JPH0437979B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a silver halide emulsion, and more particularly to a silver halide emulsion whose sensitivity has been increased by selenium sensitization and cyanine dye. Prior Art Recently, silver halide photographic materials, especially color photographic materials, have been developed under a wide range of photographic conditions, such as being able to take photographs in the dark and even fast-moving subjects without blurring. There is a strong demand for highly sensitive photosensitive materials that can respond to these demands. Therefore, sulfur sensitization methods, selenium sensitization methods, etc., which are useful as chemical ripening methods to increase the sensitivity of silver halide emulsions used in the above-mentioned light-sensitive materials, have been developed. It has attracted attention as being suitable for increasing sensitivity. Regarding such selenium sensitization methods, for example, U.S. Pat.
No. 1623499, No. 2642361, No. 2739060, No. 3420670, No. 3320069, No. 3658540,
Same No. 3408196, Same No. 3408197, Same No. 3442653,
British Patent No. 3591385, British Patent No. 255846, British Patent No.
861984, German patent no. 1033510, German patent no. 1547762
French Patent No. 2093038, French Patent No. 2093209,
Special Publication No. 52-34491, No. 52-34492, No. 53-295
No. 52-36009, No. 52-38408, No. 57-
Although it is described in various specifications and publications such as No. 22090, conventional selenium sensitization has a sensitizing effect, and is said to be particularly useful for increasing the low sensitivity, but it does not involve the occurrence of fog and is This has the disadvantage that fog is further increased during storage of the material. A method for improving the above-mentioned problems in selenium sensitization is described in, for example, Japanese Patent Publication No. 49-20970, which discloses selenium sensitization of a monodisperse silver halide emulsion. However, this method does not provide sufficiently high sensitivity. OBJECTS OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide emulsion whose sensitivity is sufficiently increased by selenium sensitization, and at the same time the occurrence of fog and storage stability are improved. Another object of the present invention is to provide a silver halide emulsion whose sensitivity is sufficiently increased scientifically and optically by selenium sensitization and spectral sensitization. The present inventors have achieved the above objects of the present invention using a silver halide emulsion that is a monodisperse emulsion that is selenium-sensitized and spectrally sensitized with a cyanine dye represented by the following general formula []. I found out what I can get. General formula [] In the formula, Z ₁ and Z ₂ each represent an atomic group necessary to complete a thiazole ring, benzothiazole ring, naphthothiazole ring, oxazole ring, benzoxazyl ring or naphthoxazole ring.
R ₁ and R ₂ each represent an alkyl group or an alkyl group having either a hydroxy group, a carboxyl group or a sulfo group, X ₁ represents an anion, n represents an integer of 1 or 2, and the sensitizing dye When forming an inner salt, n represents 1. The present invention will be explained in more detail below. In the present invention, the silver halide emulsion that is selenium-sensitized and spectrally sensitized with a cyanine dye is a monodisperse silver halide emulsion. The silver halide grains contained in the monodisperse emulsion of the present invention have a coefficient of variation of the grain size distribution of 0.15 when the grain group is observed using an electron micrograph.
Say what is below. In other words, it refers to particles in which the value of the quotient (coefficient of variation) obtained by dividing the standard deviation a of the particle size distribution by the average particle size (coefficient of variation) is 0.15 or less. Note that the standard deviation s is calculated using the following formula. The average grain size referred to here refers to the diameter in the case of spherical silver halide grains, or the diameter when the projected image is converted into a circular image of the same area in the case of grains with shapes other than cubic or spherical. It is an average value, and when the individual grain size in this sense is ri and the number is ni, it is defined by the following formula. =Σniri/Σni The above particle size can be measured by various methods commonly used in the technical field for the above purpose. A typical method is Lapland's "particle size analysis method" AS.
