JPH0518091B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical Field] The present invention relates to a silver halide photographic emulsion, which is chemically sensitized with a specific selenium compound, has high sensitivity and low red light sensitivity, has low fog, and has good storage stability. This invention relates to a silver halide photographic emulsion with excellent properties. [Prior Art] Conventionally, in order to increase the sensitivity of silver halide photographic emulsions, sensitization methods using sulfur compounds, noble metals, and selenium compounds, either alone or in combination, have been proposed. of the photograph
Process Force Edition” (The
The sensitization method described in Theory of the Photographic Process, 4th edition (Macmillan Publishing, 1977), pages 149 to 160 is known. In the so-called selenium sensitization method using a selenium compound, it is generally known that when the unstable selenium compound described in U.S. Pat. ing. In addition, a method for improving the drawback of fog formation associated with the selenium sensitization method was published in 1973.
-13489, JP-A-50-71320, US Pat. No. 3,420,670, etc., and these methods have been improved to some extent. However, in recent years there has been an increasing demand for emulsions that do not cause fog, are stable without storage deterioration over time, and are highly sensitive. It has become clear that even with the excellent sensitization method described in Publication No.-13489, it is not possible to achieve both the desired high sensitivity and stability. moreover,
It has been found that photographic emulsions sensitized by the selenium compounds have the disadvantage of being sensitive to red light and causing fog under red safe light. [Object of the Invention] Therefore, the first object of the present invention is to provide a silver halide photographic emulsion which has stable photographic properties and has increased sensitivity without causing fog. A second object of the present invention is to provide a silver halide photographic emulsion with suppressed red light sensitivity, high sensitivity, and excellent storage stability. [Structure of the Invention] As a result of intensive research, the present inventors found that a water-soluble gold compound of 1 x 10 ^-9 to 1 x 10 ^-4 mol per 1 mol of silver halide; ×10 ^-7
The objects of the present invention are achieved by a silver halide photographic emulsion characterized by being chemically sensitized with ~1×10 ^-3 mol of an unstable sulfur compound and a compound represented by the following general formula []. find out,
The present invention was completed. General formula [] [In the formula, Z is a triazole ring, a thiazole ring,
Represents a thiazoline ring, oxazole ring, thiadiazole ring, imidazole ring, benzothiazole ring, benzoxazole ring, benzimidazole ring, pyridine ring or pyrimidine ring, and R ₁ is a hydrogen atom, a lower alkyl group, a cycloalkyl group, an allyl group, or represents an aryl group, R ₂ represents a hydrogen atom, a lower alkyl group, a cycloalkyl group, an allyl group, an aryl group, or a nitrogen-containing heterocyclic group, and may be combined with R ₁ to form a heterocycle, and n
represents 0 or l. ] The compound represented by the above general formula [ ] used in the present invention is called a heterocyclic-substituted selenourea compound. This compound is disclosed in Japanese Patent Publication No. 43-13489, No. 44-
Although it is mentioned as a common name in publications such as No. 15748, its specific structure has not been clarified.
Furthermore, as shown in the examples of Japanese Patent Publication No. 43-13489, the effects of the present invention cannot be obtained even when an unstable selenourea compound is combined with a water-soluble gold salt and an unstable sulfur compound. is written. Preferred heterocyclic-substituted selenourea compounds of the general formula [] include N,N'-substituted selenoureas represented by the following general formula []. General formula [] In the formula, R ₂ , Z and n represent the contents defined in the general formula []. R ₃ represents an alkyl group, a cycloalkyl group, an allyl group, an aryl group, or a nitrogen-containing heterocyclic group, and may be combined with R ₂ to form a heterocycle. Water-soluble gold compounds useful in the present invention include, for example, U.S. Pat.
Gold chloride, potassium oleate, potassium auriolite, potassium auricyanide, potassium aurithiocyanate, gold sulfide, gold selenide, potassium chloroaurate, etc. as described in the specifications of No. 2642361, etc., as well as the following. Examples include gold compounds. These compounds are preferably added as an aqueous solution during silver halide grain formation, physical ripening, or chemical ripening, and more preferably added at the start of chemical ripening. Examples of unstable sulfur compounds used in the present invention include alkali metal thiosulfates (e.g., sodium thiosulfate, potassium thiosulfate, etc.), ammonium thiosulfate, thiosemicarbazide, isothioureas (e.g., allylisothiourea, etc.), thiocarbamic acids, thioamides ( Examples include N-methylmonothiosuccinimide, etc.) and the following thiourea compounds. These and other useful unstable sulfur compounds include U.S. Pat.
