Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/015—Apparatus or processes for the preparation of emulsions
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
  • G03C2001/03529—Coefficient of variation
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
  • G03C2001/03535—Core-shell grains
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
  • G03C2001/03564—Mixed grains or mixture of emulsions
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C2200/00—Details
  • G03C2200/06—Additive

Definitions

• the present invention relates to a photosensitive silver halide photographic emulsion, and more particularly to a silver halide emulsion containing silver halide grains mainly or silver iodobromide.
• the present invention relates to a sensitizing method and a silver halide photographic emulsion sensed by the method.
• silver halides such as silver chloride, silver bromide, silver chlorobromide, silver bromoiodide, and silver chloroiodobromide have been used as photographic silver halides.
• silver iodobromide has been used as a high-sensitivity photographic silver halide for obtaining high-sensitivity emulsions.
• OMFI bets the control of pH is also controlled and sufficient ⁇ conditions feed rate to the reaction system of Gin'i on determined theoretically and C 53 gain down I on-are required.
• the silver halide emulsions produced under these conditions are cubic, octahedral and decahedral composed of so-called normal crystal grains having various proportions of (100) and (111) faces. It has a tetrahedral shape.
• octahedral, tetradecahedral or ⁇ -shaped crystal grains having a (111) plane are usually produced under conditions of low silver density, and thus latent images are usually produced.
• silver nuclei which are known as nuclei or helmets, have the advantage of being small.
• the chemical sensitization reaction has a large crystal dependence, and for example, in a normal method,
• hydroxyazaindene compounds have been conventionally used as stabilizers for photographic emulsions in the industry because they have the property of inhibiting chemical ripening due to sulfur-containing yellowing. It is well known 1), it is added for the purpose of terminating the sulfur sensation reaction and for preventing the generation of fog or during the manufacturing process, during storage, or during development. This compound is also known to have the effect of increasing photographic sensitivity.
• a silver halide emulsion is prepared by adding azaindene prior to sulfur sensation and simultaneously or simultaneously. It is stated that the addition of a monovalent gold complex chloride containing sulfur followed by ripening increases the intrinsic sensitivity of silver halide as compared to the conventional method. However, it is not possible to obtain a sufficient effect simply by applying this sensitivity method to a silver halide emulsion.
• Japanese Patent Application Laid-Open No. 50-63914 and German Patent Application (OLS) 2, 419, 798 disclose the monodisperse pores of cubic particles having a silver bromide-containing mole ratio of 80 or more. It is described that the sensitivity is increased by adding a hydroquinone tetrazindene compound after sulfur sensitization of a silver genide grain emulsion.
• this publication discloses crystal forms outside the cube, for example,
• JP-A-51-77223 and U.S. Pat. No. 4,078,937 disclose a sulfur-sensitized silver halide photographic emulsion containing silver halide grains having an average grain size of silver halide grains. It has been described that when the size exceeds 0.5 m, the sensitivity is increased when a certain type of hydroxytetrazindene compound is contained.
• the compound was coated with the hydroxycitrazinedene compound, and the coating was not added at all.
• the I & A may have slightly higher sensitivity than the case of applying to the skin.
• the industry has traditionally added hydroxyzite lazanden compounds as stabilizers after chemical ripening, with or without impeachment.
• the method described in Japanese Patent Application Laid-Open No. 51-77223 and U.S. Pat. No. 4,073,937 is higher than the conventional method. It has not provided a new sensitization method for realizing high-sensitivity emulsions.
• the object of the present invention is to produce almost a monodisperse emulsion containing silver halide grains of octahedral or tetradecahedral crystal having (11 1) plane] ⁇ .
• a high-sensitivity silver halide photographic emulsion obtained by such a chemical sensitization method.
• An object of the present invention is to provide a silver-halogenated emulsion containing core z-shell silver halide grains with a gold sensitizer and a sulfur sensitizer or a selenium sensitizer.
• the silver halide grains are octahedral crystals or dodecahedral crystals having a (111) plane.
• the silver halide constituting the grains is substantially different from silver iodide!