TM Symposium on Light Microscope, 1955, pp. 94-122 or "Theory of the Photographic Process" by Mies and James, No. 3
Edition, published by McLamin Publishing Co., Ltd. (1966), Chapter 2. The particle size can be measured using the projected area of the particle or an approximate diameter. If the particles are of substantially uniform shape, the particle size distribution can be fairly expressed as diameter or projected area. The relationship between grain size distribution is "Empirical relationship between sensitometric distribution and grain size distribution in photographic emulsions"
The Photographic Journal, LXXIX
This can be determined by the method described in the article by Trivelli and Smith, Vol., (1949), pp. 330-338. The shape of the above-mentioned monodisperse silver halide grains according to the present invention is preferably normal crystal. Particularly preferred are normal crystals such as octahedral crystals and dodecahedral crystals. As for the composition of the silver halide, silver chloride, silver bromide, silver chloroiodide, silver chloroiodobromide, silver chlorobromide, silver iodobromide, etc., which are used in general silver halide emulsions, can be widely used. However, silver iodobromide is preferably used. In order to produce such monodisperse silver halide grains, grains of a desired size can be obtained by a double jet method while keeping pAg constant. In addition, highly monodisperse silver halide grains are
The method described in JP-A-54-48521 can be applied. For example, potassium iodobromide
It is produced by adding an aqueous gelatin solution and an ammoniacal silver nitrate aqueous solution to an aqueous gelatin solution containing silver halide seed particles at varying addition rates as a function of time. At this time, highly monodisperse silver halide grains can be obtained by appropriately selecting the time function of addition rate, pH, pAg temperature, etc. An emulsion (hereinafter referred to as
The emulsions of the present invention) are selenium sensitized according to the present invention. Examples of the selenium sensitizer used in the selenium sensitization in the present invention include aliphatic isoselenocyanates such as allyl isocyanate, selenoureas such as N,N-dimethylselenourea, selenoketones, selenoamides, and selenocarbons. Acids and esters, selenophosphates, selenides such as diethylselenide, etc. can be used, and specific examples thereof include those described in U.S. Pat. No. 1,574,944, U.S. Pat. It is stated in each specification. In the present invention, a wide range of selenium sensitizers described in the above-mentioned publications can be used, but in particular, selenium sensitizers that are more unstable than non-unstable selenium compounds such as selenite and selenocyanoate are used. can be preferably used. The term unstable (labil) mentioned above is
It has a well-known meaning in the industry,
Specifically, it is a name for a substance that produces a silver salt when added to an aqueous silver nitrate solution. For example, unstable sulfur compounds produce silver sulfide when added to an aqueous silver nitrate solution, and unstable selenium compounds produce silver selenide. The selenium sensitizers used in the present invention include a wide range of unstable selenium sensitizers, such as U.S. Pat.
No. 1, No. 1602592, etc. are helpful. Examples of the selenium sensitizer preferably used in the present invention include colloidal selenium metal and aliphatic isoselenocyanate.
Particularly useful selenium sensitizers include aliphatic substituents, such as methylselenourea, ethylselenourea, propylselenourea, isopropylselenourea, butylselenourea, and selenoketones such as selenoacetone and selenoacetophenone. , as well as selenoamide, selenocarboxylic acid, and others substituted with an aromatic group or a heterocyclic group, such as phenylselenourea, benzothiazolylselenourea, and pyridylselenourea. In addition to the above-mentioned unstable organic selenium compounds, other useful selenium sensitizers containing unstable selenium atoms can also be used in the present invention. Specific examples include tetramethylselenourea, N-(β
-carboxyethyl)-N',N'-dimethylselenourea, selenoacetamide, diethylselenide, 2-selenopropionic acid, 3-selenobutyric acid,
Methyl-3-senobutyrate, e.g. tri-p-
Examples include tolylselenophosphate. The amount of these selenium sensitizers used varies depending on the type of selenium sensitizer, properties of silver halide, aging conditions, etc., but generally per mole of silver halide.
It is 0.01-5.0 mg. The emulsion of the present invention is spectrally sensitized with a cyanine dye represented by the general formula []. In the present invention, R ₁ and
The alkyl group represented by R ₂ is as follows:
Lower alkyl groups are preferred, such as methyl, ethyl, propyl, butyl and the like.
Examples of the anion represented by X ₁ include chloride, bromide, iodide, thiocyanate, sulfamate, methylsulfate, ethylsulfate, perchlorate, and p-toluenesulfonate. In the present invention, among the sensitizing dyes represented by the general formula [], particularly useful sensitizing dyes can be represented by the following general formula []. General formula [] In the formula, Z ₃ and Z ₄ may be the same or different and represent a sulfur atom or an oxygen atom, and R ₃ and R ₄ are in the general formula []
Represents a group having the same meaning as the group represented by R ₁ and R ₂ . In addition, Y ₁ , Y ₂ , Y ₃ and Y ₄ are hydrogen atoms, respectively
Halogen atoms (e.g. chlorine, bromine, iodine, fluorine), hydroxy groups, alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, etc.), amino groups (e.g. amino, methylamino, dimethylamino, diethylamino, etc.), acylamide groups ( (e.g., acetamide, propionamide, etc.), acyloxy groups (e.g., acetoxy, propionoxy, etc.), alkoxycarbonyl groups (e.g., ethoxycarbonyl, propoxycarbonyl, etc.), alkoxycarbonylamino groups (e.g., ethoxycarbonylamino, butoxycarbonylamino, etc.), alkyl groups (e.g. methyl, ethyl, propyl, etc.)