No. 2728668, No. 2999751, No. 2999751, No. 2728668, No. 2999751, No.
3501313, British Patent No. 997031, West German Patent No.
Specifications of No. 1422869, Japanese Patent Publication No. 49-20533, Japanese Patent Publication No. Sho
No. 48-30419, No. 55-45016, No. 58-80634, etc., or as described in Journal of Photographic Science (J.Phot.Sci.) Volume 1 (1953), page 133. Compounds can be mentioned. These unstable sulfur compounds may be dissolved in water or a water-miscible organic solvent such as methanol or ethanol alone or in a mixed solvent, and added during silver halide grain formation, physical ripening, or chemical ripening, especially during chemical ripening. Preferably added at the beginning. In the above general formulas [] and [], Z represents a halogen atom (e.g. chlorine atom, bromine atom, etc.),
Alkyl groups, preferably lower alkyl groups (e.g., methyl, ethyl, etc.), aryl groups (e.g., phenyl, etc.), amino groups, preferably substituted amino groups (e.g., diethylamino, dimethylamino, etc.), alkoxy groups, preferably is a lower alkoxy group (e.g., methoxy group, ethoxy group, etc.), an alkoxycarbonyl group (e.g., methoxycarbonyl group, etc.), a sulfamoyl group, preferably a substituted sulfamoyl group (e.g., dimethylaminosulfonyl group, etc.), a carbamoyl group, preferably a substituted carbamoyl group. (e.g. dimethylaminocarbonyl group, etc.),
It may be substituted with a carboxyl group, a nitrile group, etc. Examples of the cycloalkyl group represented by R ₁ , R ₂ and R ₃ include a cyclopentyl group and a cyclohexyl group, and the alkyl group is preferably a lower alkyl group, and the lower alkyl group has 1 to 6 carbon atoms. straight-chain or branched alkyl groups (e.g. methyl, ethyl, propyl,
pentyl group, isopropyl group, 2-methylbutyl group, etc.), and the lower alkyl group includes a halogen atom (e.g., fluorine atom, chlorine atom, etc.), hydroxy group, lower alkoxy group (e.g., methoxy group, etc.), hydroxyalkoxy group. (e.g., 2-hydroxyethoxy group, etc.), alkoxyalkoxy group (e.g., 2-methoxyethoxy group, etc.), substituted amino group (e.g., dimethylamino group, etc.), alkoxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl, etc.), carbamoyl group, It may be substituted with a sulfamoyl group, a nitrile group, an aryl group, etc. In particular, alkyl groups substituted with aryl groups (e.g. benzyl group, phenethyl group, etc.)
is preferred. Examples of the aryl group include a phenyl group, tolyl group, anisole group, chlorophenyl group, diethylaminophenyl group, cyanophenyl group, carbamoylphenyl group, methylsulfonylphenyl group, and sulfamoylphenyl group. The nitrogen-containing heterocyclic group represented by R ₂ and R ₃ is a 5- or 6-membered nitrogen-containing heterocyclic group that may have a condensed ring, such as an oxadiazole ring, thiadiazole ring, pyridine ring, or quinoline ring. , indole ring, oxazole ring, benzoxazole ring,
Thiazole ring, benzothiazole ring, imidazole ring, benzimidazole ring, selenazole ring,
Examples include benzoselenazole rings and pyrimidine rings, and these heterocycles include methyl groups, methoxy groups, phenyl groups, halogen atoms (e.g., fluorine atoms, chlorine atoms, etc.), nitrile groups, methoxycarbonyl groups, and carbamoyl groups. , a sulfamoyl group, etc. Examples of the heterocycle formed by bonding with R ₁ include a piperidine ring and a morpholine ring. The compounds represented by the general formulas [] and [] can be synthesized, for example, as follows.
