JP2005181806A - Silver halide emulsion, silver halide photographic sensitive material and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide emulsion excellent in sensitivity, latent image stability and production stability, giving always stable high-quality prints, and excellent in image quality and print reproducibility in digital exposure in which high-illuminance short-time exposure is carried out, and to provide a silver halide photographic sensitive material and an image forming method. <P>SOLUTION: In the silver halide emulsion comprising silver halide grains which have a silver chloride content of ≥90 mol%, a silver iodide content of 0-2 mol% and a silver bromide content of 0.02-10 mol% and are formed by adding a solution prepared by dissolving one or more group VIII metal complexes having one or more water ligands and/or organic ligands at pH 4.0-10.0 and 0-25°C and keeping the resulting solution warm, the silver halide grains are sensitized with selenium. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention is excellent in manufacturing stability, excellent in sensitivity and latent image stability regardless of the exposure method, and can always provide a stable and high-quality print, and particularly in digital exposure where high-illumination and short-time exposure is performed. The present invention also relates to a silver halide emulsion excellent in print reproducibility, a silver halide photographic light-sensitive material, and an image forming method.

  In the recent rapid trend toward digitization, silver halide photographic light-sensitive materials (hereinafter also simply referred to as light-sensitive materials) have increased opportunities for digital exposure using laser light or the like. As a result, color paper, which is a light-sensitive material for color printing, is also required to be suitable for exposure in extremely short times, such as milliseconds to nanoseconds, with high illuminance, and for scanning exposure. I came.

  Conventionally, in color paper, a silver chloride emulsion or a silver halide emulsion having a high silver chloride content is used as a silver halide emulsion to be used as a means for achieving faster development processing. On the other hand, it is generally known that doping an iridium compound is effective for improving the reciprocity failure characteristic, which is one of the problems of silver halide emulsions. For example, a high silver chloride emulsion (for example, see Patent Document 1) having a region having a high silver bromide content in the vicinity of the apex of silver halide grains, and an iridium compound selectively in a localized region of silver bromide. It has been disclosed that a high silver chloride emulsion excellent in latent image stability and reciprocity failure characteristics can be provided by doping (see, for example, Patent Document 2). A method for forming a localized region of silver bromide using silver bromide fine particles doped with an iridium compound is disclosed (for example, see Patent Document 3). It was never enough to improve sex.

  Furthermore, with the digital exposure method that has recently become a hot topic, it is clear that sufficient practical quality cannot be obtained with existing latent image stability improvement technology alone in terms of exposure suitability in a very short time with high illuminance light. It has become. Examples of techniques applicable to such a digital exposure method include chemical sensitization and color sensitization methods suitable for forming a silver bromide localized phase (see, for example, Patent Document 4), and silver iodochloride emulsion. (For example, refer to Patent Documents 5 and 6).

  However, according to the study by the present inventors, when the digital exposure suitability is improved by the above-described technique, not only the improvement of the latent image stability is insufficient, but also the pressure resistance of the photosensitive material and the unexposed photosensitive material. Since it has been found that the stability during storage is significantly deteriorated, the development of an improved technique is desired at present.

  In addition, it has a silver bromide and silver iodide rich phase in the vicinity of the surface of the silver halide grains, and this rich phase is introduced twice before and after the addition of the mercapto compound. Although a method for improving the stagnation property of the coating solution is described (for example, see Patent Document 7), it has been found that the storage stability of the silver halide emulsion is insufficient only by this method.

  On the other hand, a reaction-inactive compound among dichalcogen compounds is added before or during precipitation of the silver halide emulsion and before or during spectroscopic / chemical sensitization, or during spectroscopic / chemical sensitization. It discloses that the increase can be improved (for example, see Patent Documents 8 and 9). Furthermore, the addition of these compounds as a solid dispersion (see, for example, Patent Document 10) allows the silver chloride emulsion to contain diaminodisulfide and sulfinate compounds in a mass ratio of 1: 1 to 1:20, which is a color photograph. It discloses that the storage stability of the photosensitive material and the performance fluctuation due to the temperature fluctuation during exposure are improved (for example, see Patent Document 11).

  Also disclosed is that low fog and high sensitivity can be obtained by adding specific disulfide compounds and sulfinates or seleninate compounds after precipitation of silver halide emulsion, before spectral / chemical sensitization or during spectral / chemical sensitization. (For example, see Patent Document 12). Fogging is reduced by a photographic element comprising a silver chloride emulsion containing a disulfide compound having a water-soluble group, and fluctuations in sensitivity due to fog, fluctuations in sensitivity and temperature during exposure are reduced when raw samples are stored. (For example, refer to Patent Document 13).

  However, in any of these methods, the latent image stability, storability and pressure resistance, particularly the description and improvement of the latent image stability, storability and pressure resistance of the emulsion exposed at high illuminance are insufficient.

  Further, a photographic light-sensitive material containing a silver halide emulsion having a high silver chloride content and a mercapto compound is disclosed (for example, see Patent Documents 14 and 15). In this embodiment, the mercapto compound is added to a coating solution. Alternatively, there is disclosure relating to a photographic element containing chemical sensitization and containing thiosulfonate and sulfinate and silver chloroiodide grains (see, for example, Patent Document 16). None of them had a limited improvement effect on photographic performance such as sensitivity, fog, latent image, reciprocity failure, storage stability, pressure resistance, and the like.

  Regarding silver sulfide, gold sulfide, gold sulfide fine particles and silver sulfide sol, disclosures centering on basic manufacturing techniques of silver sulfide, gold sulfide, gold sulfide fine particles and silver sulfide sol (see, for example, Patent Documents 17 and 18). ), However, the knowledge about recent practical emulsions, application to practical photographic light-sensitive materials, and improvement of various properties has not been sufficient.

  There is a disclosure of a photographic element containing silver chloride grains containing a selenium compound on the grain surface (see, for example, Patent Documents 19 and 20), but the effect of improving photographic performance other than sensitivity is unclear. There is no description of the gamma, latent image, and other halogen compositions and dopants that are considered essential for improving various performances, and there is no practical silver halide photographic light-sensitive material that satisfies the recently required performances. It was difficult to provide. There is a disclosure relating to a silver halide photographic light-sensitive material in which selenium sensitization or tellurium sensitization is applied to silver chloride or silver chlorobromide grains having a high silver chloride content (see, for example, Patent Documents 21, 22, and 23). However, the effects of improving various performances such as latent image stability and coating solution stagnation stability are unknown, and the effects on sensitivity and gamma are insufficient to meet the recent demand for silver halide photographic materials.

Regarding a technique for applying a group 8 metal complex having a water ligand to silver halide grains, the iridium complex having a halogen ligand and a water ligand is contained, and the localized layer of the iridium complex is halogenated. A silver halide emulsion having a silver halide grain surface phase (see, for example, Patent Document 24) or a silver halide emulsion containing an iridium complex having a water ligand in a high silver chloride silver halide grain (for example, Patent Document) On the other hand, regarding the technique of applying a group 8 metal complex having an organic ligand to silver halide grains, a hexacoordination complex other than iridium in high silver chloride grains can be used. A silver halide emulsion containing an iridium complex having a thiazole or substituted thiazole ligand (see, for example, Patent Document 26), or a water ligand or a thiocyanate in a high silver chloride silver halide grain. Although there are disclosures such as silver halide emulsions containing an iridium complex having a sol ligand and an iridium complex having a halogen ligand (see, for example, Patent Document 27), recent sensitivity, latent image stability, Insufficient demand for improvement in digital exposure suitability and improvement in production stability, there was little knowledge about how to use the above-mentioned Group 8 metal complex in order to always obtain a stable high quality print.
JP-A 64-26837 (Claims) JP-A-1-105940 (Claims) US Pat. No. 5,627,020 (Claims) US Pat. No. 5,691,119 (Claims) European Patent No. 750,222 (Claims) European Patent No. 772,079 (Claims) JP 2001-188311 A (Claims) Japanese Patent Laid-Open No. 6-19024 (Claims) JP-A-6-19026 (Claims) JP-A-6-19037 (Claims) JP-A-6-35147 (Claims) JP-A-6-202265 (Claims) JP-A-7-72580 (Example 11) JP 2002-182326 A (Claims) JP 2002-162707 A (Claims) JP-A-8-234354 (Claims) JP-A-2-198443 (Claims) Japanese Patent No. 2992925 (Claims) JP-A-5-66513 (Claims) US Pat. No. 5,240,827 (Claims) JP-A-5-313293 (Claims) Japanese Patent Laid-Open No. 9-5922 (Claims) Japanese Patent Laid-Open No. 9-5924 (Claims) JP-A-11-202440 (Claims) JP 2001-356441 A (Claims) US Pat. No. 6,107,018 (Claims) JP 2002-162708 A (Claims)

  Therefore, the object of the present invention is excellent in sensitivity, latent image stability, and production stability, and can always provide a stable and high-quality print. Especially, in digital exposure where exposure is performed for a short time at high illuminance, image quality and print reproducibility are improved. An object is to provide an excellent silver halide emulsion, a silver halide photographic light-sensitive material, and an image forming method.

  As a result of intensive studies in view of the above problems, the present inventors have produced silver halide grains using one or more of Group 8 metal complexes having one or more water ligands and / or organic ligands. The solution of the additive solution containing the Group 8 metal complex and the setting of the pH and temperature at the time of incubation were found to affect the sensitivity, latent image stability, and production stability.

  The group 8 metal complex having at least one water ligand and / or organic ligand is often used in the production of silver halide emulsions as described above. The above-mentioned prior art has no knowledge and is surprising. Further, the silver halide emulsion to which the group 8 metal complex having one or more water ligands and / or organic ligands is applied by the method according to the present invention is selected from selenium sensitization, silver sulfide, silver gold sulfide and gold sulfide. When using the chemical sensitization to which at least one kind of fine particles added and the compounds of the general formulas (1) to (4) and (S) related to the present invention are used, the production stability is improved while obtaining a remarkable improvement in photographic performance. And stable high-quality prints could be obtained.

The above object of the present invention has been achieved by the following constitution.
(Claim 1)
The silver chloride content is 90 mol% or more, the silver iodide content is 0 to 2 mol%, the silver bromide content is 0.02 to 10 mol%, and the water ligand And / or silver halide grains formed by adding a solution in which one or more of group 8 metal complexes having one or more organic ligands are dissolved and kept at pH 4.0 to 10.0 and 0 to 25 ° C. A silver halide emulsion comprising a silver halide emulsion, wherein the silver halide grains are selenium-sensitized.
(Claim 2)
The silver chloride content is 90 mol% or more, the silver iodide content is 0 to 2 mol%, the silver bromide content is 0.02 to 10 mol%, and the water ligand And / or silver halide grains formed by adding a solution in which one or more of group 8 metal complexes having one or more organic ligands are dissolved and kept at pH 4.0 to 10.0 and 0 to 25 ° C. A silver halide emulsion comprising: a silver halide grain, wherein the silver halide grains are chemically sensitized by adding at least one fine grain selected from silver sulfide, gold silver sulfide and gold sulfide. emulsion.
(Claim 3)
The silver chloride content is 90 mol% or more, the silver iodide content is 0 to 2 mol%, the silver bromide content is 0.02 to 10 mol%, and the water ligand And / or silver halide grains formed by adding a solution in which one or more of group 8 metal complexes having one or more organic ligands are dissolved and kept at pH 4.0 to 10.0 and 0 to 25 ° C. A silver halide emulsion comprising: a silver halide emulsion containing at least one of the compounds represented by the following general formulas (1) to (3): .

Formula _{(1) R-SO 2 S} -M
Formula (2) R ₁ —SO ₂ S—R ₂
Formula (3) R ₃ —SO ₂ S—L _m —SSO ₂ —R ₄
[Wherein, R, R ₁ , R ₂ , R ₃ and R ₄ each represents an aliphatic group, an aromatic group, or a heterocyclic group. R, R ₁ , R ₂ , R ₃ and R ₄ may be the same or different. M represents a cation. L represents a divalent linking group, and m represents 0 or 1. ]
(Claim 4)
The silver chloride content is 90 mol% or more, the silver iodide content is 0 to 2 mol%, the silver bromide content is 0.02 to 10 mol%, and the water ligand And / or silver halide grains formed by adding a solution in which one or more of group 8 metal complexes having one or more organic ligands are dissolved and kept at pH 4.0 to 10.0 and 0 to 25 ° C. A silver halide emulsion comprising: a silver halide emulsion containing at least one compound represented by the following general formula (4):

Formula _{(4) R 11 - (S} ) m -R 12
[Wherein, R ₁₁ and R ₁₂ each represents an aliphatic group, an aromatic group, a heterocyclic group, or an atomic group that can be bonded to each other to form a ring. R ₁₁ and R ₁₂ may be the same or different. When R ₁₁ and R ₁₂ are aliphatic groups, they may be bonded to each other to form a ring. m represents an integer of 2 to 6. ]
(Claim 5)
Silver halide by adding a solution in which one or more of Group 8 metal complexes having one or more water ligands and / or organic ligands are dissolved and kept at pH 4.0-10.0 and 0-20 ° C. The silver halide emulsion according to any one of claims 1 to 4, wherein grains are formed.
(Claim 6)
Silver halide by adding a solution in which one or more of group 8 metal complexes having one or more water ligands and / or organic ligands are dissolved and kept at pH 4.0-10.0 and 0-15 ° C. The silver halide emulsion according to any one of claims 1 to 5, wherein grains are formed.
(Claim 7)
The silver halide emulsion according to any one of claims 1 to 6, wherein the silver halide grains have a silver bromide localized phase.
(Claim 8)
The silver halide emulsion according to any one of claims 1 to 7, wherein the silver halide grains have a silver iodide localized phase.
(Claim 9)
The silver halide emulsion according to any one of claims 1 to 8, wherein the silver halide grain contains a compound represented by the following general formula (S).

[Wherein, Q represents a 5-membered or 6-membered nitrogen-containing heterocyclic ring, and M ¹ represents a hydrogen atom, an alkali metal atom, or an atomic group necessary for forming a monovalent cation. ]
(Claim 10)
A silver halide photographic material having at least one image forming layer on a support, wherein at least one of the image forming layers contains the silver halide emulsion according to any one of claims 1 to 9. A silver halide photographic light-sensitive material characterized by the above.
(Claim 11)
An image forming method comprising: performing color development after scanning exposure of the silver halide photographic light-sensitive material according to claim 10.

  Silver halide emulsion with excellent image quality and print reproducibility, especially in digital exposure, which has excellent sensitivity, latent image stability, and production stability, and always provides stable and high-quality prints. Further, a silver halide photographic light-sensitive material and an image forming method could be provided.

  Hereinafter, the present invention will be described in detail.

  The silver halide grains in the silver halide emulsion according to the present invention have a silver chloride content of 90 mol% or more, preferably a silver chloride content of 93 mol% or more, and 95 mol% or more. Is more preferable.

  The silver halide grains according to the present invention are characterized in that the silver iodide content is 0 to 2 mol%, and the silver iodide content is preferably 0.02 to 2 mol%, and 0.05 More preferably, it is ˜1 mol%.

  The silver halide grain according to the present invention preferably has a silver iodide localized phase, and more preferably has at least one silver iodide localized phase inside the grain. In the present invention, the inside of the grain means a silver halide phase excluding the grain surface in the silver halide grain. In the present invention, the silver iodide localized phase is a silver halide phase containing silver iodide having a silver iodide content of at least twice the average silver iodide content of the silver halide grains according to the present invention, It preferably contains silver iodide having a silver iodide content of at least 3 times the average silver iodide content of the silver halide grains, and preferably contains silver iodide having a silver iodide content of 5 times or more.

  In the present invention, the position of the silver iodide localized phase is preferably 60% or more, more preferably 70% or more, and more preferably 80% or more outside from the grain center. Is most preferred.

  One of the preferred forms for the silver iodide localized phase is that the silver iodide localized phase is present in a layer form inside the silver halide grains (hereinafter also referred to as a silver iodide localized layer). It is also preferable to introduce two or more silver localized layers. In this case, at least one layer (hereinafter referred to as sublayer) having a main layer introduced under the above conditions and having a concentration lower than the maximum iodide concentration is further introduced than the main layer. It is preferable to introduce near the particle surface. The I concentration of the main layer and sublayer can be arbitrarily selected according to the purpose. From the viewpoint of latent image stability, the main layer preferably has a high density as much as possible, and the sublayer preferably has a lower density than the main layer.

  In the present invention, another preferred form of the silver iodide localized phase is that the silver iodide localized phase is present in the vicinity of the apex or ridge line of the silver halide grain, and is used in combination with the above-mentioned silver iodide localized layer. It is also preferable.

As a method for introducing a silver iodide localized phase, various iodine compounds can be used. For example, a method using an aqueous solution of an iodide salt such as an aqueous solution of potassium iodide, a method using a polyiodide described in “Inorganic compound / complex dictionary” written by Katsumi Nakahara, Kodansha, page 944, etc., disclosed in JP-A-2-68538, etc. This is a method using silver halide fine particles containing silver iodide or an iodide ion releasing agent. From the viewpoint of rapid processing suitability and processing stability, potassium iodide and I ₄ or higher polyiodide are preferable, and I ₄ or higher polyiodide is more preferable. The silver iodide content of the silver iodide localized phase can be arbitrarily adjusted by the concentration and amount of the additive solution containing these iodides.

  The silver halide grains in the silver halide emulsion according to the present invention are characterized in that the silver bromide content is 0.02 to 10 mol%, and the silver bromide content is 0.05 to 8%. Is preferable, and it is further more preferable that it is 0.1-5 mol%.

  In the silver halide emulsion according to the present invention, a silver halide emulsion having a silver bromide localized phase is preferably used. In this case, the portion containing silver bromide at a high concentration is epitaxy bonded to the silver halide emulsion grains. However, it may be layered inside the silver halide grains, may be a so-called core-shell emulsion, and preferably has a silver bromide localized phase in the vicinity of the apex, and these may be used in combination. Is also preferable. A complete layer may not be formed, and there may be a region having a partially different composition. Further, the composition may change continuously or discontinuously.

  In the present invention, the silver bromide localized phase is a silver halide phase containing silver bromide having a silver bromide content of at least twice the average silver bromide content of the silver halide grains according to the present invention, It preferably contains silver bromide having a silver bromide content of 3 times or more of the average silver bromide content of the silver halide grains, and preferably contains silver bromide having a silver bromide content of 5 times or more.

  Various bromides can be used as a method for introducing a silver bromide localized phase. For example, a method using an aqueous bromide salt solution such as an aqueous potassium bromide solution, a method using silver halide fine particles containing silver bromide or a bromide ion releasing agent, and the like. From the viewpoint of rapid processing suitability and processing stability, it is preferable to use silver halide fine particles containing a bromide salt such as potassium bromide or silver bromide. The silver bromide content of the silver bromide localized phase can be arbitrarily adjusted by the concentration and amount of the additive solution containing these bromides.

  In the silver halide emulsion according to the present invention, silver halide grains contain at least one kind of group 8 metal complex having at least one water ligand and / or organic ligand at pH 4.0 to 10.0 and 0. It is formed by adding a solution dissolved and kept at -25 ° C.

  The Group 8 metal complex used in the present invention is preferably a metal complex of iron, iridium, rhodium, osmium, ruthenium, cobalt and platinum. As the metal complex, a six-coordinate complex, a five-coordinate complex, a four-coordinate complex, a two-coordinate complex, and the like can be used, and a six-coordinate complex and a four-coordinate complex are preferable.