Represents an aryl group (eg phenyl, tolyl, etc.). Y ₁ and Y ₂ and/or Y ₃ and Y ₄ may be connected to each other to form, for example, a benzene ring. This benzene ring may have a substituent. _X2
represents an anion, specifically an anion having the same meaning as X ₁ in the general formula [].
m represents an integer of 1 or 2, and m represents 1 when the sensitizing dye forms an inner salt. Typical specific examples of the sensitizing dye represented by the general formula [] used in the present invention are shown below, but the present invention is not limited thereto. [Exemplary compounds of general formula []] The sensitizing dye represented by the general formula [ ] of the present invention is described, for example, in US Pat. No. 3,397,060, US Pat. Incidentally, sensitizing dyes not described in the above specification can also be easily synthesized by those skilled in the art according to the synthesis method described above. The above-mentioned sensitizing dyes are added at the beginning of chemical ripening (also called second ripening), during ripening,
The process may be carried out at any appropriate time, such as after the completion of ripening or prior to emulsion coating. Furthermore, as a method for adding the sensitizing dye according to the present invention to the emulsion according to the present invention, various conventionally proposed methods can be applied. For example, US Patent No.
3469987, by dissolving the sensitizing dye in a volatile organic solvent, dispersing the solution in a hydrophilic colloid, and adding this dispersion to the emulsion. Furthermore, the sensitizing dyes according to the present invention may be individually dissolved in the same or different solvents,
These solutions can be mixed or added separately before being added to the emulsion. When the sensitizing dye according to the present invention is added to a silver halide emulsion, a water-miscible organic solvent such as methyl alcohol, ethyl alcohol, or acetone is preferably used as the dye solvent. When the sensitizing dye is added to a silver halide emulsion, the amount of addition is 1x per mole of silver halide.
10 ⁻⁵ mol to 2.5×10 ⁻² mol, preferably 1.0
×10 ⁻⁴ mol to 1.0×10 ⁻³ mol. The sensitizing dye used in the emulsion of the present invention can also be used in combination with other sensitizing dyes or supersensitizers. The emulsion of the present invention can be subjected to various commonly used chemical sensitization methods in addition to chemical sensitization using a selenium compound. That is, chemical sensitization can be carried out by using a chemical sensitizer such as activated gelatin; a water-soluble gold salt; a sulfur sensitizer; a reduction sensitizer such as polyamine or stannous chloride. In the present invention, it is preferable to carry out sulfur sensitization together with the selenium sensitization, and known sulfur sensitizers can be used.
For example, thiosulfate, allylthiocarbamide thiourea, allyl isothiacyanate, cystine, p-
Examples include toluenethiosulfonate and rhodanine. Other U.S. Patent Nos. 1574944 and 1574944;
Specifications of No. 2410689, No. 2278947, No. 2728668, No. 3501313, No. 3656955, German Patent No. 1422869, Japanese Patent Publication No. 56-24937, Japanese Unexamined Patent Publication No. 1983-
Sulfur sensitizers described in Japanese Patent No. 45016 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 pH, temperature, and silver halide grain size, but as a guide, it is approximately
The amount is preferably about 10 ^-7 mol to about 10 ^-1 mol. Further, in the present invention, it is preferable to carry out gold sensitization together with the selenium sensitization, and the gold sensitizer used may be a gold oxidation number of +1 or +3, and various gold compounds may be used. Typical examples include chloroaurate, potassium chloroaurate,
Aurich trichloride, potassium oligothiocyanate, potassium iodooleate, tetracyanoolithic 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. 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 the sulfur sensitization and gold sensitization. Furthermore, the emulsion of the present invention can be made to have significantly higher sensitivity by chemical ripening in the presence of a silver halide solvent. As the silver halide solvent used in the present invention, US Pat.
