JP2005292822A - Photosensitive material for silver halide color photograph - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive material for a silver halide color photograph suitable for rapid processing, having good latent image stability and high contrast, and having high sensitivity and high contrast even when exposed particularly at high illuminance. <P>SOLUTION: The photosensitive material for the silver halide color photograph has red-, green- and blue-sensitive silver halide emulsion layers on a support, wherein at least one of the silver halide emulsion layers contains a silver halide emulsion with a silver chloride in an amount of ≥95 mol%, and the silver halide emulsion contains at least one Se compound and at least one metal complex represented by the formula (D1): [M<SP>D1</SP>X<SP>D1</SP><SB>n</SB>L<SP>D1</SP><SB>(6-n)</SB>]<SP>m</SP>. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a high-contrast silver halide color photographic light-sensitive material suitable for rapid processing. The present invention relates to a silver halide color photographic light-sensitive material having good properties.

  In recent years, there has been a remarkable spread of digitization in the field of color printing using color photographic paper. For example, the digital exposure method using laser scanning exposure is an analog that directly prints with a color printer from a processed color negative film. Compared to the exposure method, it shows a dramatic increase in the penetration rate. Such a digital exposure method is characterized in that high image quality can be obtained by performing image processing, and plays an extremely important role in improving the quality of color prints using color photographic paper. In addition, high-quality color prints can be easily obtained from an electronic recording medium such as a digital camera, and further dramatic spread is expected.

  On the other hand, as a color printing method, technologies such as an ink jet method, a sublimation type method, and color xerography have advanced, and are being recognized as a color printing method, for example, to improve photographic image quality. Among these, the characteristics of the digital exposure method using color photographic paper are high image quality, high productivity, and high image robustness. These features can be further extended to make higher quality photographs easier. It is desired to provide it at a lower cost. In particular, if you receive a digital camera recording medium at a store, finish a high-quality print within a short time of about a few minutes and return it on the spot, that is, if you can provide a one-stop service for color printing, color printing using color photographic paper The advantage of printing is increasing. In addition, if the rapid processing of color photographic paper is improved, it is possible to use a printing device that is smaller and cheaper but has high productivity, and that one-stop services for color printing can be expected to become increasingly popular. From these points, it is important to improve the quick processability of color photographic paper. For this purpose, it is necessary to study from various viewpoints such as shortening the exposure time, shortening the so-called latent image time from exposure to start of processing, and shortening the time from processing to drying. It has been proposed from each perspective.

The silver halide emulsions used for color photographic paper must satisfy various requirements as described above. Silver halide emulsions with a high silver chloride content are used because of the demand for rapid processability. In addition, when a silver halide emulsion having a high silver chloride content is exposed to high illuminance such as laser exposure, a so-called high illuminance failure such as low sensitivity and softening at high illuminance occurs. In order to improve this, it is known to contain a metal complex in silver halide grains (for example, Patent Document 1).
However, when high contrast is performed using a metal complex, there is a demand for high contrast of the low illuminance characteristics in addition to the high illuminance characteristics of the above-described reciprocity law failure. When a metal complex was used so as to satisfy these, desensitization became a problem, and latent image stability was insufficient.

A technique using a selenium (Se) sensitizing compound in a silver halide emulsion having a high silver chloride content is known (for example, Patent Document 2). However, in any exposure from low illuminance to high illuminance, a technique for maintaining high sensitivity and high contrast performance and maintaining latent image stability is not sufficient, and improvement has been desired.
In Patent Document 3, a reciprocity law, latent image stability and pressure property are improved by an emulsion having a high silver chloride content, containing a metal complex containing two or more CN ligands, and further selenium-sensitized. Although a technology has been proposed, a metal complex containing many CN ligands has not been able to sufficiently achieve low brightness characteristics. Patent Document 4 proposes improving the storage stability by using an emulsion having a high silver chloride content, containing a metal complex, and further sensitized with selenium. However, there is no suggestion of a technique for improving the desensitization that occurs when a light-sensitive material is obtained with a metal complex.

  In addition, it has been proposed to improve performance by containing a small amount of silver bromide or silver iodide in grains having a high silver chloride content. For example, high sensitivity can be obtained by including a phase having a high silver bromide content in various forms in an emulsion having a high silver chloride content (Patent Document 5), and a concentration on the subsurface of the high silver chloride emulsion. Emulsions containing I having a maximum give emulsions with high sensitivity and low illuminance failure (for example, Patent Documents 6 and 7), and compounds specific to grains that have formed I bands at 93% of the grain formation. Including a reciprocity law failure, an emulsion having excellent temperature dependency and pressure property during exposure can be obtained (Patent Document 8).

  On the other hand, a combination of a metal complex such as Rh and a Se compound or Te compound having a specific structure is used as a photosensitive material for printing halftone images, and has ultra-high photographic characteristics and can be developed at a low pH. A silver halide black-and-white light-sensitive material with good storage stability has been proposed (Patent Document 9), but it is not applied to a silver halide color photographic light-sensitive material. In the method specifically described in Patent Document 9, Desensitization is great.

US Pat. No. 5,360,712 JP 2003-287838 A JP-A-4-335336 Japanese Patent Laid-Open No. 6-308652 US Pat. No. 5,399,475 US Pat. No. 5,726,005 US Pat. No. 5,736,310 European patent EP 0,928,988A specification JP-A-8-95184

  The problem to be solved by the present invention is to overcome the above-mentioned problems and to be a silver halide photographic light-sensitive material, particularly a color print, which has high sensitivity and high contrast even in high-illuminance digital exposure by laser scanning and excellent in latent image stability. It is an object to provide a suitable silver halide color photographic light-sensitive material.

Means for solving the above problems are as follows.
(1) In a silver halide color photographic light-sensitive material having red, green and blue sensitive silver halide emulsion layers on a support, at least one of the silver halide emulsion layers has a silver chloride content of 95 mol. % Silver halide emulsion containing at least 1% of a silver halide emulsion, and the silver halide emulsion contains at least one Se complex and a metal complex represented by the following general formula (D1). Photosensitive material.
General formula (D1)
[M ^D1 X ^D1 _n L ^D1 _(6-n) ] ^m
In the general formula (D1), M ^D1 represents Cr, Mo, Re, Fe, Ru, Os, Co, Rh, Pd, or Pt, and X ^D1 represents a halogen ion. L ^D1 represents an arbitrary ligand different from X ^D1 . n represents 3, 4, 5 or 6, m represents the charge of the metal complex, and represents 4-, 3-, 2-, 1-, 0 or 1+. Here, a plurality of X ^D1 may be the same or different from each other, and when a plurality of L ^D1 are present, these may be the same or different. However, the metal complex represented by the general formula (D1) does not have or has one CN ion as a ligand.

(2) The metal complex represented by the general formula (D1) is contained in silver halide grains in an amount of 1 × 10 ⁻¹⁰ to 1 × 10 ⁻⁶ mol per mol of silver (1) A silver halide color photographic light-sensitive material as described in 1.
(3) The halogenated halide as described in (1) or (2), wherein the silver halide emulsion containing a Se compound further contains at least one metal complex represented by the following general formula (D2) Silver color photographic light-sensitive material.
General formula (D2)
[IrX ^D2 _n L ^D2 _(6-n) ] ^m
In general formula (D2), X ^D2 represents a pseudohalogen ion other than a halogen ion or a cyanate ion, and L ^D2 represents an arbitrary ligand different from X ^D2 . n represents 3, 4 or 5, m is the charge of the metal complex, and represents 5-, 4-, 3-, 2-, 1-, 0 or 1+. Here, a plurality of X ^D2 may be the same as or different from each other, and when a plurality of L ^D2 are present, these may be the same or different.
(4) The silver halide emulsion containing a Se compound contains 0.05 to 1.0 mole of silver iodide per mole of silver and has a higher silver iodide concentration than the surroundings. The silver halide color photographic light-sensitive material according to any one of (1) to (3), wherein a containing phase is formed.
(5) Any one of (1) to (4), wherein the silver halide grains contained in the silver halide emulsion layer containing a Se compound have an average equivalent sphere diameter of 0.6 μm or less. A silver halide color photographic light-sensitive material as described in 1.

(6) The amount of coupler contained in the silver halide emulsion layer containing a Se compound is from 0.6 equivalents to 1 equivalent with respect to 1 mole of silver. (1) to (5) The silver halide color photographic light-sensitive material according to any one of the above.
(7) The silver halide color photographic according to any one of the total coating設銀amount is equal to or is 0.2 g / ^{m 2} or more 0.45 g / ^{m 2} or less (1) to (6) Photosensitive material.
(8) The silver halide color photographic light-sensitive material as described in any one of (1) to (7), wherein the total amount of gelatin coated is 3 g / m ² or more and 6 g / m ² or less.
(9) The silver halide color photographic light-sensitive material starts a color developing process within 9 seconds after imagewise exposure, and the color developing process is performed within 28 seconds to quickly form an image. The silver halide color photographic light-sensitive material as described in any one of (1) to (8), which is a silver halide color photographic light-sensitive material for processing.
(10) The halogen according to any one of (1) to (9), wherein the exposure is a silver halide color photographic light-sensitive material for digital exposure that is imagewise exposed by laser scanning exposure. Silver halide color photographic material.
(11) At least one of the silver halide emulsion layers contains the silver halide emulsion described in any one of (1) to (10), and the layer further includes the silver halide emulsion. The silver halide color photographic light-sensitive material according to any one of (1) to (10), which contains a silver halide emulsion having a different sensitivity and a silver chloride content of 95 mol% or more. material.
(12) In the two types of silver halide emulsions having different sensitivities, the desensitization due to at least one selected from the metal complex represented by the general formula (D1) is lower on the lower sensitivity side than on the higher sensitivity side. The silver halide color photographic light-sensitive material as described in (11), wherein the emulsion is larger.

(13) In the two types of silver halide emulsions having different sensitivities, the content per mole of at least one silver halide selected from the metal complexes represented by the general formula (D1) is higher on the high sensitivity side. The silver halide color photographic light-sensitive material as described in (11) or (12), wherein there are more emulsions on the lower sensitivity side than emulsions.
(14) The metal complex represented by the general formula (D1) is a metal complex represented by the following general formula (D1A), or any one of (1) to (13) Silver halide color photographic light-sensitive material.
General formula (D1A)
[M ^D1A X ^D1A _n L ^D1A _(6-n) ] ^m
In the general formula (D1A), M ^D1A represents Re, Ru, Os, or Rh, and X ^D1A represents a halogen ion. L ^D1A represents NO or NS when M ^D1A is Re, Ru or Os, and represents H ₂ O, OH or O when M ^D1A is Rh. n represents 3, 4, 5 or 6, m represents the charge of the metal complex, and represents 4-, 3-, 2-, 1-, 0 or 1+. Here, a plurality of X ^D1A may be the same or different from each other, and when a plurality of L ^D1A are present, these may be the same or different.
(15) The silver halide color photographic light-sensitive material as described in any one of (1) to (14), wherein M ^D1 is Rh in the metal complex represented by the general formula (D1). .
(16) The metal complex represented by the general formula (D2) is a metal complex represented by the following general formula (D2A), described in any one of (3) to (15) Silver halide color photographic light-sensitive material.
General formula (D2A)
[IrX ^D2A _n L ^D2A _(6-n) ] ^m
In the general formula (D2A), X ^D2A represents a halogen ion or a pseudohalogen ion (excluding a cyanate ion), and L ^D2A represents an arbitrary inorganic ligand different from X ^D2A . n represents 3, 4 or 5, m is the charge of the metal complex, and represents 5-, 4-, 3-, 2-, 1-, 0 or 1+. Here, a plurality of X ^D2A may be the same or different from each other, and when a plurality of L ^D2A are present, these may be the same or different.

(17) The metal complex represented by the general formula (D2) is a metal complex represented by the following general formula (D2B), described in any one of (3) to (15) Silver halide color photographic light-sensitive material.
General formula (D2B)
[IrX ^D2B _n L ^D2B _(6-n) ] ^m
In the general formula (D2B), X ^D2B represents a halogen ion or a pseudohalogen ion (excluding a cyanate ion), and L ^D2B has a base structure of a chain or cyclic hydrocarbon, or a base structure thereof Represents a ligand in which some carbon or hydrogen atoms are replaced with other atoms or atomic groups. n represents 3, 4 or 5, m is the charge of the metal complex, and represents 5-, 4-, 3-, 2-, 1-, 0 or 1+. Here, a plurality of X ^D2B may be the same or different from each other, and when a plurality of L ^D2B are present, these may be the same or different.
(18) The metal complex represented by the general formula (D2) is a metal complex represented by the following general formula (D2C), described in any one of (3) to (15) Silver halide color photographic light-sensitive material.
General formula (D2C)
[IrX ^D2C _n L ^D2C _(6-n) ] ^m
In the general formula (D2C), X ^D2C represents a halogen ion or a pseudohalogen ion (excluding a cyanate ion). L ^D2C is a 5-membered ring ligand which represents a ligand containing at least one nitrogen atom and at least one sulfur atom in the ring skeleton, and has an arbitrary substituent on a carbon atom in the ring skeleton. You can. n represents 3, 4 or 5, m is the charge of the metal complex, and represents 5-, 4-, 3-, 2-, 1-, 0 or 1+. Here, the plurality of X ^D2Cs may be the same or different from each other, and when there are a plurality of L ^D2Cs , these may be the same or different.

(19) The metal complex represented by the general formula (D2) is a metal complex represented by the following general formula (D2D), described in any one of (3) to (15) Silver halide color photographic light-sensitive material.
General formula (D2D)
[IrX ^D2D _n L ^D2D _(6-n) ] ^m
In the general formula (D2D), X ^D2D represents a halogen ion or a pseudohalogen ion (excluding a cyanate ion). L ^D2D is a 5-membered ring ligand which represents a ligand containing at least two nitrogen atoms and at least one sulfur atom in the ring skeleton, and has an arbitrary substituent on a carbon atom in the ring skeleton. It's okay. n represents 3, 4 or 5, m is the charge of the metal complex, and represents 5-, 4-, 3-, 2-, 1-, 0 or 1+. Here, the plurality of X ^D2Ds may be the same or different from each other, and when there are a plurality of L ^D2Ds , these may be the same or different.
(20) The silver halide color photographic light-sensitive material comprises a yellow dye-forming coupler-containing silver halide emulsion layer, a magenta dye-forming coupler-containing silver halide emulsion layer, and a cyan dye-forming coupler-containing silver halide emulsion layer on a reflective support. The silver halide photographic light-sensitive material as described in any one of (1) to (19), which is a silver halide color photographic light-sensitive material having at least one layer each.
(21) The silver halide color photograph as described in (20) above, wherein the silver halide emulsion of the yellow dye-forming coupler-containing silver halide emulsion layer is a silver halide emulsion having a sphere equivalent diameter of 0.6 μm or less. Photosensitive material.
(22) A silver bromide-containing phase in which at least one of the silver halide emulsions in the silver halide emulsion layer contains 0.1 to 7 mol% of silver bromide and the silver bromide concentration is higher than the surroundings. The silver halide color photographic light-sensitive material as described in any one of (1) to (21), wherein
(23) The silver halide color photographic light-sensitive material described in any one of (1) to (22), wherein the silver halide color photographic light-sensitive material is a blue semiconductor laser having an emission wavelength of 420 nm to 460 nm as a light source. The silver halide color photographic light-sensitive material according to any one of (1) to (22), which is a silver halide color photographic light-sensitive material for digital exposure which is imagewise exposed by scanning exposure.