  The ligands constituting the complex are carbonyl ligand, fullinate ligand, thiocyanate ligand, nitrosyl ligand, thionitrosyl ligand, cyano ligand, water ligand, halogen ligand, Or any of ammonia, hydroxide, nitrous acid, sulfurous acid, peroxide ligand and organic ligand can be used, but nitrosyl ligand, thionitrosyl ligand, cyano coordination It is preferable to contain one or more ligands selected from a child, a water ligand, a halogen ligand, and an organic ligand.

  In the present invention, an organic ligand refers to a compound that contains one or more H—C, C—C, or C—N—H bonds and can be coordinated to a metal ion. The organic ligand used in the present invention is selected from pyridine, pyrazine, pyrimidine, pyran, pyridazine, imidazole, thiazole, isothiazole, triazole, pyrazole, furan, furazane, oxazole, isoxazole, thiophene, phenanthroline, bipyridine, and ethylenediamine. It is preferable that the compound is a compound, an ion, or a compound obtained by introducing a substituent into these compounds.

Specific examples of the group 8 metal complex having one or more water ligands and / or organic ligands used in the present invention will be given below, but the present invention is not limited thereto. The counter cation may be any one such as potassium ion, calcium ion, sodium ion or ammonium ion. Moreover, when a metal complex is a cation, what is known in this industry, such as a nitrate ion, a halogen ion, a perchlorate ion, can be used as an anion.
(A-1) K [IrBr ₅ (H ₂ O)]
(A-2) K ₂ [IrBr ₅ (H ₂ O)]
(A-3) K ₃ [IrBr ₅ (H ₂ O)]
(A-4) K ₄ [IrBr ₅ (H ₂ O)]
(A-5) K [IrBr ₄ (H ₂ O) ₂ ]
(A-6) [IrBr ₄ (H ₂ O) ₂ ]
(A-7) [IrBr ₃ (H ₂ O) ₃ ]
(A-8) [IrBr ₃ (H ₂ O) ₃ ] Br
(A-9) K [IrCl ₅ (H ₂ O)]
(A-10) K ₂ [IrCl ₅ (H ₂ O)]
(A-11) K ₃ [IrCl ₅ (H ₂ O)]
(A-12) K ₄ [IrCl ₅ (H ₂ O)]
(A-13) K [IrCl ₄ (H ₂ O) ₂ ]
(A-14) [IrCl ₄ (H ₂ O) ₂ ]
(A-15) [IrCl ₃ (H ₂ O) ₃ ]
(A-16) [IrBr ₃ (H ₂ O) ₃ ] Cl
(B-1) K ₂ [RhCl ₅ (H ₂ O)]
(B-2) K ₂ [OsCl ₅ (H ₂ O)]
(B-3) K ₂ [RuCl ₅ (H ₂ O)]
(B-4) K [Rh (NO) (H ₂ O) Cl ₄ ]
(B-5) K [Ru (NO) (H ₂ O) Br ₄ ]
(C-1) [Ir (bipy) Cl ₄ ] ⁻
(C-2) [Ir (bipy) Br ₄ ] ⁻
(C-3) [Ir (bipy) ₃ ] ²⁺
(C-4) [Ir (py) ₆ ] ²⁺
(C-5) [Ir (phen) ₃ ] ²⁺
(C-6) [IrCl ₂ (bipy) ₂ ] ⁰
(C-7) [Ir (thia) ₆ ] ²⁺
(C-8) [IrCl ₅ (thia)] ^2-
(C-9) [IrCl ₄ (thia) ₂ ] ^1-
(C-10) [IrCl ₅ (5-methylthia)] ^2-
(C-11) [IrCl ₄ (5-methylthia) ₂ ] ^1-
(C-12) [IrBr ₅ (thia)] ^2-
(C-13) [IrBr ₄ (thia) ₂ ] ^1-
(C-14) [IrBr ₅ (5-methylthia)] ^2-
(C-15) [IrBr ₄ (5-methylthia) ₂ ] ^1-
(C-16) [Ir (phen) (bipy) ₃ ] ²⁺
(C-17) [Ir (im) ₆ ] ²⁺
(C-18) [IrCl ₅ (im)] ^2-
(C-19) [IrCl ₄ (im) ₂ ] ^1-
(C-20) [IrBr ₅ (im)] ^2-
(C-21) [IrBr ₄ (im) ₂ ] ¹⁻
(C-22) [Ir (NCS) ₂ (bipy) ₂ ] ⁰
(C-23) [Ir (CN) ₂ (bipy) ₂ ] ⁰
(C-24) [IrCl ₂ (bipy) ₃ ] ⁰
(C-25) [IrCl ₂ (bipy) ₂ ] ⁰
(C-26) [Ir (phen) (bipy) ₂ ] ²⁺
(C-27) [Ir ( NCS) 2 (bipy) 2] 0
(C-28) [Ir ( NCS) 2 (bipy) 2] 0
(C-29) [Ir (bipy) ₂ (H ₂ O) (bipy ′)] ²⁺
(C-30) [Ir (bipy) ₂ (OH) (bipy ′)] ⁺
(C-31) [Ir (bipy) Cl ₄ ] ²⁻
(C-32) [Ir (bipy) ₃ ] ³⁺
(C-33) [Ir (py) ₆ ] ³⁺
(C-34) [Ir (phen) ₃ ] ³⁺
(C-35) [IrCl ₂ (bipy) ₂ ] ⁺
(C-36) [Ir (thia) ₆ ] ³⁺
(C-37) [Ir (phen) (bipy) ₃ ] ³⁺
(C-38) [Ir (im) ₆ ] ³⁺
(C-39) [Ir (NCS) ₂ (bipy) ₂ ] ⁺
(C-40) [Ir (CN) ₂ (bipy) ₂ ] ⁺
(C-41) [IrCl ₂ (bipy) ₃ ] ⁺
(C-42) [IrCl ₂ (bipy) ₂ ] ⁺
(C-43) [Ir (phen) (bipy) ₂ ] ³⁺
(C-44) [Ir (NCS) ₂ (bipy) ₂ ] ⁺
(C-45) [Ir (NCS) ₂ (bipy) ₂ ] ⁺
(C-46) [Ir (bipy) ₂ (H ₂ O) (bipy ′)] ³⁺
(C-47) [Ir (bipy) ₂ (OH) (bipy ′)] ²⁺
(D-1) [Ru (bipy) Cl ₄ ] ⁻
(D-2) [Ru (bipy) ₃ ] ²⁺
(D-3) [Ru (py) ₆ ] ²⁺
(D-4) [Ru (phen) ₃ ] ²⁺
(D-5) [RuCl ₂ (bipy) ₂ ] ⁰
(D-6) [Ru (thia) ₆ ] ²⁺
(D-7) [Ru (phen) (bipy) ₃ ] ²⁺
(D-8) [Ru (im) ₆ ] ²⁺
(D-9) [Ru (NCS) ₂ (bipy) ₂ ] ⁰
(D-10) [Ru (CN) ₂ (bipy) ₂ ] ⁰
(D-11) [RuCl ₂ (bipy) ₃ ] ⁰
(D-12) [RuCl ₂ (bipy) ₂ ] ⁰
(D-13) [Ru (phen) (bipy) ₂ ] ²⁺
(D-14) [Ru (NCS) ₂ (bipy) ₂ ] ⁰
(D-15) [Ru (NCS) ₂ (bipy) ₂ ] ⁰
(D-16) [Fe (bipy) Cl ₄ ] ⁻
(D-17) [Fe (bipy) ₃ ] ²⁺
(D-18) [Fe (py) ₆ ] ²⁺
(D-19) [Fe (phen) ₃ ] ²⁺
(D-20) [FeCl ₂ (bipy) ₂ ] ⁰
(D-21) [Fe (thia) ₆ ] ²⁺
(D-22) [Fe (phen) (bipy) ₃ ] ²⁺
(D-23) [Fe (im) ₆ ] ²⁺
(D-24) [Fe (NCS) ₂ (bipy) ₂ ] ⁰
(D-25) [Fe (CN) ₂ (bipy) ₂ ] ⁰
(D-26) [FeCl ₂ (bipy) ₃ ] ⁰
(D-27) [FeCl ₂ (bipy) ₂ ] ⁰
(D-28) [Fe (phen) (bipy) ₂ ] ²⁺
(D-29) [Fe ( NCS) 2 (bipy) 2] 0
(D-30) [Fe ( NCS) 2 (bipy) 2] 0
(D-31) [Os (bipy) Cl ₄ ] ⁻
(D-32) [Os (bipy) ₃ ] ²⁺
(D-33) [Os (py) ₆ ] ²⁺
(D-34) [Os (phen) ₃ ] ²⁺
(D-35) [OsCl ₂ (bipy) ₂ ] ⁰
(D-36) [Os (thia) ₆ ] ²⁺
(D-37) [Os (phen) (bipy) ₃ ] ²⁺
(D-38) [Os (im) ₆ ] ²⁺
(D-39) [Os (NCS) ₂ (bipy) ₂ ] ⁰
(D-40) [Os (CN) ₂ (bipy) ₂ ] ⁰
(D-41) [OsCl ₂ (bipy) ₃ ] ⁰
(D-42) [OsCl ₂ (bipy) ₂ ] ⁰
(D-43) [Os (phen) (bipy) ₂ ] ²⁺
(D-44) [Os (NCS) ₂ (bipy) ₂ ] ⁰
(D-45) [Os (NCS) ₂ (bipy) ₂ ] ⁰
(D-46) [Co (bipy) Cl ₄ ] ⁻
(D-47) [Co (bipy) ₃ ] ²⁺
(D-48) [Co (py) ₆ ] ²⁺
(D-49) [co (phen) ₃ ] ²⁺
(D-50) [CoCl ₂ (bipy) ₂ ] ⁰
(D-51) [Co (thia) ₆ ] ²⁺
(D-52) [Co (phen) (bipy) ₃ ] ²⁺
(D-53) [Co (im) ₆ ] ²⁺
(D-54) [Co (NCS) ₂ (bipy) ₂ ] ⁰
(D-55) [Co (CN) ₂ (bipy) ₂ ] ⁰
(D-56) [CoCl ₂ (bipy) ₃ ] ⁰
(D-57) [CoCl ₂ (bipy) ₂ ] ⁰
(D-58) [Co (phen) (bipy) ₂ ] ²⁺
(D-59) [Co (NCS) ₂ (bipy) ₂ ] ⁰
(D-60) [Co (NCS) ₂ (bipy) ₂ ] ⁰
(D-61) [Rh (bipy) Cl ₄ ] ⁻
(D-62) [Rh (bipy) ₃ ] ²⁺
(D-63) [Rh (py) ₆ ] ²⁺
(D-64) [Rh (phen) ₃ ] ²⁺
(D-65) [RhCl ₂ (bipy) ₂ ] ⁰
(D-66) [Rh (thia) ₆ ] ²⁺
(D-67) [Rh (phen) (bipy) ₃ ] ²⁺
(D-68) [Rh (im) ₆ ] ²⁺
(D-69) [Rh (NCS) ₂ (bipy) ₂ ] ⁰
(D-70) [Rh (CN) ₂ (bipy) ₂ ] ⁰
(D-71) [RhCl ₂ (bipy) ₃ ] ⁰
(D-72) [RhCl ₂ (bipy) ₂ ] ⁰
(D-73) [Rh (phen) (bipy) ₂ ] ²⁺
(D-74) [Rh ( NCS) 2 (bipy) 2] 0
(D-75) [Rh ( NCS) 2 (bipy) 2] 0
In the examples of Group 8 metal compounds or Group 8 metal complexes, the abbreviations represent the following.

bipy = bipyridine bidentate ligand bipy ′ = bipyridine monodentate ligand im = imidazole py = pyridine phen = phenanthroline thia = thiazole 5-methylthia = 5-methylthiazole and other bipyridine complexes described in JP-A-5-341426 are also preferred. Can be used.

  In the formation of the silver halide emulsion according to the present invention, in addition to adding one or more of group 8 metal complexes having one or more water ligands and / or organic ligands, the following general formula (A It is preferable to add at least one of group 8 metal complexes represented by

Formula _{(A) R n [MX m} Y 6-m]
In the formula, M represents a metal selected from Group 8 elements of the periodic table, and is iron, cobalt, ruthenium, iridium, rhodium, osmium, or platinum, and more preferably iron, ruthenium, rhodium, iridium, or osmium. R represents an alkali metal and is preferably cesium, sodium or potassium. m represents an integer of 0 to 6, and n represents an integer of 0 to 4. X and Y represent ligands, such as a carbonyl ligand, a fluorinate ligand, a thiocyanate ligand, a nitrosyl ligand, a thionitrosyl ligand, a cyano ligand, a halogen ligand, ammonia, water Represents oxide, nitrous acid, sulfurous acid, and peroxide ligands.

Specific examples of the Group 8 metal compound and Group 8 metal complex used in the present invention are listed below, but the present invention is not limited to these. The counter cation may be any one such as potassium ion, calcium ion, sodium ion or ammonium ion. Moreover, when a metal complex is a cation, what is known in this industry, such as a nitrate ion, a halogen ion, a perchlorate ion, can be used as an anion.
(E-1) K ₂ [IrCl ₆ ]
(E-2) K ₃ [IrCl ₆ ]
(E-3) K ₂ [Ir (CN) ₆ ]
(E-4) K ₃ [Ir (CN) ₆ ]
(E-5) K ₂ [Ir (NO) (CN) ₅ ]
(E-6) K ₂ [IrBr ₆ ]
(E-7) K ₃ [IrBr ₆ ]
(E-8) K ₂ [IrBr ₄ Cl ₂ ]
(E-9) K ₃ [IrBr ₄ Cl ₂ ]
(E-10) K ₂ [IrBr ₃ Cl ₃ ]
(E-11) K ₃ [IrBr ₃ Cl ₃ ]
(E-12) K ₂ [IrBr ₅ Cl]
(E-13) K ₃ [IrBr ₅ Cl]
(E-14) K ₂ [IrBr ₅ I]
(E-15) K ₃ [IrBr ₅ I]
(E-16) K ₃ [IrBr (CN) ₅ ]
(E-17) K ₃ [IrBr ₂ (CN) ₄ ]
(E-18) K ₂ [Ir (CN) ₅ (H ₂ O)]
(E-19) K ₃ [Ir (CN) ₅ (H ₂ O)]
(E-20) K [Ir (NO) Cl ₅ ]
(E-21) K [Ir (NS) Cl ₅ ]
(F-1) K ₂ [RuCl ₆ ]
(F-2) K ₂ [FeCl ₆ ]
(F-3) K ₂ [PtCl ₆ ]
(F-4) K ₃ [RhCl ₆ ]
(F-5) K ₂ [OsCl ₆ ]
(F-6) K ₂ [RuBr ₆ ]
(F-7) K ₂ [FeBr ₆ ]
(F-8) K ₂ [PtBr ₆ ]
(F-9) K ₃ [RhBr ₆ ]
(F-10) K ₂ [OsBr ₆ ]
(F-11) K ₂ [Pt (SCN) ₄ ]
(F-12) K ₄ [Ru (CNO) ₆ ]
(F-13) K ₄ [Fe (CNO) ₆ ]
(F-14) K ₂ [Pt (CNO) ₄ ]
(F-15) K ₃ [Co (NH 3) ₆ ]
(F-16) K ₃ [Co (CNO) ₆ ]
(F-17) K ₄ [Os (CNO) ₆ ]
(F-18) Cs ₂ [Os (NO) Cl ₅ ]
(F-19) K ₂ [Ru (NO) Cl ₅ ]
(F-20) K ₂ [Ru (CO) Cl ₅ ]
(F-21) Cs ₂ [Os (CO) Cl ₅ ]
(F-22) K ₂ [Fe (NO) Cl ₅ ]
(F-23) K ₂ [Ru (NO) Br ₅ ]
(F-24) K ₂ [Ru (NO) I ₅ ]
(F-25) K ₂ [Ru (NS) Cl ₅ ]
(F-26) K ₂ [Os (NS) Cl ₅ ]
(F-27) K ₂ [Ru (NS) Br ₅ ]
(F-28) K ₂ [Ru (NS) (SCN) ₅ ]
(F-29) K ₂ [RuBr ₆ ]
(F-30) K ₂ [FeBr ₆ ]
(F-31) K ₄ [Fe (CN) ₆ ]
(F-32) K ₃ [Fe (CN) ₆ ]
(F-33) K ₄ [Ru (CN) ₆ ]
(F-34) K ₄ [Os (CN) ₆ ]
(F-35) K ₃ [Rh (CN) ₆ ]
(F-36) K ₄ [RuCl (CN) ₅ ]
(F-37) K ₄ [OsBr (CN) ₅ ]
(F-38) K ₄ [OsCl (CN) ₅ ]
(F-39) K ₃ [RhF (CN) ₅ ]
(F-40) K ₃ [Fe (CO) (CN) ₅ ]
(F-41) K ₄ [RuF ₂ (CN) ₄ ]
(F-42) K ₄ [OsCl ₂ (CN) ₄ ]
(F-43) K ₄ [RhI ₂ (CN) ₄ ]
(F-44) K ₄ [Ru (CN) ₅ (OCN)]
(F-45) K ₄ [Ru (CN) ₅ (N ₃ ) ₄ ]
(F-46) K ₄ [Os (CN) ₅ (SCN)]
(F-47) K ₄ [Rh (CN) ₅ (SeCN)]
(F-48) K ₄ [RuF ₂ (CN) ₄ ]
(F-49) K ₃ [Fe (CN) ₃ Cl ₃ ]
(F-50) K ₄ [Os (CN) Cl ₅ ]
(F-51) K ₃ [Co (CN) ₆ ]
(F-52) K ₂ [RuBr (CN) ₅ ]
(F-53) K ₂ [Os (NS) (CN) ₅ ]
(F-54) K [Ru (NO) ₂ Cl ₄ ]
(F-55) K ₄ [Ru (CN) ₅ (N ₃ ) ₄ ]
(F-56) K ₂ [Os (NS) Cl (SCN) ₄ ]
(F-57) K ₂ [Ru (NS) I ₅ ]
(F-58) K ₂ [Os (NS) Cl ₄ (TeCN) ₄ ]
(F-59) K ₂ [Rh (NS) Cl ₅ ]
(F-60) K ₂ [Ru (NO) (CN) ₅ ]
(F-61) K [Rh (NO) ₂ Cl ₄ ]
(F-62) K ₂ [Rh (NO) Cl ₅ ]
In the present invention, in order to contain a group 8 metal compound, doping may be performed during physical ripening of the silver halide grains, or the formation process of the silver halide grains (generally, a water-soluble silver salt and a water-soluble halide). During addition of alkali), doping may be performed, or doping may be performed in a state in which silver halide grain formation is temporarily stopped, and then grain formation may be continued. Nucleation is performed in the presence of a group 8 metal compound. Or physical ripening or particle formation.

The concentration of the group 8 metal compound used in the present invention is generally in the range of 1 × 10 ⁻⁹ mol to 1 × 10 ⁻² mol per mol of silver halide, more preferably 1 × 10 6. The range is from ⁻⁹ mol to 1 × 10 ⁻³ mol, and particularly preferably from 2 × 10 ⁻⁹ to 1 × 10 ⁻⁴ mol.

  In the present invention, in order to make the silver halide grains contain a group 8 metal compound, they may be dispersed directly in the emulsion, or added in water, methanol, ethanol or the like alone or in a mixed solvent. In general, a method of adding an additive to a silver halide emulsion can be applied in the art. Further, the group 8 metal compound can be added to the silver halide emulsion together with the silver halide fine grains, and the silver halide fine grains containing the group 8 metal compound can be added during the formation of the silver halide grains.

  Regarding the production method of adding silver halide fine grains containing a Group 8 metal compound during the formation of silver halide grains in the silver halide emulsion, the methods described in JP-A Nos. 11-212201 and 2000-89403 are used. You can refer to it.