• the halogenation (the number of fluctuations in the particle size distribution of the particles is 0.18 or less)), and gold-sulfur in the presence of a nitrogen-containing complex compound that forms a complex with silver or silver ion. It is altered by the method of manufacturing silver halide emulsions, which are characterized by the sensation or sensitization of gold-selenium.
• the halogenated ⁇ grains contained in the silver halide emulsion are converted from an octahedral or tetradecahedral crystal having a (111) face.
• Monodisperse core-shell silver iodobromide particles, and a selenium sensitizer and gold are added in the presence of a nitrogen-containing heterocyclic compound which forms a complex with silver in an amount sufficient to cover the particles. It is based on the discovery that if the ratio between the sensitizer and the ratio between the sulfur sensitizer and the gold sensitizer j is controlled within a certain range, markedly higher sensitivity can be achieved.
• the effect of the present invention is that when a known gold-sulfur sensitization method or gold-selenium sensitization method is applied to octahedral or tetradecahedral silver iodide grains, the (111) face is sulfided. (4) A large number of photosensitive nuclei are formed on a single silver iodobromide grain because the nuclei are easily formed, and the quantum efficiency does not increase.
• the effect of the present invention is that the silver iodobromide grains are converted to a coanoshell type in a monodisperse emulsion, and a complex is formed with silver or silver ion. This was obtained by intentionally controlling the photonucleation reaction on the (111) plane in the presence of a nitrogen-containing heterocyclic compound.
• Cubic silver halide grains have each vertex of the cube at each (100) plane.] 3 Photosensitive nuclei are easily generated, and the photosensitive nuclei are selectively apexed without special attention. Because it is generated.
• the mono-dispersed octahedral or tetradecahedral silver iodobromide emulsion of the anochel type may be subjected to gold-sulfur sensitization or gold-selenium sensitization in the absence of a nitrogen-containing heterocyclic compound.
• the fruit is small.
• iodine in silver bromide grains increases quantum efficiency and increases gold-sulfur sensitization or gold-selenium sensitization sensitivity, but contains iodine.] 3 lattice defect And the interstitial silver ion increases accordingly.
• iodine atoms present on the crystal surface suppress gold-sulfur sensitization or gold-selenium sensitization reaction.
• the nitrogen-containing heterocyclic compound forms a complex with silver ion on the surface to reduce the amount of interstitial silver ion to the amount required for the chemical sensitization reaction and to enhance the chemical sensitivity reaction. It seems that this contributes to the generation of a small number of effective photosensitive nuclei, but does not prevent the iodine atom on the surface from suppressing the chemical sensitization reaction. From these facts, good results can be obtained by sensitizing a core-shell octahedral or tetradecahedral silver iodobromide emulsion to gold-sulfur or gold-selenium sensitization in the presence of a nitrogen-containing heterocyclic compound. However, the degree of sensitization obtained was more remarkable than expected.] 3, it seems that a synergistic effect other than that predicted by the inventors was obtained.
• the present invention controls the reaction of forming a chemically sensitized nucleus by adopting the above-mentioned technical constitution, and uses a combination of gold-sulfur or gold-selenium sensitization. Conventionally, the effect is markedly manifested.] On the other hand, it is described in Japanese Patent Application Laid-Open No. 50-S3914 and West German Patent Application (OLS) 2, 419, 798.
• the sensitization method used is that at the end of yellow sensitization, the nitrogen-containing heterocyclic compound OMH, ⁇ ' ⁇ From this fact, the improvement of the latent image formation efficiency by controlling the silver ion and the like in the vicinity of the silver iodide grain surface and in the vicinity thereof. It is presumed that the invention was aimed at, and both are different skill bites.
• Makikai No. 51-77223 and U.S. Pat. No. 4,078,937 disclose that a silver halide emulsion having an average grain size of more than 0.5 m is sensitive to sulfur.
• a method for increasing the sensitivity of a silver halide emulsion containing a loxacitrazinden compound is sensitive to sulfur.
• the publication does not completely disclose the constitution and effect of the present invention, and in particular, all of the examples are prepared by adding hydroxycitrazaindene compound after completion of chemical ripening. For that reason, the sensitizing effect of the method depends on the average grain size, and the crystal habit of the silver halide grains is a technique different from the present invention, such as selection.