In other words, (1), a symmetric heterocyclic group-substituted selenourea is prepared by dissolving an excess amount of an amine compound represented by the following general formula [] in an inert solvent such as carbon tetrachloride or benzene, and heating the solution in a nitrogen atmosphere. Reflux and add carbon diselenide dropwise to react. Stop the reaction when hydrogen selenide gas generation stops,
The desired product can be obtained by concentrating, cooling, collecting, and recrystallizing if necessary. General formula [] In the formula, Z and n are Z in the general formula []
and n. In addition, (2), an asymmetric heterocyclic group-substituted selenourea is obtained by dissolving a primary amine compound among the amine compounds represented by the general formula [] or [] in an inert solvent such as carbon tetrachloride or benzene. Carbon diselenide is introduced and reacted in a nitrogen gas atmosphere to form a diselenocarbamate, then an excess amount of one of the amine compounds is added, and the mixture is heated under reflux until the generation of hydrogen selenide gas stops. If necessary, the desired product can be obtained by washing off excess amine with water, drying and concentrating to precipitate crystals, collecting and recrystallizing. General formula [] In the formula, R ₁ and R ₂ are R 1 and R ₂ in the general formula [],
Synonymous with R ₂ . Next, compounds represented by the general formulas [] and [] (hereinafter referred to as selenourea compounds of the present invention).
A specific example will be given, but the invention is not limited thereto. The selenourea compound of the present invention is dissolved in water or a water-miscible organic solvent such as methanol or ethanol, alone or in a mixture, and added at any time during emulsion production, preferably at the start of chemical ripening. The amount of the selenourea compound used in the present invention varies depending on the type of silver halide photographic emulsion, the type of compound used, etc., but is usually 3 x 10 ^-7 mol to 1 mol per mol of silver halide. The amount is preferably ×10 ⁻⁴ mol. pAg during chemical ripening (logarithm of reciprocal of silver ion concentration)
The value of is preferably 8.0 to 11.0. Other chemical sensitizers can also be used in combination during chemical ripening. Chemical sensitizers that can be used in combination include, for example, selenium compounds described in U.S. Pat. No. 3,420,670, U.S. Pat.
No. 2518698, No. 2521925, No. 2521926, No. 2521925, No. 2521926, No.
Reducing substances such as amines and stannous salts described in US Pat. Nos. 2419973, 2694637, and 2983610, US Pat.
Examples include salts of noble metals such as platinum, palladium, iridium, and rhodium, which are described in No. 2,566,263, and the like. Sulfur sensitization using the compound of the present invention may be carried out in the presence of a silver halide solvent such as a thiocyanate (ammonium thiocyanate, etc.) or a 4-substituted thiourea (tetramethylurea, etc.). The silver halide photographic emulsion of the present invention may be of any halogen composition such as silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, or silver chloride. ), Chimie et
Physique Photographique) (published by Paul Montel)
1967); GFDuffin
Author, Photographic Emuls−ion Chemistry
(The Focal Press, 1966); co-authored by VLZel-ikman et al., Making and Coating Photographic Emulsion (Making and Coating Photographic Emulsion)
Photographic Emulsion) (published by The Focal Press)
(1964) and others. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt and soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. . Alternatively, a method in which particles are formed in an excess of silver ions (so-called back mixing method) can also be used. 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. Although the silver halide grain size distribution of the silver halide photographic emulsion of the present invention may be narrow or wide, so-called monodisperse grains having a narrow distribution width and uniform grain size are preferred. Here, monodisperse means 20% or less, preferably 20% or less, when the variation in silver halide grain size is expressed by the following formula CV (size distribution).
It means that it is 15% or less. CV=S/γ×100 S=√Σ(γ−γi) ² ni/Σni where S is the standard deviation value, and is the diameter γi of each particle and its From the number ni =Σni represents the average particle size defined by the formula γi/Σni. The silver halide grains contained in the silver halide emulsion of the present invention may have regular shapes such as cubes, octahedrons, and tetradecahedrons, irregular shapes such as twin crystals, or both. It may be mixed, but
Preferably regular particles are preferred. The effects of the present invention are particularly remarkable in the above-mentioned monodisperse core/shell type silver halide grains. The ratio of the halogen composition content between the interior (core part) and the surface layer (shell part) of the core/shell type silver halide grains preferably used in the present invention is as follows:
It may have a sharp boundary or it may change substantially continuously. The method for producing the core/shell type silver halide grains is described in, for example, West German Patent No. 1169290, British Patent No. 1027146, and Japanese Patent Application Laid-Open No. 154232/1983.