  In the silver halide emulsion according to the present invention, at least one of the group 8 metal complexes having one or more of the above water ligand and / or organic ligand is pH 4.0 to 10.0 and 0 to 25 ° C. It is characterized in that silver halide grain formation is performed by adding a solution which has been dissolved and kept warm. One or more group 8 metal complexes having one or more water ligands and / or organic ligands are preferably dissolved and kept at a temperature of 0 to 20 ° C, more preferably 0 to 15 ° C. preferable. The pH is preferably 5.0 to 9.5, and more preferably 6.0 to 9.0. The stagnation time from dissolution of one or more Group 8 metal complexes having one or more water ligands and / or organic ligands to addition to the silver halide emulsion during the formation of silver halide grains is 360. It is preferably within minutes, and more preferably within 240 minutes.

  In the present invention, when the group 8 metal complex having one or more water ligands and / or organic ligands is dissolved and kept at a temperature lower than pH 4.0 or higher than 25 ° C., 8 according to the present invention. Changes in the valence and ligands of the metal complex are likely to occur, which leads to unintended changes in photographic performance. Furthermore, there is a concern that the variation in photographic performance between production lots will increase. On the other hand, if the pH is higher than 10.0, fogging is likely to occur in the silver halide grains. In addition, changes in the valence and ligand in the group 8 metal complex increase over time after dissolution. Therefore, in order to suppress changes in the valence and ligand as much as possible, addition from the dissolution to the silver halide emulsion It is better that the stagnation time is as short as the manufacturing conditions allow. In particular, when an iridium complex is used, it is likely that desensitization, reciprocity failure characteristics, and fluctuations in latent image behavior of silver halide grains are likely to occur under dissolution / heat retention conditions outside the scope of the present invention.

  The silver halide emulsion according to claim 1 of the present invention is characterized in that the silver halide grains are selenium-sensitized.

  The selenium sensitizer that can be used in the present invention is preferably an unstable selenium compound that can react with silver nitrate in an aqueous solution to form a precipitate of silver selenide. For example, U.S. Pat. Nos. 1,574,944, 1,602,592, 1,623,499, JP-A-60-150046, JP-A-4-25832, and 4-109240. 4-147250 and the like.

  Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (such as allyl isoselenocyanate), selenoureas (such as N, N-dimethylselenourea, N, N, N'-triethylseleno). Urea, N, N, N ′, N′-tetramethylselenourea, N, N, N′-trimethyl-N′-heptafluoroselenourea, N, N′-dimethyl-N, N′-bis (carboxymethyl) ) Selenourea, N, N, N′-trimethyl-N′-heptafluoropropylcarbonylselenourea, N, N, N′-trimethyl-N′-4-nitrophenylcarbonylselenourea, etc.), selenoketones (for example, Selenoacetone, selenoacetophenone, etc.), selenoamide (for example, selenoacetamide, N, N-dimethylselenobenzamide, N, -Diethyl-4-octylaminosulfonylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (eg 2-selenopropionic acid, methyl-3-selenobutyrate etc.), selenophosphates (eg tri-p- Tolylselenophosphate, pentafluorophenyl-diphenylselenophosphate, etc.), selenides (eg, dimethyl selenide, tributylphosphine selenide, triphenylphosphine selenide, tri-P-tolylphosphine selenide, pentafluoro Phenyl-diphenylphosphine selenide, trifurylphosphine selenide, tripyridylphosphine selenide, etc.). Particularly preferred selenium sensitizers are selenourea, selenoamides, and selenides.

  Specific examples of techniques for using these selenium sensitizers are disclosed in the following patents. U.S. Pat. Nos. 1,574,944, 1,602,592, 1,623,499, 3,297,466, 3,297,447, 3, 320,069, 3,408,196, 3,408,197, 3,442,653, 3,420,670, 3,591,385, French Patent Nos. 2,693,038, 2,093,209, Japanese Patent Publication Nos. 52-34491, 52-34492, 53-295, 57-22090, Japanese Patent Laid-Open No. 59-180536 No. 59-185330 No. 59-181337 No. 59-187338 No. 59-192241 No. 60-150046 No. 60-151637 No. 61-246738 No. 3-4221 3- 4537, 3-1111838, 3-116132, 3-148648, 3-237450, 4-16838, 4-25832, 4-32831, 4-33043 4-96059, 4-109240, 4-140738, 4-140739, 4-147250, 4-184331, 4-190225, 4-191729, 4-195035, 5-11385, 5-40324, 5-24332, 5-24333, 5-24333, 5-303157, 5-306268, 6-306269, 6- 27573, 6-75328, 6-175259, 6-208184, 6-208186, 6-317867, 7-9259 7-98483, 7-104415, 7-140579, 7-301879, 7-301880, 8-114882, 9-19760, 9-138475, 9-166841, 9-138475, 9-189799, 10-10666, JP-A-2001-343721, British Patent Nos. 255,846, 861,984, etc. And H. E. It is also disclosed in research papers such as Spencer et al., Journal of Photographic Science, Vol. 31, 158-169 (1983).

The preferable addition amount of the selenium sensitizer according to the present invention is 1 × 10 ⁻⁹ to 1 × 10 ⁻¹ mol / mol AgX, more preferably 1 × 10 ⁻⁸ to 1 × 10 ⁻² mol / mol AgX. .

  In order to add the selenium sensitizer according to the present invention to a silver halide emulsion, a method commonly used in the art when an additive is added to a photographic emulsion can be applied. For example, in the case of a water-soluble compound, an aqueous solution having an appropriate concentration is used. In the case of a compound that is insoluble or sparingly soluble in water, any organic solvent that can be mixed with water, for example, alcohols, glycols, ketones It can be dissolved in a solvent that does not adversely affect photographic properties, such as esters and amides, and added as a solution.

  In the present invention, it is preferable to use a sulfur sensitizer in combination. Specifically, thiourea derivatives such as 1,3-diphenylthiourea, triethylthiourea, 1-ethyl-3- (2-thiazolyl) thiourea, rhodanine derivatives, dithiacarbamic acids, polysulfide organic compounds, thiosulfates, Sulfur alone is preferred. In addition, as sulfur simple substance, the alpha-sulfur which belongs to an orthorhombic system is preferable. In addition, U.S. Pat. Nos. 1,574,944, 2,410,689, 2,278,947, 2,728,668, 3,501,313, No. 3,656,955, etc., West German Published Application (OLS) 1,422,869, JP-A-56-24937, 55-45016, etc. are used. I can do it.

  In the present invention, it is preferable to use noble metal salts such as gold, platinum, palladium and iridium described in Research Disclosure (hereinafter abbreviated as RD) 307, 307105, etc. It is preferable to use together. Useful gold sensitizers include U.S. Pat. Nos. 2,597,856, 5,049,485, and Japanese Patent Publication No. 44-15748 in addition to chloroauric acid, gold thiosulfate, gold thiocyanate and the like. And organic gold compounds disclosed in JP-A-1-147537 and 4-70650. Further, when performing a sensitization method using a gold complex salt, it is preferable to use a gold ligand such as thiosulfate, thiocyanate, and thioether as an auxiliary agent, and in particular, it is preferable to use thiocyanate. .

The addition amount of the sulfur sensitizer and a gold sensitizer, the type of the silver halide emulsion, the type of compound used, but are not ripening conditions, usually 1 mol of silver halide per 1 × 10 ^-9 ~ It is preferably 1 × 10 ⁻⁵ mol. More preferably, it is 1 × 10 ⁻⁸ mol to 1 × 10 ⁻⁴ mol.

  Depending on the nature of the sensitizer used, the above-mentioned various sensitizers may be added by dissolving them in water or an organic solvent such as methanol alone or in a mixed solvent, or by premixing with a gelatin solution. The method of addition may be the method disclosed in JP-A-4-140739, that is, the method of adding in the form of an emulsified dispersion of a mixed solution with an organic solvent-soluble polymer.

  In the present invention, a reduction sensitizer can be used in combination, and reducing compounds described in RD magazine 307, 307105, JP-A-7-78685 and the like can be used.

  Specifically, aminoiminomethanesulfinic acid (also known as thiourea dioxide), borane compounds (eg, dimethylamine borane), hydrazine compounds (eg, hydrazine, p-tolylhydrazine, etc.), polyamine compounds (eg, diethylenetriamine, Triethylenetetramine, etc.), stannous chloride, silane compounds, reductones (for example, ascorbic acid, etc.), sodium sulfite, aldehyde compounds, hydrogen gas, and the like. Further, reduction sensitization may be carried out in an atmosphere of high pH or excessive silver ions disclosed in Japanese Patent Application Nos. 8-2777938, 8-251486, and 8-182835.

  In the silver halide emulsion according to claim 2 of the present invention, the silver halide grains are chemically sensitized by adding at least one fine grain selected from silver sulfide, gold sulfide and gold sulfide. And It is preferable that at least one kind of fine particles selected from the silver sulfide, silver gold sulfide and gold sulfide are gold sulfide fine particles.

  There is no limitation on the method for producing at least one kind of fine grains selected from silver sulfide, gold silver sulfide and gold sulfide according to the present invention, and the fine grains may be produced in advance before addition to the silver halide emulsion. The salt may be removed in advance, but the method described in Japanese Patent No. 2929325, that is, an aqueous silver salt solution or an aqueous gold salt solution and an aqueous sulfide solution is simultaneously performed in the presence of a protective colloid while controlling reaction conditions. It is preferable to produce by supplying and reacting.

  In the present invention, the at least one fine particle selected from silver sulfide, gold sulfide silver and gold sulfide has an average diameter in terms of projected area circle (hereinafter also referred to as an average particle diameter in the present invention) of 1 to 15 nm. And preferably 1 to 10 nm, more preferably 1 to 5 nm. The coefficient of variation of the particle diameter is preferably 0.30 or less, more preferably 0.20 or less. The particle size of the silver sulfide, gold sulfide and gold sulfide fine particles and the coefficient of variation of the particle size are obtained by sampling the silver sulfide, silver silver sulfide and gold sulfide produced by the above method, removing salts by a method such as centrifugation, It can be confirmed by observing and applying image processing as necessary after being placed on a mesh of a transmission electron microscope and dried.

  At least one kind of fine particles selected from silver sulfide, silver silver sulfide and gold sulfide according to the present invention can be used by producing two or more kinds of fine particles having different particle diameters and compositions and arbitrarily combining them.

  Any reaction reagent used in the production of at least one fine particle selected from silver sulfide, gold silver sulfide and gold sulfide according to the present invention can be used. For example, when producing silver sulfide, In general, an aqueous silver nitrate solution can be used. As the sulfide aqueous solution, for example, an aqueous solution containing a salt such as sodium sulfide or sodium thiosulfate, or an aqueous solution containing thiourea or a thiourea derivative can be used. For example, an aqueous solution containing chloroauric acid can be generally used as the gold salt aqueous solution for producing gold silver sulfide and gold sulfide, but other inorganic compounds or gold complexes of organic compounds can also be used.

  In the production of at least one kind of fine particles selected from silver sulfide, gold sulfide and gold sulfide according to the present invention, the addition of silver salt aqueous solution, gold salt aqueous solution, gold silver aqueous solution and sulfide aqueous solution can be performed simultaneously while controlling the reaction conditions. It is preferable to form fine particles by supplying an aqueous solution.

  The reaction conditions vary depending on the composition, particle size, distribution, and the like of the fine particles to be produced, but the temperature at which the fine particles are formed is preferably 5 to 80 ° C, more preferably 5 to 60 ° C, and most preferably 5 to 50 ° C. The pH is preferably 2.0 to 10.0, more preferably 4.0 to 9.0, and most preferably 5.0 to 8.5. 4-11 are preferable, as for pAg, 5-10 are more preferable, and 6-9 are the most preferable.

  In the present invention, the fine particles are preferably produced in the presence of a hydrophilic protective colloid. As the hydrophilic protective colloid, an aqueous solution containing the hydrophilic protective colloid may be supplied simultaneously with the supply of the silver salt aqueous solution, the gold salt aqueous solution, the gold silver aqueous solution and the sulfide aqueous solution, or the fine particles are formed in the reaction vessel. In this case, a hydrophilic protective colloid can be present in the reaction vessel in advance. As the hydrophilic protective colloid, gelatin and other compounds described later can be used. The concentration of the hydrophilic protective colloid is preferably 0.01 to 10%, more preferably 0.03 to 5%, and most preferably 0.05 to 3%.

  In the present invention, when at least one kind of fine grains selected from silver sulfide, gold sulfide and gold sulfide is added to the silver halide emulsion for chemical sensitization, the fine grains may be added once or more than once. It may be added in portions, may be added instantaneously, or may be added continuously, but two or more divided additions or continuous additions are preferred. The time is preferably 10 seconds to 100 minutes, more preferably 10 seconds to 60 minutes, and most preferably 10 seconds to 40 minutes.

In the present invention, at least one kind of fine grains selected from silver sulfide, gold silver sulfide and gold sulfide is added to the silver halide emulsion for chemical sensitization. In this case, the reaction temperature is preferably 20 to 90 ° C., 30 -80 ° C is more preferable, and 40-70 ° C is most preferable. The pH is preferably 2.0 to 10.0, more preferably 4.0 to 9.0, and most preferably 5.0 to 8.0. 4-11 are preferable, as for pAg, 5-10 are more preferable, and 6-9 are the most preferable. The addition amount is preferably 1 × 10 ⁻¹⁰ to 1 × 10 ⁻⁴ mol / Ag mol, and more preferably 5 × 10 ^{−9 to} 5 × 10 ⁻⁵ mol / Ag mol.

  In the silver halide emulsion according to claim 3 of the present invention, the silver halide grain emulsion is prepared by using at least one of the compounds represented by the following general formulas (1) to (3). And

Formula _{(1) R-SO 2 S} -M
Formula (2) R ₁ —SO ₂ S—R ₂
Formula (3) R ₃ —SO ₂ S—L _m —SSO ₂ —R ₄
[Wherein, R, R ₁ , R ₂ , R ₃ and R ₄ each represents an aliphatic group, an aromatic group, or a heterocyclic group. R, R ₁ , R ₂ , R ₃ and R ₄ may be the same or different. M represents a cation. L represents a divalent linking group, and m represents 0 or 1. ]
In the general formulas (1) to (3), the aliphatic group represented by R and R _{1 to} R ₄ is a saturated or unsaturated linear, branched or cyclic aliphatic hydrocarbon group, preferably An alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, and an alkynyl group.

  Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, Examples of the alkenyl group include an allyl group and a butenyl group. Examples of the alkynyl group include a propargyl group.

The aromatic group represented by R or R _{1 to} R ₄ includes a monocyclic or condensed ring aromatic group. Preferred aromatic groups are those having 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

The heterocyclic group represented by R, R _{1 to} R ₄ includes a monocyclic or condensed heterocyclic group, and contains at least an atom selected from a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom. And a group derived from a 3- to 10-membered heterocycle having one and at least one carbon atom. Preferred heterocyclic groups are 3 to 6-membered heterocyclic groups such as pyrrolidine ring group, piperidine ring group, pyridine ring group, tetrahydrofuran ring group, thiophene ring group, oxazole ring group, thiazole ring group, imidazole ring. Group, benzothiazole ring group, benzoxazole ring group, benzimidazole ring group, selenazole ring group, benzoselenazole ring group, tetrazole ring group, triazole ring group, benzotriazole ring group, oxadiazole ring group, thiadiazole ring group, etc. Is mentioned.

The aliphatic group, aromatic group and heterocyclic group represented by R, R _{1 to} R ₄ may further have a substituent. Examples of these substituents include an alkyl group (for example, a methyl group, Ethyl group, hexyl group), alkoxy group (for example, methoxy group, ethoxy group, octyloxy group), aryl group (for example, phenyl group, naphthyl group, tolyl group), hydroxy group, halogen atom (fluorine atom, chlorine atom, Bromine atom, iodine atom), aryloxy group (for example, phenoxy group), alkylthio group (for example, methylthio group, butylthio group), arylthio group (for example, phenylthio group), acyl group (for example, acetyl group, propionyl group, butyryl group) , Valeryl group), sulfonyl group (for example, methylsulfonyl group, phenylsulfonyl group), acylamino group (for example, aceto group) Ruamino group, benzoylamino group), sulfonylamino group (for example, methanesulfonylamino group, benzenesulfonylamino group), acyloxy group (for example, acetoxy group, benzoxy group), carboxy group, cyano group, sulfo group, amino group,- Examples include SO ₂ SM and the aliphatic groups, aromatic groups, and heterocyclic groups represented by R and R _{1 to} R ₄ described above.

The divalent linking group represented by L is an atom or atomic group containing at least one atom selected from a carbon atom, a nitrogen atom, a sulfur atom, and an oxygen atom. Specifically, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, —O—, —S—, —NH—, —CO—, —SO ₂ — or the like alone or a combination thereof is used.

The divalent linking group represented by L is preferably a divalent aliphatic group or a divalent aromatic group. For example, — (CH ₂ ) _n — <n = 1 to 12>, —CH ₂ — CH = CH—CH ₂ —, —CH ₂ —C≡C—CH ₂ —, xylylene group, phenylene group, naphthylene group, 1,4-cyclohexanedimethylene group and the like can be mentioned.

  The divalent linking group represented by L may be further substituted with the above-described substituent.

  M is preferably a metal ion, an ammonium ion or an organic cation. Examples of the metal ion include lithium ion, sodium ion, and potassium ion. Examples of the organic cation include alkyl ammonium ions (for example, tetramethylammonium and tetrabutylammonium), phosphonium ions (for example, tetraphenylphosphonium), and guanidyl groups.

  Moreover, the compound represented by General formula (1)-(3) may be contained in the polymer as a component of a polymer. When the compound represented by the general formulas (1) to (3) is contained in the polymer, examples of the repeating unit include the following.

  The polymer containing these repeating units may be a homopolymer or a copolymer with another copolymerization monomer.

  Specific examples of the compounds represented by the general formulas (1) to (3) and specific examples of the polymer containing the compounds represented by the general formulas (1) to (3) as constituent elements are listed below. However, the present invention is not limited to these.

  The silver halide emulsion according to claim 4 of the present invention is characterized in that the silver halide grain emulsion is prepared by using at least one compound represented by the following general formula (4).

Formula _{(4) R 11 - (S} ) m -R 12
In the formula, each of R ₁₁ and R ₁₂ represents an aliphatic group, an aromatic group, a heterocyclic group, or an atomic group that can be bonded to each other to form a ring. R ₁₁ and R ₁₂ may be the same or different. When R ₁₁ and R ₁₂ are aliphatic groups, they may be bonded to each other to form a ring. m represents an integer of 2 to 6.

In the general formula (4), the aliphatic group represented by R ₁₁ and R ₁₂ is a linear or branched alkyl, alkenyl, alkynyl or cycloalkyl having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. Each group is mentioned. Specifically, for example, methyl, ethyl, propyl, butyl, hexyl, decyl, dodecyl, isopropyl, t-butyl, 2-ethylhexyl, allyl, 2-butenyl, 7-octenyl, propargyl, 2-butynyl, cyclopropyl, cyclopentyl , Cyclohexyl, cyclododecyl and the like. Examples of the aromatic group represented by R ₁₁ and R ₁₂ include those having 6 to 20 carbon atoms, and specific examples include groups such as phenyl, naphthyl, and anthranyl. The heterocyclic group represented by R ₁₁ and R ₁₂ may be a monocyclic ring or a condensed ring, and is a 5- to 6-membered heterocyclic group having at least one of O, S and N atoms and an amine oxide group in the ring. Is mentioned.