  The silver halide light-sensitive material of the present invention is suitable for rapid processing, has an excellent latent image stability and has a high contrast, particularly a high sensitivity and a high contrast even when exposed at high illuminance.

The present invention is described in detail below.
First, the (Se) compound (selenium compound) used in the present invention will be described.
In the present invention, any selenium compound that sensitizes a silver halide emulsion may be used, but a compound represented by the following general formula (SE1), (SE2) or (SE3) is preferred.
General formula (SE1)

In General Formula (SE1), M ¹ and M ² are each independently a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, acyl group, amino group, alkoxy group, hydroxy group, or carbamoyl. Represents a group. Q represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, OM ³ or NM ⁴ M ⁵ . Here, M ^{3 to} M ⁵ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. M ¹ , M ² and Q may be bonded to each other to form a ring structure.
General formula (SE2)

In General Formula (SE2), X ¹ , X ² and X ³ each independently represent an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, OJ ¹ or NJ ² J ³ . Here, J ¹ through J ³ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group.
General formula (SE3)

In General Formula (SE3), E ¹ and E ² each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or a carbamoyl group. E ¹ and E ² may be the same or different.

  Next, the selenium compound represented by the general formula (SE1) will be described in detail.

In general formula (SE1), the alkyl group represented by M ^{1 to} M ⁵ and Q represents a linear, branched, or cyclic substituted or unsubstituted alkyl group. Preferably, it is a substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms (for example, methyl, ethyl, isopropyl, n-propyl, n-butyl, t-butyl, 2-pentyl, n-hexyl, n- Octyl, t-octyl, 2-ethylhexyl, 1,5-dimethylhexyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, hydroxyethyl, hydroxypropyl, 2,3-dihydroxypropyl, carboxymethyl, carboxy Ethyl, sodium sulfoethyl, diethylaminoethyl, diethylaminopropyl, butoxypropyl, ethoxyethoxyethyl, n-hexyloxypropyl, etc.), a substituted or unsubstituted cyclic alkyl group having 3 to 18 carbon atoms (for example, cyclopropyl, cyclopentyl, cyclohexyl, It represents a cyclohexyl or the like cyclohexane) - cyclooctyl, adamantyl, cyclododecyl, 3-oxo. Further, it is a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms (that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms, for example, bicyclo [1,2,2 Heptan-2-yl, bicyclo [2,2,2] octane-3-yl), and a tricyclo structure having more ring structures. The alkenyl group represented by M ^{1 to} M ⁵ and Q represents an alkenyl group having 2 to 16 carbon atoms (for example, allyl, 2-butenyl, 3-pentenyl, etc.), represented by M ^{1 to} M ⁵ and Q. The alkynyl group is an alkynyl group having 2 to 10 carbon atoms (for example, propargyl, 3-pentynyl, etc.).

Examples of the aryl group represented by M ^{1 to} M ⁵ and Q include substituted or unsubstituted phenyl and naphthyl groups having 6 to 20 carbon atoms (for example, unsubstituted phenyl group, unsubstituted naphthyl, 3,5-dimethylphenyl, 4-butoxyphenyl, 4-dimethylaminophenyl, etc.), and as the heterocyclic group, at least one heteroatom (preferably a nitrogen atom, an oxygen atom, a sulfur atom) having 0 to 20 carbon atoms is a ring structure A 3- to 12-membered heterocyclic group contained as an atom is preferable, and examples thereof include pyridyl, furyl, imidazolyl, piperidyl, morpholyl and the like.

In the general formula (SE1), the acyl group represented by M ¹ and M ² is preferably an acyl group having 1 to 30 carbon atoms, and examples thereof include acetyl, formyl, benzoyl, pivaloyl, caproyl, n-nonanoyl and the like. The amino group is preferably an amino group having 0 to 30 carbon atoms, and examples thereof include unsubstituted amino, methylamino, hydroxyethylamino, n-octylamino, dibenzylamino, dimethylamino, diethylamino and the like. As an alkoxy group, a C1-C30 alkoxy group is preferable, for example, methoxy, ethoxy, n-butyloxy, cyclohexyloxy, n-octyloxy, n-decyloxy etc. are mentioned. The carbamoyl group is preferably a carbamoyl group having 1 to 30 carbon atoms, and examples thereof include unsubstituted carbamoyl, N, N-diethylcarbamoyl, and N-phenylcarbamoyl.

If the general formula ^{M 1} and ^M 2 in (SE1), Q and ^{M 1} or Q and ^{M 2,} may be bonded together to form a ring structure, further Q represents ^NM 4 ^{M 5,} and ^{M 4} M ⁵ may be bonded to each other to form a ring structure.

In the general formula (SE1), M ^{1 to} M ⁵ and Q may have a substituent as much as possible. Examples of the substituent include a halogen atom (fluorine, chloro, bromine, or iodine), alkyl Groups (straight chain, branched and cyclic alkyl groups, including bicycloalkyl groups and active methine groups), alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups (regardless of where they are substituted), acyl groups, alkoxycarbonyls Group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, N-hydroxycarbamoyl group, N-acylcarbamoyl group, N-sulfonylcarbamoyl group, N-carbamoylcarbamoyl group, thiocarbamoyl group, N-sulfamoylcarbamoyl Group, carbazoyl group, carboxy group or a salt thereof, oxalyl group, oxamoy Group, cyano group, carbonimidoyl group (Carbonimidoyl group), formyl group, hydroxy group, alkoxy group (including groups containing ethyleneoxy group or propyleneoxy group unit), aryloxy group, heterocyclic oxy group, acyloxy group , (Alkoxy or aryloxy) carbonyloxy group, carbamoyloxy group, sulfonyloxy group, amino group, (alkyl, aryl, or heterocyclic) amino group, acylamino group, sulfonamide group, ureido group, thioureido group, N-hydroxy Ureido group, imide group, (alkoxy or aryloxy) carbonylamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, ammonio group, oxamoylamino group, N- (a Alkyl or aryl) sulfonylureido group, N-acylureido group, N-acylsulfamoylamino group, hydroxyamino group, nitro group, heterocyclic group containing a quaternized nitrogen atom (eg, pyridinio group, imidazolio group, quinolinio) Group, isoquinolinio group), isocyano group, imino group, mercapto group, (alkyl, aryl, or heterocyclic) thio group, (alkyl, aryl, or heterocyclic) dithio group, (alkyl or aryl) sulfonyl group, (alkyl or Aryl) sulfinyl group, sulfo group or salt thereof, sulfamoyl group, N-acylsulfamoyl group, N-sulfonylsulfamoyl group or salt thereof, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group And a silyl group.

Here, the active methine group means a methine group substituted with two electron-withdrawing groups, and the electron-withdrawing group here preferably has a Hammett's σ _p value of 0 or more. An acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a trifluoromethyl group, a cyano group, a nitro group, and a carbonimidoyl group (Carbonimidoyl group) can be mentioned. Here, the two electron withdrawing groups may be bonded to each other to form a cyclic structure. The salt means a cation such as alkali metal, alkaline earth metal or heavy metal, or an organic cation such as ammonium ion or phosphonium ion. These substituents may be further substituted with these substituents.

As a preferable compound represented by the general formula (SE1), M ¹ and M ² are each independently a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 6 carbon atoms, and 3 to 3 carbon atoms. A substituted or unsubstituted cyclic alkyl group having 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a substituted or unsubstituted phenyl group having 6 to 10 carbon atoms, a heterocyclic group, and an acyl group, and Q is a carbon number 1-6 substituted or unsubstituted linear or branched alkyl groups, C3-C6 substituted or unsubstituted cyclic alkyl groups, C2-C6 alkenyl groups, C6-C10 substituted or unsubstituted A substituted phenyl group, or NM ⁴ M ⁵ , wherein M ⁴ and M ⁵ are each independently a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 6 carbon atoms, or 3 to 6 carbon atoms. Substituted or unsubstituted rings And a substituted alkyl group having 2 to 6 carbon atoms, a substituted or unsubstituted phenyl group having 6 to 10 carbon atoms, and a heterocyclic group.

As a more preferable compound represented by the general formula (SE1), M ¹ and M ² are each independently a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 6 carbon atoms, or 2 carbon atoms. -6 alkenyl group, substituted or unsubstituted phenyl group having 6 to 10 carbon atoms, and Q is a substituted or unsubstituted linear or branched alkyl group having 1 to 6 carbon atoms, substituted with 6 to 10 carbon atoms Or an unsubstituted phenyl group, or NM ⁴ M ⁵ , wherein M ⁴ and M ⁵ are each independently a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 6 carbon atoms, or 2 carbon atoms It is a case where it is a -6 alkenyl group and a C6-C10 substituted or unsubstituted phenyl group.

As a more preferable compound represented by the general formula (SE1), Q is NM ⁴ M ⁵ , and M ⁴ and M ⁵ are each independently a hydrogen atom, a substituted or unsubstituted straight chain having 1 to 6 carbon atoms. Or a branched alkyl group, an alkenyl group having 2 to 6 carbon atoms, and a substituted or unsubstituted phenyl group having 6 to 10 carbon atoms.
Specific examples of the compound represented by the general formula (SE1) are shown below, but the present invention is not limited thereto.

  The compound represented by the general formula (SE1) of the present invention can be obtained by a known method such as Chemical Reviews (Chem. Rev.), 55, 181-228 (1955), Journal of Organic Chemistry (J. Org. Chem.), 24, 470-473 (1959), Journal of Heterocyclic Chemistry (J. Heterocycl. Chem.), 4,605-609 (1967), "Pharmaceutical Journal" 82, 36-. 45 (1962), JP-B-39-26203, JP-A-63-229449, OLS-2,043,944, or a method analogous thereto. Next, the selenium compound represented by the general formula (SE2) will be described in detail.

In General Formula (SE2), the alkyl group, alkenyl group, alkynyl group, aryl group, and heterocyclic group represented by X ^{1 to} X ³ and J ^{1 to} J ³ are each represented by M ^{1 to} M in General Formula (SE1). It is synonymous with the alkyl group, alkenyl group, alkynyl group, aryl group and heterocyclic group represented by ⁵ and Q, and the preferred range is also the same. X ^{1 to} X ³ and J ^{1 to} J ³ may have a substituent as much as possible, and examples of the substituent may include M ^{1 to} M ⁵ and Q in the general formula (SE1). Synonymous with good substituents.

As the compound represented by the general formula (SE2), X ^{1 to} X ³ are preferably each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted carbon group having 6 to 10 carbon atoms, or It is a case where it represents an unsubstituted phenyl group or a heterocyclic group, and more preferably, X ^{1 to} X ³ each independently represents a substituted or unsubstituted phenyl group having 6 to 10 carbon atoms.
Although the specific example of a compound represented by general formula (SE2) below is given, this invention is not limited to these.

  The compound represented by the general formula (SE2) of the present invention can be obtained by a known method, for example, Organic Phosphorus Compounds (Vol. 4, pp. 1-73), Journal Chemical Society B (J. Chem.). Soc. (B), 1416, 1968), Journal Organic Chemistry (J. Org. Chem. 32, 1717, 1967), Journal Organic Chemistry (J. Org. Chem. 32, 2999, 1967), Tetrahedron (20, 449, 1964), Journal American Chemical Society (J. Am. Chem. Soc., 91, 2915, 1969). Method described in etc. Other can be readily synthesized by methods analogous thereto.

  Next, the selenium compound represented by the general formula (SE3) will be described in detail.

The alkyl group, alkenyl group, alkynyl group, aryl group and heterocyclic group represented by E ¹ and E ² in the general formula (SE3) are each an alkyl group represented by M ^{1 to} M ⁵ and Q in the general formula (SE1). , An alkenyl group, an alkynyl group, an aryl group and a heterocyclic group, and the preferred range is also the same. As the acyl group represented by E ¹ and E ² , an acyl group having 1 to 30 carbon atoms is preferable, and examples thereof include acetyl, formyl, benzoyl, pivaloyl, caproyl, n-nonanoyl, and the like. An alkoxycarbonyl group having 2 to 30 carbon atoms is preferred, and examples thereof include methoxycarbonyl, ethoxycarbonyl, n-butyloxycarbonyl, cyclohexyloxycarbonyl, n-octyloxycarbonyl, n-decyloxycarbonyl and the like. Is preferably an aryloxycarbonyl group having 6 to 30 carbon atoms, such as a phenoxycarbonyl group or a naphthoxycarbonyl group. The carbamoyl group is preferably a carbamoyl group having 1 to 30 carbon atoms, for example, an unsubstituted carbonyl group. Bamoiru, N, N- diethylcarbamoyl, etc. N- phenylcarbamoyl and the like. E ¹ and E ² may have a substituent as much as possible, and examples of the substituent are the same as the substituents that M ^{1 to} M ⁵ and Q may have in the general formula (SE1). The preferred range is also the same.

In the present invention, a preferable compound represented by the formula (SE3) is selected from groups represented by the following general formulas (T1) to (T4) in which either E ¹ or E ² is selected. More preferably, both E ¹ and E ² are selected from the groups represented by the following general formulas (T1) to (T4). In this case, E ¹ and E ² may be the same or different.

In General Formula (T1), Y represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, OR ¹ or NR ² R ³ , and R ^{1 to} R ³ each independently represents an alkyl group or an alkenyl group. Represents an alkynyl group, an aryl group or a heterocyclic group. In General Formula (T2), L represents a divalent linking group, and EWG represents an electron withdrawing group. L and EWG may be bonded to each other to form a ring. In General Formula (T3), A ¹ represents an oxygen atom, a sulfur atom, or NR ⁷ , and R ^{4 to} R ⁷ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. Represent. R ⁵ and R ⁶ may be bonded to each other to form a ring. In General Formula (T4), A ² represents an oxygen atom, a sulfur atom, or NR ¹¹ . R ⁸ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group or an acyl group, and R ^{9 to} R ¹¹ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group Represents a group or a heterocyclic group. R ⁹ and R ¹⁰ may be bonded to each other to form a ring. Z represents a substituent, and n represents an integer of 0 to 4. When n is 2 or more, the plurality of Z may be the same or different. Here, the electron withdrawing group is preferably a group having a Hammett σ _m value of 0 or more.

In General Formula (T1), Y represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, OR ¹ or NR ² R ³ , and R ^{1 to} R ³ each independently represents an alkyl group or an alkenyl group. , An alkynyl group, an aryl group, or a heterocyclic group, the alkyl group here is synonymous with the alkyl group represented by M ^{1 to} M ⁵ and Q in General Formula (SE1), and the preferred range is also the same. Similarly, the alkenyl group, alkynyl group, aryl group, and heterocyclic group are the same as the alkenyl group, alkynyl group, aryl group, and heterocyclic group represented by M ^{1 to} M ⁵ and Q in the general formula (SE1), respectively. The preferable range is also the same.

  In the general formula (T1), in the present invention, Y is preferably an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and more preferably an alkyl group or an aryl group.