Specifications of No. 3574628, JP-A-54-1019 and JP-A No. 54
(a) organic thioethers described in JP-A-158917, etc., (b) thiourea derivatives described in JP-A-53-82408, JP-A-55-77737 and JP-A-55-2928, etc. (c) Silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom, described in JP-A-53-144319, JP-A-53-144319;
Examples include (d) imidazoles, (e) sulfites, and (f) thiocyanates described in JP 54-100717, and specific compound examples are listed below. The amount of silver halide solvent used varies depending on the type; for example, in the case of thiocyanate, the preferred amount is in the range of 5 mg to 1 g per mole of silver halide. As described in detail above, the present invention is characterized in that it is a monodispersed emulsion that is selenium-sensitized and spectrally sensitized with a cyanine dye represented by the general formula []. The emulsion of the present invention has a high sensitivity in which the sensitivity is effectively increased by using octahedral and/or tetradecahedral crystal grains as silver halide grains, and the occurrence of capri is improved. As mentioned above, the emulsion of the present invention is subjected to sulfur sensitization and/or gold sensitization in addition to selenium sensitization and spectral sensitization with cyanine dye, so that the sensitization effect is further improved. Ru. Further, the emulsion of the present invention can preferably be further subjected to chemical ripening in the presence of a silver halide solvent. In the present invention, the timing of adding each of the sensitizers to the emulsion is not particularly limited as long as it is at the beginning of chemical ripening or during the progress of chemical ripening, and the order of addition does not need to be particularly defined. It is most preferable that the emulsion of the present invention constitutes an emulsion layer by itself, but if necessary, it can also be mixed with other emulsions to form an emulsion layer. In this case, the emulsion in the emulsion layer is Preferably, 70% or more is the emulsion of the present invention. The emulsion of the present invention may contain various compounds after chemical ripening in order to prevent fogging during its manufacturing process, storage, or development, or to further stabilize photographic performance. . For example, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzimidazoles, aminotriazoles, benztriazoles, nitrobenzotriazoles mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines, mercaptotriazines, thioketo compounds such as oxazolinthione, and also benzenethiosulfinic acid, benzenesulfinic acid, benzene Many compounds known as antifoggants or stabilizers can be added, such as sulfonic acid amides, hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives, ascorbic acid derivatives, and the like. These chemicals are preferably added during chemical ripening or before coating. Various hydrophilic colloids including gelatin are used as the binder for the emulsion of the present invention. Gelatin includes not only gelatin but also derivative gelatin, and derivative gelatin includes a reaction product of gelatin and an acid anhydride, a reaction product of gelatin and isocyanate, or a reaction product of gelatin and a compound having an active halogen atom. Products, 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,
Examples include p-bromophenyl isocyanate, p-chlorophenyl isocyanate, p-tolyl isocyanate, p-nitrophenyl isocyanate, and naphthylisocyanate. 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 emulsions, colloidal albumin, agar, gum arabic, dextran, alginic acid, such as acetyl content 19 ~26%
cellulose derivatives such as previously hydrolyzed cellulose acetate, 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, a polymer obtained by polymerizing a protein or a saturated acylated protein with a monomer having a vinyl group, polyvinylpyridine, polyvinylamine, polyaminoethyl methacrylate, polyethyleneimine, etc. can also be used. The silver halide emulsion of the present invention includes coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesive prevention, and photographic properties improvement (e.g. development acceleration, high contrast, sensitization).
Various known surfactants may be included for various purposes. 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, U.S. Patent No. 2739891, U.S. Patent No. 1179290
No. 1198450, No. 2739891, No. 2739891, No.
No. 2823123, No. 3058101, No. 3415649, No. 3666478, No. 3756828, British Patent No.
1397218, 3113816, 3411413, 3473174, 3345974, 3726683,
Belgian Patent No. 3843368, Belgian Patent No. 731126, British Patent No. 1138514, Belgian Patent No. 1159825, Belgian Patent No. 1374780
No., U.S. Patent No. 2271623, U.S. Patent No. 2288226, U.S. Patent No.