• British Patent No. 1,315,755 discloses a method of adding gold-sulfur by adding an azaindene compound and then adding a sulfur-containing monovalent gold complex chloride as described above.
• the crystal habit, core / shell structure, and the like of the silver halide grains are not mentioned, and the present invention cannot be predicted from the literature.
• Halogenated octahedral or tetradecahedral crystals of the present invention have a halogenated composition of 0.5 to 15 mol silver iodide. It is preferable that the substance substantially consists of silver chloride, but even if silver chloride is contained within a range that does not impair the effect of the present invention, it is possible to obtain the same effect.
• the form of the silver halide grains is substantially an octahedron formed by the (111) plane, or a tetrahedron formed by the (111 :) plane and the (100 :) plane. . Their particle size is determined.
• the ratio of the (111) plane to the (100) plane of the surface of the tetradecahedral silver halide grains used in the present invention is not limited to a specific one, at least the total of the grains is not limited. 5 of surface area
• the upper part has the (111) plane], and the larger the ratio of the (111) plane, the greater the sensitizing effect of the method of the present invention.]
• the (111 :) plane Is 40 or more.
• the effect of the present invention increases as the percentage of the silver halide particles of the present invention out of the silver halide particles contained in the emulsion increases.
• the ratio is 50
• the top is preferred, and the 70 is more preferred, and the emulsion in which silver halide grains are substantially composed of the haguchi genated ⁇ grains of the present invention is most preferred.
• a so-called monodispersed emulsion in which the variation coefficient of the particle size distribution of silver halide particles contained in the silver halide emulsion is 0.18 ° or less is used.
• the halogenated surface is treated with a nitrogen-containing heterocyclic compound capable of forming a complex with silver or silver ion to form a gold-selenium sensitization reaction or gold.
• a nitrogen-containing heterocyclic compound capable of forming a complex with silver or silver ion to form a gold-selenium sensitization reaction or gold.
• the average particle size of the halo-danned particles contained in the silver halide emulsion is calculated by dividing the standard difference S of the particle size distribution represented by the following formula (1) by the average particle size 7. Value, the coefficient of variation of the particle size distribution
• the average particle size referred to here is the average value of the diameter when a projected image of a silver halide particle is a circular image of the same area ⁇ ⁇ ⁇ .
• the diameter is ri]? And its number is ni, by the following formula? Is defined.
• the particle size of the above IS can be measured by various methods used for killing in the technical field for the above purpose.
• a typical method is the Lapland's “Particle Size Analysis Method”, ST-1 Symposium, On • Light Microscoby, 1955, pp. 94-122. It is also described in Chapter 2 of The Photographic Process Theory, co-authored by Mice and James, Third Edition, published by McMillan (1966).
• an emulsion having a dispersity of 0.18 or less is called a monodispersed emulsion.
• the silver halide emulsion of the present invention is
• the method of reacting the soluble ⁇ salt with the soluble halogen salt may be any of the injection mixing method, the simultaneous mixing method, and any combination thereof.
• One method of the double jet method is to use a method in which the pAg in the liquid phase in which silver halide is formed is kept constant, i.e., the so-called control * double jet method.
• the core Z-shell type halogenated silver halide grains according to the present invention can be composed of two layers having different silver iodide contents and a layered structure composed of two layers. ]), And the iodide content in the vicinity of the surface of the two or more layers is preferably lower.
• the vicinity of the surface refers to a portion having a thickness of 0.001 to 0.1 from the surface. Near the surface and it
• the difference in the silver iodide content contained in the inside be 5 m or more.
• Emulsions containing such silver halide grains have high sensitizing efficiency and are particularly suitable for obtaining surface latent image type emulsions.
• the inclination caused by the difference in the silver iodide content from the higher layer to the lower layer is low. It may have a sharp border, or it may be a clear and continuous change.
• the distribution state of silver iodide in the silver halide grains described above can be detected by the physical measurement method of each S. For example, the Photographic Society of Japan, Annual Meeting of 1982 As described in the abstract. 3 ⁇ 4 Luminescence at low temperatures can also be checked.
• silver iodide is contained in the vicinity of the surface of the grains in an amount of 0 to 4 mol ⁇ , and iodide is contained inside. It is silver halide containing 2 to 15 moles of silver.