In the general formula (T2), the divalent linking group represented by L represents an alkylene group having 2 to 20 carbon atoms, an alkenylene group or an alkynylene group, and particularly a linear, branched or cyclic group having 2 to 10 carbon atoms. An alkylene group (for example, ethylene, propylene, cyclopentylene, cyclohexylene), an alkenylene group (for example, vinylene), and an alkynylene group (for example, propynylene) are preferable. More preferable L is a cycloalkylene group, and those shown in the following general formula (L1) or general formula (L2), and more preferable are those shown in the following general formula (L1) and general formula (L2).
General formula (L1)

General formula (L2)

In General Formula (L1) and General Formula (L2), G ¹ , G ² , G ³ , and G ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heterocyclic group having 1 to 10 carbon ^{atoms, G 1, G 2, G} 3 may form a ring by linking these with each other. G ¹ , G ² , G ³ and G ⁴ are preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group.

In the general formula (T2), EWG represents an electron withdrawing group. The electron withdrawing group here is a substituent having a positive Hammett's substituent constant σ _p value, preferably σ _p value is 0.2 or more, and the upper limit is 1.0 or less. Represents a substituent of Specific examples of the electron withdrawing group having a σ _p value of 0.2 or more include an acyl group, a formyl group, an acyloxy group, an acylthio group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, and a dialkyl. Phosphono group, diarylphosphono group, dialkylphosphinyl group, diarylphosphinyl group, phosphoryl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, A thiocyanate group, a thiocarbonyl group, an imino group, an imino group substituted with an N atom, a carboxy group (or a salt thereof), an alkyl group substituted with at least two or more halogen atoms, and substituted with at least two or more halogen atoms An alkoxy group, at least Two or more aryloxy groups substituted with a halogen atom, an acylamino group, at least two or more alkyl amino group substituted with a halogen atom, at least two or more alkylthio groups substituted with a halogen atom, sigma _p value Examples include aryl groups, heterocyclic groups, halogen atoms, azo groups, and selenocyanate groups substituted with 0.2 or more other electron-withdrawing groups. In the present invention, EWG is preferably an acyl group, formyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkylphosphono group, diarylphosphono group, dialkylphosphinyl group, diarylphosphine group. Finyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, thiocarbonyl group, imino group, imino group substituted with N atom, phosphoryl group, carboxy group (or salt thereof), at least An alkyl group substituted with two or more halogen atoms, an aryl group substituted with another electron-withdrawing group having a σ _p value of 0.2 or more, a heterocyclic group, or a halogen atom, more preferably an acyl group Group, formyl group, carbamoyl group, alkoxy group Bonyl group, aryloxycarbonyl group, cyano group, nitro group, alkylsulfonyl group, arylsulfonyl group, carboxy group, alkyl group substituted with at least two halogen atoms, more preferably acyl group, formyl group, A cyano group, a nitro group, an alkylsulfonyl group, an arylsulfonyl group, or an alkyl group substituted with at least two halogen atoms.

In the general formula (T3), R ^{4 to} R ⁷ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and the alkyl group referred to here is represented by the general formula (SE1) Are the same as the alkyl group represented by M ^{1 to} M ⁵ and Q, and the preferred range is also the same. Similarly, the alkenyl group, alkynyl group, aryl group and heterocyclic group are the same as the alkenyl group, alkynyl group, aryl group and heterocyclic group represented by the general formula (SE1) M ^{1 to} M ⁵ and Q, respectively. The range is the same.

In the present invention, R ⁴ is preferably an alkyl group. R ⁵ and R ⁶ are each independently preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, and most preferably one is a hydrogen atom and the other is a hydrogen atom or an alkyl group. R ⁷ is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, and most preferably an alkyl group.

In the general formula (T3), A ¹ represents an oxygen atom, a sulfur atom or NR ^{7. In} the present invention, A ¹ is preferably an oxygen atom or a sulfur atom, and most preferably an oxygen atom.

  Next, the group represented by Formula (T4) will be described.

In General Formula (T4), the alkyl group represented by R ^{8 to} R ¹¹ has the same meaning as the alkyl group represented by M ^{1 to} M ⁵ and Q in Formula (SE1), and the preferred range is also the same. Similarly, the alkenyl group, alkynyl group, aryl group and heterocyclic group are the same as the alkenyl group, alkynyl group, aryl group and heterocyclic group represented by M ^{1 to} M ⁵ and Q, respectively, and the preferred ranges are also the same. . Examples of the acyl group represented by R ⁸ include an acetyl group, a formyl group, a benzoyl group, a pivaloyl group, a caproyl group, and an n-nonanoyl group.

In General Formula (T4), Z represents a substituent, and examples thereof include the same substituents that M ^{1 to} M ⁵ and Q may have in General Formula (SE1).

  In the present invention, Z is preferably a halogen atom, alkyl group, aryl group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-acylcarbamoyl group, N-sulfonylcarbamoyl group, N- Carbamoylcarbamoyl group, thiocarbamoyl group, N-sulfamoylcarbamoyl group, carbazoyl group, carboxy group (including its salt), cyano group, formyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, Acyloxy group, nitro group, amino group, (alkyl, aryl, or heterocyclic) amino group, acylamino group, sulfonamide group, ureido group, thioureido group, alkylthio group, arylthio group, heterocyclic thio group, (alkyl or aryl) Sulfo Group, (alkyl or aryl) sulfinyl group, sulfo group (including salts thereof), sulfamoyl group, etc., more preferably halogen atom, alkyl group, aryl group, heterocyclic group, carboxy group (and salts thereof). Including), hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, amino group, (alkyl, aryl, or heterocyclic) amino group, acylamino group, ureido group, thioureido group, alkylthio group, arylthio group , A heterocyclic thio group, a sulfo group (including a salt thereof) and the like, more preferably an alkyl group, an aryl group, a carboxy group (including a salt thereof), a hydroxy group, an alkoxy group, an aryloxy group, (alkyl , Aryl, or heterocyclic) amino group, ureido group, alkylthio , An arylthio group, (including and salts thereof) a sulfo group and the like.

  In general formula (T4), n represents an integer of 0 to 4. In the present invention, n preferably represents 0 to 2, more preferably 0 or 1.

In the general formula (T4), A ² represents an oxygen atom, a sulfur atom or NR ¹¹ , but in the present invention, it preferably represents an oxygen atom or a sulfur atom.

In the present invention, among the compounds represented by general formula (SE3), preferred compounds are those in which E ¹ is general formula (T1), E ² is general formula (T1), E ¹ is general formula (T1), and E ² is formula (T2), ^{E 2} is the formula by ^{E 1} general formula ^{(T1) (T3), E} 2 is the formula by ^{E 1} general formula ^{(T1) (T4), E} 1 is the general formula (T2) E ² is general formula (T3), E ¹ is general formula (T2), E ² is general formula (T4), E ¹ is general formula (T3), E ² is general formula (T3), and E ¹ is general In the formula (T3), E ² is the general formula (T4), E ¹ is the general formula (T4), and E ² is the general formula (T4). More preferably, E ¹ is the general formula (T1) and E ² There general formula (T1), ^{E 2} is the formula by ^{E 1} general formula ^{(T1) (T2), E} 2 is the formula by ^{E 1} general formula (T1) (T3), ^{E 1} is the general formula (T1 ) E ² is general formula (T4), E ¹ is general formula (T2), E ² is general formula (T3), E ¹ is general formula (T3), E ² is general formula (T4), and E ¹ is general formula ( ^{E 2} in T4) is a case of the general formula (T4), more preferably ^{E 2} is the general formula ^{E 1} is the general formula (T1) (T2), ^{E 1} is ^{E 2} in the general formula (T1) is generally in formula (T3), ^{E 2} is the formula by ^{E 1} general formula ^{(T1) (T4), E} 2 is the formula by ^{E 1} general formula (T2) (T3), ^{E 1} is the general formula (T3) E ² is the case of general formula (T4), most preferably E ¹ is general formula (T1), E ² is general formula (T2), E ¹ is general formula (T1) and E ² is general formula (T3 ), E ¹ is general formula (T2) and E ² is general formula (T3).

  Specific examples of the selenium compound represented by the general formula (SE3) are shown below, but the compound of the present invention is not limited thereto. In addition, the three-dimensional structure of a compound in which a plurality of stereoisomers can exist is not limited.

  The compound represented by the general formula (SE3) is already known in the following literature, edited by S. Patai, Z. Rappoport, The Chemistry of Organic Selenium and Tellurium Compounds, No. Volume 1 (1986), Volume 2 (1987), D.C. It can be easily synthesized by the method described in Liotta, Organo-selenium Chemistry, (1987) or a similar method.

  In the present invention, as selenium compounds other than those described above, JP-B-43-13489, JP-A-44-15748, JP-A-4-25832, JP-A-4-109240, JP-A-4-271341, and JP-A-5-40324. 5-11385, 6-51415, 6-175258, 6-180478, 6-208186, 6-208184, 6-317867, 7-92599, Publications such as No. 7-98483, No. 7-140579, No. 7-301879, No. 7-301880, No. 8-111882, No. 9-138475, No. 9-197603, No. 10-10666, etc. Selenium compounds, specifically colloidal metal selenium, selenoketones (for example, selenobenzophenone), isoselenosi Sulfonates, such as selenocarboxylic acids can be used. Furthermore, non-labile selenium compounds described in JP-B-46-4553 and JP-A-52-34492, such as selenious acid, selenocyanic acids (for example, potassium selenocyanate), selenazoles, selenides and the like are also used. be able to. Of these, selenocyanic acids are particularly preferred.

  As mentioned above, although the structure which can be preferably used as a selenium compound has been shown, this invention is not limited to these. The selenium compound used in the present invention preferably has a binding energy value of 3d orbital electrons of selenium atoms of 54.0 eV or more and 65.0 eV or less as measured with an X-ray photoelectron spectrometer in terms of high contrast and low fog.

The amount of selenium sensitizer used in the present invention varies depending on the selenium compound used, silver halide grains, chemical ripening conditions, etc., but is generally 10 ^-8 to 10 ^-4 mol per mol of silver halide, preferably 10 ^{About -7} to 10 ^-5 mol is used. Moreover, there is no restriction | limiting in particular as conditions for the chemical sensitization in this invention, However, 0-7 are preferable as pCl, 0-5 are more preferable, and 1-3 are still more preferable. As temperature, 40-95 degreeC is preferable and 50-85 degreeC is more preferable.

  The selenium compound used in the present invention can be added at any stage from immediately after grain formation to immediately before the end of chemical sensitization. The preferred addition time is between the chemical sensitization step after desalting.

In the present invention, sulfur sensitization, tellurium sensitization, other gold sensitization and noble metal sensitization can be used in combination. As the gold sensitizer, colloidal gold sulfide or a gold sensitizer having a complex stability constant log β ₂ of gold of 21 or more and 35 or less can be preferably used in combination. In addition to these, commonly used gold compounds (for example, chloroaurate, potassium chloroaurate, auric trichloride, potassium aurothiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, pyridyltrichlorogold, etc.) Can be used together.
In addition, the gold sensitizer used in the present invention can be added at any stage from immediately after the formation of particles to immediately before the end of chemical sensitization. A preferable addition time is between the chemical sensitization process after the desalting.

  Reduction sensitizers can also be used in combination. Specific examples include stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives, borane compounds, silane compounds, and polyamine compounds.

In the present invention, chemical sensitization with a selenium compound is preferably performed in the presence of a silver halide solvent. Specific examples of the silver halide solvent include thiocyanate (for example, potassium thiocyanate) and thioether compounds (for example, US Pat. Nos. 3,021,215 and 3,271,157). , Compounds described in JP-B-58-30571, JP-A-60-136736, etc., in particular 3,6-dithia-1,8-octanediol, etc., tetrasubstituted thiourea compounds (for example, No. 59-11892, U.S. Pat. No. 4,221,863, etc., especially tetramethylthiourea, etc.), and thione compounds described in JP-B-60-11341, JP-B-63- A mercapto compound described in Japanese Patent No. 29727, a mesoionic compound described in Japanese Patent Application Laid-Open No. 60-163042, described in US Pat. No. 4,782,013 Seleno ether compounds, Teruroeteru compounds described in JP-A-2-118566, sulfites, and the like. Among these, thiocyanate, thioether compound, tetrasubstituted thiourea compound and thione compound can be preferably used. The amount used can be about 10 ⁻⁵ to 10 ⁻² mole per mole of silver halide.

The metal complex represented by the following general formula (D1) used in the present invention will be described. In addition, the metal complex represented by the general formula (D1) is a complex (high contrast complex) used to make the gradation of the photosensitive material high.
General formula (D1)
[M ^D1 X ^D1 _n L ^D1 _(6-n) ] ^m
In the general formula (D1), M ^D1 represents Cr, Mo, Re, Fe, Ru, Os, Co, Rh, Pd, or Pt, and X ^D1 represents a halogen ion. L ^D1 represents an arbitrary ligand different from X ^D1 . n represents 3, 4, 5 or 6, m represents the charge of the metal complex, and represents 4-, 3-, 2-, 1-, 0 or 1+. Here, a plurality of X ^D1 may be the same or different from each other, and when a plurality of L ^D1 are present, these may be the same or different. However, the metal complex represented by the general formula (D1) does not have or has one CN ion as a ligand.

Among the metal complexes represented by the general formula (D1), a metal complex represented by the following general formula (D1A) is preferable.
General formula (D1A)
[M ^D1A X ^D1A _n L ^D1A _(6-n) ] ^m
In the general formula (D1A), M ^D1A represents Re, Ru, Os, or Rh, and X ^D1A represents a halogen ion. L ^D1A represents NO or NS when M ^D1A is Re, Ru or Os, and represents H ₂ O, OH or O when M ^D1A is Rh. n represents 3, 4, 5 or 6, m represents the charge of the metal complex, and represents 4-, 3-, 2-, 1-, 0 or 1+. Here, a plurality of X ^D1A may be the same or different from each other, and when a plurality of L ^D1A are present, these may be the same or different.
X ^D1A has the same meaning as X ^{D1 in} formula (D1), and the preferred range is also the same.

Although the preferable specific example of a metal complex represented by general formula (D1) below is given, this invention is not limited to these.
[ReCl ₆ ] ^2-
[ReCl ₅ (NO)] ^2-
[RuCl ₆ ] ^2-
[RuCl ₆ ] ^3-
[RuCl ₅ (NO)] ^2-
[RuCl ₅ (NS)] ^2-
[RuBr ₅ (NS)] ^2-
[OsCl ₆ ] ^4-
[OsCl ₅ (NO)] ^2-
[OsBr ₅ (NS)] ^2-
[RhCl ₆ ] ^3-
[RhCl ₅ (H ₂ O)] ^2-
[RhCl ₄ (H ₂ O) ₂ ] ^-
[RhBr ₆ ] ^3-
[RhBr ₅ (H ₂ O)] ^2-
[RhBr ₄ (H ₂ O) ₂ ] ^-
[PdCl ₆ ] ^2-
[PtCl ₆ ] ^2-
Among these, [OsCl ₅ (NO)] ²⁻ or [RhBr ₆ ] ³⁻ is particularly preferable.