No. 2944900, No. 3235919, No. 3671247, No. 3772021, No. 3589906, No. 3666478,
No. 3754924, West German patent application OLS 1961683 specifications and Japanese Patent Application Laid-open Nos. 50-117414 and 50-59025,
It is described in Japanese Patent Publications No. 40-378, No. 40-379, 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 glycols, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl amines or amides, silicones polyethylene oxide adducts), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, and nonionic interfaces such as urethanes or ethers. activator,
Tritenopenoid saponins, alkyl carboxylates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurates, sulfosuccinates, sulfoalkyl Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc., such as polyoxyethylene alkyl phenyl ethers and polyoxyethylene alkyl phosphate esters; amino acids; , aminoalkylsulfonic acids,
Ampholytic surfactants such as aminoalkyl sulfates or phosphoric acid esters, alkyl betaines, amine imides, amine oxides, alkyl amine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic surfactants such as pyridium, imidazolium, etc. Cationic surfactants such as quaternary ammonium salts and aliphatic or sulfonium salts can be used. In the emulsion of the present invention, in addition to the above-mentioned surfactants, West German patent application (OLS) No. 2002871
No. 2445611, No. 2360878, British Patent No.
It may contain imidazoles, thioethers, selenoethers, etc. described in the specifications of No. 1352196. In addition, in order to apply the emulsion of the present invention to a color photographic material, a blue-sensitive silver halide emulsion, a silver halide emulsion adjusted to have green sensitivity and red sensitivity, and a combination of yellow, magenta and cyan couplers are required. The method and materials used for color light-sensitive materials, such as color photosensitive materials, may be used, and 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 ion. 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). Furthermore, the coupler may be one in which the product of the coupling reaction is colorless. As the yellow coupler, a known open-chain ketomethylene coupler can be used. Among these, benzoylacetanilide and pivaloylacetanilide compounds can be advantageously used. Specific examples of yellow couplers that can be used are:
U.S. Patent No. 2875057, U.S. Patent No. 3408194, U.S. Patent No.
No. 3519429, Japanese Patent Publication No. 47-26133, Japanese Patent Publication No. 48-29432,
No. 50-87650, No. 51-17438, No. 51-102636
No., Special Publication No. 45-19956, No. 51-33410, No. 51-
It is stated in No. 10783, No. 46-19031, etc.
Particularly preferred yellow couplers include the following compounds. 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 color forming couplers that can be used include U.S. Pat. No. 2,600,788;
3062653, 3408194, 3519429, JP 49-111631, 56-29236, 57-
There is a description in No. 94752, Special Publication No. 48-27930, etc.
Particularly preferred couplers include the following compounds. (12) 1-(2,4,6-trichlorophenyl)-
3-(3-acrylamidobenzamide)-4-
Pyrazolyl-5-oxo-2-pyrazoline and n
- Polymer coupler latex made of a 20:80 copolymer of butyl acrylate impregnated with the above magenta coupler (2) As the cyan coloring coupler, phenolic compounds, naphthol compounds, etc. can be used. Specific examples include U.S. Pat. No. 2,423,730 and U.S. Pat.
No. 2474293, No. 2895826, Japanese Patent Application Publication No. 1974-117422
Particularly preferred cyan couplers include the following compounds. As colored magenta couplers, for example, U.S. Patent No. 2801171, U.S. Pat.
Particularly preferred colored magenta couplers are the compounds shown below. Colored cyan couplers are described, for example, in US Pat. No. 1,084,480, Japanese Patent Publication No. 55-32461, etc., and particularly preferred colored cyan couplers include the following compounds. Two or more of the above various couplers may be contained in the same layer. Further, 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. 2,332,027 can be used. Examples include 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 laurylamide), etc., or organic solvents with a boiling point of about 30°C to 150°C, such as lower alkyl acetates such as ethyl acetate, butyl acetate, propion After being dissolved in ethyl acid, 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 silver halide emulsion layer. Further, a DIR compound can be used in the emulsion of the present invention, and examples of the DIR compound include US Pat. No. 2,327,554, US Pat.
No. 3615506, Japanese Patent Publication No. 52-82424, No. 54-145135
Compounds described in Japanese Patent Publication No. 57-151944, Japanese Patent Publication No. 51-16141, etc. can be preferably used.
Particularly preferred DIR compounds include the following compounds. Anti-staining agents that can be effectively used in the emulsion of the present invention are described, for example, in U.S. Pat. Compounds can be mentioned. As the antistatic agent used in the present invention, diacetylcellulose, styrene perfluoroalkylridium maleate copolymer, alkali salt of a reaction product of styrene-maleic anhydride copolymer and p-aminobenzenesulfonic acid, etc. are effective. It is. 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 terraces 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.