Specifically, for example, pyrrolidine, piperidine, tetrahydrofuran, tetrahydropyran, oxirane, morpholine, thiomorpholine, thiopyran, tetrahydrothiophene, pyrrole, pyridine, furan, thiophene, imidazole, pyrazole, oxazole, thiazole, isoxazole, isothiazole, triazole , Tetrazole, thiadiazole, oxadiazole, and groups derived from these benzerogues. Examples of the ring forming with R ₁₁ and R ₁₂ include a 4- to 7-membered ring. Preferably it is a 5-7 membered ring.

Preferred groups for R ₁₁ and R ₁₂ are a heterocyclic group and an aromatic group, and more preferably a heteroaromatic group. The aliphatic group, aromatic group or heterocyclic group represented by R ₁₁ and R ₁₂ may be further substituted with a substituent, such as a halogen atom (for example, a chlorine atom, a bromine atom, etc.) , Alkyl groups (eg, methyl group, ethyl group, isopropyl group, hydroxyethyl group, methoxymethyl group, trifluoromethyl group, t-butyl group, etc.), cycloalkyl groups (eg, cyclopentyl group, cyclohexyl group, etc.), aralkyl Group (for example, benzyl group, 2-phenethyl group, etc.), aryl group (for example, phenyl group, naphthyl group, p-tolyl group, p-chlorophenyl group, etc.), alkoxy group (for example, methoxy group, ethoxy group, isopropoxy) Group, butoxy group, etc.), aryloxy group (eg, phenoxy group, 4-methoxyphenoxy group, etc.), cyano group, acyl Mino group (eg acetylamino group, propionylamino group etc.), alkylthio group (eg methylthio group, ethylthio group, butylthio group etc.), arylthio group (eg phenylthio group, p-methylphenylthio group etc.), sulfonylamino Group (for example, methanesulfonylamino group, benzenesulfonylamino group, etc.), ureido group (for example, 3-methylureido group, 3,3-dimethylureido group, 1,3-dimethylureido group, etc.), sulfamoylamino group (Eg, dimethylsulfamoylamino group, diethylsulfamoylamino group, etc.), carbamoyl group (eg, methylcarbamoyl group, ethylcarbamoyl group, dimethylcarbamoyl group, etc.), sulfamoyl group (eg, ethylsulfamoyl group, dimethyl) Sulfamoyl group), Lucoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (for example, phenoxycarbonyl group, p-chlorophenoxycarbonyl group, etc.), sulfonyl group (for example, methanesulfonyl group, butanesulfonyl group, Phenylsulfonyl group etc.), acyl group (eg acetyl group, propanoyl group, butyroyl group etc.), amino group (eg methylamino group, ethylamino group, dimethylamino group etc.), hydroxy group, nitro group, nitroso group, Amine oxide groups (for example, pyridine / oxide groups, etc.), imide groups (for example, phthalimide groups, etc.), disulfide groups (for example, benzene disulfide groups, benzthiazolyl-2-disulfide groups, etc.), heterocyclic groups (for example, pyridyl groups, Benzimidazolyl Group, benzthiazolyl group, benzoxazolyl group, etc.). Substituents containing electron withdrawing groups are particularly preferred. R ₁₁ and R ₁₂ may have one or more of these substituents. Further, each substituent may be further substituted with the above-described substituent. m is an integer of 2-6, preferably 2-3.

  Although the specific example of a compound represented by General formula (4) concerning this invention below is given, this invention is not limited to these.

  In addition to the above, disulfide compounds described in JP-A No. 2002-148750 can also be preferably used.

The preferable addition amount of the compounds represented by the general formulas (1) to (3) and (4) according to the present invention is 1 × 10 ⁻⁸ to 1 mol / mol AgX, more preferably 1 × 10 ⁻⁷ to 1 × 10 ⁻¹ mol / mol AgX.

  In order to add the compounds represented by the general formulas (1) to (3) and (4) according to the present invention to a silver halide emulsion, a method usually used in the art when an additive is added to a photographic emulsion. Can be applied. For example, in the case of a water-soluble compound, an aqueous solution having an appropriate concentration is used. In the case of a compound that is insoluble or sparingly soluble in water, any organic solvent that can be mixed with water, for example, alcohols, glycols, ketones It can be dissolved in a solvent that does not adversely affect photographic properties, such as esters and amides, and added as a solution.

  In the present invention, the compounds represented by the general formulas (1) to (3) and (4) are used at any time from the formation of silver halide grains to the end of chemical sensitization of the silver halide emulsion. However, one of the preferred forms is (a) after silver halide grain formation and before the start of addition of chemical sensitizers such as gold and other noble metal sensitizers and sulfur sensitizers. Another preferred form is (b) after 50% end of chemical sensitization, more preferably after 70% end of chemical sensitization, more preferably after 90% end of chemical sensitization and It is added before the completion of chemical sensitization, and is most preferably carried out in combination with the above (a) and (b).

  The silver halide emulsion according to the present invention preferably contains a compound represented by the above general formula (S) inside the silver halide grains.

  The compound represented by general formula (S) is demonstrated below.

  In the general formula (S), examples of the 5-membered heterocyclic ring represented by Q include imidazole ring, tetrazole ring, thiazole ring, oxazole ring, selenazole ring, benzimidazole ring, naphthimidazole ring, benzothiazole ring, and naphthothiazole. Ring, benzoselenazole ring, naphthoselenazole ring, benzoxazole ring and the like. Examples of the 6-membered heterocyclic ring represented by Q include a pyridine ring, a pyrimidine ring, a quinoline ring, and the like. The 6-membered heterocyclic ring includes those having a substituent.

In the general formula (S), examples of the alkali metal atom represented by M ¹ include a sodium atom and a potassium atom.

  The compound represented by the general formula (S) is preferably a compound represented by the following general formulas (S-1), (S-2), (S-3), and (S-4). More preferably, it is a compound represented by the following general formula (S-2).

In the formula, R ¹ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, a halogen atom, a carboxyl group or a salt thereof, a sulfo group or a salt thereof, or an amino group, and Z represents —NH—, —O—, or represents -S-, M ¹ has the same meaning as M ¹ in the general formula (S).

  In the formula, Ar represents the following group,

R ² represents an alkyl group, an alkoxy group, a carboxyl group or a salt thereof, a sulfo group or a salt thereof, a hydroxyl group, an amino group, an acylamino group, a carbamoyl group, or a sulfonamide group. n represents an integer of 0 to 2. M ¹ has the same meaning as M ¹ in the general formula (S).

In the general formulas (S-1) and (S-2), examples of the alkyl group represented by R ¹ and R ² include a methyl group, an ethyl group, and a butyl group. Examples of the alkoxy group include a methoxy group and an ethoxy group. Examples of the salt of a carboxyl group or a sulfo group include a sodium salt and an ammonium salt.

In the general formula (S-1), examples of the aryl group represented by R ¹ include a phenyl group and a naphthyl group, and examples of the halogen atom include a chlorine atom and a bromine atom.

In the general formula (S-2), examples of the acylamino group represented by R ² include a methylcarbonylamino group and a benzoylamino group. Examples of the carbamoyl group include an ethylcarbamoyl group and a phenylcarbamoyl group. Examples of the group include a methylsulfoamide group and a phenylsulfoamide group.

  The alkyl group, alkoxy group, aryl group, amino group, acylamino group, carbamoyl group, sulfonamide group and the like further include those having a substituent.

In the formula, Z represents —NR ³ —, an oxygen atom or a sulfur atom. R ³ represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, —SR ³¹ , —NR ³² (R ³³ ) —, —NHCOR ³⁴ , —NHSO ₂ R ³⁵ or a heterocyclic group, and R ³¹ It represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, -COR ^34, or represents -SO ₂ R ^35, R ³² and R ³³ represents a hydrogen atom, an alkyl group, or aryl group, R ³⁴ And R ³⁵ represents an alkyl group or an aryl group. M ¹ has the same meaning as M ¹ in formula (S).

Examples of the alkyl group represented by R ³ , R ³¹ , R ³² , R ³³ , R ^34, and R ^{35 in the} general formula (S-3) include a methyl group, a benzyl group, an ethyl group, and a propyl group as an aryl group. Includes a phenyl group, a naphthyl group, and the like.

Examples of the alkenyl group represented by R ³ and R ³¹ include a propenyl group, and examples of the cycloalkyl group include a cyclohexyl group. Examples of the heterocyclic group represented by R ³ include a furyl group and a pyridinyl group.

The alkyl group and aryl group represented by the above R ³ , R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ , the alkenyl group and cycloalkyl group represented by R ³ and R ³¹ , and R ³ The heterocyclic group further includes those having a substituent.

In the formula, R ³ and M ¹ each represent a group having the same meaning as R ³ and M ¹ in formula (S-3). R ³¹ and R ³² each represent a group having the same meaning as R ³¹ and R ³² in formula (S-3).

  Specific examples of the compound represented by the general formula (S) are shown below, but the present invention is not limited thereto.

  Examples of the compound represented by the general formula (S) include Japanese Patent Publication No. 40-28496, Japanese Patent Laid-Open No. 50-89034, Journal of Chemical Society (J. Chem. Soc.) 49, 1748 (1927). 4237 (1952), Journal of Organic Chemistry (J. Org. Chem.) 39, 2469 (1965), US Pat. No. 2,824,001, Journal of Chemical Society, 1723 (1951). And compounds described in JP-A-56-1111846, U.S. Pat. No. 1,275,701, U.S. Pat. Nos. 3,266,897, 2,403,927, and the like. It can be synthesized according to the method described.

  In order to contain the compound represented by the general formula (S) according to the present invention (hereinafter referred to as the compound (S)) in the silver halide emulsion layer according to the present invention, water or an organic compound arbitrarily mixed with water is used. What is necessary is just to add, after melt | dissolving in a solvent (for example, methanol, ethanol, etc.). The compound (S) may be used alone or in combination with another compound represented by the general formula (S) or another stabilizer other than the compound represented by the general formula (S) or a fog inhibitor. May be.

  In the present invention, the inside of the silver halide grains refers to a silver halide phase excluding the surface of the silver halide grains.

In the present invention, the content of the compound represented by the general formula (S) in the silver halide grains is preferably 1 × 10 ⁻⁸ to 1 × 10 ⁻¹ mol / mol AgX, and 1 × 10 ⁻⁷ to 1 ×. 10 ⁻² mol / mol AgX is more preferred.

  In the silver halide emulsion according to the present invention, the silver halide emulsion preferably contains gelatin that is substantially free of calcium ions. In the present invention, gelatin substantially free of calcium ions is gelatin having a calcium content of 100 ppm or less, preferably 50 ppm or less, more preferably 30 ppm or less. Gelatin substantially free of calcium ions according to the present invention can be obtained by a cation exchange treatment using an ion exchange resin or the like.

  In the silver halide emulsion according to the present invention, gelatin containing substantially no calcium ions is any one or more from silver halide grain formation to the end of desalting, dispersion, chemical sensitization and / or color sensitization. It is preferably used in the silver halide emulsion preparation step, but preferably before chemical sensitization and / or color sensitization. 10% by weight or more of the total dispersion medium in the prepared silver halide emulsion is preferably gelatin substantially free of calcium ions, more preferably 30% by weight or more, and more preferably 50% by weight or more. More preferably it is.

  In the silver halide emulsion according to the present invention, the silver halide grains are preferably formed and / or desalted using chemically modified gelatin in which the silver halide grains are substituted with amino groups. As the chemically modified gelatin, a chemically modified gelatin substituted with an amino group of gelatin described in JP-A-5-72658, JP-A-9-197595, JP-A-9-251193, or the like is preferably used. it can. When the chemically modified gelatin is used in particle formation and / or desalting, 10 mass percent or more of the total dispersion medium used for particle formation is preferably the chemically modified gelatin, and more preferably 30 mass percent or more. More preferably, it is 50 mass percent or more. The substitution ratio of the amino group is preferably 30% or more, more preferably 50% or more, and further preferably 80% or more.

  In the production of a silver halide photographic emulsion according to the present invention, desalting is preferably carried out after grain formation. Desalting can be performed, for example, by the method of RD17643, Item II.

  More specifically, in order to remove unnecessary soluble salts from the precipitated product or the emulsion after physical ripening, a nudelle washing method in which gelatin is gelled may be used, and inorganic salts and anionic surfactants may be used. An anionic polymer (for example, polystyrene sulfonic acid) can be used, and a precipitation method using a gelatin derivative and a chemically modified gelatin (for example, acylated gelatin or carbamoylated gelatin) can also be preferably used. Further, ultrafiltration using membrane separation can be preferably used for desalting.

  Regarding ultrafiltration using membrane separation, Chemical Engineering Handbook, Revised 5th Edition (Chemical Engineering Society, Maruzen), pages 924-954, RD 102, 10208 and 131, 1312, or Japanese Patent Publication No. 59-43727, JP-A-62-27008, JP-A-62-113137, JP-A-57-209823, JP-A-59-43727, JP-A-61-219948, JP-A-62-23035, JP-A-63-40137, JP-A-63-40039, Reference can also be made to the methods described in JP-A-3-140946, JP-A-2-172816, JP-A-2-172817, JP-A-4-22942 and the like. In the present invention, when ultrafiltration is used, it is preferable to use the apparatus or method described in JP-A-11-339923 or JP-A-11-231448.

  The dispersion medium used in the production of the silver halide emulsion according to the present invention is a compound having protective colloid properties for silver halide grains. The dispersion medium is preferably present from the nucleation step at the time of silver halide grain formation to the grain growth step. Examples of the dispersion medium that can be preferably used in the present invention include gelatin and hydrophilic colloid. Examples of gelatin include alkali-treated gelatin, acid-treated gelatin having a molecular weight of about 100,000, oxidized gelatin, Bull. Soc. Sci. Photo. Japan No. 16, P30 (1966), enzyme-treated gelatin can be preferably used. In the nucleation of silver halide grains, gelatin having an average molecular weight of 10,000 to 70,000 is preferably used, and gelatin having an average molecular weight of 10,000 to 50,000 is more preferably used. In order to reduce the average molecular weight of gelatin, gelatin can be decomposed using gelatin-degrading enzyme, hydrogen peroxide, or the like. Similarly, the use of gelatin having a low methionine content at the time of nucleation is particularly preferred when forming tabular silver halide grains. The methionine content per unit mass (gram) of the dispersion medium is preferably 50 μmol or less, and more preferably 20 μmol or less. The methionine content in gelatin can be reduced by oxidizing the gelatin with hydrogen peroxide or the like.

  Examples of hydrophilic colloids include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates, sodium alginate, starch derivatives Sugar derivatives such as: polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinyl pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, various kinds such as copolymers such as polyvinyl pyrazole Synthetic hydrophilic polymer materials can be used. Examples of gelatin include lime-processed gelatin, acid-processed gelatin, and Bull. Soc. Sci. Photo. Japan. No. 16. An enzyme-treated gelatin as described in P30 (1966) may be used, and a hydrolyzate or enzyme-decomposed product of gelatin can also be used.

  The silver halide grains according to the present invention may have any shape, but one preferred example is a cube having a (100) plane as the crystal surface. Also, U.S. Pat. Nos. 4,183,756, 4,225,666, JP-A-55-26589, JP-B-55-42737, The Journal of Photographic Science (J. Photogr. Sci.) 21, 39 (1973). ), Etc., particles having an octahedral, tetradecahedral, dodecahedron, etc. shape can be produced and used. Furthermore, particles having twin planes may be used.

  The silver halide grains according to the present invention are preferably grains having a single shape, but two or more monodispersed silver halide emulsions can be added to the same layer.

  The grain size of the silver halide grain according to the present invention is not particularly limited. However, when cubic grains are used in consideration of other photographic performances such as rapid processability and sensitivity, preferably 0.1-1. The range is 2 μm, more preferably 0.15 to 1.0 μm.

  This particle size can be measured using the projected area or diameter approximation of the particle. If the particles are substantially uniform in shape, the particle size distribution can be expressed fairly accurately as a diameter or projected area.

  The grain size distribution of the silver halide grains of the present invention is preferably monodispersed silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less. Here, the variation coefficient is a coefficient representing the breadth of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / R
(Here, S represents the standard deviation of the particle size distribution, and R represents the average particle size.)
The particle diameter here means the diameter in the case of spherical silver halide grains, and the diameter when the projected image is converted into a circular image of the same area in the case of grains other than a cube or a sphere. Represent.

  As a silver halide emulsion preparation apparatus and method, various methods known in the art can be used.

  The silver halide emulsion may be obtained by any of the acidic method, neutral method and ammonia method. The particles may be grown at one time, or may be grown after producing seed particles. The method for producing seed particles and the method for growing them may be the same or different.

  The form of reacting the soluble silver salt and the soluble halide may be any of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, and the like, but those obtained by the simultaneous mixing method are preferred. Furthermore, as one form of the simultaneous mixing method, the pAg controlled double jet method described in JP-A No. 54-48521 can also be used.

  Further, a device for supplying a water-soluble silver salt and a water-soluble halide aqueous solution from an adding device arranged in a reaction mother liquor described in JP-A-57-92523, JP-A-57-92524 and the like; An apparatus for continuously adding water-soluble silver salt and water-soluble halide aqueous solution described in No. 921,164 etc., taking out the reaction mother liquor outside the reactor described in JP-B-56-501776, etc. An apparatus that forms grains while keeping the distance between silver halide grains constant by concentrating by ultrafiltration may be used.

  Further, if necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound, or a compound such as a sensitizing dye may be added and used at the time of forming silver halide grains or after the completion of grain formation.

  The silver halide emulsion can be used in combination of a sensitizing method using a gold compound and a sensitizing method using a chalcogen sensitizer.

  As a chalcogen sensitizer applied to the silver halide emulsion, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer and the like can be used, and a sulfur sensitizer is preferred.

  Examples of the sulfur sensitizer include thiosulfate, allylthiocarbamide, thiourea, allyl isothiocyanate, cystine, p-toluenethiosulfonate, rhodanine, inorganic sulfur and the like.

The amount of sulfur sensitizer added is preferably changed depending on the type of silver halide emulsion to be applied and the magnitude of the expected effect, but 5 × 10 ^{−10 to} 5 × 10 ⁻⁵ per mole of silver halide. The mole is preferably in the range of 5 × 10 ^{−8 to} 3 × 10 ⁻⁵ mol.

As the gold sensitizer, various gold complexes such as chloroauric acid and gold sulfide can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, mercaptotriazole and the like. The amount of gold compound used is not uniform depending on the type of silver halide emulsion, the type of compound used, ripening conditions, etc., but usually 1 × 10 ⁻⁴ to 1 × 10 ⁻⁸ mol per mol of silver halide. It is preferable that it is 1 * 10 < ^-5 > -1 * 10 <^-8> mol.

  As chemical sensitization of silver halide emulsions, reduction sensitization may be used.

  For the silver halide emulsion, known antifoggants and stabilizers are used for the purpose of preventing fogging during the preparation process of the light-sensitive material, reducing fluctuations in performance during storage, and preventing fogging during development. be able to. As an example of a preferable compound used for such purpose, there can be mentioned a compound represented by the general formula [II] described in JP-A-2-14636, page 7, lower column, and more preferable specific compounds include IIa-1 to IIa-8 and IIb-1 to IIb-7 described on page 8 of the same publication, 1- (3-methoxyphenyl) -5-mercaptotetrazole, 1- (4-ethoxyphenyl)- Mention may be made of compounds such as 5-mercaptotetrazole.