The metal complex represented by the following general formula (D2) preferably used in the present invention will be described.
General formula (D2)
[IrX ^D2 _n L ^D2 _(6-n) ] ^m
In general formula (D2), X ^D2 represents a pseudohalogen ion other than a halogen ion or a cyanate ion, and L ^D2 represents an arbitrary ligand different from X ^D2 . n represents 3, 4 or 5, m is the charge of the metal complex, and represents 5-, 4-, 3-, 2-, 1-, 0 or 1+. Here, a plurality of X ^D2 may be the same as or different from each other, and when a plurality of L ^D2 are present, these may be the same or different.
In the above, the pseudohalogen (halogenoid) ion is an ion having properties similar to a halogen ion. For example, cyanide ion (CN ⁻ ), thiocyanate ion (SCN ⁻ ), selenocyanate ion (SeCN ^−). ), Tellurocyanate ion (TeCN ⁻ ), azidodithiocarbonate ion (SCSN ₃ ⁻ ), cyanate ion (OCN ⁻ ), thunderate ion (ONC ⁻ ), azide ion (N ₃ ⁻ ) and the like.
X ^D2 is preferably fluoride ion, chloride ion, bromide ion, iodide ion, cyanide ion, isocyanate ion, thiocyanate ion, nitrate ion, nitrite ion, or azide ion, among which chloride Particularly preferred are ions and bromide ions. L ^D2 is not particularly limited and may be an inorganic compound or an organic compound, and may be charged or uncharged, but may be an uncharged inorganic compound or organic compound. preferable.

Among the metal complexes represented by the general formula (D2), a metal complex represented by the following general formula (D2A) is preferable.
General formula (D2A)
[IrX ^D2A _n L ^D2A _(6-n) ] ^m
In the general formula (D2A), X ^D2A represents a halogen ion or a pseudohalogen ion (excluding a cyanate ion), and L ^D2A represents an arbitrary inorganic ligand different from X ^D2A . n represents 3, 4 or 5, m is the charge of the metal complex, and represents 5-, 4-, 3-, 2-, 1-, 0 or 1+. Here, a plurality of X ^D2A may be the same or different from each other, and when a plurality of L ^D2A are present, these may be the same or different.
X ^D2A has the same meaning as X ^{D2 in} formula (D2), and the preferred range is also the same. L ^D2A is preferably water, OCN, ammonia, phosphine, or carbonyl, and particularly preferably water.

Among the metal complexes represented by the general formula (D2), the metal complex represented by the following general formula (D2B) is more preferable.
General formula (D2B)
[IrX ^D2B _n L ^D2B _(6-n) ] ^m
In the general formula (D2B), X ^D2B represents a halogen ion or a pseudohalogen ion (excluding a cyanate ion), and L ^D2B has a base structure of a chain or cyclic hydrocarbon, or a base structure thereof Represents a ligand in which some carbon or hydrogen atoms are replaced with other atoms or atomic groups. n represents 3, 4 or 5, m is the charge of the metal complex, and represents 5-, 4-, 3-, 2-, 1-, 0 or 1+. Here, a plurality of X ^D2B may be the same or different from each other, and when a plurality of L ^D2B are present, these may be the same or different.
X ^D2B has the same meaning as X ^{D2 in} formula (D2), and the preferred range is also the same. L ^D2B represents a ligand in which a chain or cyclic hydrocarbon is a base structure, or a carbon or hydrogen atom in a part of the base structure is replaced with another atom or atomic group. Ions are not included. L ^D2B is preferably a heterocyclic compound. More preferably, it is a 5-membered ring compound, and among the 5-membered ring compounds, a compound containing at least one nitrogen atom and at least one sulfur atom in the 5-membered ring skeleton is more preferable.

Among the metal complexes represented by the general formula (D2B), the metal complex represented by the following general formula (D2C) is more preferable.
General formula (D2C)
[IrX ^D2C _n L ^D2C _(6-n) ] ^m
In the general formula (D2C), X ^D2C represents a halogen ion or a pseudohalogen ion (excluding a cyanate ion). L ^D2C is a 5-membered ring ligand which represents a ligand containing at least one nitrogen atom and at least one sulfur atom in the ring skeleton, and has an arbitrary substituent on a carbon atom in the ring skeleton. You can. n represents 3, 4 or 5, m is the charge of the metal complex, and represents 5-, 4-, 3-, 2-, 1-, 0 or 1+. Here, the plurality of X ^D2Cs may be the same or different from each other, and when there are a plurality of L ^D2Cs , these may be the same or different.
X ^D2C has the same meaning as X ^{D2 in} formula (D2), and the preferred range is also the same. The substituent on the carbon atom in the ring skeleton in L ^D2C is preferably a substituent having a smaller volume than the n-propyl group. As a substituent, methyl group, ethyl group, methoxy group, ethoxy group, cyano group, isocyano group, cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, formyl group, thioformyl group, hydroxy group, mercapto group, amino group, hydrazino group , An azido group, a nitro group, a nitroso group, a hydroxyamino group, a carboxyl group, a carbamoyl group, and a halogen atom (fluoro group, chloro group, bromo group, iodo group) are preferred.

Among the metal complexes of the general formula (D2C), a metal complex represented by the following general formula (D2D) is more preferable.
General formula (D2D)
[IrX ^D2D _n L ^D2D _(6-n) ] ^m
In the general formula (D2D), X ^D2D represents a halogen ion or a pseudohalogen ion (excluding a cyanate ion). L ^D2D is a 5-membered ring ligand which represents a ligand containing at least two nitrogen atoms and at least one sulfur atom in the ring skeleton, and has an arbitrary substituent on a carbon atom in the ring skeleton. It's okay. n represents 3, 4 or 5, m is the charge of the metal complex, and represents 5-, 4-, 3-, 2-, 1-, 0 or 1+. Here, the plurality of X ^D2Ds may be the same or different from each other, and when there are a plurality of L ^D2Ds , these may be the same or different.
X ^D2D has the same meaning as X ^{D2 in} formula (D2), and the preferred range is also the same. L ^D2D is preferably a compound having a thiadiazole as a skeleton, and a substituent other than hydrogen is preferably bonded to a carbon atom in the compound. Preferred substituents are halogen atoms (fluorine, chlorine, bromine, iodine), methoxy group, ethoxy group, carboxyl group, methoxycarboxyl group, acyl group, acetyl group, chloroformyl group, mercapto group, methylthio group, thioformyl group, thiol Carboxy group, dithiocarboxy group, sulfino group, sulfo group, sulfamoyl group, methylamino group, cyano group, isocyano group, cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, hydroxyamino group, hydroxyimino group, carbamoyl group, nitroso Group, nitro group, hydrazino group, hydrazono group or azide group, more preferably halogen (fluorine, chlorine, bromine, iodine), chloroformyl group, sulfino group, sulfo group, sulfamoyl group, isocyano group, cyanato group, Isoshi Anato group, thiocyanato group, isothiocyanato group, hydroxyimino group, nitroso group, nitro group, or azido group. Of these, chlorine, bromine, chloroformyl group, isocyano group, cyanato group, isocyanato group, and thiocyanato group are particularly preferable. n is preferably 4 or 5, and m is preferably 2- or 1-.

Although the preferable specific example of a metal complex represented by general formula (D2) below is given, this invention is not limited to these.
[IrCl ₅ (H ₂ O)] ^2-
[IrCl ₄ (H ₂ O) ₂ ] ^-
[IrCl ₅ (H ₂ O)] ^-
[IrCl ₄ (H ₂ O) ₂ ] ⁰
[IrCl ₅ (OH)] ^3-
[IrCl ₄ (OH) ₂ ] ^2-
[IrCl ₅ (OH)] ^2-
[IrCl ₄ (OH) ₂ ] ^-
[IrCl ₅ (O)] ^4-
[IrCl ₄ (O) ₂ ] ^5-
[IrCl ₅ (O)] ^3-
[IrCl ₄ (O) ₂ ] ^4-
[IrBr ₅ (H ₂ O)] ^2-
[IrBr ₄ (H ₂ O) ₂ ] ^-
[IrBr ₅ (H ₂ O)] ^-
[IrBr ₄ (H ₂ O) ₂ ] ⁰
[IrBr ₅ (OH)] ^3-
[IrBr ₄ (OH) ₂ ] ^2-
[IrBr ₅ (OH)] ^2-
[IrBr ₄ (OH) ₂ ] ^-
[IrBr ₅ (O)] ^4-
[IrBr ₄ (O) ₂ ] ^5-
[IrBr ₅ (O)] ^3-
[IrBr ₄ (O) ₂ ] ^4-
[IrCl ₅ (OCN)] ^3-
[IrBr ₅ (OCN)] ^3-
[IrCl ₅ (thiazole)] ^2-
[IrCl ₄ (thiazole) ₂ ] ^-
[IrCl ₃ (thiazole) ₃ ] ⁰
[IrBr ₅ (thiazole)] ^2-
[IrBr ₄ (thiazole) ₂ ] ^-
[IrBr ₃ (thiazole) ₃ ] ⁰
[IrCl ₅ (5-methylthiazole)] ^2-
[IrCl ₄ (5-methylthiazole) ₂ ] ^-
[IrBr ₅ (5-methylthiazole)] ^2-
[IrBr ₄ (5-methylthiazole) ₂ ] ^-
Among these, [IrCl ₅ (5-methylthiazole)] ^2- is particularly preferable.

The metal complex mentioned above is an anion, and when a salt is formed with a cation, the metal complex that is easily dissolved in water as the counter cation is preferable. Specifically, alkali metal ions such as sodium ion, potassium ion, rubidium ion, cesium ion and lithium ion, ammonium ion and alkylammonium ion are preferable. In addition to water, these metal complexes should be dissolved in a mixed solvent with an appropriate organic solvent (for example, alcohols, ethers, glycols, ketones, esters, amides, etc.) that can be mixed with water. Can do. Metal complex represented by the general formula (D1), preferably added 1 × 10 ^-6 mol 1 × 10 ^-11 mol per mol of silver in the grain formation, 1 × 10 from 1 × 10 ^-10 mol ^-6 mol is more preferable, and 1 × 10 ⁻¹⁰ mol to 1 × 10 ⁻⁷ mol is most preferable. Metal complex represented by the general formula (D2), preferably added 1 × 10 ^-3 mol 1 × 10 ^-10 mol per mol of silver in the grain formation, 1 × 10 from 1 × 10 ^-8 mol It is most preferable to add ^-5 mol.

  In the present invention, the above metal complex is added directly to the reaction solution at the time of silver halide grain formation, or added to an aqueous halide solution for forming silver halide grains, or in other solutions to form grains. It is preferably incorporated into the silver halide grains by adding to the reaction solution. It is also preferable to physically ripen the fine particles in which the metal complex has been previously incorporated in the grains and to incorporate them in the silver halide grains. Further, these methods can be combined and contained in the silver halide grains.

  When these metal complexes are incorporated into silver halide grains, they can be uniformly present inside the grains, but disclosed in JP-A-4-208936, JP-A-2-125245, and JP-A-3-188437. As described above, it is also preferable to exist only in the particle surface layer, and it is also preferable to add a layer containing the complex only inside the particle and not containing the complex on the particle surface. Further, as disclosed in US Pat. Nos. 5,252,451 and 5,256,530, physical ripening is performed with fine particles in which the complex is incorporated in the particles to modify the particle surface phase. It is also preferable. Further, these methods can be used in combination, and a plurality of types of complexes may be incorporated in one silver halide grain. The halogen composition at the position where the above complex is contained is not particularly limited, but the hexacoordinate complex having Ir as the central metal, in which all six ligands are Cl, Br or I, has a silver bromide concentration maximum. It is preferable to contain.

  The silver halide emulsion of the present invention contains specific silver halide grains. The particle shape is not particularly limited, but is substantially a cubic or tetradecahedral crystal particle having {100} faces (they may have rounded particle vertices and may have higher-order faces), 8 It is preferable that the crystal grain of a plane body and the main surface consist of a tabular grain having an aspect ratio of 3 or more and comprising a {100} plane or {111} plane. The aspect ratio is a value obtained by dividing the diameter of a circle corresponding to the projected area by the thickness of the particle.

  In the present invention, the silver chloride content is 95 mol% or more, and from the viewpoint of rapid processability, the silver chloride content is preferably 96 mol% or more, more preferably 97 mol% or more. The silver bromide content is preferably 0.1 to 7 mol%, more preferably 0.5 to 5 mol%, since it is a high contrast and has excellent latent image stability. The silver iodide content is preferably 0.02-1 mol%, more preferably 0.05-1.0 mol%, more preferably 0.05-0. 50 mol% is more preferable, and 0.07 to 0.40 mol% is most preferable. The specific silver halide grains of the present invention are preferably silver iodobromochloride grains, more preferably silver iodobromochloride grains having the above halogen composition.

  The specific silver halide grains in the silver halide emulsion of the present invention preferably have a silver bromide-containing phase and / or a silver iodide-containing phase. Here, the silver bromide or silver iodide-containing phase means a portion where the concentration of silver bromide or silver iodide is higher than the surroundings. The halogen composition of the silver bromide-containing phase or silver iodide-containing phase and its surroundings may change continuously or may change sharply. Such a silver bromide or silver iodide-containing phase may form a layer having a substantially constant width at a certain portion in the grain, or may be a maximum point having no spread. The local silver bromide content of the silver bromide-containing phase is preferably 5 mol% or more, more preferably 10 to 80 mol%, and most preferably 15 to 50 mol%. The local silver iodide content of the silver iodide-containing phase is preferably 0.3 mol% or more, more preferably 0.5 to 8 mol%, and more preferably 1 to 5 mol%. Most preferred. Further, a plurality of such silver bromide or silver iodide-containing phases may be formed in layers in each grain, and the silver bromide or silver iodide content may be different, but at least one of each. It is necessary to have a contained phase of

  It is important that the silver bromide-containing phase or the silver iodide-containing phase of the silver halide emulsion of the present invention is layered so as to surround each grain. In one preferred embodiment, the silver bromide-containing phase or the silver iodide-containing phase formed in layers so as to surround the grains has a uniform concentration distribution in the circumferential direction of the grains in each phase. However, in the silver bromide-containing phase or silver iodide-containing phase that are layered so as to surround the grain, the maximum or minimum point of the silver bromide or silver iodide concentration exists in the circumferential direction of the grain, and the concentration distribution You may have. For example, when a silver bromide-containing phase or silver iodide-containing phase is formed in a layer so as to surround the grain in the vicinity of the grain surface, the silver bromide or silver iodide concentration at the grain corner or edge is different from the main surface. There is a case. In addition to the silver bromide-containing phase and the silver iodide-containing phase that are layered so as to surround the grain, the silver bromide-containing phase that is completely isolated in a specific part of the surface of the grain and does not surround the grain Alternatively, there may be a silver iodide containing phase.

  When the silver halide emulsion of the present invention contains a silver bromide-containing phase, the silver bromide-containing phase is preferably formed in a layered manner so as to have a silver bromide concentration maximum inside the grain. Further, when the silver halide emulsion of the present invention contains a silver iodide-containing phase, the silver iodide-containing phase is preferably formed in a layered manner so as to have a silver iodide concentration maximum on the surface of the grain. Such a silver bromide-containing phase or silver iodide-containing phase is composed of a silver amount of 3% to 30% of the grain volume in order to increase the local concentration with a smaller silver bromide or silver iodide content. It is preferable that the silver content is 3% or more and 15% or less.