• the silver halide composition other than the above-mentioned iodide is mainly silver bromide, but the silver halide may be included in D as long as the effect of the present invention is not impaired. In fact, the limit is about less than one mole.
• the silver halide emulsion according to the present invention may be a mixture of octahedral and tetradecahedral grains.
• the silver halide emulsion having the coz shell type silver halide silver halide emulsion of the present invention comprises monodisperse silver halide particles as cores, which are coated with shells. By doing so, it can be manufactured.
• a potassium salt for example, a potassium salt, a zinc salt, a calcium salt, a thallium salt, an iridium salt or These complex salts, rhodium salts or their salts may coexist.
• examples of the nitrogen-containing heterocycle include a virazole ring and a bilimidine.
• azazine den ring compounds having an azazine den ring.] ?, and azazine den compounds having a hydroxy group as a substituent, for example, hydroxyzide More preferred are rearazine den, tetrahydroxyazadinden, and hydroxypentazanedenide compounds.
• the heterocyclic ring may have a substituent other than the ⁇ -pixy group.
• substituents include an alkyl group, an alkylthio group, an amino group, a hydroxyamino group, an alkylamino group, a dialkylamino group, Arylamino group, calpoxy group, alkoxycarbonyl group, halogen atom, acylamino Group, cyano group, and mercapto group.
• This addition amount can be added by a control in an adsorption equilibrium state due to a change in pH and temperature during maturation or temperature change.
• the nitrogen-containing heterocyclic compound can be used in combination with a sensitizing dye for the gold-sulfur or gold-selenium sensitization of the present invention.
• the total amount of the nitrogen-containing purifying ring compound and the dye-sensitive dye added is such that a total of 10 molecular layers is formed from a monomolecular layer on the surface of the silver halide particles.
• the sensitizing dye is added in an amount exceeding 70, which is an amount capable of forming a single molecular layer on the surface of the silver halide grains.
• the amount of addition required to form a monolayer can be determined by creating an adsorption isotherm.
• the grain surface of a silver iodobromide emulsion consisting of 0.6 octahedral grains can be determined to be 41-hydrogen.
• the required addition amount is about 210 ⁇ / A mol] 9, therefore , occupied area that by this compound ⁇ is one molecule those 3 to about 3 0 1 2.
• particles having different particle diameters may be added in proportion to the area based on the above example.
• the nitrogen-containing heterocyclic compound of the present invention is preferably a colorless compound.
• the method of adding the nitrogen-containing heterocyclic compound of the present invention to an emulsion is carried out by dissolving in a suitable solvent (for example, a permanent or alkaline solution) which does not adversely affect the photoemulsion to form a solution.
• a suitable solvent for example, a permanent or alkaline solution
• Can be added with The compound may be present at the time of gold-sulfur sensitization or gold-selenium sensitization, but it may be added when a sulfur sensitizer or a selenium sensitizer is added to the emulsion. Or Sir is preferred.
• the gold sensitizer may be added during or at the end of the ripening for sensitization of Ryuhyo or Selenium.
• the term “complex” means a bond of two or more compounds or ions.
• sulfur sensitizers can be used.
• sulfur sensitizers for example, sulphate sulphate, sulphate sulphate, sulphate sulphate, sulphate sulphate, Loadan, and the like.
• Sulfur sensitizers described in, for example, JP-A-55-45016 can also be used.
• the addition amount of the sulfur sensitizer may be an amount sufficient to effectively increase the sensitivity of the emulsion. This amount varies over a considerable range under various conditions, such as the amount of the nitrogen-containing nitrogen-containing compound added, pH, temperature, and the size of the silver halide grains. Is 14 halogen silver halide equivalent]?
• a selenium sensitizer can be used in place of the sulfur sensitizer, but the selenium sensitizer is aryluso celenosinate.
• Aliphatic isoselenocynates, selenoureas, selenoketones, selenoamides, selenocarbons and esters Serenides such as tellurium, serenophosphites, getylserenide, and getyldiselenide can be used. Examples of U.S. Pat.Nos. 1,574,944, 1,602,592, and 1,623,499
• Addition amount Suruga vary over a wide range like the sulfur ⁇ agent, is a guideline, c b gate Nkagin 1 molar equivalent]) about 10 ⁇ tau mole or al 10- 1 model about Le is preferred.