Depending on the purpose, these compounds are added in steps such as a silver halide emulsion grain preparation step, a chemical sensitization step, a chemical sensitization step, and a coating solution preparation step. When chemical sensitization is performed in the presence of these compounds, it is preferably used in an amount of about 1 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol per mol of silver halide. When added at the end of chemical sensitization, the amount is preferably about 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol per mol of silver halide, more preferably 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol. . When added to the silver halide emulsion layer in the coating solution preparation step, the amount of 1 × 10 ^-6 to 1 × 10 ^-1 mol per mol of silver halide is preferred, 1 × 10 ^-5 ~ × 10 ^{- Two} moles are more preferred. When added to a layer other than the silver halide emulsion layer, the amount in the coating film is preferably about 1 × 10 ⁻⁹ to 1 × 10 ⁻³ mol per 1 m ² .

  For the photosensitive material, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any known compound can be used. In particular, as dyes having absorption in the visible region, dyes AI-1 to 11 described in JP-A-3-251840, page 30 and JP-A-6 The dyes described in No.-3770 are preferably used, and as the infrared absorbing dye, compounds represented by the general formulas (I), (II) and (III) described in JP-A-1-280750, page 2, lower left column are preferable. It has spectral characteristics, is not affected by photographic characteristics of photographic emulsions, and is free from contamination by residual colors. Specific examples of preferred compounds include the exemplified compounds (1) to (45) listed in the same publication, page 3, lower left column to page 5, lower left column. For the purpose of improving sharpness, the amount of these dyes added is preferably such that the spectral reflection density at 680 nm of the untreated sample of the light-sensitive material is 0.7 to 3.0, more preferably 0.8 to More preferably, it is 3.0.

  It is preferable to add a fluorescent brightening agent to the light-sensitive material because white background can be improved. Preferred examples of the compound include compounds represented by the general formula [II] described in JP-A-2-232652.

  When the light-sensitive material of the present invention is used as a color light-sensitive material, it has a layer containing a silver halide emulsion spectrally sensitized in a specific region of a wavelength region of 400 to 900 nm in combination with a yellow coupler, a magenta coupler, and a cyan coupler. . The silver halide emulsion contains one or more sensitizing dyes in combination.

  As the spectral sensitizing dye used in the present invention, any known compound can be used. As the blue-sensitive sensitizing dye, BS-1 to BS-8 described in JP-A-3-251840, page 28, are used. Can be preferably used alone or in combination. As the green photosensitive sensitizing dye, GS-1 to GS-5 described on page 28 of the same publication are preferable, and as the red photosensitive sensitizing dye, RS-1 to RS-8 described on page 29 of the same publication. Is preferably used. In addition, when image exposure is performed with infrared light using a semiconductor laser or the like, it is necessary to use an infrared photosensitive sensitizing dye. As an infrared photosensitive sensitizing dye, JP-A-4-285950 can be used. No. 6-8 pages, IRS-1 to IRS-11 dyes are preferably used. In addition, these infrared, red, green and blue photosensitive sensitizing dyes are supersensitizers SS-1 to SS-9 described in JP-A-4-285950, pages 8 to 9 and JP-A-5-66515. The compounds S-1 to S-17 described on pages 15 to 17 are preferably used in combination.

  The time for adding the sensitizing dye may be any time from the formation of silver halide grains to the end of chemical sensitization.

  As a method for adding a sensitizing dye, it may be added as a solution by dissolving in water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone, dimethylformamide or water, or as a solid dispersion. Also good.

  As the coupler used in the light-sensitive material of the present invention, any compound capable of forming a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by a coupling reaction with an oxidized form of a color developing agent is used. However, particularly representative couplers include a yellow dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a magenta dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm, and a wavelength range of 600 to Those known as cyan dye-forming couplers having a spectral absorption maximum wavelength at 750 nm may be mentioned.

  Examples of cyan couplers that can be preferably used include couplers represented by the general formulas [CI] and [C-II] described in JP-A-4-114154, page 5, lower left column. Examples of the compound include those described as CC-1 to CC-9 in page 5, lower right column to page 6, lower left column.

Examples of magenta couplers that can be preferably used include couplers represented by the general formulas [M-I] and [M-II] described in JP-A-4-114154, page 4, upper right column. Examples of the compound include those described as MC-1 to MC-11 in page 4, lower left column to page 5, upper right column. Among the magenta couplers, more preferred is a coupler represented by the general formula [M-I], and among them, a coupler in which R _{M of the} general formula [M-I] is a tertiary alkyl group is a light fastness. And particularly preferred. MC-8 to MC-11 described in the upper column on page 5 of the same publication are preferable because they are excellent in reproducing colors ranging from blue to purple and red, and are excellent in detail descriptive power.

Examples of yellow couplers that can be preferably used include couplers represented by the general formula [YI] described in JP-A-4-114154, page 3, upper right column. What is described as YC-1 to YC-9 after the column can be mentioned. Among them, a coupler in which R _Y1 in the general formula [Y-1] is an alkoxy group, or a coupler represented by the general formula [I] described in JP-A-6-67388 is preferable because it can reproduce yellow having a preferable color tone. Among these, as particularly preferred compound examples, YC-8 and YC-9 described in JP-A-4-114154, page 4, upper left column and Nos. (1) to (47) described in JP-A-6-67388, pages 13-14. ) Can be mentioned. The most preferred compounds are those represented by the general formula [Y-1] described in JP-A-4-81847, pages 1 and 11-17.

  When using an oil-in-water type emulsion dispersion method to add a coupler or other organic compound used in a light-sensitive material, usually a water-insoluble high-boiling organic solvent having a boiling point of 150 ° C. or higher is used. And / or dissolved in combination with a water-soluble organic solvent, and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As the dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, or the like can be used. A step of removing the low boiling point organic solvent may be added after the dispersion or simultaneously with the dispersion.

  High boiling point organic solvents that can be used to dissolve and disperse couplers include phthalic acid esters such as dioctyl phthalate, di-i-decyl phthalate, and dibutyl phthalate, and phosphoric acid such as tricresyl phosphate and trioctyl phosphate. Esters are preferably used. The dielectric constant of the high boiling point organic solvent is preferably 3.5 to 7.0. Two or more high boiling point organic solvents can be used in combination.

  Further, instead of using a high-boiling organic solvent or in combination with a high-boiling organic solvent, a water-insoluble and organic solvent-soluble polymer compound is dissolved in a low-boiling and / or water-soluble organic solvent as necessary. In addition, a method of emulsifying and dispersing by various dispersing means using a surfactant in a hydrophilic binder such as an aqueous gelatin solution can also be employed. Examples of the water-insoluble and organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

  Preferred compounds as surfactants used to disperse photographic additives and adjust the surface tension during application include those containing a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof in one molecule. Is mentioned. Specific examples include A-1 to A-11 described in JP-A No. 64-26854. A surfactant having a fluorine atom substituted on an alkyl group is also preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, but it is better that the time until dispersion is added to the coating solution after dispersion and the time after addition to the coating solution is shorter. Each is preferably within 10 hours, more preferably within 3 hours and within 20 minutes.

  Each of the above couplers is preferably used in combination with an anti-fading agent in order to prevent fading of the formed dye image due to light, heat, humidity and the like. Particularly preferred compounds include phenyl ether compounds represented by general formulas [I] and [II] described on page 3 of JP-A-2-665541, and phenols represented by general formula [IIIB] described in JP-A-3-174150. Compounds, amine compounds represented by general formula [A] described in JP-A No. 64-90445, general formulas [XII], [XIII], [XIV], [XV] described in JP-A No. 62-182741 Are particularly preferred for magenta dyes. Further, compounds represented by the general formula [I] described in JP-A-1-196049 and compounds represented by the general formula [II] described in JP-A-5-11417 are particularly preferred for yellow and cyan dyes.

  For the purpose of shifting the absorption wavelength of the coloring dye, compounds such as compound d-11 described in JP-A-4-114154, page 9, lower left column, compound A'-1 described in page 10, upper left column, and the like can be used. . In addition, the fluorescent dye releasing compound described in US Pat. No. 4,774,187 can also be used.

  In light-sensitive materials, a compound that reacts with the oxidized developer is added to the layer between the light-sensitive layer to prevent color turbidity, or it is added to the silver halide emulsion layer to improve fog and the like. It is preferable. The compound for this purpose is preferably a hydroquinone derivative, more preferably a dialkyl hydroquinone such as 2,5-di-t-octyl hydroquinone. Particularly preferred compounds are compounds represented by the general formula [II] described in JP-A-4-13356, and are compounds II-1 to II-14 described on pages 13 to 14 and compounds-1 described on page 17 Is mentioned.

  In the photosensitive material, it is preferable to add an ultraviolet absorber to prevent static fogging or to improve the light resistance of the dye image. Preferred ultraviolet absorbers include benzotriazoles, and particularly preferred compounds are those represented by general formula [III-3] described in JP-A-1-250944, and general formula [III described in JP-A 64-66646. A compound represented by general formula [I] described in JP-A No. 63-187240, a compound represented by general formula [I] described in JP-A No. 4-1633, and a general formula described in JP-A No. 5-165144. Examples include compounds represented by formulas (I) and (II).

  In the light-sensitive material of the present invention, it is advantageous to use gelatin as a binder, but if necessary, gelatin derivatives, gelatin and other polymer graft polymers, proteins other than gelatin, sugar derivatives, cellulose derivatives, single or Hydrophilic colloids such as synthetic hydrophilic polymer materials such as copolymers can also be used.

  As these binder hardeners, vinylsulfone type hardeners, chlorotriazine type hardeners, and carboxyl group active hardeners are preferably used alone or in combination. It is preferable to use compounds described in JP-A Nos. 61-249054 and 61-245153. Further, in order to prevent the growth of soot and bacteria that adversely affect photographic performance and image storage stability, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 in the colloid layer. In order to improve the physical properties of the surface of the photosensitive material or processed sample, it is preferable to add a slipping agent or a matting agent described in JP-A-6-118543 and JP-A-2-73250 to the protective layer.

  As the support used for the photosensitive material, any material may be used, including paper coated with polyethylene or polyethylene terephthalate, paper support made of natural pulp or synthetic pulp, vinyl chloride sheet, and white pigment. Good polypropylene, polyethylene terephthalate support, baryta paper and the like can be used. Among these, a support having a water-resistant resin coating layer on both sides of the base paper is preferable.

  As the water resistant resin, polyethylene, polyethylene terephthalate or a copolymer thereof is preferable.

  As the white pigment used for the support, inorganic and / or organic white pigments can be used, and inorganic white pigments are preferably used. For example, alkaline earth metal sulfate such as barium sulfate, alkaline earth metal carbonate such as calcium carbonate, silica such as fine silicate, synthetic silicate, calcium silicate, alumina, alumina hydrate, titanium oxide, oxidation Examples include zinc, talc, and clay. The white pigment is preferably barium sulfate or titanium oxide.

  The amount of the white pigment contained in the water-resistant resin layer on the surface of the support is preferably 13% by mass or more, and more preferably 15% by mass or more for improving sharpness.

  The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, and more preferably 0.15 or less, as the coefficient of variation described in the publication.

  Further, it is more preferable that the average surface roughness (SRa) of the support is 0.15 μm or less, and further 0.12 μm or less, because the effect of good gloss is obtained. In addition, in order to improve the whiteness by adjusting the spectral reflection density balance of the white background after processing in the white pigment-containing water-resistant resin of the reflective support or in the coated hydrophilic colloid layer, ultramarine, oil-soluble dyes, etc. It is preferable to add a small amount of a blue tinting agent or a red tinting agent.

  The photosensitive material is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the support surface as necessary, and then directly or undercoat layer (support surface adhesion, antistatic properties, dimensional stability, friction resistance) May be applied via one or more subbing layers for improving the properties, hardness, antihalation properties, frictional properties and / or other properties.

  When coating a light-sensitive material using a silver halide emulsion, a thickener may be used to improve the coating property. As the coating method, extrusion coating and curtain coating capable of simultaneously coating two or more layers are particularly useful.

  In order to form a photographic image using the photosensitive material of the present invention, the image recorded on the negative may be optically imaged and printed on the photosensitive material to be printed. After conversion to information, the image may be formed on a CRT (cathode ray tube), and the image may be formed on a photosensitive material to be printed and printed, or the intensity of laser light based on digital information. The image may be printed by scanning while changing the above.

  The present invention is preferably applied to a photosensitive material in which a developing agent is not incorporated in the photosensitive material, and is particularly preferably applied to a photosensitive material that directly forms an image for viewing. Examples thereof include color paper, color reversal paper, a photosensitive material for forming a positive image, a photosensitive material for display, and a photosensitive material for color proof. In particular, it is preferably applied to a photosensitive material having a reflective support.

As the aromatic primary amine developing agent used in the present invention, known compounds can be used. Examples of these compounds include the following compounds.
CD-1: N, N-diethyl-p-phenylenediamine CD-2: 2-amino-5-diethylaminotoluene CD-3: 2-amino-5- (N-ethyl-N-lauryl) aminotoluene CD-4 : 4- (N-ethyl-N-β-hydroxyethyl) aminoaniline CD-5: 2-methyl-4- (N-ethyl-N-β-hydroxyethyl) amino aniline CD-6: 4-amino-3 -Methyl-N-ethyl-N- (β-methanesulfonamido) ethylaniline CD-7: 4-amino-3-β-methanesulfonamidoethyl-N, N-diethylaniline CD-8: N, N-dimethyl -P-phenylenediamine CD-9: 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline CD-10: 4-amino-3-methyl-N-ethyl-N- (β- Toxiethyl) aniline CD-11: 4-amino-3-methyl-N-ethyl-N- (γ-hydroxypropyl) ethylaniline In the present invention, the color developer can be used in any pH range. From the viewpoint of treatment, the pH is preferably 9.5 to 13.0, more preferably pH 9.8 to 12.0.

  The processing temperature for color development in the present invention is preferably 35 to 70 ° C. The higher the temperature, the shorter the treatment possible, which is preferable. However, it is preferable that the temperature is not so high in terms of the stability of the treatment liquid, and treatment at 37 to 60 ° C is preferred.

  Conventionally, the color development time is generally about 3 minutes 30 seconds, but in the present invention, it is preferably within 40 seconds, and more preferably within 25 seconds.

  In addition to the above color developing agent, a known developer component compound can be added to the color developer. Usually, an alkali agent having a pH buffering action, a development inhibitor such as chlorine ions and benzotriazoles, a preservative, and a chelating agent are used.

  The photosensitive material is subjected to bleaching and fixing after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process, a washing process is usually performed. Moreover, you may perform a stabilization process as an alternative of a water-washing process.

  The development processing apparatus used for processing the photosensitive material of the present invention is an endless type that transports a photosensitive material fixed to a belt even if it is a roller transport type that transports the photosensitive material sandwiched between rollers disposed in a processing tank. Although a belt system may be used, a processing tank is formed in a slit shape, a processing liquid is supplied to the processing tank and a photosensitive material is conveyed, a spraying method for spraying the processing liquid, and a processing liquid impregnated. A web system by contact with a supported carrier, a system using a viscous treatment liquid, or the like can also be used. In the case of processing in large quantities, it is normal that the running processing is performed using an automatic processor. In this case, the replenishing amount of the replenisher is preferably as small as possible, and the most preferable processing form in view of environmental suitability is the tablet as a replenishing method. The method described in the published technique 94-16935 is most preferable.

The light-sensitive material for printing of the present invention is preferable because the light-sensitive material of the present invention has a large improvement in image quality, particularly when an image is formed by exposure through a negative film having an area per screen of 3 to 7 cm ² . The negative film may have information recording ability.

  Hereinafter, although an example is given and explained concretely, the present invention is not limited to these examples.

Example 1
A silver halide emulsion was prepared by the following method.

<Preparation of blue-sensitive silver halide emulsion>
[Preparation of silver halide emulsion (B-1)]
Both ion exchange-treated ossein gelatin (calcium content 10 ppm) kept at 40 ° C. In 1 liter of 2% gelatin aqueous solution, the following (A1 solution) and (B1 solution) were adjusted to pAg = 7.3, pH = 3.0 It added simultaneously over 30 minutes, controlling. Subsequently, the following (A2 solution) and (B2 solution) were simultaneously added over 150 minutes while controlling pAg = 8.0 and pH = 5.5. Furthermore, the following (A3 liquid) and (B3 liquid) were added simultaneously over 30 minutes while controlling pAg = 8.0 and pH = 5.5. At this time, the pH of (A2 solution) was adjusted to 5.0, the dissolution / warming temperature was maintained at 35 ° C., and the time from the start of dissolution of (A2 solution) to the start of addition of (B2 solution) was 120 minutes. The pAg was controlled by the method described in JP-A-59-45437, and the pH was controlled and adjusted using sulfuric acid or a sodium hydroxide aqueous solution.

(A1 solution)
Sodium chloride 3.42g
Potassium bromide 0.03g
200ml with water
(A2 liquid)
Sodium chloride 71.9g
K ₂ [IrCl ₅ (H ₂ O)] 4.0 × 10 ⁻⁷ mol / mol AgX
K ₄ [Fe (CN) ₆ ] 5.0 × 10 ⁻⁶ mol / mol AgX
Potassium bromide 0.7g
420ml with water
(A3 liquid)
Sodium chloride 30.8g
Potassium bromide 0.3g
180ml with water
(B1 solution)
Silver nitrate 10g
200ml with water
(B2 liquid)
210g silver nitrate
420ml with water
(B3 liquid)
90g silver nitrate
180ml with water
After completion of the addition, a 5% aqueous solution containing 30 g of chemically modified gelatin (modified ratio 95%) in which the amino group is phenylcarbamoylated is added using the method described in JP-A-5-72658, and then desalted. Monodispersed when mixed with an aqueous solution and having an average particle size (cubic equivalent particle size) of 0.50 μm, a particle size variation coefficient of 0.07, a silver chloride content of 99.5 mol%, and a silver bromide content of 0.5 mol% A cubic silver halide emulsion (B-1) was prepared.

  In the silver halide emulsion (B-1), the part of the grain grown by (A1 liquid) and (B1 liquid) is the seed part, the part of the grain grown by (A2 liquid) and (B2 liquid) is the core part, and (A3 liquid) ) And (B3 liquid), the part where the particles grow is defined as the shell part. The volume ratios occupied by the silver halide grains in the seed part, core part and shell part were 3.3%, 66.7% and 30.0%, respectively.

[Preparation of silver halide emulsion (B-2)]
A silver halide emulsion (B-2) was prepared in the same manner as in the preparation of the silver halide emulsion (B-1) except that the dissolution / warming temperature of (A2 solution) was maintained at 22 ° C.

[Preparation of silver halide emulsion (B-3)]
A silver halide emulsion (B-3) was prepared in the same manner as in the preparation of the silver halide emulsion (B-1) except that the dissolution / warming temperature of (A2 solution) was maintained at 18 ° C.

[Preparation of silver halide emulsion (B-4)]
A silver halide emulsion (B-4) was prepared in the same manner as in the preparation of the silver halide emulsion (B-1) except that the dissolution / warming temperature of (A2 solution) was maintained at 13 ° C.

[Preparation of silver halide emulsion (B-5)]
In the preparation of the silver halide emulsion (B-4), after all the additions of silver nitrate and halide were completed, 0.0055 mol of silver bromide fine particles (particle size: 0.02 μm) were further added, and an odor was observed near the top. Except for forming a silver halide localized layer, the average particle size (cubic equivalent particle size) is 0.50 μm, the variation coefficient of the particle size is 0.07, the silver chloride content is 99.2 mol%, and silver bromide is contained. A monodispersed cubic silver halide emulsion (B-5) having a ratio of 0.8 mol% was prepared.