Examples include sodium maleate copolymer and alkyl vinyl ether-maleic acid copolymer. Supports for light-sensitive 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, cellulose acetate, cellulose nitrate, polyvinyl acetal, polypropylene. For example, there are polyester films such as polyethylene terephthalate, polystyrene, etc., and these supports are appropriately selected depending on the intended use of each photosensitive 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 photosensitive 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-and-white negative developer, then exposed to white light or treated with a bath containing a fogging agent, and then 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; for example, representative methods include a method in which, after color development, bleach-fixing treatment is performed, and if necessary, washing with water and stabilization treatment are performed;
Alternatively, a method can be applied in which bleaching and fixing are carried out separately after color development, and further washing with water and stabilization treatment are carried out as necessary. The emulsion of the present invention is particularly preferred for color applications, but it has extremely high photographic sensitivity and low fog, so it is preferably applied to many light-sensitive materials. For example, the photosensitive materials according to the present invention include black and white general use, X-ray use, color use, infrared use, micro use, silver dye bleaching use,
It can be used for various purposes such as reversal and diffusion transfer. The present invention will be specifically explained below with reference to Examples. Example 1 1-1) Comparative polydisperse emulsion A polydisperse silver iodobromide emulsion (containing 4 mol % of silver iodide) with an average grain size of 1.7 μm was prepared according to the method disclosed in Japanese Patent Publication No. 1417/1983. A comparative emulsion was prepared and designated as Emulsion A. (1-2) Preparation of seed emulsion Seed emulsions were prepared using the eight types of solutions shown below. [Solution 1-A] Ossein gelatin 40 g Distilled water 4000 ml Polyisopropylene-polyethyleneoxy-disuccinate ester sodium salt 10% ethanol aqueous solution 10 ml AgNO ₃ 170 mg 10% H ₂ SO ₄ 35 ml [Solution 1-B ] AgNO ₃ 23 g Make up to 1350ml with distilled water. [Solution 1-C] AgNO ₃ 577 g Make up to 1700 ml with distilled water. [Solution 1-D] Ossein gelatin 27 g KBr 15.6 g KI 0.44 g Polyisopropylene-polyethyleneoxy-disuccinate sodium salt 10% ethanol aqueous solution 5 ml 10% H ₂ SO ₄ 19 ml Make up to 1340 ml with distilled water. [Solution 1-E] Ossein gelatin 33 g KBr 396.5 g KI 11.3 g Polyisopropylene-polyethyleneoxy-disuccinate sodium salt 10% ethanol aqueous solution 6 ml 10% H ₂ SO ₄ 18.5 ml Make up to 1700 ml with distilled water. [Solution 1-F] KBr 20 g Distilled water 672 ml [Solution 1-G] KBr 70 g Distilled water 180 ml [Solution 1-H] 7% sodium carbonate aqueous solution 208 ml Add solution 1-A to solution 1-A at 60°C. B and solution 1
-D was added by simultaneous mixing method with an addition time of 29.5 minutes. The addition rate was increased linearly with time according to the method described in Japanese Patent Application No. 56-123070. 2 minutes after the addition is complete,
Solutions 1-C and 1-E were added using the simultaneous mixing method over an addition time of 83 minutes. The addition rate was increased with time as above. During the addition of solutions 1-B and 1-D, and solutions 1-C and 1-E, solution 1-F was used to control the pAg value of solution 1-A to 4.0 (EAg value + 340 mV). Three minutes after the addition of solutions I-C and 1-E was completed, solution 1-G was added. After another 2 minutes, solution 1-H was added. Next, after washing with water and desalting, 500ml of an aqueous solution of ossein gelatin (containing 50g of ossein gelatin)
and dispersed by stirring at 55℃ for 30 minutes.