• gold compounds having an oxidation number of +1 or +3 and various kinds of gold compounds may be used. Typical examples are gold chloride, potassium black mouth oleate, smart trick chloride, and potassium molybdenum. , California oleate, tetrasino liquefied acid, ummo-momo thiosipate, pyridyl tri cros And so on.
• the addition amount of the gold ⁇ agent Shi preferred range of in is but by D Ru different in a variety of conditions as a guide Ha Russia gain Nkagin 1 molar equivalent]? About 10 moles or, et al. ⁇ 1 molar or .
• gold nuclei and silver sulfide gold nuclei or silver selenide gold nuclei are formed as photosensitive nuclei.
• the composition of silver sulfide nuclei or silver selenide gold nuclei has a significant effect on electron trapping or imageability.
• the ratio of the gold sensitizer to the sulfur sensitizer or selenium sensitizer greatly affects the sensitizing effect. Therefore, in order to effectively increase the sensitivity of the emulsion depending on the ripening conditions, it is necessary to use sulfur.
• the addition ratio of the sensitizer or selenium sensitizer and gold sensitizer depends on the number of sulfur atoms that form silver sulfide with silver ion among the sulfur atoms contained in the sulfur sensitizer Or selenium atoms contained in the selenium sensitizer
• the number of gold atoms must be in the range of 12 to 1Z200 for the number of selenium atoms that produce silver selenide.
• sodium thiosulfate is used as the sulfur sensitizer and sodium chloroaurate is used as the gold sensitizer, the latter is reduced by about 1 / Add in the range of 200.
• the pAg of the emulsion to be subjected to the gold-cyan yellow sensitization or the gold selenium sensitization in the present invention is preferably in the range of 7.5 to 10.0, and the pH is preferably in the range of 5.0 to 9.0.
• the sensitization method of the present invention can be used in combination with a sensitization method using another noble metal, for example, a noble metal such as platinum, palladium, iridium, or rhodium or a salt thereof. .
• a noble metal such as platinum, palladium, iridium, or rhodium or a salt thereof.
• a reduction sensation can be further used in combination.
• the reducing agent is not particularly limited, and examples thereof include known stannous chloride, thiourea dioxide, hydrazine derivatives, and silane compounds.
• the sensitizing method of the present invention is a remarkable spectral sensitizing method in which a sensitizing dye is used in combination with the gold-sulfur sensitization or the gold-selenium sensitization of the present invention.
• the "sensitizing dye” means a dye that extends the photosensitive region of silver halide to the electromagnetic wave outside the intrinsic photosensitive wavelength range.
• the sensitizing dyes useful in the present invention include sianin-based, melocyanin-based, hemocyanin-based quinolone-based, and hemidine-based sensitizing dyes. Sonor And complex melocyan-based dyes, such as those described by F.
• And 3 ⁇ 4 represent a 5- or 6-membered heterocyclic nucleus, for example, a thiazoline nucleus (for example, thiazoline, 4-methylthiazole, 41-fluorothiazole).
• oxazoline nucleus eg, oxazoline, 4-methylisoxazoline, etc.
• serenazolin nucleus serenazolin, 4-methylselenazo Phosphorus
• thiazole nuclei for example, thiazol, 4-methylthiazole, 41-fu
• PENTZIMI Dazol nuclei for example, Benzimidazole, 31-ethylbenzimidazole, 11-Fe-zul 5,6—Dichloropentzimidazol, etc.
• Indrain nucleus eg, 3,3—dimethylindrain, 3,3—ethylindrain, 3,3,7—trimethylinline
• Naphtho thiazol nucleus for example, naphtho [2,1-d] thiazol, naphtho [1,2-d] thiazol, 5-meth Kinesin (2,3-d) thiazole, etc.
• naphthoxazole core for example, naphtho [2,1—d] oxazole, naphtho [1,2—d) ]
• Naphtho-selenazole nuclei for example, naphtho [2,1-d] serenazole, naphtho [1,2-d] serenazole, etc.