[Preparation of silver halide emulsion (B-6)]
In the preparation of the silver halide emulsion (B-5), the compound (S-2-5) was finally added to the (A1 liquid), (A2 liquid) (A3 liquid) in the final silver halide grains. In the same manner, except that 2.1 × 10 ⁻⁶ mol / mol AgX, 5.3 × 10 ⁻⁵ mol / mol AgX, and 9.0 × 10 ⁻⁶ mol / mol AgX were added, respectively. B-6) was prepared.

[Preparation of silver halide emulsion (B-7)]
A silver halide emulsion (B-7) was prepared in the same manner as in the preparation of the silver halide emulsion (B-6) except that the iridium compound in (A2 solution) was changed to the following.

Iridium compound used in silver halide emulsion (B-7) K ₂ [IrCl ₆ ] 8.0 × 10 ⁻⁹ mol / mol AgX
K ₂ [IrBr ₆ ] 5.0 × 10 ⁻⁹ mol / mol AgX
K ₂ [IrCl ₅ (H ₂ O)] 9.0 × 10 ⁻⁸ mol / mol AgX
K ₂ [IrCl ₅ (thiazole)] 5.0 × 10 ⁻⁹ mol / mol AgX
[Preparation of silver halide emulsion (B-8)]
Emulsion (B-8) was prepared in the same manner as in the preparation of silver halide emulsion (B-6), except that the iridium compound in (A2 solution) was changed to the following.

Iridium compound used in silver halide emulsion (B-8) K ₂ [IrCl ₆ ] 7.0 × 10 ⁻⁹ mol / mol AgX
K ₂ [IrBr ₆ ] 5.0 × 10 ⁻⁹ mol / mol AgX
K ₂ [IrCl ₅ (H ₂ O)] 1.0 × 10 ⁻⁷ mol / mol AgX
K ₂ [IrBr ₅ (H ₂ O)] 9.0 × 10 ⁻⁹ mol / mol AgX
K ₂ [IrCl ₅ (thiazole)] 3.0 × 10 ⁻⁹ mol / mol AgX
[Preparation of silver halide emulsion (B-9)]
In the preparation of the silver halide emulsion (B-6), instead of adding (A3 liquid) and (B3 liquid), the following (A4 liquid) and (B4 liquid) are added simultaneously, and then the following (A5 liquid) ) And (B5 solution) are added at the same time, and when the addition of (B5 solution) is completed 30%, the addition of silver nitrate and halide solution is interrupted, and 36 ml of 0.05 mol / L silver iodide aqueous solution is added. In the same manner as above, except that the operation of resuming the addition of silver nitrate and halide liquid was performed, and the iridium compound in (A2 liquid) was changed to the following, and having a silver bromide localized layer near the apex, and grains Average grain size (cubic equivalent grain size) of 0.50 μm with localized layer of silver bromide and silver iodide inside, variation coefficient of grain size of 0.07, silver chloride content of 96.2 mol%, odor Monodispersed cubes having a silver iodide content of 3.7 mol% and a silver iodide content of 0.1 mol% Was prepared androgenic Halide Emulsion (B-9).

(A4 liquid)
Sodium chloride 12.3g
6.5 g of potassium bromide
Add water 530ml
(A5 liquid)
Sodium chloride 15.4g
Potassium bromide 0.15g
133ml with water
(B4 liquid)
45 g of silver nitrate
Add water 530ml
(B5 liquid)
45 g of silver nitrate
133ml with water
Iridium compound used for silver halide emulsion (B-9) K ₂ [IrCl ₆ ] 9.0 × 10 ⁻⁹ mol / mol AgX
K ₂ [IrBr ₆ ] 5.0 × 10 ⁻⁹ mol / mol AgX
K ₂ [IrCl ₅ (H ₂ O)] 1.4 × 10 ⁻⁷ mol / mol AgX
K ₂ [IrBr ₅ (H ₂ O)] 7.0 × 10 ⁻⁹ mol / mol AgX
K ₂ [IrCl ₅ (imidazole)] 4.0 × 10 ⁻⁹ mol / mol AgX
[Preparation of blue-sensitive silver halide emulsions (B-1a) and (B-2a)]
The following sensitizing dyes (BS-1) and (BS-2) were added to the silver halide emulsions (B-1) and (B-2) at 60 ° C., pH 5.8, and pAg 7.5, Subsequently, the following sodium thiosulfate, triphenylphosphine selenide, and chloroauric acid were sequentially added to perform spectral sensitization and chemical sensitization. After the chemical sensitizer was added and optimally ripened, the following compounds S-2-5, S-2-2, and S-2-3 were sequentially added to stop the ripening, and each blue-sensitive silver halide emulsion (B-1a) and (B-2a) were obtained.

Sodium thiosulfate 3.9 × 10 ⁻⁶ mol / mol AgX
Triphenylphosphine selenide 2.6 × 10 ⁻⁶ mol / mol AgX
Chloroauric acid 1.9 × 10 ⁻⁵ mol / mol AgX
Compound S-2-5 3.0 × 10 ⁻⁴ mol / mol AgX
Compound S-2-2 3.0 × 10 ⁻⁴ mol / mol AgX
Compound S-2-3 3.0 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye BS-1 5.2 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye BS-2 1.3 × 10 ⁻⁴ mol / mol AgX
[Blue-sensitive silver halide emulsions (B-2b), (B-3a), (B-4a), (B-5a), (B-6a), (B-7a), (B-8a) and ( Preparation of B-9a)]
The silver halide emulsions (B-2), (B-3), (B-4), (B-5), (B-6), (B-7), (B-8) and (B- 9), the following sensitizing dyes (BS-1) and (BS-2) were added at 60 ° C., pH 5.8, and pAg 7.5, followed by the following sodium thiosulfate, trifurylphosphine selenide, and Chloroauric acid was sequentially added to give spectral and chemical sensitization. After the chemical sensitizer was added and optimally ripened, the following compounds S-2-5, S-2-2, and S-2-3 were sequentially added to stop the ripening, and each blue-sensitive silver halide emulsion (B-2b), (B-3a), (B-4a), (B-5a), (B-6a), (B-7a), (B-8a) and (B-9a) were obtained. .

Sodium thiosulfate 3.9 × 10 ⁻⁶ mol / mol AgX
Trifurylphosphine selenide 2.6 × 10 ⁻⁶ mol / mol AgX
Chloroauric acid 1.9 × 10 ⁻⁵ mol / mol AgX
Compound S-2-5 3.0 × 10 ⁻⁴ mol / mol AgX
Compound S-2-2 3.0 × 10 ⁻⁴ mol / mol AgX
Compound S-2-3 3.0 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye BS-1 5.2 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye BS-2 1.3 × 10 ⁻⁴ mol / mol AgX
[Preparation of silver halide emulsions (G-1) to (G-9)]
In the preparation of the silver halide emulsions (B-1) to (B-4), (A1 solution), (B1 solution), (A2 solution), (B2 solution), (A3 solution) and (B3 solution) Except that the addition time was appropriately changed, the average particle size (cubic equivalent particle size) was 0.35 μm, the variation coefficient of the particle size was 0.08, the silver chloride content was 99.5 mol%, and the silver bromide content was 0. Silver halide emulsions (G-1) to (G-4) which were .5 mol% monodispersed cubic emulsions were prepared.

  In the preparation of the silver halide emulsions (B-5) to (B-8), (A1 solution), (B1 solution), (A2 solution), (B2 solution), (A3 solution) and (B3 solution) Except that the addition time was appropriately changed, the average particle size (cubic equivalent particle size) was 0.35 μm, the variation coefficient of the particle size was 0.08, the silver chloride content was 99.2 mol%, and the silver bromide content was 0. Silver halide emulsions (G-5) to (G-8) which were .8 mol% monodispersed cubic emulsions were prepared.

  In the preparation of the silver halide emulsion (B-9), (A1 solution), (B1 solution), (A2 solution), (B2 solution), (A4 solution) and (B4 solution), (A5 solution) and ( In the same manner except that the addition time of the solution (B5) was changed as appropriate, the average particle size (cubic equivalent particle size) was 0.35 μm, the particle size variation coefficient was 0.08, the silver chloride content was 96.2 mol%, bromide A silver halide emulsion (G-9), which is a monodispersed cubic emulsion having a silver content of 3.7 mol% and a silver iodide content of 0.1 mol%, was prepared.

[Preparation of green-sensitive silver halide emulsions (G-1a) and (G-2a)]
To the silver halide emulsions (G-1) and (G-2), the following sensitizing dye (GS-1) was added at 60 ° C., pH 5.8, and pAg 7.5, followed by the following sodium thiosulfate, Triphenylphosphine selenide and chloroauric acid were sequentially added to perform spectral sensitization and chemical sensitization. After the chemical sensitizer was added and optimally ripened, the following compound S-2-5 was added to stop the ripening to obtain green-sensitive silver halide emulsions (G-1a) and (G-2a), respectively. It was.

Sensitizing dye (GS-1) 5.2 × 10 ⁻⁴ mol / mol AgX
Sodium thiosulfate 4.5 × 10 ⁻⁶ mol / mol AgX
Triphenylphosphine selenide 3.2 × 10 ⁻⁶ mol / mol AgX
Chloroauric acid 1.9 × 10 ⁻⁵ mol / mol AgX
Compound (S-2-5) 1.5 × 10 ⁻⁴ mol / mol AgX
[Green-sensitive silver halide emulsions (G-2b), (G-3a), (G-4a), (G-5a), (G-6a), (G-7a), (G-8a) and ( Preparation of G-9a)]
The silver halide emulsions (G-2), (G-3), (G-4), (G-5), (G-6), (G-7), (G-8) and (B- 9), the following sensitizing dyes (BS-1) and (BS-2) were added at 60 ° C., pH 5.8, and pAg 7.5, followed by the following sodium thiosulfate, trifurylphosphine selenide, and Chloroauric acid was sequentially added to give spectral and chemical sensitization. After the chemical sensitizer was added and optimally ripened, the following compound S-2-5 was added to stop the ripening, and the green-sensitive silver halide emulsions (G-2b), (G-3a), ( G-4a), (G-5a), (G-6a), (G-7a), (G-8a) and (G-9a) were obtained.

Sensitizing dye (GS-1) 5.2 × 10 ⁻⁴ mol / mol AgX
Sodium thiosulfate 4.5 × 10 ⁻⁶ mol / mol AgX
Trifurylphosphine selenide 3.2 × 10 ⁻⁶ mol / mol AgX
Chloroauric acid 1.9 × 10 ⁻⁵ mol / mol AgX
Compound (S-2-5) 1.5 × 10 ⁻⁴ mol / mol AgX
[Preparation of silver halide emulsions (R-1) to (R-9)]
In the preparation of the silver halide emulsions (B-1) to (B-4), (A1 solution), (B1 solution), (A2 solution), (B2 solution), (A3 solution) and (B3 solution) Except that the addition time was appropriately changed, the average particle size (cubic equivalent particle size) was 0.30 μm, the variation coefficient of the particle size was 0.08, the silver chloride content was 99.5 mol%, and the silver bromide content was 0. Silver halide emulsions (R-1) to (R-4) which were .5 mol% monodispersed cubic emulsions were prepared.

  In the preparation of the silver halide emulsions (B-5) to (B-8), (A1 solution), (B1 solution), (A2 solution), (B2 solution), (A3 solution) and (B3 solution) Except that the addition time was appropriately changed, the average particle size (cubic equivalent particle size) was 0.30 μm, the variation coefficient of the particle size was 0.08, the silver chloride content was 99.2 mol%, and the silver bromide content was 0. Silver halide emulsions (R-5) to (R-8) which were .8 mol% monodispersed cubic emulsions were prepared.

  In the preparation of the silver halide emulsion (B-9), (A1 solution), (B1 solution), (A2 solution), (B2 solution), (A4 solution) and (B4 solution), (A5 solution) and ( In the same manner except that the addition time of (B5 liquid) was appropriately changed, the average particle diameter (cubic conversion particle diameter) was 0.30 μm, the coefficient of variation of the particle diameter was 0.08, the silver chloride content was 96.2 mol%, bromide A silver halide emulsion (R-9), which is a monodispersed cubic emulsion having a silver content of 3.7 mol% and a silver iodide content of 0.1 mol%, was prepared.

[Preparation of red-sensitive silver halide emulsions (R-1a) and (R-2a)]
The following sensitizing dyes (RS-1) and (RS-2) were added to the silver halide emulsions (R-1) and (R-2) at 60 ° C., pH 5.0, and pAg 7.1, Subsequently, the following sodium thiosulfate, triphenylphosphine selenide, and chloroauric acid were sequentially added to perform spectral sensitization and chemical sensitization. After the chemical sensitizer was added and optimally ripened, the following compound S-2-5 was added to stop the ripening to obtain red-sensitive silver halide emulsions (R-1a) and (R-2a), respectively. It was.

Sodium thiosulfate 9.6 × 10 ⁻⁶ mol / mol AgX
Triphenylphosphine selenide 5.4 × 10 ⁻⁶ mol / mol AgX
Chloroauric acid 1.8 × 10 ^-5 mol / mol AgX
Compound (S-2-5) 1.2 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye (RS-1) 1.2 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye (RS-2) 1.2 × 10 ⁻⁴ mol / mol AgX
[Red-sensitive silver halide emulsions (R-2b), (R-3a), (R-4a), (R-5a), (R-6a), (R-7a), (R-8a) and ( Preparation of R-9a)
The silver halide emulsions (R-2), (R-3), (R-4), (R-5), (R-6), (R-7), (R-8) and (R-) 9), the following sensitizing dyes (RS-1) and (RS-2) were added at 60 ° C., pH 5.8, and pAg 7.5, followed by the following sodium thiosulfate, trifurylphosphine selenide, and Chloroauric acid was sequentially added to give spectral and chemical sensitization. After the chemical sensitizer was added and optimally ripened, the following compound S-2-5 was added to stop the ripening, and red-sensitive silver halide emulsions (R-2b), (R-3a), ( R-4a), (R-5a), (R-6a), (R-7a), (R-8a) and (R-9a) were obtained.

Sodium thiosulfate 9.6 × 10 ⁻⁶ mol / mol AgX
Trifurylphosphine selenide 5.4 × 10 ⁻⁶ mol / mol AgX
Chloroauric acid 1.8 × 10 ^-5 mol / mol AgX
Compound (S-2-5) 1.2 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye (RS-1) 1.2 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye (RS-2) 1.2 × 10 ⁻⁴ mol / mol AgX
In the preparation of the red-sensitive silver halide emulsion, 2.0 × 10 ⁻³ mol / mol AgX of SS-1 was added at the end of the preparation.

<< Preparation of silver halide color photographic material >>
[Preparation of Sample 101]
High-density molten polyethylene containing anatase-type titanium oxide dispersed in a content of 15% by mass is laminated on the photosensitive layer coated surface of paper pulp having a basis weight of 180 g / m ² , and the back surface has a high density. A silver halide color photographic light-sensitive material is formed by subjecting a reflective support laminated with polyethylene to corona discharge treatment, and then providing a gelatin subbing layer and further coating each photographic constituent layer having the constitution shown in Tables 1 and 2. Sample 101 was prepared.

  The coating solution was prepared as follows.

First layer coating solution 3.34 g of yellow coupler (Y-1), 10.02 g of yellow coupler (Y-2), 1.67 g of yellow coupler (Y-3), 1.67 g of dye image stabilizer (ST-1) , Dye image stabilizer (ST-2) 1.67 g, Dye image stabilizer (ST-5) 3.34 g, Stain inhibitor (HQ-1) 0.167 g, Image stabilizer A 2.67 g, Image stabilizer B1 .34 g, 5.0 g of high boiling point organic solvent (DBP) and 1.67 g of high boiling point organic solvent (DNP) were dissolved by adding 60 ml of ethyl acetate, and 7% containing 5 ml of 10% surfactant (SU-1) 500 ml of a yellow coupler dispersion was prepared by emulsifying and dispersing in 320 ml of an aqueous gelatin solution using an ultrasonic homogenizer. This dispersion was mixed with a blue-sensitive silver halide emulsion (B-1a) prepared under the above conditions to prepare a first layer coating solution.

Second to seventh layer coating solutions Each of the second to seventh layer coating solutions was prepared so that the coating amounts in Tables 1 and 2 were the same as the first layer coating solution.

In addition, (H-1) and (H-2) were added as a hardening agent to the second layer, the fourth layer, and the seventh layer. Further, surfactants (SU-2) and (SU-3) were added to each layer as coating aids for adjusting the surface tension. Moreover, the antifungal agent (F-1) was added to each layer so that the whole quantity might be set to 0.04 g / m < ² >. The silver halide emulsions listed in the table are shown in terms of silver.

  Details of each additive used for preparation of the sample 101 are as follows.

SU-1: Sodium tri-i-propylnaphthalene sulfonate SU-2: Disulfosulfonic acid di (2-ethylhexyl) / sodium SU-3: Disulfosulfonic acid di (2,2,3,3,4,4,5 , 5-octafluoropentyl) .sodium DBP: dibutyl phthalate DNP: dinonyl phthalate DOP: dioctyl phthalate DIDP: di-i-decyl phthalate H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro -6-hydroxy-s-triazine sodium HQ-1: 2,5-di-t-octyl hydroquinone HQ-2: 2,5-di-sec-dodecyl hydroquinone HQ-3: 2,5-di-sec- Tetradecyl hydroquinone HQ-4: 2-sec-dodecyl-5-sec-tetradecyl high Hydroquinone HQ-5: 2,5-di [(1,1-dimethyl-4-hexyloxycarbonyl) butyl] hydroquinone image stabilizer A: P-t-octylphenol image stabilizer B: poly (t-butylacrylamide)

[Production of Samples 102 to 110]
In the preparation of Sample 101, the blue-sensitive silver halide emulsion B-1a, the green-sensitive silver halide emulsion G-1a, and the red-sensitive silver halide emulsion R-1a were changed to the silver halide emulsions shown in Table 3, respectively. Similarly, samples 102 to 110 were produced.

<< Evaluation of silver halide color photographic material >>
The samples 101 to 110 produced above were evaluated for sensitivity and latent image stability according to the methods described below.

Each sample was subjected to wedge exposure using a xenon flash high-intensity exposure sensitometer (Yamashita Denso Co., Ltd. Model SX-20) exposed at 10 ⁻⁶ seconds, and allowed to stand for 5 minutes after exposure. The color development processing was performed according to the above. This is called process A. On the other hand, in the above method, after 5 seconds have passed from the exposure, the color development processing is similarly performed, and this is referred to as processing B.

  The yellow image reflection density of each sample developed as described above was measured using an optical densitometer (PDA-65 model manufactured by Konica Minolta Photo Imaging), and the vertical axis—reflection density (D), horizontal A characteristic curve of a yellow image composed of the axis-exposure amount (Log E) was created, and each characteristic value was calculated as follows.

  The sensitivity of the sample in treatment A was calculated according to Equation 1 below. Here, the sensitivity is expressed by setting the sensitivity in the processing A of the sample 101 to 100. Further, the lowest density value in each characteristic curve was used as the fog density.

  Next, the gradation γ (γa) in the process A and the gradation γ (γb) in the process B were calculated according to the following expression 2, and the variation value Δγ was calculated according to the following expression 3. Note that Δγ indicates that the closer the value is to 100, the better the latent image stability.