The method described in Japanese Patent Publication No. 51-1417 can be employed. In the present invention, two or more silver halide emulsions formed separately may be optionally mixed and used. 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. The silver halide emulsions of this invention may be spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. Any of the basic heterocyclic nuclei commonly used in cyanine dyes can be used for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; nuclei 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, i.e., indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole Nucleus, quinoline nucleus, etc. can be applied. These nuclei may be substituted on carbon atoms. The merocyanine dye or composite merocyanine dye includes a nucleus having a ketomethylene structure such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, A 5- to 6-membered heterocyclic nucleus such as a thiobarbituric acid nucleus can be applied. Useful sensitizing dyes are e.g. German Patent No. 929080
No. 2,231,658, U.S. Pat. No. 2,493,748, U.S. Pat.
No. 2503776, No. 2519001, No. 2912329, No. 3655394, No. 3656959, No. 3672897,
No. 3694217, British Patent No. 1242588, Special Publication No. 1973
−14030, etc. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Typical examples are U.S. Patent No. 268-545, U.S. Patent No. 2977229,
Same No. 3397060, Same No. 3522052, Same No. 3527641,
Same No. 3617293, Same No. 3628964, Same No. 3666480,
Same No. 3679428, Same No. 3703377, Same No. 3769301,
No. 3814609, No. 3837862, British Patent No.
It is described in No. 1344281, Special Publication No. 43-4936, etc. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, aminostilbene compounds substituted with a nitrogen-containing heterocyclic group (such as those described in U.S. Pat. No. 2,933,390 and U.S. Pat. No. 3,635,721),
They may also include aromatic organic acid formaldehyde condensates (such as those described in US Pat. No. 3,743,510), cadmium salts, azaindene compounds, and the like. U.S. Patent No. 3615613, U.S. Patent No. 3615641, U.S. Patent No.
The combinations described in No. 3617295 and No. 3635721 are particularly useful. The silver halide photographic emulsion of the present invention has increased sensitivity,
For the purpose of increasing contrast or accelerating development, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholins, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, and 3-pyrazolidones. etc. may also be included. For example, U.S. Patent No. 2400532;
Those described in No. 2423549, No. 2716062, No. 3617280, No. 3772021, No. 3808003, etc. can be used. The silver halide emulsion of the present invention may contain an antifoggant or a stabilizer. As the compound, those described in the "Antifoggants and stabilizers" section of Product Licensing Index, Vol. 92, P107 can be used. The silver halide emulsion may contain a developing agent. As a developing agent, “Developing
Those described in the section ``agents'' can be used. Silver halide can be dispersed in colloids that can be hardened with various organic or inorganic hardeners. As a hardening agent, “Harden-
Those listed in the section ``Ers'' can be used. Silver halide emulsions may contain coating aids. As coating aids, those described in the "Coating aids" section of Product Licensing Index, Vol. 92, p. 108 can be used. The silver halide emulsion of the present invention is a so-called color emulsion.
A coupler may be included. As the color coupler, those described in the "Color materials" section of Product Licensing Index, Volume 92, P110 can be used. A photographic material prepared using the silver halide photographic emulsion of the present invention may contain a dye in the photographic emulsion layer or other hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. As such dyes, Product Licensing Index, Vol. 92
The dyes listed in the "Absorbing and filter dyes" section on page 109 are used. The silver halide photographic emulsion of the present invention may also contain antistatic agents, plasticizers, matting agents, lubricants, ultraviolet absorbers, fluorescent whitening agents, air antifoggants, and the like. The silver halide emulsion used in the present invention is used as a vehicle in the "Vehicles" section of Product Licensing Index, Vol. 92, p. 108 (December 1971).
Use the vehicle listed in Month). The silver halide emulsion of the present invention is coated on a support together with other photographic layers if necessary. The application method is based on the Product Licensing Index,
The method described in the "Coating procedures" section of Volume 92, P109 can be used. Also, the support is Product Licensing Index, Volume 92
You can use what is listed in the "Supports" section on page 108. The silver halide photographic emulsion of the present invention is used for various purposes. For example, it is used for the following purposes. Emulsions for color positives, emulsions for color paper, emulsions for color negatives, emulsions for color reversal (which may or may not contain couplers), emulsions for photosensitive materials for plate making (e.g. lithium film, etc.),
Emulsions used in photosensitive materials for cathode ray tube displays, emulsions used in photosensitive materials for X-ray recording (especially materials for direct and indirect photography using screens),
Colloid transfer process
emulsions used in silver salt diffusion transfer processes (e.g., as described in U.S. Pat. No. 2,716,059);
process) (e.g., U.S. Pat. No. 2,352,014;
No. 2543181, US Pat. No. 3020155, US Pat. No. 2861885, etc.);
No. 2983606, No. 3253915, No. 3253915, No.