• quinoline nuclei eg, 2-quinoline, 3—methyl-2—quinoline, 6—chloro-2—quinoline, 8-hydroxyl-2 —Quinoline, 4-quinoline, 6 — methoxy 4-quinoline, 1-isoquinoline, 3,4 — dihydro 11-isoquino , 3-isoquinoline, etc.
• X is an acid ion group (eg, If, C, Br, I, C 0 4,, C3 ⁇ 4 SO *,
• the processing method is not particularly limited, and any processing method can be applied.
• a typical example thereof is After color development, bleach-fix processing is performed and then water washing and stabilization processing are performed as necessary.Or, after color development, white and fixing are separated and further water washing and stabilization processing are performed as needed. It is possible to apply the operation method.
• the silver halide photographic emulsion produced by the method of the present invention has a remarkable and high photographic sensitivity, and has a high illuminance failure and a small force prep. Applied to silver halide photographic materials and optical materials.
• An octahedral monodispersed pigment having an average grain size of 0.9 * ⁇ and having a core of silver iodobromide containing 56 mol of silver iodide and a shell of silver bromide having an average thickness of 0.016 Am was prepared. According to the method described in JP-A-54-48521, the double jet method in which pAg and pH are controlled is prepared (this emulsion is prepared as follows). Emulsion (1)). In the emulsion, the particle size distribution of silver halide grains was 0.15. In the usual way 1?
• this milk Divided into 9 parts, and as shown in Table 1, a predetermined amount of 4-human, lip- ⁇ -6-methyl-1, 3,3a, 7-tetrazide den ( Compound (I)) was added, and if necessary, the mixture was adjusted to a predetermined pH with an aqueous solution of hydroxylated hydration.
• each of the thus-adjusted powders is adjusted at a ripening temperature of 55 ° C. so that the ripening time is adjusted as low as possible and a high sensation is obtained. Sulfur sensation was applied.
• the above compound (I) was added to each emulsion in a constant amount (1.4 ⁇ / mol AgX). Further, to each of these emulsions, a spreading agent, a thickening agent, a hardening agent, etc.—a general copying additive—are added, and then the polyethylene telephone is extracted. Samples f * Ll to 9 were prepared by coating and drying on a rate film paste so that the amount of Ag was 50 dnf.
• Sensitometry of these samples was performed as follows. Exposure is performed using a tungsten lamp (color temperature 5,400
• Exposure through an optical knives was performed using 1 ) and exposure was performed for 10 -6 seconds using a xenon flash. The image was run for 10 minutes at 20 in the following developer.
• Emulsion (1) obtained in Example 11 was divided into two emulsions, and these emulsions were added with pancro-sensitivity cumulative hydro-3,3'- ⁇ -(3-sulfur (Prop.) 1 5,5'- ⁇ Cro 0-9 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ - ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ 4 4 4 Five minutes after the addition, Compound (I) was added to 21 OwZ mol AgX to one emulsion, and the pH was adjusted to 6.5.
• each of these emulsions was subjected to ripening at a ripening temperature of 53 ° C., and a gold-sulfuric acid was increased by adjusting the ripening time so that a high sensitivity S was obtained. After ripening, compound (I) was further added so that each emulsion had a constant content (1,4 mol AgX :).
• compound (B) 1-phenyl-5-mercaptotetrazole (hereinafter, referred to as compound (B)) and the following coupler solutions, and other commonly used emulsions
• photo-forming additives such as spreading agents and hardening agents
• Example 11 After subjecting the above sample to wet exposure in the same manner as in Example 11, the sample was subjected to color development for 38 TC for 3 minutes using a color developing solution having the following composition.
• Table 1 shows the results. As can be seen from Table 12, a sample obtained by further adding a sensitizing dye to the promising heterocyclic compound of the present invention when performing the gold-sulfur sensitization of the present invention. The sensitivity is remarkably high.
• the core and average thickness of silver iodide containing 2 mol of silver iodide were determined by a controlled double-jet method of pAg and pH.
• a tetrahedral monodisperse emulsion (hereinafter referred to as an emulsion ⁇ ) having a silver shell of 16 and an average particle diameter of 0.9 was prepared.