The total volume was adjusted to 1500 ml with distilled water. Hereinafter, this emulsion will be referred to as "T-1". Electron microscopic observation revealed that this emulsion was a monodisperse emulsion consisting of cubic grains with a side length of 0.30 μm and a coefficient of variation in particle size distribution of 0.068. (1-3) Preparation of cubic monodisperse emulsion The seed emulsion of Example 1 was grown using the seven types of solutions shown below to prepare cubic monodisperse emulsions. [Solution 2-A] Ossein gelatin 54 g Distilled water 5426 ml Polyisopropylene-polyethyleneoxy-disuccinate ester sodium salt 10% ethanol aqueous solution 4 ml Acetic acid 28 ml NH ₄ OH 0.71 mol The above T-1 type emulsion 15.8 ml [Solution 2-B] Ossein gelatin 45.3g KBr 554g KI 15.8g Make up to 2265ml with distilled water. [Solution 2-C] AgNO ₃ 945 g Distilled water 1130 ml NH ₄ OH 11.67 mol Make up to 2649 ml with distilled water. [Solution 2-D] KBr 150 g Distilled water 300 ml [Solution 2-E] 56% acetic acid aqueous solution 2000 ml [Solution 2-F] KBr 105.5 g Distilled water 211 ml At 40°C, add Solution 2-A to Solution 2-A. B and Solution 2-C were added using the simultaneous mixing method for an addition time of 93.5 minutes. The addition rate increased linearly with addition over time. During each solution addition, solution 2-D is used to calculate the pAg value of solution 2-A.
8.9 and also using solution 2-E.
The PH value of A was controlled to decrease over time. Two minutes after the addition of solutions 2-B and 2-C was completed, solution 2-E was added, and after another 2 minutes, solution 2-F was added.
The pH value of the emulsion was adjusted to 6.0 by adding . Next, after washing with water and desalting, 800 ml of an aqueous solution of ossein gelatin (Ossein gelatin 80
After dispersion by stirring at 40°C for 20 minutes, the total volume was adjusted to 2400ml with distilled water. This emulsion will be referred to as "B" hereinafter. (1-4) Preparation of a 14-hedral monodispersed emulsion A 14-hedral monodispersed emulsion was prepared (emulsion C) in the same manner as in (1-3) above, except for the solution addition rate, pH and pAg. (1-5) Preparation of octahedral monodispersed emulsion An octahedral monodispersed emulsion was prepared (emulsion D) in the same manner as in (1-3) above except for the solution addition rate, pH and pAg. For each of the above emulsions, 23 ml of a 1% ammonium thiocyanate aqueous solution per mole of silver, and the following sensitizing dye.
Add 120ml, 0.7ml of 0.02% chloroauric acid tetrahydrate aqueous solution, 2.1ml of dimethylselenourea 0.1% aqueous solution as a selenium compound, and 2.1ml of 0.05% sodium thiosulfate pentahydrate solution, and perform optimal chemical ripening at 55℃. Summer. After chemical ripening, 4-hydroxy-
6-Methyl-1,3,3a,7-tetraazaindene and phenylmercaptratrazole are added and then 1-(2,4,6-
trichlorophenyl)-3-[3-(2,4-di-
t-Amylphenoxyacetamido)benzamide]-5-pyrazolone (15 g) was dissolved in 30 ml of ethyl acetate and 15 ml of dibutyl phthalate, and this was dissolved in Alkanol B (alkylnaphthalene sulfonate,
The mixture was mixed with 20 ml of a 10% aqueous solution (manufactured by DuPont) and 200 ml of a 5% aqueous gelatin solution, emulsified and dispersed in a colloid mill, and added to 1 kg of the emulsion. Immediately after preparation, after storage at 40° C. for 4 hours, and after storage for 8 hours, each emulsion was coated on a triacetate base at a silver content of 20 mg/dm ² as samples Nos. 1 to 6. The sensitizing dyes include the sensitizing dyes (-1) and (-17) of the exemplary compounds according to the present invention, or the comparative sensitizing dyes shown below for comparison.
Experiments were conducted using Samples 1, 2, and 3.