3227550, 3227551, 3227552, 3415644, 3415645, 3415646,
Research Disclosure Volume 151 No. 15162,
Emulsions used in P75-87 (described in, e.g., November 1976), the tie transfer process (lmbibition transfer process) (U.S. Patent No.
Emulsions used in (described in No. 2882156 etc.)
Silver dye bleaching method [Friedman's illistory of Color]
Photography “American Photographic”
Pudlishers Co 1944 (especially Chapter 24) and British
Journal of Photography” Vol111, P-308～
309APr.71964)], direct positive light-sensitive materials (for example,
No. 2497875, No. 2588982, No. 3367778, No. 3501306, No. 3501305, No. 3672900,
Same No. 3477852, Same No. 2717833, Same No. 3023102,
U.S. Pat. No. 3,050,395, U.S. Pat. No. 3,501,307, etc.);
3148122, British Patent No. 1110046, etc.), and emulsions used in physical development photosensitive materials (for example, described in British Patent No. 920277, British Patent No. 1131238, etc.). . The silver halide emulsion of the present invention is particularly suitable for internal color in a multilayer structure, particularly for reversal color, negative color emulsion, black and white negative emulsion (black and white high-sensitivity negative, micro negative, etc.), and color diffusion transfer process emulsion. It is advantageously used as an emulsion for use in direct positive light-sensitive materials, and as a core/shell internal latent image emulsion. Exposure to obtain a photographic image may be carried out using a conventional method. That is, any of the various known light sources can be used, such as natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, and the like. Exposure times include not only exposure times of 1/1000 seconds to 1 second normally used in cameras, but also exposures shorter than 1/1000 seconds, such as longer than 1/10 ⁴ to 1/10 ⁸ seconds using xenon flash lamps and cathode ray tubes. Exposure can also be used. If necessary, the spectral composition of the light used for exposure can be adjusted using a color filter. Laser light can also be used for exposure. Also, electron beams, X-rays, γ-rays, α
Exposure may be by light emitted from a phosphor excited by a line or the like. Any known method can be used for photographic processing of the light-sensitive material prepared using the photographic emulsion of the present invention. For example, "Processing" in Product Licensing Index, Volume 92, P110.
The photographic processes described in section 1 can be used. [Example] Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. Example 1 In order to clarify the difference in sensitizing effect and stability of conventionally known unstable selenium compounds, pAg was used.
An octahedral emulsion of silver iodobromide (silver iodide content: 2.0 mol %) with a grain size of 0.8 μm was prepared by a controlled double jet method with a grain size of 8.0 μm. This emulsion was divided into eight equal parts, each emulsion was heated to 50°C, and 1 mg of potassium chloroaurate, 3 mg of sodium thiosulfate, and a selenium sensitizer shown in Table 1 below were added per mol of silver halide. Optimum ripening was carried out. After chemical ripening, appropriate amounts of saponin as a coating aid and hydroxy-dichloro-s-triazine as a hardening agent were added, and each emulsion was coated on a cellulose acetate film support with 45 mg of silver/100 cm ² ,
Apply gelatin at a ratio of 30 mg/100 cm ² to sample 1~
8 was created. Samples 1 to 8 were exposed to tungsten light for 1/50 second through a wedge, developed for 5 minutes at 20 DEG C. using a developer having the composition shown below, and then fixed and washed with water. [Developer composition] [Hydroquinone 9.0 g Phenidone 0.5 g Potassium bromide 4.0 g Anhydrous sodium sulfite 80 g Adjusted to pH 10.0 and 1.0 with soda carbonate and water. A photographic characteristic curve was determined for each developed sample using an automatic densitometer (manufactured by Konishiroku Photo Industry Co., Ltd.), and the sensitivity was determined by the reciprocal of the exposure amount required to give an optical density of [fog + 0.1]. expressed. The results are shown in Table-1. Note that the sensitivity is expressed as a relative value with the sensitivity of sample 1 as 100.

