly consist of silver bromide. 13 The silver halide of the above silver halide grains is 50
Contains more than mol% of silver bromide, and the content ratio of silver iodide is
The silver halide photographic material according to claims 10 to 12, which contains 10 mol% or less. 14 Silver halide of the above silver halide grains is 90
The silver halide photographic material according to claims 10 to 13, which contains silver bromide in an amount of mol % or more. 15 The addition ratio of the sulfur sensitizer or selenium sensitizer to the gold sensitizer depends on the number of sulfur atoms that produce silver sulfide in the sulfur sensitizer or the number of selenium atoms that produce silver selenide in the selenium sensitizer. 15. The silver halide photographic material according to claim 10, wherein the number of gold atoms is 1/2 to 1/200 of the number of gold atoms. 16. The silver halide according to claims 10 to 15, wherein the amount of the azaindene compound is an amount necessary to coat the surface of the silver halide grains with a thickness of monomolecular layer to 10 molecular layers. Photographic material. 17. The silver halide photographic material according to any one of claims 10 to 16, wherein the silver halide emulsion contains at least one sensitizing dye represented by the following general formula: . [In the formula, R ₁₂ , R ₁₃ and R ₁₄ each represent a group selected from an alkyl group, a substituted alkyl group, an aryl group and a substituted aryl group, and L ₁ , L ₂ and
L ₃ each represents a methine group or a substituted methine group, Z ₁ , Z ₂ and Z ₃ each represent an atom or atomic group necessary to complete a substituted or unsubstituted 5- or 6-membered heterocyclic nucleus, and P and Q are respectively cyano group, COOR ₁₅ group, COR ₁₅ group, SO ₂ R ₁₅
The group (R ₁₅ is an alkyl group) Q ₂ and Q ₁ are each substituted or unsubstituted thioxazolone ring, pyrazolone ring, oxindole ring, barbiturate ring,
2-thiobarbituric acid, 2,4-oxazolidinedione, 2,4-thiazolidinedione, 2,4
-Imidazolidinedione, 2-thio-2,4-oxazolidinedione, 2-thio-2,4-thiazolidinedione, 2-thio-2,4-selenazolidinedione, 2-thio-2,5-thiazolidinedione , 2-thiohydantoin ring, 4-oxazolinone ring, 4-thiazolinone ring, and 4-imidazolinone ring, and Y represents a hydrogen atom, an amino group, an alkylamino group, a dialkylamino group, or a halogen. Represents a group selected from atoms, alkoxy groups and alkyl groups, m ¹ and m ²
represents 0 or 1, n ¹ and n ² are 0 or 2
, X represents an acid anion group, and l represents 1 or 2. However, when the compound forms an inner salt, l represents 1. 18. The silver halide photographic material according to claims 10 to 17, wherein the sulfur sensitization or selenium sensitization and gold sensitization are performed at a pAg of 7.5 to 10.0 and a pH of 5.0 to 9.0.