Formula 1
Sensitivity = 1 / (exposure amount indicating fog + 1.0 density)
Formula 2
Gradation γ = 1 / [Log (exposure amount indicating fog + 0.8 density) −Log (exposure amount indicating fog + 1.8 density)]
Formula 3
Δγ = (γb / γa) × 100
[Color development processing]
Processing step Processing temperature Time Replenishment amount Color development 38.0 ± 0.3 ° C 45 seconds 80 ml / m ²
Bleach fixing 35.0 ± 0.5 ° C 45 seconds 120ml / m ²
Stabilization 30-34 ° C 60 seconds 150ml / m ²
Drying 60-80 ° C. 30 seconds (composition of each developing solution for color development processing)
<Color developer tank solution and replenisher>
Tank liquid Replenisher Pure water 800ml 800ml
Triethylenediamine 2g 3g
Diethylene glycol 10g 10g
Potassium bromide 0.01g −
Potassium chloride 3.5g −
Potassium sulfite 0.25g 0.5g
N-ethyl-N- (β methanesulfonamidoethyl) -3-methyl-4-
Aminoaniline sulfate 6.0 g 10.0 g
N, N-diethylhydroxylamine 6.8 g 6.0 g
Triethanolamine 10.0 g 10.0 g
Diethylenetriaminepentaacetic acid sodium salt 2.0 g 2.0 g
Optical brightener (4,4'-diaminostilbene disulfonic acid derivative)
2.0g 2.5g
Potassium carbonate 30g 30g
Water was added to adjust the total volume to 1 liter, the tank liquid was adjusted to pH 10.10, and the replenisher was adjusted to pH 10.60.

<Bleach fixer tank solution and replenisher>
65 g of diethylenetriaminepentaacetic acid ferric ammonium dihydrate
Diethylenetriaminepentaacetic acid 3g
Ammonium thiosulfate (70% aqueous solution) 100 ml
2-amino-5-mercapto-1,3,4-thiadiazole 2.0 g
Ammonium sulfite (40% aqueous solution) 27.5 ml
Water was added to bring the total volume to 1 liter, and the pH was adjusted to 5.0 with potassium carbonate or glacial acetic acid.

<Stabilizing liquid tank liquid and replenisher liquid>
o-Phenylphenol 1.0g
5-Chloro-2-methyl-4-isothiazolin-3-one 0.02 g
2-Methyl-4-isothiazolin-3-one 0.02 g
Diethylene glycol 1.0g
Fluorescent brightener (Chinopearl SFP) 2.0g
1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g
Bismuth chloride (45% aqueous solution) 0.65 g
Magnesium sulfate heptahydrate 0.2g
PVP (Polyvinylpyrrolidone) 1.0g
Ammonia water (25% ammonium hydroxide aqueous solution) 2.5 g
Nitrilotriacetic acid trisodium salt 1.5g
Water was added to bring the total volume to 1 liter, and the pH was adjusted to 7.5 with sulfuric acid or aqueous ammonia.

  Table 4 shows the results obtained as described above.

  As is apparent from Table 4, each sample using the silver halide emulsion according to the present invention was superior in sensitivity and latent image stability to the comparative sample. The green sensitivity and red sensitivity were also evaluated in the same manner, and each sample using the silver halide emulsion according to the present invention showed excellent performance as well as the blue sensitivity.

Example 2
Next, the production stability was evaluated by the following method.

  Ten lots of each of the silver halide emulsions (B-1) to (B-9) prepared in Example 1 were produced and subjected to color sensitization and chemical sensitization in the same manner as in Example 1. A silver halide color light-sensitive material was prepared using these silver halide emulsions instead of the silver halide emulsion (B-1a) of the first layer, and the sensitivity and latent image stability were evaluated in the same manner as in Example 1. did.

  The sensitivity stability between production lots of the silver halide emulsion (B-1) was determined by the following equation.

Sensitivity stability (%) between production lots of silver halide emulsion (B-1) = (standard deviation of sensitivity for 10 lots of silver halide emulsion (B-1)) / (silver halide emulsion (B−) 1) Average of 10 lots of sensitivity) x 100
Similarly, for silver halide emulsions (B-2) to (B-9), the sensitivity stability between production lots was determined, and the sensitivity stability between production lots of silver halide emulsion (B-1) was determined to be 100. And expressed as a relative value.

  The latent image stability between production lots of the silver halide emulsion (B-1) was determined by the following equation.

Latent image stability (%) between production lots of silver halide emulsion (B-1) = (standard deviation of latent image stability for 10 lots of silver halide emulsion (B-1)) / (silver halide) Emulsion (B-1) latent image stability average of 10 lots) × 100
Similarly, the latent image stability between the production lots of the silver halide emulsions (B-2) to (B-9) was determined, and these were determined as the latent image stability between the production lots of the silver halide emulsion (B-1). Is expressed as a relative value where 100 is 100.

  The results are shown in Table 5.

  As is apparent from Table 5, each sample using the silver halide emulsion according to the present invention is superior in sensitivity stability between production lots and latent image stability between production lots compared to a sample using a comparative emulsion. It was.

Example 3
The sample produced in Example 1 was processed into a 127 mm wide roll, and the suitability for digital exposure was evaluated as follows.

  The developed negative image of Konica Color New CENTURIA 400 was converted into digital data using a film scanner Qscan1202JW manufactured by Konica Minolta Photo Imaging, and an environment that can be handled by Adobe's software photoshop (Ver. 5.5). The captured image was manipulated so that it could be exposed as a single image data by adding characters and fine lines of various sizes as one image data.

A YAG solid-state laser (oscillation wavelength 946 nm) using a semiconductor laser GaAlAs (oscillation wavelength 808.5 nm) as a light source as an excitation light source was converted by KNbO ₃ SHG crystal and was extracted at 473 nm, and a semiconductor laser GaAlAs (oscillation wavelength 808.7 nm). ) Using a YVO ₄ solid-state laser (oscillation wavelength: 1064 nm) with a KTP SHG crystal as the excitation light source and AlGaInP (oscillation wavelength of about 670 nm). An apparatus capable of sequentially scanning and exposing on the color photographic paper by moving the laser beams of the three colors in the direction perpendicular to the scanning direction by the polygon mirror was produced. For the exposure amount, the amount of light of the semiconductor laser was electrically controlled. The scanning exposure was performed at 400 dpi (dpi represents 1 inch, that is, the number of dots per 2.54 cm), and the exposure time per pixel at this time was 5 × 10 ⁻⁸ seconds.

  After various exposures were adjusted so that an optimal print image could be obtained for each sample, and after scanning exposure, the processing of Example 1 was changed as follows to obtain a cabinet-size print image.

Processing step Processing temperature Time Replenishment amount Color development 38.0 ± 0.3 ° C. 22 seconds 81 ml / m ²
Bleach fixing 35.0 ± 0.5 ℃ 22 seconds 54ml / m ²
Stabilization 30-34 ° C 25 seconds 150ml / m ²
Drying 60 to 80 ° C. 30 seconds The composition of the developing solution is shown below.

(Color developer tank solution and replenisher) Tank solution Replenisher Pure water 800 ml 800 ml
Diethylene glycol 10g 10g
Potassium bromide 0.01g −
Potassium chloride 3.5g −
Potassium sulfite 0.25g 0.5g
N-ethyl-N- (β methanesulfonamidoethyl) -3-methyl-4-
Aminoaniline sulfate 6.0 g 10.5 g
N, N-diethylhydroxylamine 3.5 g 6.0 g
N, N-bis (2-sulfoethyl) hydroxylamine
3.5g 6.0g
Triethanolamine 10.0 g 10.0 g
Diethylenetriaminepentaacetic acid pentasodium salt 2.0 g 2.0 g
Optical brightener (4,4'-diaminostilbene disulfonic acid derivative)
2.0g 2.5g
Potassium carbonate 30g 30g
Water is added to make the total volume 1 liter, the tank liquid is adjusted to pH = 10.1, and the replenisher is adjusted to pH = 10.6.

(Bleaching fixer tank solution and replenisher) Tank solution Replenisher diethylenetriamine pentaacetic acid ferric ammonium dihydrate
100g 50g
Diethylenetriaminepentaacetic acid 3g 3g
Ammonium thiosulfate (70% aqueous solution) 200 ml 100 ml
2-Amino-5-mercapto-1,3,4-thiadiazole
2.0g 1.0g
Ammonium sulfite (40% aqueous solution) 50ml 25ml
Add water to bring the total volume to 1 liter, adjust the pH to 7.0 with potassium carbonate or glacial acetic acid, and adjust the replenisher to pH 6.5.

(Stabilizer liquid and replenisher)
o-Phenylphenol 1.0g
5-Chloro-2-methyl-4-isothiazolin-3-one 0.02 g
2-Methyl-4-isothiazolin-3-one 0.02 g
Diethylene glycol 1.0g
Fluorescent brightener (Chinopearl SFP) 2.0g
1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g
PVP 1.0g
Ammonia water (25% ammonium hydroxide aqueous solution) 2.5 g
Ethylenediaminetetraacetic acid 1.0 g
Ammonium sulfite (40% aqueous solution) 10ml
Water is added to make a total volume of 1 liter, and the pH is adjusted to 7.5 with sulfuric acid or ammonia water.

  About the obtained print image, 20 observers evaluated the clarity of fine lines and characters, the skin color reproducibility of a person, and the green reproducibility of trees based on the following criteria. Further, after 100 sheets were exposed, the processing was immediately performed, and the print reproducibility of the first and 100th sheets was visually evaluated according to the following criteria.

(1) Criteria for evaluating the clarity of thin lines and characters ◎: Gray thin lines and characters can be clearly distinguished ○: Gray thin lines and characters can be clearly distinguished, but the outline is slightly blurred △: Gray thin lines and characters Can be distinguished, but blurry is conspicuous.

(2) Human skin color reproducibility ◎: Bright and natural reproduction ○: Natural reproduction Δ: Slightly dull ×: Insufficient redness

(3) Green reproducibility of trees ◎: Bright and vivid reproduction ○: Vivid reproduction △: Slightly dull ×: Dull.

(4) Print reproducibility ◎: The print difference cannot be recognized. ○: A slight print difference can be recognized, but it can be treated as almost the same. It can be considered a practical problem.

  The evaluation results are shown in Table 6.

  The samples according to the present invention showed excellent performance with respect to the clarity of fine lines and characters, the skin color reproduction of a person, the green reproduction of trees, and the print reproduction.

Example 4
From the developed negative image of Konica Color New CENTURIA 400, the developed positive image of Konica Chrome SINBI200 high quality, and the captured image data of the digital camera Digital Revio KD-200Z manufactured by Konica Minolta Camera, respectively, print images are obtained as follows. It was.

  The sample produced in Example 1 was processed into a 127 mm wide roll, and the digital minilab system QD-21SUPER (print processor QDP-1500SUPER manufactured by Konica Minolta Photo Imaging Co., Ltd., using ECOJET-HQA-P as the processing chemical, The film was subjected to exposure treatment according to the name CPK-HQA-P and evaluated in the same manner as in Example 3. The results are shown in Table 7. As in Example 3, excellent effects were obtained in the sample according to the present invention.

Example 5
[Preparation of blue-sensitive silver halide emulsions (B-11a) and (B-12a)]
To the silver halide emulsions (B-1) and (B-2) prepared in Example 1, the following sensitizing dyes (BS-1) and (BS-2) at 60 ° C., pH 5.8, and pAg 7.5. Subsequently, 9.0 × 10 ⁻⁶ mol / mol AgX was added to the gold sulfide silver fine particles (average particle size 60 mm) prepared by the method described in Japanese Patent No. 2,929,325, and spectral sensitization and chemical sensitization were added. A feeling was given. After the chemical sensitizer was added and optimally ripened, the following compounds S-2-5, S-2-2, and S-2-3 were sequentially added to stop the ripening, and each blue-sensitive silver halide emulsion (B-11a) and (B-12a) were obtained.

Compound S-2-5 3.0 × 10 ⁻⁴ mol / mol AgX
Compound S-2-2 3.0 × 10 ⁻⁴ mol / mol AgX
Compound S-2-3 3.0 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye BS-1 4.0 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye BS-2 1.0 × 10 ⁻⁴ mol / mol AgX
[Blue-sensitive silver halide emulsions (B-12b), (B-13a), (B-14a), (B-15a), (B-16a), (B-17a), (B-18a) and ( Preparation of B-19a)]
Silver halide emulsions (B-2), (B-3), (B-4), (B-5), (B-6), (B-7), (B-8) prepared in Example 1 ) And (B-9), the sensitizing dyes (BS-1) and (BS-2) were added at 60 ° C., pH 5.8, and pAg 7.5, and subsequently, Patent No. 2,929,325. Fine particles of gold sulfide (average particle size of 40 mm) prepared by the method described above were added at 9.0 × 10 ⁻⁶ mol / mol AgX, and spectral sensitization and chemical sensitization were performed. After the chemical sensitizer was added and optimally ripened, the compounds S-2-5, S-2-2, and S-2-3 were sequentially added to stop the ripening, and each blue-sensitive silver halide emulsion (B-12b), (B-13a), (B-14a), (B-15a), (B-16a), (B-17a), (B-18a) and (B-19a) were obtained. .

[Preparation of green-sensitive silver halide emulsions (G-11a) and (G-12a)]
To the silver halide emulsions (G-1) and (G-2) prepared in Example 1, the following sensitizing dye (GS-1) was added at 60 ° C., pH 5.8, and pAg 7.5, and then 1.2 × 10 ⁻⁵ mol / mol AgX of gold sulfide silver fine particles (average particle diameter of 60 mm) prepared by the method described in Japanese Patent No. 2929325 was added to perform spectral sensitization and chemical sensitization. After the chemical sensitizer was added and optimally ripened, the following compound S-2-5 was added to stop the ripening to obtain green-sensitive silver halide emulsions (G-11a) and (G-12a), respectively. It was.

Sensitizing dye (GS-1) 4.0 × 10 ⁻⁴ mol / mol AgX
Compound (S-2-5) 1.5 × 10 ⁻⁴ mol / mol AgX
[Green-sensitive silver halide emulsions (G-12b), (G-13a), (G-14a), (G-15a), (G-16a), (G-17a), (G-18a) and ( Preparation of G-19a)]
Silver halide emulsions (G-2), (G-3), (G-4), (G-5), (G-6), (G-7), (G-8) prepared in Example 1 ) And (B-9), the sensitizing dyes (BS-1) and (BS-2) were added at 60 ° C., pH 5.8, and pAg 7.5, and subsequently by the method described in Japanese Patent No. 2929325. The prepared gold sulfide fine particles (average particle size 4 nm) were added at 1.2 × 10 ⁻⁵ mol / mol AgX, and spectral sensitization and chemical sensitization were performed. After the chemical sensitizer was added and optimally ripened, the compound S-2-5 was added to stop the ripening, and the green-sensitive silver halide emulsions (G-12b), (G-13a), ( G-14a), (G-15a), (G-16a), (G-17a), (G-18a) and (G-19a) were obtained.

[Preparation of red-sensitive silver halide emulsions (R-11a) and (R-12a)]
For the silver halide emulsions (R-1) and (R-2) prepared in Example 1, the following sensitizing dyes (RS-1) and (RS-2) at 60 ° C., pH 5.0, and pAg 7.1. Subsequently, 1.6 × 10 ⁻⁵ mol / mol AgX of silver sulfide gold fine particles (average particle size 6 nm) prepared by the method described in Japanese Patent No. 2,929,325 is added, and spectral sensitization and chemical sensitization are added. A feeling was given. After the chemical sensitizer was added and optimally ripened, the following compound S-2-5 was added to stop the ripening to obtain red-sensitive silver halide emulsions (R-11a) and (R-12a), respectively. It was.

Compound (S-2-5) 1.2 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye (RS-1) 1.0 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye (RS-2) 1.0 × 10 ⁻⁴ mol / mol AgX
[Red-sensitive silver halide emulsions (R-12b), (R-13a), (R-14a), (R-15a), (R-16a), (R-17a), (R-18a) and ( Preparation of R-19a)]
Silver halide emulsions (R-2), (R-3), (R-4), (R-5), (R-6), (R-7), (R-8) prepared in Example 1 ) And (R-9), the sensitizing dyes (RS-1) and (RS-2) are added at 60 ° C., pH 5.0, and pAg 7.1, and subsequently by the method described in Japanese Patent No. 2929325. The prepared gold sulfide fine particles (average particle size 4 nm) were added at 1.4 × 10 ⁻⁵ mol / mol AgX, and spectral sensitization and chemical sensitization were performed. After the addition of chemical sensitizers and when optimally ripened, compound S-2-5 was added to stop ripening, and red-sensitive silver halide emulsions (R-12b), (R-13a), ( R-14a), (R-15a), (R-16a), (R-17a), (R-18a) and (R-19a) were obtained.

In the preparation of the red-sensitive silver halide emulsion, 2.0 × 10 ⁻³ mol / mol AgX of SS-1 was added at the end of the preparation.

  In sample 101 in Example 1, the first layer of silver halide emulsion (B-1a), the third layer of silver halide emulsion (G-1a), and the fifth layer of silver halide emulsion (R-1a) Instead, samples 201 to 210 were prepared using the silver halide emulsions having the structures shown in Table 8 and evaluated in the same manner. The results are shown in Table 9.

  As is clear from Table 9, each sample using the silver halide emulsion according to the present invention gave good results in sensitivity and latent image stability compared to the comparative sample.

Example 6
Evaluation similar to Example 3 was performed using the samples 201-210 produced in Example 5. The results are shown in Table 10. An excellent effect was obtained with the sample of the present invention relative to the comparative sample.

Example 7
Evaluation similar to Example 4 was performed using the samples 201-210 produced in Example 5. The results are shown in Table 11. An excellent effect was obtained with the sample of the present invention relative to the comparative sample.

Example 8
[Preparation of blue-sensitive silver halide emulsions (B-21a) and (B-22a)]
With respect to the silver halide emulsions (B-1) and (B-2) prepared in Example 1, the compound (1-21) according to the present invention was prepared as follows: 1. at 60 ° C., pH 5.8, pAg 7.5. 0 × 10 ⁻⁴ mol / mol AgX was added, followed by addition of the following sensitizing dyes (BS-1) and (BS-2), followed by the subsequent addition of sodium thiosulfate and chloroauric acid in order, Chemical sensitization was applied. At the end of 90% of the chemical ripening time from the addition of sodium thiosulfate to the addition of compound (S-2-5), 1.0 × 10 ⁻⁴ mol of compound (1-2) according to the present invention was further added. / Mol AgX was added. After the chemical sensitizer was added and matured optimally, the following compounds (S-2-5), (S-2-2), and (S-2-3) were sequentially added to stop the ripening, and blue Sensitive silver halide emulsions (B-21a) and (B-22a) were obtained.

Sodium thiosulfate 5.0 × 10 ⁻⁶ mol / mol AgX
Chloroauric acid 1.5 × 10 ⁻⁵ mol / mol AgX
Compound S-2-5 2.0 × 10 ⁻⁴ mol / mol AgX
Compound S-2-2 2.0 × 10 ⁻⁴ mol / mol AgX
Compound S-2-3 3.0 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye BS-1 4.0 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye BS-2 1.0 × 10 ⁻⁴ mol / mol AgX
[Blue-sensitive silver halide emulsions (B-22b), (B-23a), (B-24a), (B-25a), (B-26a), (B-27a), (B-28a) and ( Preparation of B-29a)]
Silver halide emulsions (B-2), (B-3), (B-4), (B-5), (B-6), (B-7), (B-8) prepared in Example 1 ) And (B-9), 8.0 × 10 ⁻⁵ mol / mol AgX of the compound (1-21) related to the present invention was added at 60 ° C., pH 5.8, pAg 7.5, and the increase was continued. Dye sensitizing dyes (BS-1) and (BS-2) were added, and then sodium thiosulfate and chloroauric acid were sequentially added to perform spectral sensitization and chemical sensitization. At the end of 90% of the chemical ripening time from the addition of sodium thiosulfate to the addition of compound (S-2-5), 1.2 × 10 ⁻⁴ mol of compound (1-2) according to the present invention was further added. / Mol AgX was added. After addition of chemical sensitizers and when optimally ripened, the compounds (S-2-5), (S-2-2), and (S-2-3) were added sequentially to stop ripening, Blue-sensitive silver halide emulsions (B-22b), (B-23a), (B-24a), (B-25a), (B-26a), (B-27a), (B-28a) and (B -29a) was obtained.