  The silver halide emulsion of the present invention preferably contains both a silver bromide-containing phase and a silver iodide-containing phase. In this case, the silver bromide-containing phase and the silver iodide-containing phase may be at the same place or different places in the grain, but it is preferable that the silver bromide-containing phase and the silver iodide-containing phase are in different places from the viewpoint of facilitating control of grain formation. Further, the silver bromide-containing phase may contain silver iodide, and conversely, the silver iodide-containing phase may contain silver bromide. In general, iodide added during the formation of high silver chloride grains tends to ooze out on the grain surface than bromide, so the silver iodide-containing phase tends to be formed near the grain surface. Therefore, when the silver bromide-containing phase and the silver iodide-containing phase are at different locations in the grain, the silver bromide-containing phase is preferably formed inside the silver iodide-containing phase. In such a case, another silver bromide-containing phase may be provided further outside the silver iodide-containing phase near the grain surface.

  The silver bromide content or silver iodide content necessary for exhibiting the effects of the present invention such as high sensitivity and high contrast is such that the silver bromide-containing phase or silver iodide-containing phase is formed inside the grain. There is a risk that the amount of silver chloride may be reduced more than necessary, and the rapid processability may be impaired. Therefore, in order to concentrate these functions for controlling the photographic action near the surface in the grain, the silver bromide-containing phase and the silver iodide-containing phase are preferably adjacent to each other. From these points, the silver bromide-containing phase is formed at any of the positions of 50% to 100% of the grain volume as measured from the inside, and the silver iodide-containing phase is any of the positions at 85% to 100% of the grain volume. It is preferable to form it. Further, the silver bromide-containing phase is formed at any position from 70% to 95% of the grain volume, and the silver iodide-containing phase is further formed at any position from 90% to 100% of the grain volume. preferable.

  Introducing bromide or iodide ions to contain silver bromide or silver iodide in the silver halide emulsion of the present invention may be carried out by adding a bromide salt or iodide salt solution alone, Along with the addition of the chloride salt solution, a bromide salt or iodide salt solution may be added. In the latter case, bromide salt or iodide salt solution and high chloride salt solution may be added separately or as a mixed solution of bromide salt or iodide salt and high chloride salt. The bromide salt or iodide salt is added in the form of a soluble salt such as an alkali or alkaline earth bromide salt or iodide salt. Alternatively, it can be introduced by cleaving bromide ions or iodide ions from organic molecules described in US Pat. No. 5,389,508. As another bromide or iodide ion source, fine silver bromide grains or fine silver iodide grains can also be used.

The addition of the bromide salt or iodide salt solution may be concentrated during a period of grain formation or may be performed over a certain period. The position of introduction of iodide ions into the high chloride emulsion is limited in obtaining a high sensitivity and low fog emulsion. Iodide ions are introduced more into the emulsion grains and the increase in sensitivity is smaller. Therefore, the iodide salt solution is preferably added outside 50% of the grain volume, more preferably outside 70%, and most preferably outside 85%. Further, the addition of the iodide salt solution is preferably completed within 98% of the grain volume, and most preferably within 96%. The addition of the iodide salt solution is completed slightly inside from the grain surface, whereby an emulsion with higher sensitivity and lower covering can be obtained.
On the other hand, the addition of the bromide salt solution is preferably performed outside 50% of the particle volume, more preferably outside 70%.

  Distribution of bromide or iodide ion concentration in the depth direction in the grain is measured by etching / TOF-SIMS (Time of Flight-Secondary Ion Mass Spectrometry) method, for example, using TRIFT II type TOF-SIMS manufactured by Phi Evans. it can. The TOF-SIMS method is specifically described in “Surface Analysis Technology Selection Secondary Ion Mass Spectrometry” Maruzen Co., Ltd. (1999), edited by the Surface Science Society of Japan. When the emulsion grains are analyzed by the etching / TOF-SIMS method, it is possible to analyze that iodide ions ooze out toward the grain surface even when the addition of the iodide salt solution is finished inside the grains. The emulsion of the present invention is analyzed by etching / TOF-SIMS method, and it is preferable that iodide ions have a maximum concentration on the grain surface, and the iodide ion concentration is attenuated toward the inside. It is preferable to have a concentration maximum inside. The local concentration of silver bromide can also be measured by X-ray diffraction if the silver bromide content is somewhat high.

  In this specification, the equivalent sphere diameter is represented by the diameter of a sphere having a volume equal to the volume of each particle. The emulsion of the present invention is preferably composed of grains having a monodispersed grain size distribution. The variation coefficient of the equivalent sphere diameter of all the particles of the present invention is preferably 20% or less, more preferably 15% or less, and still more preferably 10% or less. The variation coefficient of the equivalent sphere diameter is expressed as a percentage of the standard deviation of the equivalent sphere diameter of each particle with respect to the average equivalent sphere diameter. At this time, for the purpose of obtaining a wide latitude, it is preferable to use the above monodispersed emulsion by blending it in the same layer or to carry out multilayer coating.

  The present invention relates to a silver halide color photographic material having at least one each of a yellow dye-forming coupler-containing silver halide emulsion layer, a magenta dye-forming coupler-containing silver halide emulsion layer, and a cyan dye-forming coupler-containing silver halide emulsion layer. Applied. In this case, the sphere equivalent diameter of the silver halide emulsion of the yellow dye-forming coupler-containing silver halide emulsion layer is preferably 0.6 μm or less, more preferably 0.5 μm or less, and 0.4 μm or less. Most preferably, the lower limit is not particularly limited, but is usually 0.05 μm. The sphere equivalent diameter of the silver halide emulsion of the magenta dye-forming coupler-containing silver halide emulsion layer and the cyan dye-forming coupler-containing silver halide emulsion layer is preferably 0.5 μm or less, and preferably 0.4 μm or less. More preferably, it is most preferably 0.3 μm or less, and the lower limit is not particularly limited, but is usually 0.05 μm. In this specification, the equivalent sphere diameter is represented by the diameter of a sphere having a volume equal to the volume of each particle. Particles with a sphere equivalent diameter of 0.6 μm correspond to cubic particles with a side length of about 0.48 μm, particles with a sphere equivalent diameter of 0.5 μm correspond to cubic particles with a side length of about 0.40 μm, and a sphere equivalent diameter of 0.4 μm. These particles correspond to cubic particles having a side length of about 0.32 μm, and particles having a sphere equivalent diameter of 0.3 μm correspond to cubic particles having a side length of about 0.24 μm. The silver halide emulsion of the present invention may contain silver halide grains other than the silver halide grains (that is, specific silver halide grains) contained in the silver halide emulsion defined in the present invention. However, the silver halide emulsion defined in the present invention requires that 50% or more of the total projected area of all grains be silver halide grains as defined in the present invention, and preferably 80% or more. More preferably, it is 90% or more.

  The specific silver halide grains in the silver halide emulsion of the present invention further contain an iridium complex in which all six ligands are composed of Cl, Br or I in addition to the iridium complex represented by the general formula (D2). be able to. In this case, Cl, Br, or I may be mixed in the hexacoordinate complex. It is particularly preferable that the iridium complex having Cl, Br or I as a ligand is contained in the silver bromide-containing phase in order to obtain a high gradation at high illumination exposure.

Specific examples of iridium complexes in which all six ligands are Cl, Br, or I are given below, but are not limited thereto.
[IrCl ₆ ] ^2-
[IrCl ₆ ] ^3-
[IrBr ₆ ] ^2-
[IrBr ₆ ] ^3-
[IrI ₆ ] ^3-

  In the present invention, in addition to the metal complexes described above, other metal ions can be doped inside and / or on the surface of silver halide grains. As a metal ion to be used, a transition metal ion is preferable, and iron, ruthenium, osmium, lead, cadmium, or zinc is particularly preferable. Further, these metal ions are more preferably used as a hexacoordinate octahedral complex with a ligand. When an inorganic compound is used as a ligand, cyanide ion, halide ion, thiocyan, hydroxide ion, peroxide ion, azide ion, nitrite ion, water, ammonia, nitrosyl ion, or thiol It is preferable to use a nitrosyl ion, and it is also preferable to use it in coordination with any of the above metal ions of iron, ruthenium, osmium, lead, cadmium, or zinc, and a plurality of kinds of ligands are contained in one complex molecule. It is also preferable to use it. An organic compound can also be used as the ligand, and preferred organic compounds include a chain compound having 5 or less carbon atoms in the main chain and / or a 5-membered or 6-membered heterocyclic compound. . More preferable organic compounds are compounds having a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom in the molecule as a coordination atom to the metal, particularly preferably furan, thiophene, oxazole, isoxazole, thiazole, isothiazole. , Imidazole, pyrazole, triazole, furazane, pyran, pyridine, pyridazine, pyrimidine, and pyrazine, and compounds in which these compounds are used as a basic skeleton and substituents are introduced into them are also preferable.

A combination of metal ions and ligands is preferably a combination of iron ions, ruthenium ions and cyanide ions. In the present invention, it is preferable to use these compounds in combination with the metal complexes described above. In these compounds, the cyanide ion preferably accounts for a majority of the coordination number to iron or ruthenium as the central metal, and the remaining coordination sites are thiocyanate, ammonia, water, nitrosyl ion, dimethyl sulfoxide, pyridine, It is preferably occupied by pyrazine or 4,4′-bipyridine. Most preferably, all six coordination sites of the central metal are occupied by cyanide ions to form a hexacyanoiron complex or a hexacyanoruthenium complex. It is preferable to add 1 × 10 ⁻⁸ mol to 1 × 10 ⁻² mol per mol of silver, and 1 × 10 ⁻⁶ mol to 5 × 10 5 of these complexes having cyanide ions as ligands. It is most preferable to add ^-4 mol.

  The silver halide emulsion used in the present invention is preferably subjected to gold sensitization known in the art. This is because gold sensitization can increase the sensitivity of the emulsion, and can reduce variations in photographic performance when scanning exposure is performed with laser light or the like. For gold sensitization, various inorganic gold compounds, gold (I) complexes having inorganic ligands, and gold (I) compounds having organic ligands can be used. Examples of the inorganic gold compound include chloroauric acid or a salt thereof, and a gold (I) complex having an inorganic ligand, for example, a gold dithiocyanate such as gold (I) potassium dithiocyanate or gold (I) 3 dithiosulfate. Compounds such as gold dithiosulfate compounds such as sodium can be used.

Examples of the gold (I) compound having an organic ligand (organic compound) include bisgold (I) mesoionic heterocycles described in JP-A-4-267249, such as bis (1,4,5-trimethyl-1). , 2,4-triazolium-3-thiolate) orate (I) tetrafluoroborate, organomercaptogold (I) complexes described in JP-A-11-218870, such as potassium bis (1- [3- (2-sulfo) Natobenzamido) phenyl] -5-mercaptotetrazole potassium salt) aurate (I) pentahydrate, gold (I) compound coordinated with nitrogen compound anion described in JP-A-4-268550, for example, bis (1- Methyl hydantoinato) gold (I) sodium salt tetrahydrate. The gold (I) compound having these organic ligands should be synthesized and isolated in advance, or mixed with an organic ligand and an Au compound (for example, chloroauric acid or a salt thereof). Can be added to the emulsion without generation and isolation. Furthermore, an organic ligand and an Au compound (for example, chloroauric acid or a salt thereof) may be separately added to the emulsion to generate a gold (I) compound having an organic ligand in the emulsion.
Further, gold (I) thiolate compounds described in US Pat. No. 3,503,749, JP-A-8-69074, JP-A-8-69075, and JP-A-9-269554 Gold compounds, U.S. Pat. Nos. 5,620,841, 5,912,112, 5,620,841, 5,939,245, and 5,912,111 The compounds described in the documents can also be used.

The addition amount of these compounds may vary widely depending on the case, but is 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol, preferably 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol per mol of silver halide. is there.

Colloidal gold sulfide can also be used. The manufacturing method thereof is Research Disclosure (37154), Solid State Ionics 79, 60-66, 1995, Compt. Rend. Hebt. Seances Acad. Sci. Sect. B 263, 1328, 1966, etc. The Research Disclosure describes a method using a thiocyanate ion in the production of colloidal gold sulfide, but a thioether compound such as methionine or thiodiethanol can be used instead.
Various sizes of colloidal gold sulfide can be used, those having an average particle diameter of 50 mm or less are preferred, average particle diameters of 10 nm or less are more preferred, and average particle diameters of 3 nm or less are even more preferred. This particle size can be measured from a TEM photograph. The composition of the colloidal gold sulfide may also Au ₂ S _1, may be of Au ₂ S ₁ ~Au ₂ S ₂ in such sulfur excess composition, sulfur excess composition is preferred. Au ₂ S _1.1 ~Au ₂ S _1.8 is more preferred.
The composition analysis of the colloidal gold sulfide can be obtained, for example, by taking out gold sulfide particles and determining the gold content and sulfur content by using an analysis method such as ICP or iodometry, respectively. If gold ions and sulfur ions (including hydrogen sulfide and its salts) dissolved in the liquid phase are present in the gold sulfide colloid, the composition analysis of the gold sulfide colloid particles will be affected. The analysis is performed after separation. The addition amount of the gold sulfide colloid may vary widely depending on the case, but 5 × ¹⁰ -7 ~5 × ^{10 -3} mol as per mole of silver halide gold atoms, preferably 5 × ¹⁰ -6 ~5 × ^{10 - 4} moles.

Chalcogen sensitization together with gold sensitization is also possible to perform the same molecule, AuCh ^- it can be used capable of releasing molecule. Here, Au represents Au (I), and Ch represents a sulfur atom, a selenium atom, or a tellurium atom. AuCh ^- The releasable molecules, for example, gold compounds represented by AuCh-L. Here, L represents an atomic group constituting a molecule by bonding with AuCh. Further, one or more ligands may be coordinated with Au together with Ch-L. In addition, the gold compound represented by AuCh-L, when reacted in a solvent in the presence of silver ions, easily produces AgAuS when Ch is S, AgAuSe when Ch is Se, and AgAuTe when Ch is Te It is what has. Examples of such a compound include those in which L is an acyl group, and other examples include compounds represented by the following formula (AuCh1), formula (AuCh2), and formula (AuCh3).

Formula (AuCh1) R ₁ -X-M-ChAu
Here, Au represents Au (I), Ch represents a sulfur atom, selenium atom or tellurium atom, M represents a substituted or unsubstituted methylene group, X represents an oxygen atom, sulfur atom, selenium atom, NR ₂ R ₁ represents an atomic group (for example, an organic group such as an alkyl group, an aryl group, or a heterocyclic group) that forms a molecule by binding to X, and R ₂ represents a hydrogen atom and a substituent (for example, Represents an organic group such as an alkyl group, an aryl group, and a heterocyclic group. R ₁ and M may be bonded to each other to form a ring.
In the compounds of the formula (AuCh1), Ch is preferably a sulfur atom, and selenium atom, X represents an oxygen atom, a sulfur atom are preferred, R ₁ is an alkyl group, an aryl group is preferable. Examples of more specific compounds include Au (I) salts of thiosugars (α is gold thioglucose such as thioglucose, gold peracetylthioglucose, gold thiomannose, gold thiogalactose, gold thioarabinose, etc.), seleno Au (I) salts of sugars (gold peracetylselenoglucose, gold peracetylselenomannose, etc.), Au (I) salts of tellurosugar, and the like. Here, thio sugar, seleno sugar, and telluro sugar represent compounds in which the anomeric hydroxyl group of the sugar is replaced with an SH group, a SeH group, and a TeH group, respectively.