【table】

[Table] As is clear from Table 1, the combination sensitization using selenium compounds according to the present invention increases sensitivity and suppresses fog compared to the combination sensitization using conventionally known selenium compounds. Example 2 Next, in order to demonstrate that the combination technology of the present invention has superior storage stability compared to the conventional technology, high temperature storage treatment was performed. A hexahedral silver iodobromide (silver iodide content of 4 mol%) emulsion (emulsion A and core/shell type silver iodobromide (silver iodide content of 4 mol %) with an average grain size of 0.6 μm covered by a 0.02 μm thick AgBr shell 6
A hedron emulsion (referred to as emulsion B) was prepared. Emulsion A and Emulsion B were each divided into six parts, and each emulsion was treated with 1 mg of chloroauric acid, 2 mg of N-ethyl-N'-(2-thiazolyl)thiourea, and selenium shown in Table 2 below per mole of silver halide. Optimal chemical ripening was performed at 50°C with the addition of a sensitizer. Next, each emulsion was added with 4-hydroxy-6 as a stabilizer.
-methyl-1,3,3a,7-tetrazaindene,
Samples 9 to 20 were prepared by adding 1-phenyl-5-mercaptotetrazole and an appropriate amount of saponin as a coating aid, coating on a cellulose acetate-based support, and drying. Each sample was heated at 55℃±2℃ and relative humidity 55±5.
% for 72 hours, and exposed, developed, fixed, washed with water, and measured the density of the aged and untreated samples in the same manner as in Example 1 to obtain photographic characteristic curves. The results obtained are shown in Table-2. The sensitivity display method is the same as in Example-1,
The sensitivity of sample 14 without aging treatment is set as 100 and is expressed as a relative value.

[Development conditions]

Processing process (38℃) Processing time Color development...2 minutes 45 seconds Bleaching...6 minutes 30 seconds Washing...3 minutes 15 seconds Fixing...6 minutes 30 seconds Washing...3 minutes 15 seconds Stabilization...1 minute 30 seconds The composition of the treatment liquid used in each treatment step is as follows. Color developer composition: 4-amino-3-methyl-N-ethyl-N-
(β-hydroxyethyl)-aniline sulfate 4.8g Anhydrous sodium sulfite 0.14g Hydroxyamine 1/2 sulfate 1.98g Sulfuric acid 0.74mg Anhydrous potassium carbonate 28.85g Anhydrous potassium bicarbonate 3.46g Anhydrous potassium sulfite 5.10g Potassium bromide 1.16 g Sodium chloride 0.14g Nitrilotriacetic acid trisodium salt (monohydrate) 1.20g Potassium hydroxide 1.48g Add water to make 1. Bleach solution composition: Ethylenediaminetetraacetic acid iron ammonium salt 100.0g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0ml Add water to make 1, and use ammonia water.
Adjust to PH6.0. Fixer composition: Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.6g Sodium metasulfite 2.3g Add water to make 1, and adjust to PH6.0 using acetic acid. Stabilizing liquid composition: [Formalin (37% aqueous solution) 1.5ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5ml Add water to make 1. The density of each of the obtained dye images was measured through a green filter to determine the green light sensitivity and fog. The results obtained are shown in Table 3. The sensitivity display method is the same as in Example-1,
For each emulsion, the sensitivity of samples 21, 25, and 29 in 1/100 second exposure processing was set as 100, and relative values are shown.

[Table] As is clear from Table 3 above, samples sensitized by combining the selenium compounds of the present invention (23,
It can be seen that samples 24, 27, 28, 31, and 32) all have higher green light sensitivity than the other samples. On the other hand, the red light sensitivity and maximum density showed small values for the sample according to the present invention, suggesting that the red light safety light fog characteristics were improved. Furthermore, although the common effects of the invention are shown for all the emulsions used, it is clear that even better results can be obtained for monodisperse emulsions, and even better for core/shell type monodisperse emulsions. .

Claims (1)

[Claims] 1 1×10 ^-9 to 1× per mole of silver halide
Chemically sensitized with 10 ^-4 mol of a water-soluble gold compound, 1 x 10 ^-7 to 1 x 10 ^-3 mol of an unstable sulfur compound per 1 mol of silver halide, and a compound represented by the following general formula [] A silver halide photographic emulsion characterized by: General formula [] [In the formula, Z is a triazole ring, a thiazole ring,
Represents a thiazoline ring, oxazole ring, thiadiazole ring, imidazole ring, benzothiazole ring, benzoxazole ring, benzimidazole ring, pyridine ring or pyrimidine ring, and R1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an allyl group or an aryl group. R2 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an allyl group, an aryl group, or a nitrogen-containing heterocyclic group, and may be combined with R1 to form a heterocycle, and n is o or 1
represents. ]