[Preparation of green-sensitive silver halide emulsions (G-21a) and (G-22a)]
The silver halide emulsions (G-1) and (G-2) prepared in Example 1 were obtained at 60 ° C., pH 5.8, pAg 7.5 at 60 ° C., pH 5.8, pAg 7.5. Add 1.2 × 10 ⁻⁴ mol / mol AgX of the compound (1-21) related to the invention, then add the following sensitizing dye (GS-1), then add the following sodium thiosulfate and chloroauric acid successively. And spectral sensitization and chemical sensitization. At the end of 90% of the chemical ripening time from the addition of sodium thiosulfate to the addition of compound (S-2-5), 1.2 × 10 ⁻⁴ mol of compound (1-2) according to the present invention was further added. / Mol AgX was added. After the chemical sensitizer was added and optimally ripened, the following compound (S-2-5) was added to stop the ripening, and green-sensitive silver halide emulsions (G-21a) and (G-22a) were respectively added. Got.

Sensitizing dye (GS-1) 4.0 × 10 ⁻⁴ mol / mol AgX
Sodium thiosulfate 4.0 × 10 ⁻⁶ mol / mol AgX
Chloroauric acid 1.2 × 10 ⁻⁵ mol / mol AgX
Compound (S-2-5) 1.5 × 10 ⁻⁴ mol / mol AgX
[Green-sensitive silver halide emulsions (G-22b), (G-23a), (G-24a), (G-25a), (G-26a), (G-27a), (G-28a) and ( Preparation of G-29a)]
Silver halide emulsions (G-2), (G-3), (G-4), (G-5), (G-6), (G-7), (G-8) prepared in Example 1 ) And (B-9) at 60 ° C., pH 5.8, pAg 7.5 at 60 ° C., pH 5.8, pAg 7.5, 1.0 × 10 ⁻⁴ mol / mol AgX was added, then the sensitizing dye (GS-1) was added, and then the sodium thiosulfate and chloroauric acid were sequentially added to perform spectral and chemical sensitization. At the end of 90% of the chemical ripening time from the addition of sodium thiosulfate to the addition of compound (S-2-5), 1.5 × 10 ⁻⁴ mol of compound (1-2) according to the present invention was further added. / Mol AgX was added. After the chemical sensitizer was added and optimally ripened, the compound (S-2-5) was added to stop the ripening, and green-sensitive silver halide emulsions (G-22b) and (G-23a), respectively. , (G-24a), (G-25a), (G-26a), (G-27a), (G-28a) and (G-29a) were obtained.

[Preparation of red-sensitive silver halide emulsions (R-21a) and (R-22a)]
With respect to the silver halide emulsions (R-1) and (R-2) prepared in Example 1, the compound (1-21) according to the present invention was obtained in 1.3 at 60 ° C., pH 5.0 and pAg 7.1. × 10 ⁻⁴ mol / mol AgX was added, followed by addition of the following sensitizing dyes (RS-1) and (RS-2), followed by the subsequent addition of sodium thiosulfate and chloroauric acid in this order, spectral sensitization and chemistry Sensitized. In addition, at the end of 90% of the chemical ripening time from the addition of sodium thiosulfate to the addition of compound (S-2-5), the compound (1-2) according to the present invention was further added to 1.3 × 10 ⁻⁴ mol. / Mol AgX was added. Following the addition of chemical sensitizers and when optimally ripened, the following compound (S-2-5) was added to stop ripening, and red-sensitive silver halide emulsions (R-21a) and (R-22a), respectively. Got.

1: Sodium thiosulfate 1.2 × 10 ⁻⁵ mol / mol AgX
2: Chloroauric acid 1.3 × 10 ⁻⁵ mol / mol AgX
3: Compound (S-2-5) 1.8 × 10 ⁻⁴ mol / mol AgX
4: Sensitizing dye (RS-1) 1.0 × 10 ⁻⁴ mol / mol AgX
5: Sensitizing dye (RS-2) 1.0 × 10 ⁻⁴ mol / mol AgX
[Red-sensitive silver halide emulsions (R-22b), (R-23a), (R-24a), (R-25a), (R-26a), (R-27a), (R-28a) and ( Preparation of R-29a)
Silver halide emulsions (R-2), (R-3), (R-4), (R-5), (R-6), (R-7), (R-8) prepared in Example 1 ) And (R-9) at a temperature of 60 ° C., a pH of 5.8 and a pAg of 7.5, 1.3 × 10 ⁻⁴ mol / mol AgX of the compound (1-21) according to the present invention was added, Sensitizing dyes (RS-1) and (RS-2) were added, and then sodium thiosulfate and chloroauric acid were sequentially added to perform spectral and chemical sensitization. In addition, at the end of 90% of the chemical ripening time from the addition of sodium thiosulfate to the addition of compound (S-2-5), the compound (1-2) according to the present invention was further added to 1.3 × 10 ⁻⁴ mol. / Mol AgX was added. After the chemical sensitizer was added and optimally ripened, the compound (S-2-5) was added to stop the ripening, and red-sensitive silver halide emulsions (R-22b) and (R-23a), respectively. , (R-24a), (R-25a), (R-26a), (R-27a), (R-28a) and (R-29a) were obtained.

In the preparation of the red-sensitive silver halide emulsion, 2.0 × 10 ⁻³ mol / mol AgX of SS-1 was added at the end of the preparation.

  In sample 101 in Example 1, the first layer of silver halide emulsion (B-1a), the third layer of silver halide emulsion (G-1a), and the fifth layer of silver halide emulsion (R-1a) Instead, samples 301 to 310 were prepared using the silver halide emulsions having the constitution shown in Table 12, and evaluated in the same manner. The results are shown in Table 13.

  As is clear from Table 13, each sample using the silver halide emulsion according to the present invention gave good results in sensitivity and latent image stability compared to the comparative sample.

Example 9
Evaluation similar to Example 3 was performed using the samples 301 to 310 produced in Example 8. The results are shown in Table 14. An excellent effect was obtained with the sample of the present invention relative to the comparative sample.

Example 10
Evaluation similar to Example 4 was performed using the samples 301 to 310 produced in Example 8. The results are shown in Table 15. An excellent effect was obtained with the sample of the present invention relative to the comparative sample.

Example 11
[Preparation of blue-sensitive silver halide emulsions (B-31a) and (B-32a)]
To the silver halide emulsions (B-1) and (B-2) prepared in Example 1, the compound (4-6) according to the present invention was added at 60 ° C., pH 5.8, and pAg 7.5. 0 × 10 ⁻⁶ mol / mol AgX was added, followed by addition of the following sensitizing dyes (BS-1) and (BS-2), followed by sequential addition of the following sodium thiosulfate and chloroauric acid, and spectral sensitization and Chemical sensitization was applied. When 90% of the chemical ripening time from the addition of sodium thiosulfate to the addition of compound (S-2-5) was completed, compound (4-0) according to the present invention was further added at 3.0 × 10 ⁻⁶ mol. / Mol AgX was added. After the chemical sensitizer was added and matured optimally, the following compounds (S-2-5), (S-2-2), and (S-2-3) were sequentially added to stop the ripening, and blue Sensitive silver halide emulsions (B-31a) and (B-32a) were obtained.

Sodium thiosulfate 5.0 × 10 ⁻⁶ mol / mol AgX
Chloroauric acid 1.5 × 10 ⁻⁵ mol / mol AgX
Compound S-2-5 2.0 × 10 ⁻⁴ mol / mol AgX
Compound S-2-2 2.0 × 10 ⁻⁴ mol / mol AgX
Compound S-2-3 3.0 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye BS-1 4.0 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye BS-2 1.0 × 10 ⁻⁴ mol / mol AgX
[Blue-sensitive silver halide emulsions (B-32b), (B-33a), (B-34a), (B-35a), (B-36a), (B-37a), (B-38a) and ( Preparation of B-39a)]
Silver halide emulsions (B-2), (B-3), (B-4), (B-5), (B-6), (B-7), (B-8) prepared in Example 1 ) And (B-9), 6.0 × 10 ⁻⁶ mol / mol AgX of the compound (4-6) according to the present invention was added at 60 ° C., pH 5.8, and pAg 7.5, and the increase was continued. Dye sensitizing dyes (BS-1) and (BS-2) were added, and then sodium thiosulfate and chloroauric acid were sequentially added to perform spectral sensitization and chemical sensitization. When 90% of the chemical ripening time from the addition of sodium thiosulfate to the addition of compound (S-2-5) was completed, compound (4-0) according to the present invention was further added at 2.2 × 10 ⁻⁶ mol. / Mol AgX was added. After addition of chemical sensitizers and when optimally ripened, the compounds (S-2-5), (S-2-2), and (S-2-3) were added sequentially to stop ripening, Blue-sensitive silver halide emulsions (B-32b), (B-33a), (B-34a), (B-35a), (B-36a), (B-37a), (B-38a) and (B -39a) was obtained.

[Preparation of green-sensitive silver halide emulsions (G-31a) and (G-32a)]
The silver halide emulsions (G-1) and (G-2) prepared in Example 1 were obtained at 60 ° C., pH 5.8, pAg 7.5 at 60 ° C., pH 5.8, pAg 7.5. Add the compound (4-6) related to the invention to 5.2 × 10 ⁻⁶ mol / mol AgX, then add the following sensitizing dye (GS-1), then add the following sodium thiosulfate and chloroauric acid sequentially And spectral sensitization and chemical sensitization. At the end of 90% of the chemical ripening time from the addition of sodium thiosulfate to the addition of compound (S-2-5), 3.2 × 10 ⁻⁶ mol of compound (4-0) according to the present invention was further added. / Mol AgX was added. After the chemical sensitizer was added and optimally ripened, the following compound (S-2-5) was added to stop the ripening, and green-sensitive silver halide emulsions (G-31a) and (G-32a) were respectively added. Got.

Sensitizing dye (GS-1) 4.0 × 10 ⁻⁴ mol / mol AgX
Sodium thiosulfate 4.0 × 10 ⁻⁶ mol / mol AgX
Chloroauric acid 1.2 × 10 ⁻⁵ mol / mol AgX
Compound (S-2-5) 1.5 × 10 ⁻⁴ mol / mol AgX
[Green-sensitive silver halide emulsions (G-32b), (G-33a), (G-34a), (G-35a), (G-36a), (G-37a), (G-38a) and ( Preparation of G-39a)]
Silver halide emulsions (G-2), (G-3), (G-4), (G-5), (G-6), (G-7), (G-8) prepared in Example 1 ) And (B-9) at 60 ° C., pH 5.8, pAg 7.5 at 60 ° C., pH 5.8, pAg 7.5, 4.0 × 10 ⁻⁶ mol / mol AgX was added, then the sensitizing dye (GS-1) was added, and then the sodium thiosulfate and chloroauric acid were sequentially added to perform spectral and chemical sensitization. When 90% of the chemical ripening time from the addition of sodium thiosulfate to the addition of compound (S-2-5) was completed, compound (4-0) according to the present invention was further added at 2.0 × 10 ⁻⁶ mol. / Mol AgX was added. After the chemical sensitizer was added and optimally ripened, the compound (S-2-5) was added to stop the ripening, and the green-sensitive silver halide emulsions (G-32b) and (G-33a) were added. , (G-34a), (G-35a), (G-36a), (G-37a), (G-38a) and (G-39a) were obtained.
[Preparation of red-sensitive silver halide emulsions (R-31a) and (R-32a)]
For the silver halide emulsions (R-1) and (R-2) prepared in Example 1, the compound (4-6) according to the present invention was 4.3 at 60 ° C., pH 5.0, and pAg 7.1. × 10 ^-6 mol / mol AgX was added, followed by addition of the following sensitizing dyes (RS-1) and (RS-2), followed by the subsequent addition of sodium thiosulfate and chloroauric acid, followed by spectral sensitization and chemistry. Sensitized. At the end of 90% of the chemical ripening time from the addition of sodium thiosulfate to the addition of compound (S-2-5), 2.3 × 10 ⁻⁶ mol of compound (4-0) according to the present invention was further added. / Mol AgX was added. After the chemical sensitizer was added and optimally ripened, the following compound (S-2-5) was added to stop the ripening, and red-sensitive silver halide emulsions (R-31a) and (R-32a) were added. Got.

1: Sodium thiosulfate 1.2 × 10 ⁻⁵ mol / mol AgX
2: Chloroauric acid 1.3 × 10 ⁻⁵ mol / mol AgX
3: Compound (S-2-5) 1.8 × 10 ⁻⁴ mol / mol AgX
4: Sensitizing dye (RS-1) 1.0 × 10 ⁻⁴ mol / mol AgX
5: Sensitizing dye (RS-2) 1.0 × 10 ⁻⁴ mol / mol AgX
[Red-sensitive silver halide emulsions (R-32b), (R-33a), (R-34a), (R-35a), (R-36a), (R-37a), (R-38a) and ( Preparation of R-39a)
Silver halide emulsions (R-2), (R-3), (R-4), (R-5), (R-6), (R-7), (R-8) prepared in Example 1 ) And (R-9), the compound (4-6) according to the present invention was added at 3.3 × 10 ⁻⁶ mol / mol AgX at 60 ° C., pH 5.0 and pAg 7.1, Sensitizing dyes (RS-1) and (RS-2) were added, and then sodium thiosulfate and chloroauric acid were sequentially added to perform spectral and chemical sensitization. At the end of 90% of the chemical ripening time from the addition of sodium thiosulfate to the addition of compound (S-2-5), 2.3 × 10 ⁻⁶ mol of compound (4-0) according to the present invention was further added. / Mol AgX was added. After the chemical sensitizer was added and optimally ripened, the compound (S-2-5) was added to stop the ripening, and red-sensitive silver halide emulsions (R-32b) and (R-33a), respectively. , (R-34a), (R-35a), (R-36a), (R-37a), (R-38a) and (R-39a) were obtained.

In the preparation of the red-sensitive silver halide emulsion, 2.0 × 10 ⁻³ mol / mol AgX of SS-1 was added at the end of the preparation.

  In sample 101 in Example 1, the first layer of silver halide emulsion (B-1a), the third layer of silver halide emulsion (G-1a), and the fifth layer of silver halide emulsion (R-1a) Instead, samples 401 to 410 were prepared using the silver halide emulsions having the constitution shown in Table 16 and evaluated in the same manner. The results are shown in Table 17.

  As is apparent from Table 17, each sample using the silver halide emulsion according to the present invention gave good results in sensitivity and latent image stability compared to the comparative sample.

Example 12
Evaluation similar to Example 3 was performed using the samples 401-410 produced in Example 11. The results are shown in Table 18. An excellent effect was obtained with the sample of the present invention relative to the comparative sample.

Example 13
Evaluation similar to Example 4 was performed using the samples 401 to 410 produced in Example 11. The results are shown in Table 19. An excellent effect was obtained with the sample of the present invention relative to the comparative sample.

Example 14
Ten lots of each of the silver halide emulsions prepared in Example 5, Example 8 and Example 11 were prepared, and the sensitivity and stability of the latent image were evaluated in the same manner as in Example 2.

  The sample using the silver halide emulsion according to the present invention was excellent in sensitivity stability and latent image stability between production lots compared to the sample using the comparative emulsion.

Claims (11)

A silver chloride content of 90 mol% or more, a silver iodide content of 0 to 2 mol%, a silver bromide content of 0.02 to 10 mol%, and a water ligand And / or silver halide grains formed by adding a solution in which one or more of Group 8 metal complexes having one or more organic ligands are dissolved and kept at pH 4.0 to 10.0 and 0 to 25 ° C. A silver halide emulsion comprising a silver halide emulsion, wherein the silver halide grains are selenium-sensitized. The silver chloride content is 90 mol% or more, the silver iodide content is 0 to 2 mol%, the silver bromide content is 0.02 to 10 mol%, and the water ligand And / or silver halide grains formed by adding a solution in which one or more of Group 8 metal complexes having one or more organic ligands are dissolved and kept at pH 4.0 to 10.0 and 0 to 25 ° C. A silver halide emulsion containing a silver halide, wherein the silver halide grains are chemically sensitized by adding at least one kind of fine grains selected from silver sulfide, silver gold sulfide and gold sulfide emulsion. The silver chloride content is 90 mol% or more, the silver iodide content is 0 to 2 mol%, the silver bromide content is 0.02 to 10 mol%, and the water ligand And / or silver halide grains formed by adding a solution in which one or more of group 8 metal complexes having one or more organic ligands are dissolved and kept at pH 4.0 to 10.0 and 0 to 25 ° C. A silver halide emulsion comprising: a silver halide emulsion containing at least one of the compounds represented by the following general formulas (1) to (3): .
Formula _{(1) R-SO 2 S} -M
Formula (2) R ₁ —SO ₂ S—R ₂
Formula (3) R ₃ —SO ₂ S—L _m —SSO ₂ —R ₄
[Wherein, R, R ₁ , R ₂ , R ₃ and R ₄ each represents an aliphatic group, an aromatic group, or a heterocyclic group. R, R ₁ , R ₂ , R ₃ and R ₄ may be the same or different. M represents a cation. L represents a divalent linking group, and m represents 0 or 1. ] The silver chloride content is 90 mol% or more, the silver iodide content is 0 to 2 mol%, the silver bromide content is 0.02 to 10 mol%, and the water ligand And / or silver halide grains formed by adding a solution in which one or more of group 8 metal complexes having one or more organic ligands are dissolved and kept at pH 4.0 to 10.0 and 0 to 25 ° C. A silver halide emulsion comprising: a silver halide emulsion containing at least one compound represented by the following general formula (4):
Formula _{(4) R 11 - (S} ) m-R 12
[Wherein, R ₁₁ and R ₁₂ each represents an aliphatic group, an aromatic group, a heterocyclic group, or an atomic group that can be bonded to each other to form a ring. R ₁₁ and R ₁₂ may be the same or different. When R ₁₁ and R ₁₂ are aliphatic groups, they may be bonded to each other to form a ring. m represents an integer of 2 to 6. ] Silver halide added with a solution in which one or more of group 8 metal complexes having at least one water ligand and / or organic ligand are dissolved and kept at pH 4.0-10.0 and 0-20 ° C. The silver halide emulsion according to any one of claims 1 to 4, wherein grains are formed. Silver halide by adding a solution in which one or more of group 8 metal complexes having one or more water ligands and / or organic ligands are dissolved and kept warm at pH 4.0-10.0 and 0-15 ° C. The silver halide emulsion according to any one of claims 1 to 5, wherein grains are formed. The silver halide emulsion according to any one of claims 1 to 6, wherein the silver halide grains have a silver bromide localized phase. The silver halide emulsion according to any one of claims 1 to 7, wherein the silver halide grains have a silver iodide localized phase. The silver halide emulsion according to any one of claims 1 to 8, wherein the silver halide grain contains a compound represented by the following general formula (S).

[Wherein, Q represents a 5-membered or 6-membered nitrogen-containing heterocyclic ring, and M ¹ represents a hydrogen atom, an alkali metal atom, or an atomic group necessary for forming a monovalent cation. ] A silver halide photographic material having at least one image forming layer on a support, wherein at least one of the image forming layers contains the silver halide emulsion according to any one of claims 1 to 9. A silver halide photographic light-sensitive material characterized by the above. An image forming method, wherein the silver halide photographic light-sensitive material according to claim 10 is subjected to color development after scanning exposure.