• the dispersion box of the particle size distribution of silver halide particles in the emulsion (2) was 0.14. After desalting, the solution is divided into three parts, one of which is used as a control, and the other amount of the compound shown in Table 13 is added. Made.
• Example 1 in contrast to emulsion (1), the average grain size of the emulsion (1) (the octahedral grains and the same body) was a shell-type silver iodobromide grain (core silver iodide 2 mol *).
• Emulsion (3); dispersity: 0.15) from silver iodobromide, silver bromide having an average thickness of 0.02 Jtm, and conventional products.
• Example 1 was carried out using an emulsion composed of irregularly-shaped twinned silver iodobromide grains (containing 2 mol of silver iodide) (hereinafter referred to as “Emulsion (4). Dispersion degree: 0.14”).
• Emulsion (1) obtained in Example 1 was replaced with 1,1 -'- phenylthiourea (sensitizer A) instead of sodium sulfate instead of sulfuric acid.
• a comparative experiment similar to that of Example 11 was performed using N-ethyl- ⁇ '-4-thiozirylthiourea (sensitizer ⁇ ). The results are shown in Table 1-5.
• the Agl content was 8 mol, the average grain size was 0.65 m, the core was silver iodobromide, the shell was silver bromide, and the shell thickness was 0.015 ⁇ :).
• To each emulsion was added 5 mol AgX of the following sensitizing dye ⁇ , 40 «? Z mol AgX of sensitizing dye B and 90 ⁇ / mol AgX of compound (I), and further sodium thiosulfate. Then, ammonium chloroauric acid, ammonium thiocyanate 5QwZmol AgX was added, and the same palm as in Example 11 was subjected to chemical sensitization and spectral sensitization.
• a silver iodobromide refining agent containing octahedral crystals having an average grain size of 0.65 ⁇ (silver iodide content: 6 mol *, dispersion 2), wherein the content of silver iodide is uniformly distributed in the silver iodide (hereinafter referred to as “agent (5)”) and the average grain size is 0.6.
• a silver iodobromide emulsion (silver iodide content: 8 mol, dispersity: 0 * 1 2) consisting of 5 ⁇ -octahedral crystal silver phosphide, with a thickness of 0.016 / i «
• a silver-coated silver iodide emulsion (hereinafter referred to as “Eon, Emulsion (6)”) coated with a silver shell was prepared from the above emulsions (5) and (6). After adding compound (I) to each of the compounds in an amount of 220 mol / mol AgX, two kinds of sensitizations of sulfur sensitization and gold-sulfur sensitization were performed in the same manner as in Example 11.
• Emulsion (7) silver iodobromide polydisperse bi-crystalline emulsion with an average particle size of 0.65 in (dispersion degree 0,34, silver iodide content 8 mols)
• Emulsion (8) is a cubic crystal
• Emulsion (9) is an octahedral crystal
• Emulsion is a fourteen-sided crystal. From body crystals.
• the core of silver iodide containing 10 mol of silver iodide 56 and the average thickness of 0.0 were obtained by the controlled double jet method of pA and ⁇ as in Example 11.
• a tetrahedral monodispersed emulsion having a silver bromide shell of 16 ⁇ . And an average particle size of 0.9 ⁇ «and a dispersity of 0.15 was prepared. After desalting, this emulsion was divided into nine parts, three of which were used as controls, and the other amount of the compound shown in Table 9 was added to make the desired ⁇ and pAg did.
• the emulsion thus prepared was subjected to gold-sulfur sensitization and dye sensitization in the same manner as in Example 12. Further, the same photographic additive as in Example 12 was added, and the mixture was applied and dried to prepare Samples NDL 45 to 53. These samples were evaluated in the same manner as in Example 12, and the results are shown below.
• the sensitizing dye is the following j? O
• the sample obtained according to the present invention has less rash and high sensitivity.
• the sample of the present invention is improved while the comparative sample has a large high illuminance sensitivity failure.
• Example 12 in the same manner as in Example 12 except that benzotriazole was added instead of compound (I).
• Example 12 when benzothiazole was added in place of compound (I), a good sensitizing effect was obtained as in Example 12.
• Example 12 even when penzimidazole was added instead of compound (I), a good sensitizing effect was obtained as in Example 12.

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• 1981
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