Similar experiments were also conducted to examine differences in emulsions, the effects of the presence or absence of selenium sensitizers, and the synergistic effects of each. The composition of each emulsion sample is shown in Table 1 below. Next, each sample was exposed to 1/50 second wedge light through a green light filter (manufactured by Tokyo Shibaura Electric KK), and then subjected to negative development processing using the processing method described below. [Development conditions] Processing process (38℃) Processing time Color development 2 minutes 45 seconds Bleaching 6 minutes 30 seconds Washing with water 3 minutes 15 seconds Fixing 6 minutes 30 seconds Washing with water 3 minutes 15 seconds Stabilization 1 minute 30 seconds Each process The composition of the treatment liquid used in the process is as follows. Color developer composition: 4-amino-3-methyl-N-ethyl-N-
(β-hydroxyethyl)-aniline sulfate
4.8 g Anhydrous sodium sulfite 0.14 g Hydroxyamine 1/2 sulfate 1.98 g Sulfuric acid 0.74 mg Anhydrous potassium carbonate 28.85 g Anhydrous potassium bicarbonate 3.46 g Anhydrous potassium sulfite 5.10 g Potassium bromide 1.16 g Sodium chloride 0.14 g Nitrilotriacetic acid-3 Sodium salt (monohydrate) 1.20 g Potassium hydroxide 1.48 g Add water to make 1. Bleach solution composition: Ethylenediaminetetraacetic acid iron-ammonium salt 100.0 g Ethylenediaminetetraacetic acid 2-ammonium salt 10.0 g Ammonium bromide 150.0 g Ice Acetic acid 10.0ml Add water to make 1, and adjust the pH using ammonia water.
Adjust to 6.0. Fixer composition: Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.6 g Sodium metasulfite 2.3 g Add water to make 1, and adjust to PH6.0 using acetic acid. Stabilizing liquid composition: Formalin (37% aqueous solution) 1.5 ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5 ml 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. Sensitivity is expressed as the reciprocal of the exposure amount required to obtain a density of fog + 0.1. In addition, each of these samples was heated at 20% relative humidity and 55°C
Forced to deteriorate for several days, exposed, developed, and measured.
The results are shown in Table 1 below.

[Table] As can be seen from the results in Table 1, an emulsion sensitized by a selenium compound has high photosensitivity when a polydisperse emulsion is used with a sensitizing dye having the structure of the present invention, but fogging may occur. Although it is not suitable for practical use because it is expensive and causes a large increase in fog due to storage over time, it can be seen that by making the emulsion a monodisperse emulsion, a high-sensitivity emulsion that overcomes this drawback can be obtained. It can also be seen that better results can be obtained with a tetradecahedral or octahedral monodispersed emulsion than with a cubic monodispersed emulsion.
With comparative sensitizing dyes, such fog after storage over time is relatively small, but because of their low sensitivity, they are disadvantageous in the production of highly sensitive light-sensitive materials. Example 2 An exemplary sensitizing dye (-
23) and (-46) and the following comparison sensitizing dyes -4, -5 and -6 were compared, and the results are shown in Table 2 below.

[Table] Table 2 shows the relationship between the sensitizing dye according to the present invention and the comparative sensitizing dye when only the coupler and sensitizing dye were changed using the formulation of Sample 8 of Example 1 as described above. The table above shows the difference in sensitizing effect, and it is clear from the above table that excellent sensitization is achieved when the sensitizing dye according to the present invention is used. Example 3 An emulsion was prepared in the same manner as in Example 2, except that chloroauric acid or sodium thiosulfate was omitted.
The effects of gold compounds and unstable sulfur compounds were investigated. The results are shown in Table 3 below.

[Table] As is clear from the above table, both the gold compound and the unstable sulfur compound give favorable results in terms of fog and sensitivity. Effects of the Invention An emulsion consisting of monodisperse silver halide grains chemically ripened in the presence of a selenium sensitizer and a cyanine dye represented by the above general formula [] has high sensitivity and is stable against fogging and storage. properties are significantly improved.

Claims (1)

[Scope of Claims] 1. A silver halide emulsion characterized in that it is a monodisperse emulsion that is selenium-sensitized and spectrally sensitized with a cyanine dye represented by the following general formula []. General formula [] (In the formula, Z ₁ and Z ₂ each represent an atomic group necessary to complete a thiazole ring, benzothiazole ring, naphthothiazole ring, oxazole ring, benzoxazole ring, or naphthoxazole ring. R ₁ and R ₂ are each represents an alkyl group or an alkyl group having either a hydroxy group, a carboxyl group or a sulfo group, and X ₁
represents an anion, n represents an integer of 1 or 2, and n represents 1 when the sensitizing dye forms an inner salt. 2. The silver halide emulsion according to claim 1, wherein the silver halide grains contained in the monodispersed emulsion are mainly composed of tetradecahedral crystal grains and/or octahedral crystal grains. 3. The monodisperse emulsion is gold-sensitized. Claim 1 or 2.
The silver halide emulsion described in . 4. The silver halide emulsion according to claim 1 or 2, wherein the monodisperse emulsion is sulfur-sensitized.