Formula (AuCh2) W ₁ W ₂ C = CR ₃ ChAu
Here, Au represents Au (I), Ch represents a sulfur atom, a selenium atom, or a tellurium atom, and R ₃ and W ₂ represent substituents (for example, a hydrogen atom, a halogen atom, an alkyl group, and an aryl group). , And an organic group such as a heterocyclic group), and W ₁ represents an electron-withdrawing group having a positive Hammett's substituent constant σ _p value. R ₃ and W ₁ , R ₃ and W ₂ , W ₁ and W ₂ may be bonded to each other to form a ring.
In the compound represented by the formula (AuCh2), those in which Ch is a sulfur atom and a selenium atom are preferable, R ₃ is preferably a hydrogen atom and an alkyl group, and W ₁ and W ₂ are Hammett's substituent constants σ _p An electron withdrawing group having a value of 0.2 or more is preferred. More specific examples of the compound include (NC) ₂ C═CHSAu, (CH ₃ OCO) ₂ C═CHSAu, CH ₃ CO (CH ₃ OCO) C═CHSAu, and the like.

Formula (AuCh3) W ₃ -E-ChAu
Here, Au represents Au (I), Ch represents a sulfur atom, a selenium atom, or a tellurium atom, E represents a substituted or unsubstituted ethylene group, and W ₃ represents a positive Hammett substituent constant σp value. The value represents an electron-withdrawing group.
In the compounds of the formula (AuCh3), Ch sulfur atom, and preferably has a selenium atom, E is an ethylene group having an electron attractive group is a substituent constant sigma _p value is a positive value of Hammett W ₃ is preferably an electron-withdrawing group having Hammett's substituent constant σ _p value of 0.2 or more. The addition amount of these compounds may vary widely depending on the case, but is 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol, preferably 3 × 10 ^{−6 to} 3 × 10 ⁻⁴ mol per mol of silver halide. is there.

  To the silver halide emulsion of the present invention, various compounds or precursors thereof may be added for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing the photographic performance. Can do. Specific examples of these compounds are preferably those described on pages 39 to 72 of JP-A-62-215272. Furthermore, 5-arylamino-1,2,3,4-thiatriazole compounds described in EP 0447647 (the aryl residue has at least one electron-withdrawing group) are also preferably used.

  In the present invention, in order to enhance the storage stability of the silver halide emulsion, both ends are adjacent to the hydroxamic acid derivative described in JP-A-11-109576 and the carbonyl group described in JP-A-11-327094. Cyclic ketones having a double bond substituted with an amino group or a hydroxyl group (particularly those represented by the general formula (S1), paragraph numbers 0036 to 0071 can be incorporated in the present specification), The sulfo-substituted catechol and hydroquinones described in JP-A-11-143011 (for example, 4,5-dihydroxy-1,3-benzenedisulfonic acid, 2,5-dihydroxy-1,4-benzenedisulfonic acid, 3,4- Dihydroxybenzenesulfonic acid, 2,3-dihydroxybenzenesulfonic acid, 2,5-dihydroxybenzenesulfonic acid 3,4,5-trihydroxybenzenesulfonic acid and salts thereof), hydroxylamines represented by the general formula (A) in US Pat. No. 5,556,741 (US Pat. No. 5,556,56) No. 741 column 4, line 56 to column 11, line 22 is preferably applied also in this specification and is incorporated as part of this specification), JP-A-11-102045 The water-soluble reducing agents represented by the general formulas (I) to (III) are also preferably used in the present invention.

  The silver halide emulsion of the present invention may contain a spectral sensitizing dye for the purpose of imparting so-called spectral sensitivity exhibiting photosensitivity in a desired light wavelength range. Examples of spectral sensitizing dyes used for spectral sensitization in the blue, green, and red regions include F.I. M.M. Examples include those described in Harmer's Heterocyclic compounds-Cyanine dyes and related compounds (John Wiley & Sons [New York, London, 1964)]. As specific examples of compounds and spectral sensitization, those described in JP-A-62-215272, page 22, right upper column to page 38 are preferably used. Further, as a red-sensitive spectral sensitizing dye of silver halide emulsion grains having a particularly high silver chloride content, the spectral sensitizing dye described in JP-A-3-123340 is stable, adsorbed, and exposed. This is very preferable from the viewpoint of temperature dependency.

The amount of these spectral sensitizing dyes to be added varies widely depending on the case, and is preferably in the range of 0.5 × 10 ⁻⁶ mol to 1.0 × 10 ⁻² mol per mol of silver halide. More preferably, it is in the range of 1.0 × 10 ⁻⁶ mol to 5.0 × 10 ⁻³ mol.

  The silver halide color photographic light-sensitive material of the present invention (hereinafter sometimes simply referred to as “light-sensitive material”) contains a silver halide emulsion layer containing a yellow dye-forming coupler and a magenta dye-forming coupler on a support. In the silver halide color photographic material having at least one silver halide emulsion layer and a silver halide emulsion layer containing a cyan dye-forming coupler, at least one of the silver halide emulsion layers of the present invention It contains a silver halide emulsion. In the present invention, the silver halide emulsion layer containing the yellow dye-forming coupler contains a yellow coloring layer, the silver halide emulsion layer containing the magenta dye-forming coupler contains a magenta coloring layer, and the cyan dye-forming coupler. The silver halide emulsion layer functions as a cyan color-developing layer. The silver halide emulsions contained in the yellow coloring layer, the magenta coloring layer and the cyan coloring layer, respectively, are sensitive to light in different wavelength regions (for example, light in the blue region, green region and red region). It is preferable to have.

In the present invention, it is preferable that the silver halide emulsion layer contains at least two types of silver halide emulsions having different silver chloride contents having a sensitivity of 90 mol% or more. Two or more types of silver halide emulsions having different sensitivities may be used, but two or three types are preferable in the design of the photosensitive material. When three or more types of silver halide emulsions having different sensitivities are used, the present invention is applied to at least one type of silver halide emulsion. The two types of silver halide emulsions may be different in the type and amount of grain size, halogen composition and structure, sensitizing dye, chemical sensitizer, antifoggant and the like. However, the two silver halide emulsions must have different sensitivities. Sensitivity is preferably 0.05 to 0.8 log E, and is preferably 0.15 to 0.5 log E when image-wise exposure is performed for 10 ⁻⁴ seconds in the configuration of the photosensitive material used and development processing used is performed. More preferably, they are different.

  It is preferable that at least two types of silver halide emulsions having different silver chloride contents of 95 mol% or more having different sensitivities are mixed in the same silver halide emulsion layer. However, emulsions having different sensitivities are mixed in separate emulsion layers. It may be painted separately. However, these layers are required to have almost the same color sensitivity and color hue. Here, in the case of a color photographic light-sensitive material, substantially equal color sensitivities are, for example, blue color sensitivities, green color sensitivities, or red color sensitivities. Good. In the case of a color photographic light-sensitive material, for example, yellow color development, magenta color development, or cyan color development, and the color development hues may be different within the range.

  At least one of the silver halide emulsions having a silver chloride content of 95 mol% or more having at least two different sensitivities contains the above metal complex. Both of the two types of silver halide emulsions having different sensitivities preferably contain the above metal complex, and more preferably all the silver halide emulsions in the silver halide emulsion layer contain the above metal complex.

  In the silver halide emulsion having a silver chloride content of 95 mol% or more having different sensitivities of at least two types, the content of the above metal complex per mol of silver halide is lower on the lower sensitivity side than on the higher sensitivity side. More emulsion is preferred. Furthermore, the average content per grain is preferably higher in the low-sensitivity emulsion than in the high-sensitivity emulsion. In these cases, the above-mentioned metal complex may not be contained in the high-sensitivity emulsion, but is preferably contained in a smaller amount than the emulsion on the low-sensitivity side.

  At least two types of silver halide emulsions having different silver chloride contents with different sensitivities, the desensitization by the above metal complex is larger in the low-sensitivity emulsion than in the high-sensitivity emulsion. preferable. Here, the desensitization by the metal complex represents the sensitivity difference when the corresponding metal complex is not contained in the same emulsion and the sensitivity difference when it is contained, with the desensitization direction being positive. When one of the emulsions does not contain the corresponding metal complex, the desensitization is zero. The desensitization of each of the high-sensitivity emulsion and the low-sensitivity emulsion is preferably 0 to 0.8 log E, and more preferably 0.1 to 0.5 log E. The desensitization due to the corresponding metal complex in the emulsion on the low sensitivity side is preferably 0.1 to 0.8 log E larger than that of the emulsion on the high sensitivity side, and more preferably 0.1 to 0.5 log E larger.

  The light-sensitive material of the present invention may have a hydrophilic colloid layer, an antihalation layer, an intermediate layer, and a colored layer, which will be described later, if desired, in addition to the yellow coloring layer, magenta coloring layer, and cyan coloring layer.

Conventionally known photographic materials and additives can be used in the light-sensitive material of the present invention.
For example, as the photographic support, a transmissive support or a reflective support can be used. As the transmissive support, transparent films such as cellulose nitrate film and polyethylene terephthalate, and polyester of 2,6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG), NDCA, terephthalic acid and EG are used. A polyester provided with an information recording layer such as a magnetic layer is preferably used. In the present invention, a reflective support (also referred to as a reflective support) is preferable, and the reflective support is particularly laminated with a plurality of polyethylene layers or polyester layers, and such a water-resistant resin layer (laminate layer). A reflective support containing a white pigment such as titanium oxide in at least one layer is preferred.

  In the present invention, more preferred reflective supports include those having a polyolefin layer having fine pores on the paper substrate on the side on which the silver halide emulsion layer is provided. The polyolefin layer may consist of multiple layers, in which case the polyolefin layer adjacent to the gelatin layer on the silver halide emulsion layer side preferably has no micropores (eg, polypropylene, polyethylene) and is on a paper substrate. More preferred is a polyolefin (for example, polypropylene or polyethylene) having micropores on the near side. The density of the multi-layer or single-layer polyolefin layer located between the paper substrate and the photographic constituent layer is preferably 0.40 to 1.0 g / ml, more preferably 0.50 to 0.70 g / ml. The thickness of the multilayer or single layer of polyolefin positioned between the paper substrate and the photographic composition layer is preferably 10 to 100 μm, and more preferably 15 to 70 μm. Further, the ratio of the thickness of the polyolefin layer to the paper substrate is preferably 0.05 to 0.2, more preferably 0.1 to 0.15.

  In addition, it is also preferable to provide a polyolefin layer on the opposite side (back surface) to the photographic constituent layer of the paper substrate from the viewpoint of increasing the rigidity of the reflective support. In this case, the back surface polyolefin layer has a matte polyethylene surface. Alternatively, polypropylene is preferable, and polypropylene is more preferable. The polyolefin layer on the back surface is preferably 5 to 50 μm, more preferably 10 to 30 μm, and further preferably the density is 0.7 to 1.1 g / ml. In the reflective support in the present invention, preferred embodiments relating to the polyolefin layer provided on the paper substrate are disclosed in JP-A-10-333277, JP-A-10-333278, JP-A-11-52513, and JP-A-11-65024. Examples are described in EP0880065 and EP0880066.

Furthermore, it is preferable to contain a fluorescent brightening agent in the water-resistant resin layer. Further, a hydrophilic colloid layer containing the fluorescent brightening agent in a dispersed manner may be separately formed. As the optical brightener, benzoxazole-based, coumarin-based, and pyrazoline-based compounds can be preferably used, and benzoxazolylnaphthalene-based and benzoxazolyl stilbene-based fluorescent brighteners are more preferable. Although the usage-amount is not specifically limited, Preferably it is 1-100 mg / m < ² >. The mixing ratio in the case of mixing with a water-resistant resin is preferably 0.0005 to 3 mass%, more preferably 0.001 to 0.5 mass%, based on the resin.

  The reflective support may be a transmissive support or a reflective colloid coated with a hydrophilic colloid layer containing a white pigment. Further, the reflective support may be a support having a specular or second-type diffuse reflective metal surface.

  Further, as a support used in the light-sensitive material of the present invention, a white polyester support or a support in which a layer containing a white pigment is provided on a support having a silver halide emulsion layer is used for a display. May be. In order to further improve the sharpness, an antihalation layer is preferably coated on the silver halide emulsion layer coating side or the back surface of the support. In particular, the transmission density of the support is preferably set in the range of 0.35 to 0.8 so that the display can be viewed with either reflected light or transmitted light.

  In the light-sensitive material of the present invention, a dye which can be decolored by processing as described in pages 27 to 76 of European Patent EP0,337,490A2 is applied to a hydrophilic colloid layer for the purpose of improving the sharpness of an image. Among them, oxonol dyes are added so that the optical reflection density at 680 nm of the light-sensitive material is 0.70 or more, or divalent to tetravalent alcohols (for example, trimethylolethane) are added to the water-resistant resin layer of the support. ) Etc. It is preferable to contain 12% by mass or more (more preferably 14% by mass or more) of titanium oxide surface-treated.

  In the light-sensitive material of the present invention, the processing described in pages 27 to 76 of EP 0337490 A2 is carried out on the hydrophilic colloid layer for the purpose of preventing irradiation and halation or improving the safety light safety. It is preferable to add a decolorizable dye (in particular, an oxonol dye or a cyanine dye). Furthermore, the dyes described in European Patent EP0819977 are also preferably added to the present invention. Some of these water-soluble dyes degrade color separation and safelight safety when the amount used is increased. As a dye that can be used without deteriorating color separation, water-soluble dyes described in JP-A Nos. 5-127324, 5-127325, and 5-216185 are preferable.

  In the present invention, a colored layer that can be decolored by treatment in place of the water-soluble dye or in combination with the water-soluble dye is used. The colored layer that can be decolored by the treatment used may be in direct contact with the emulsion layer, or may be disposed so as to be in contact with an intermediate layer containing a treatment color mixing inhibitor such as gelatin or hydroquinone. This colored layer is preferably placed under the emulsion layer (support side) that develops the same primary color as the colored color. It is possible to install all the colored layers corresponding to each primary color individually, or to select and install only some of them. It is also possible to install a colored layer that has been colored corresponding to a plurality of primary color gamuts. The optical reflection density of the colored layer is the wavelength having the highest optical density in the wavelength range used for exposure (visible light range of 400 nm to 700 nm for normal printer exposure, wavelength of the scanning exposure light source used for scanning exposure). The optical density value at is preferably 0.2 or more and 3.0 or less. More preferably, it is 0.5 or more and 2.5 or less, and particularly preferably 0.8 or more and 2.0 or less.

  In order to form the colored layer, a conventionally known method can be applied. For example, the dyes described in JP-A-2-282244, page 3 from the upper right column to page 8, and the dyes described in JP-A-3-7931, page 3 from upper right column to page 11, lower left column are solid. A method of incorporating a hydrophilic colloid layer in the form of a fine particle dispersion, a method of mordanting an anionic dye into a cationic polymer, a method of adsorbing a dye to fine particles such as silver halide and fixing it in the layer, JP-A-1-239544 For example, a method using colloidal silver as described in Japanese Patent Publication. As a method of dispersing a fine powder of a pigment in a solid state, for example, a method of containing a fine powder dye which is substantially water-insoluble at least at pH 6 or less but substantially water-soluble at least at pH 8 or more is disclosed in Japanese Patent Application Laid-Open No. Hei. No. 2-308244, pages 4 to 13. Further, for example, a method for mordanting an anionic dye into a cationic polymer is described on pages 18 to 26 of JP-A-2-84737. US Pat. Nos. 2,688,601 and 3,459,563 show preparation methods for colloidal silver as a light absorber. Among these methods, a method of containing a fine powder dye and a method of using colloidal silver are preferable.

  The silver halide photographic light-sensitive material of the present invention is used for a color negative film, a color positive film, a color reversal film, a color reversal photographic paper, a color photographic paper, etc., among which it is preferably used as a color photographic paper. The color photographic paper preferably has at least one yellow color-forming silver halide emulsion layer, magenta color-forming silver halide emulsion layer, and cyan color-forming silver halide emulsion layer. The silver halide emulsion layer is a yellow color forming silver halide emulsion layer, a magenta color forming silver halide emulsion layer, and a cyan color forming silver halide emulsion layer in order from the support.

However, a different layer structure may be used.
The silver halide emulsion layer containing a yellow coupler may be disposed at any position on the support. However, when the yellow coupler-containing layer contains silver halide tabular grains, a magenta coupler-containing silver halide is contained. It is preferably coated at a position farther from the support than at least one of the emulsion layer or the cyan coupler-containing silver halide emulsion layer. Further, from the viewpoints of accelerating color development, accelerating desilvering, and reducing residual color by sensitizing dye, the yellow coupler-containing silver halide emulsion layer is coated at a position farthest from the support than other silver halide emulsion layers. It is preferable to be provided. Further, from the viewpoint of reducing Blix fading, the cyan coupler-containing silver halide emulsion layer is preferably the center layer of other silver halide emulsion layers, and from the viewpoint of reducing photobleaching, cyan coupler-containing silver halide emulsion layers. Is preferably the lowermost layer. Each of the color developing layers of yellow, magenta and cyan may be composed of two layers or three layers. For example, couplers containing no silver halide emulsion, as described in JP-A-4-75055, 9-1114035, 10-246940, US Pat. No. 5,576,159, etc. It is also preferable to provide a layer adjacent to the silver halide emulsion layer to form a coloring layer.

  As silver halide emulsions and other materials (additives, etc.) and photographic composition layers (layer arrangement, etc.) applied in the present invention, and processing methods and processing additives applied to process this photosensitive material, Disclosed in JP-A-62-215272, JP-A-2-33144, European Patent EP0,355,660A2, and particularly described in European Patent EP0,355,660A2. Are preferably used. Furthermore, JP-A-5-34889, JP-A-4-359249, JP-A-4-313733, JP-A-4-270344, JP-A-5-66527, JP-A-4-34548, JP-A-4-145433. No. 2-854, No. 1-158431, No. 2-90145, No. 3-194539, No. 2-93641, EP-A-0520457A2, and the like. A silver halide color photographic light-sensitive material and a processing method thereof are also preferable.

  In particular, in the present invention, the reflection type support and silver halide emulsion described above, further different metal ion species doped in the silver halide grains, storage stabilizer or antifoggant for silver halide emulsion, chemical enhancement, Sensitization method (sensitizer), spectral sensitization method (spectral sensitizer), cyan, magenta, yellow coupler and its emulsifying dispersion method, color image preservability improving agent (stain inhibitor and anti-fading agent), dye (coloring) As for the layer), gelatin type, layer structure of the photosensitive material, and coating pH of the photosensitive material, those described in each part of the patent shown in Table 1 below are particularly preferably applied.

Other examples of cyan, magenta and yellow couplers used in the present invention include those described in JP-A-62-215272, page 91, upper right column, line 4 to page 121, upper left column, line 6; JP-A-2-33144. Page 3, upper right column, line 14 to page 18, upper left column, last line, page 30, upper right column, line 6 to page 35, lower right column, line 11 and page 0, line 15 to 27 of EP0355,660A2. Couplers described in the 5th line, 5th page, 30th line to 28th page, 45th page, 29th line to 31st line, 47th page, 23rd line to 63rd page, 50th line are also useful.
In the present invention, compounds represented by general formulas (II) and (III) of WO 98/33760 and general formula (D) of JP-A-10-221825 may be preferably added.

  As a cyan dye-forming coupler (sometimes simply referred to as “cyan coupler”) that can be used in the present invention, a pyrrolotriazole coupler is preferably used, and is represented by the general formula (I) or (II) of JP-A-5-313324. ), Couplers represented by general formula (I) of JP-A-6-347960, and exemplified couplers described in these patents are particularly preferred. Phenol-based and naphthol-based cyan couplers are also preferable. For example, cyan couplers represented by the general formula (ADF) described in JP-A-10-333297 are preferable. Other cyan couplers include pyrroloazole-type cyan couplers described in EP 0488248 and EP 0491197A1, and 2,5-diacylaminophenol couplers described in US Pat. No. 5,888,716. US Pat. Nos. 4,873,183 and 4,916,051, pyrazoloazole type cyan couplers having an electron-attracting group and a hydrogen-bonding group at the 6-position, Pyrazoloazole type cyan couplers having a carbamoyl group at the 6-position described in JP-A-8-171185, JP-A-8-311360, and JP-A-8-339060 are also preferable.

  Further, in addition to the diphenylimidazole cyan coupler described in JP-A-2-33144, a 3-hydroxypyridine cyan coupler described in European Patent EP 0333185A2 (among others of the coupler (42) listed as a specific example). A 4-equivalent coupler having a chlorine leaving group to give 2 equivalents, couplers (6) and (9) are particularly preferred) and cyclic active methylene-based cyan couplers described in JP-A 64-32260 (among others) Examples of couplers 3, 8, and 34 listed as specific examples are particularly preferred), pyrrolopyrazole cyan couplers described in EP 0456226A1, and pyrroloimidazole cyan couplers described in EP 0484909 are used. You can also.

  Of these cyan couplers, pyrroloazole cyan couplers represented by the general formula (I) described in JP-A No. 11-282138 are particularly preferred. The couplers (1) to (47) are applied to the present specification as they are, and are preferably incorporated as a part of the present specification.

  Examples of the magenta dye-forming coupler used in the present invention (sometimes simply referred to as “magenta coupler”) include 5-pyrazolone-based magenta couplers and pyrazoloazole-based magenta couplers described in the publicly known literatures in the above table. Among them, a secondary or tertiary alkyl group as described in JP-A-61-65245 is the 2, 3, or 6 position of the pyrazolotriazole ring among them in terms of hue, image stability, color developability, etc. A pyrazolotriazole coupler directly connected to a pyrazoloazole coupler containing a sulfonamide group in the molecule as described in JP-A-61-65246, as described in JP-A-61-147254 Pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group, European Patent No. 226,849A, Use of pyrazoloazole couplers having a 6-position alkoxy or aryloxy group as described in the 294,785A Pat are preferred. In particular, the magenta coupler is preferably a pyrazoloazole coupler represented by the general formula (M-I) described in JP-A-8-122984, and paragraphs 0009 to 0026 of the patent are applied to the present specification as they are. , Incorporated herein as part of this specification. In addition to this, pyrazoloazole couplers having sterically hindered groups at both the 3-position and the 6-position described in EP 854384 and EP 844640 are also preferably used.

  Further, as yellow dye-forming couplers (sometimes simply referred to as “yellow couplers”), in addition to the compounds described in the above table, a 3- to 5-membered cyclic group is added to the acyl group described in European Patent EP 0447969A1. An acylacetamide type yellow coupler having a structure, a malondianilide type yellow coupler having a cyclic structure described in European Patent EP 0 482 552 A1, European Patent Publication Nos. 935870A1, 953871A1, and 957,72A1 Pyrrole-2 or 3-yl or indole-2 or 3-ylcarbonylacetic acid anilide type couplers described in U.S. Pat. Nos. 5,953,873, 953874, 1,953875A1, etc. Described in the specification of 5,118,599 Acylacetamide yellow couplers or JP acetanilide type yellow couplers heterocyclic acyl group is substituted as described in 2003-173007 JP preferably used having a dioxane structure. Among them, an acylacetamide type yellow coupler in which the acyl group is a 1-alkylcyclopropane-1-carbonyl group, a malondianilide type yellow coupler in which one of the anilides constitutes an indoline ring, or an acetanilide in which a heterocyclic ring is substituted on the acyl group The use of type yellow couplers is preferred. These couplers can be used alone or in combination.

  The coupler used in the present invention is impregnated into a loadable latex polymer (eg, US Pat. No. 4,203,716) in the presence (or absence) of the high boiling organic solvent described in the above table. Alternatively, it is preferably dissolved together with a water-insoluble and organic solvent-soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution. Water-insoluble and organic solvent-soluble polymers that can be preferably used are described in U.S. Pat. No. 4,857,449, columns 7 to 15, and International Publication WO 88/00723, pages 12 to 30. The described homopolymers or copolymers are mentioned. More preferably, use of a methacrylate or acrylamide polymer, particularly an acrylamide polymer is preferred in view of color image stability.

In the present invention, known color mixing inhibitors can be used, and among them, those described in the following patents are preferable.
For example, high molecular weight redox compounds described in JP-A-5-333501, phenidone and hydrazine compounds described in WO98 / 33760, US Pat. No. 4,923,787, etc. White couplers described in Japanese Patent No. 249637, Japanese Patent Application Laid-Open No. 10-282615, German Patent No. 19629142A1, and the like can be used. In particular, in the case of increasing the pH of the developer to speed up development, German Patent No. 19618786A1, European Patent No. 839623A1, European Patent No. 842975A1, German Patent No. 180686846A1 And redox compounds described in French Patent No. 2760460A1 are also preferable.

  In the present invention, a compound having a triazine skeleton with a high molar extinction coefficient is preferably used as the ultraviolet absorber, and for example, compounds described in the following patent specifications can be used. These are preferably added to the photosensitive layer and / or the non-photosensitive layer. For example, JP-A-46-3335, JP-A-55-15276, JP-A-5-197074, JP-A-5-232630, JP-A-5-307232, JP-A-6-218131, and 8- No. 53427, No. 8-234364, No. 8-239368, No. 9-31067, No. 10-115898, No. 10-147777, No. 10-182621, German Patent No. The compounds described in the specification of 19739797A, European Patent No. 711804A and JP-A-8-501291 can be used.

As the binder or protective colloid that can be used in the light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic colloids can be used alone or in combination with gelatin. As a preferable gelatin, the heavy metal contained as impurities such as iron, copper, zinc and manganese is preferably 5 ppm or less, more preferably 3 ppm or less. The amount of calcium contained in the light-sensitive material is preferably 20 mg / m ² or less, more preferably 10 mg / m ² or less, and most preferably 5 mg / m ² or less.

  In the present invention, an antibacterial / antifungal agent as described in JP-A-63-271247 is added in order to prevent various wrinkles and bacteria that propagate in the hydrophilic colloid layer and degrade the image. Is preferred. Further, the film pH of the photosensitive material is preferably 4.0 to 7.0, more preferably 4.0 to 6.5.

Total Coating amount of gelatin photographic constituent layer in the present invention is more preferably preferably not more than 3 g / ^{m 2} or more 6 g / ^{m 2,} is 3 g / ^{m 2} or more 5 g / ^{m 2} or less. Further, even in the case of ultra-rapid processing, in order to satisfy development progress, fixing bleachability, and residual color, the film thickness of the entire photographic constituent layer is preferably 3 μm to 7.5 μm, and more preferably 3 μm to 6. It is preferably 5 μm. The dry film thickness can be measured by measuring the change in film thickness before and after peeling the dry film, or by observing the cross section with an optical microscope or an electron microscope. In the present invention, the swelling film thickness is preferably 8 μm to 19 μm, and more preferably 9 μm to 18 μm, in order to achieve both development progress and increase in the drying speed. The swelling film thickness can be measured by the dot method in a state where the dried photosensitive material is immersed in an aqueous solution at 35 ° C. and swelled to reach a sufficient equilibrium. Coated silver amount in the present invention ^is more preferably is preferably ^{0.2g / m 2 ~0.5g / m 2} , a ^{0.2g / m 2 ~0.45g / m 2} , 0.2g and most preferably / ^{m 2} ~0.40g / ^m 2.

In the present invention, a surfactant can be added to the photosensitive material from the viewpoints of improving the coating stability of the photosensitive material, preventing the generation of static electricity, and adjusting the charge amount. Examples of the surfactant include an anionic surfactant, a cationic surfactant, a betaine surfactant, and a nonionic surfactant, and examples thereof include those described in JP-A-5-333492. The surfactant used in the present invention is preferably a fluorine atom-containing surfactant. In particular, a fluorine atom-containing surfactant can be preferably used. These fluorine atom-containing surfactants may be used alone or in combination with other conventionally known surfactants, but are preferably used in combination with other conventionally known surfactants. The amount of these surfactants added to the light-sensitive material is not particularly limited, but is generally 1 × 10 ^{−5 to} 1 g / m ² , preferably 1 × 10 ⁻⁴ to 1 × 10 ^{−. 1} g / m ² , more preferably 1 × 10 ⁻³ to 1 × 10 ⁻² g / m ² .

The photosensitive material of the present invention can form an image by an exposure process in which light is irradiated according to image information and a development process in which the photosensitive material irradiated with light is developed.
The photosensitive material of the present invention is suitable for a scanning exposure system using a cathode ray (CRT) in addition to being used in a printing system using a normal negative printer. The cathode ray tube exposure apparatus is simpler and more compact and less expensive than an apparatus using a laser. Also, the adjustment of the optical axis and color is easy. As the cathode ray tube used for image exposure, various light emitters that emit light in the spectral region are used as necessary. For example, any one of red light emitters, green light emitters, and blue light emitters, or a mixture of two or more thereof may be used. The spectral region is not limited to the above red, green, and blue, and a phosphor that emits light in the yellow, orange, purple, or infrared region is also used. In particular, a cathode ray tube that emits white light by mixing these light emitters is often used.

  When the photosensitive material has a plurality of photosensitive layers having different spectral sensitivity distributions, and the cathode tube also has a phosphor exhibiting light emission in a plurality of spectral regions, a plurality of colors are exposed at the same time, that is, a plurality of colors are applied to the cathode ray tube. It is also possible to emit light from the tube surface by inputting a color image signal. A method of sequentially inputting image signals for each color to cause each color to emit light sequentially and exposing through a film that cuts the colors other than that color (surface sequential exposure) may be adopted. However, since a high-resolution cathode ray tube can be used, it is preferable for improving image quality.

  The photosensitive material of the present invention is a monochromatic high light source such as a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser, or a second harmonic light source (SHG) using a combination of a solid state laser using a semiconductor laser and a nonlinear optical crystal. A digital scanning exposure method using density light is preferably used. In order to make the system compact and inexpensive, it is preferable to use a second harmonic generation light source (SHG) that combines a semiconductor laser, a semiconductor laser, or a solid-state laser and a nonlinear optical crystal. In particular, in order to design a compact, inexpensive, long-life and high-stability device, it is preferable to use a semiconductor laser, and at least one of the exposure light sources is preferably a semiconductor laser.

When such a scanning exposure light source is used, the spectral sensitivity maximum wavelength of the photosensitive material of the present invention can be arbitrarily set according to the wavelength of the scanning exposure light source to be used. In a solid laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser and a nonlinear optical crystal, the oscillation wavelength of the laser can be halved, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the photosensitive material can be given to the usual three wavelength regions of blue, green, and red. When the exposure time in such scanning exposure is defined as the time for exposing the pixel size when the pixel density is 400 dpi, the preferable exposure time is 1 × 10 ⁻⁴ seconds or less, more preferably 1 × 10 ⁻⁶ seconds. It is as follows.

When the present invention is applied to a silver halide color photographic light-sensitive material, it is preferable to perform imagewise exposure with a blue laser coherent light having an emission wavelength of 420 nm to 460 nm. Among blue lasers, it is particularly preferable to use a blue semiconductor laser.
Specifically, as a laser light source, a blue semiconductor laser having a wavelength of 430 to 450 nm (announced by Nichia Chemical Co., Ltd. at the 48th Applied Physics Related Conference in March 2001) and a semiconductor laser (oscillation wavelength of about 940 nm) are used. waveguide-like inverted domain structure about 470nm blue laser taken out by wavelength conversion by the SHG crystal of LiNbO ₃ having the semiconductor laser SHG crystal of LiNbO ₃ having a reversal domain structure of (oscillation wavelength of about 1060 nm) a waveguide-like A green laser having a wavelength of about 530 nm, a red semiconductor laser having a wavelength of about 685 nm (Hitachi type No. HL6738MG), a red semiconductor laser having a wavelength of about 650 nm (Hitachi type No. HL6501MG), and the like are preferably used.

  The silver halide photographic light-sensitive material of the present invention can be preferably used in combination with the exposure and development systems described in the following known materials. Examples of the developing system include an automatic printing and developing system described in JP-A-10-333253, a photosensitive material conveying apparatus described in JP-A-2000-10206, and an image reading apparatus described in JP-A-11-215312. , An exposure system comprising a color image recording system described in JP-A-11-88619 and JP-A-10-202950, and a digital photo print including a remote diagnosis system described in JP-A-10-210206 And a photo print system including an image recording apparatus described in Japanese Patent Laid-Open No. 2000-310822.

  Preferred scanning exposure systems applicable to the present invention are described in detail in the patent specifications listed in the above table.

When the light-sensitive material of the present invention is subjected to printer exposure, it is preferable to use a band stop filter described in US Pat. No. 4,880,726. This removes light color mixing and remarkably improves color reproducibility.
In the present invention, as described in European Patents EP0789270A1 and EP0789480A1, the yellow microdot pattern may be pre-exposed in advance and copy control may be performed before image information is added. .

  In the processing of the photosensitive material of the present invention, JP-A-2-207250, page 26, lower right column, line 1 to page 34, upper right column, line 9 and JP-A-4-97355, page 5, upper left column. The processing materials and processing methods described in the 17th line to the 18th page, lower right column, 20th line are preferably applicable. As the preservative used in the developer, compounds described in the patent specifications listed in the above table are preferably used.

The present invention is applied as a light-sensitive material having rapid processing suitability. The color development time is 28 seconds or less, preferably 25 seconds or less and 6 seconds or more, more preferably 20 seconds or less and 6 seconds or more. Similarly, the bleach-fixing time is preferably 30 seconds or shorter, more preferably 25 seconds or shorter and 6 seconds or longer, more preferably 20 seconds or shorter and 6 seconds or longer. The washing or stabilizing time is preferably 60 seconds or less, more preferably 40 seconds or less and 6 seconds or more.
The color development time refers to the time from when the photosensitive material enters the color developer until it enters the bleach-fixing solution in the next processing step. For example, when processed by an automatic developing machine, the time during which the photosensitive material is immersed in the color developer (so-called submerged time) and the photosensitive material leaves the color developer for bleaching and fixing in the next processing step. The total of both the time during which air is conveyed toward the bath (so-called air time) is referred to as color development time. Similarly, the bleach-fixing time refers to the time from when the photosensitive material enters the bleach-fixing solution until the next washing or stabilizing bath. The water washing or stabilization time refers to the time (so-called liquid time) that the photosensitive material is in the liquid for the drying process after entering the water washing or stabilizing liquid.

The light-sensitive material of the present invention can be developed after exposure using a conventional developing method containing an alkali agent and a developing agent, an activator such as an alkaline solution containing the developing agent in the photosensitive material and not containing the developing agent. In addition to a wet method such as a method of developing with a beta solution, a thermal development method that does not use a processing solution can be used. In particular, the activator method is a preferable method from the viewpoint of environmental protection because it does not contain a developing agent in the processing solution, so that the processing solution can be easily managed and handled, and the load during processing of the waste liquid is small.
In the activator method, as a developing agent or a precursor thereof incorporated in the photosensitive material, for example, JP-A-8-234388, JP-A-9-152686, JP-A-9-152893, and JP-A-9-212814. The hydrazine type compounds described in JP-A-9-160193 are preferred.

  Further, a developing method in which the amount of silver applied to the photosensitive material is reduced and image amplification processing (compensation processing) using hydrogen peroxide is preferably used. In particular, it is preferable to use this method for the activator method. Specifically, an image forming method using an activator solution containing hydrogen peroxide described in JP-A-8-297354 and 9-152695 is preferably used. In the activator method, after processing with an activator solution, desilvering is usually performed. However, in the image amplification processing method using a low silver amount of light-sensitive material, desilvering is omitted and washing or stabilization is simplified. Can be done. Further, in a method of reading image information from a photosensitive material with a scanner or the like, it is possible to adopt a processing form that does not require a desilvering process even when a high silver amount photosensitive material such as a photographic photosensitive material is used.

  For the activator solution, desilvering solution (bleaching / fixing solution), water washing and stabilizing solution used in the present invention, known processing materials and processing methods can be used. Preferably, those described in Research Disclosure Item 36544 (September 1994), pages 536 to 541 and JP-A-8-234388 can be used.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1
(Preparation of blue-sensitive layer emulsion BH-1)
High silver chloride cubic particles were prepared by a method in which silver nitrate and sodium chloride were simultaneously added to and mixed with deionized distilled water containing stirred deionized gelatin. In the course of this preparation, Cs ₂ [OsCl ₅ (NO)] was added from 60% to 80% addition of silver nitrate. From the 80% to 90% addition of silver nitrate, potassium bromide (1.5 mol% per mole of finished silver halide) and K ₄ [Fe (CN) ₆ ] were added. K ₂ [IrCl ₆ ] was added from 83% to 88% addition of silver nitrate. K ₂ [IrCl ₅ (H ₂ O)] and K [IrCl ₄ (H ₂ O) ₂ ] were added from 92% to 98% addition of silver nitrate. When 94% of the addition of silver nitrate was completed, potassium iodide (0.27 mol% per mol of the finished silver halide) was added with vigorous stirring. The obtained emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.54 μm and a coefficient of variation of 8.5%. This emulsion was subjected to precipitation desalting treatment, and gelatin, compounds Ab-1, Ab-2, Ab-3, and calcium nitrate were added thereto and redispersed.

The redispersed emulsion was dissolved at 40 ° C., and sensitizing dye S-1, sensitizing dye S-2, and sensitizing dye S-3 were added so as to optimize spectral sensitization. Next, sodium benzenethiosulfate, triethylthiourea as a sulfur sensitizer, and compound-1 as a gold sensitizer were added and ripened so as to optimize chemical sensitization. Thereafter, 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound-2, compound-3 having compound 2 or 3 as a main component (terminal X ₁ and X ₂ are hydroxyl groups), Compound -4 and potassium bromide were added to complete the chemical sensitization. The emulsion thus obtained was designated as Emulsion BH-1.

(Preparation of blue-sensitive layer emulsion BL-1)
In preparation of emulsion BH-1, the temperature and the addition speed of the step of adding and mixing silver nitrate and sodium chloride at the same time were changed, and the amounts of various metal complexes added during the addition of silver nitrate and sodium chloride were changed. Thus, emulsion grains were obtained. The emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.44 μm and a coefficient of variation of 9.5%. After redispersing this emulsion, Emulsion BL-1 was prepared in the same manner except that the amount of various compounds added was changed from that of BH-1.

(Preparation of green sensitive layer emulsion GH-1)
Silver nitrate aqueous solution and sodium chloride were simultaneously added to the stirred deionized distilled water containing deionized gelatin while stirring by the control double jet (CDJ) method to prepare high silver chloride cubic particles. In the course of this preparation, potassium bromide (2 mol% per mol of the finished silver halide) was added from the point of 80% to 90% addition of silver nitrate. Further, K ₄ [Ru (CN) ₆ ] was added so as to be 1 × 10 ⁻⁵ mol / mol silver with respect to the total silver amount from the time point when addition of silver nitrate was 80% to 90%. From the time when the addition of silver nitrate was 83% to 88%, K ₂ [IrCl ₆ ] was added so as to be 1 × 10 ⁻⁷ mol / mol silver based on the total silver amount. The obtained emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.42 μm and a coefficient of variation of 8.0%. This emulsion was subjected to precipitation desalting by a conventional flocculation method, and then gelatin, compounds Ab-1, Ab-2, Ab-3, and calcium nitrate were added and redispersed.

  This emulsion was dissolved at 40 ° C. and sodium benzenethiosulfate, p-glutaramide phenyl disulfide, sodium thiosulfate pentahydrate as a sulfur sensitizer and (bis (1,4,5-trimethyl-1) as a gold sensitizer. , 2,4-triazolium-3-thiolate) orate (I) tetrafluoroborate) and ripened to optimize chemical sensitization. Thereafter, 1- (3-acetamidophenyl) -5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound-2, compound-4 and potassium bromide were added. Furthermore, spectral sensitization was performed by adding sensitizing dyes S-4, S-5, S-6 and S-7 as sensitizing dyes during the emulsion preparation process. The emulsion thus obtained was designated as Emulsion GH-1.

(Preparation of emulsion RH-1 for red-sensitive layer)
High silver chloride cubic particles were prepared by a method in which silver nitrate and sodium chloride were simultaneously added to and mixed with deionized distilled water containing stirred deionized gelatin. In the course of this preparation, Cs ₂ [OsCl ₅ (NO)] was added from 60% to 80% addition of silver nitrate. K ₄ [Ru (CN) ₆ ] was added from the time point when the addition of silver nitrate was 80% to 90%. Potassium bromide (1.3 mol% per mol of finished silver halide) was added from the 80% to 100% addition of silver nitrate. K ₂ [IrCl ₅ (5-methylthiazole)] was added from 83% to 88% when silver nitrate was added. When the addition of silver nitrate was completed 88%, potassium iodide (amount of silver iodide to be 0.05 mol% per mol of finished silver halide) was added with vigorous stirring. Further, K ₂ [IrCl ₅ (H ₂ O)] and K [IrCl ₄ (H ₂ O) ₂ ] were added when the addition of silver nitrate was 92% to 98%. The obtained emulsion grains were monodispersed cubic silver iodobromochloride emulsion grains having a cube side length of 0.39 μm and a coefficient of variation of 10%. The obtained emulsion was subjected to precipitation desalting and redispersion in the same manner as described above.

  This emulsion is dissolved at 40 ° C., and sensitizing dye S-8, compound-5, triethylthiourea as sulfur sensitizer and compound-1 as gold sensitizer are added to optimize chemical sensitization. Aged. Thereafter, 1- (3-acetamidophenyl) -5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound-2, compound-4, and potassium bromide were added. The emulsion thus obtained was designated as Emulsion RH-1.

(Preparation of emulsion RL-1 for red-sensitive layer)
In preparation of emulsion RH-1, the temperature and rate of addition of silver nitrate and sodium chloride are added and mixed, and the amounts of various metal complexes added during the addition of silver nitrate and sodium chloride are changed. Thus, emulsion grains were obtained. The emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.29 μm and a coefficient of variation of 9.9%. This emulsion was subjected to precipitation desalting treatment and redispersion, and then emulsion RL-1 was prepared in the same manner except that the amount of various compounds added was changed from that of emulsion RH-1.

Preparation of first layer coating solution 34 g of yellow coupler (Ex-Y), 1 g of color image stabilizer (Cpd-1), 1 g of color image stabilizer (Cpd-2), 8 g of color image stabilizer (Cpd-8), color image 1 g of stabilizer (Cpd-18), 2 g of color image stabilizer (Cpd-19), 15 g of color image stabilizer (Cpd-20), 1 g of color image stabilizer (Cpd-21), color image stabilizer (Cpd-23) 15 g, 0.1 g of additive (ExC-1), 1 g of color image stabilizer (UV-A) 23 g of solvent (Solv-4), 4 g of solvent (Solv-6), 23 g of solvent (Solv-9) and acetic acid Dissolve in 60 ml of ethyl, and emulsify and disperse this liquid in 270 g of a 20% by weight gelatin aqueous solution containing 4 g of sodium dodecylbenzenesulfonate using a high-speed stirring emulsifier (dissolver), and add 900 g of emulsion dispersion A by adding water. did.
On the other hand, the emulsified dispersion A and the emulsions BH-1 and BL-1 were mixed and dissolved to prepare a first layer coating solution having a composition described later. The emulsion coating amount indicates the silver coating amount.

The coating solutions for the second to seventh layers were prepared in the same manner as the first layer coating solution. As the gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt (H-1), (H-2), (H-3) was used. Further, each layer Ab-1, Ab-2, and Ab-3 the total amount each ^{15.0mg / m 2, 60.0mg / m} 2, 5.0mg / m 2 and 10.0 mg / ^{m 2} and so as Added to.

1- (3-Methylureidophenyl) -5-mercaptotetrazole was added to the second, fourth and sixth layers, 0.2 mg / m ² , 0.2 mg / m ² and 0.6 mg / m ^{2 respectively.} It added so that it might become. For the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene is respectively 1 × 10 ⁻⁴ mol, 2 ×, per mol of silver halide. ^10-4 mol was added. 0.05 g / m ² of a copolymer latex of methacrylic acid and butyl acrylate (mass ratio 1: 1, average molecular weight 200,000 to 400,000) was added to the red sensitive emulsion layer. The second layer, was added the fourth layer and the sixth layer in disodium catechol-3,5-disulfonate as respectively a ^{6mg / m 2, 6mg / m} 2, 18mg / m 2. Sodium polystyrene sulfonate was added to each layer as necessary to adjust the viscosity of the coating solution. In order to prevent irradiation, the following dyes were added (the amount in parentheses represents the coating amount).

(Layer structure)
The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.
Support Polyethylene resin-laminated paper [White pigment (TiO ₂ ; content: 16% by mass, ZnO; content: 4% by mass), polyethylene brightening agent (4,4′-bis (5- Methylbenzoxazolyl) stilbene (content 0.03% by mass) and bluish dye (ultraviolet, content 0.33% by mass) The amount of polyethylene resin is 29.2 g / m ² )
First layer (blue photosensitive emulsion layer)
Emulsion (5: 5 mixture of BH-1 and BL-1 (silver molar ratio)) 0.16
Gelatin 1.32
Yellow coupler (Ex-Y) 0.34
Color image stabilizer (Cpd-1) 0.01
Color image stabilizer (Cpd-2) 0.01
Color image stabilizer (Cpd-8) 0.08
Color image stabilizer (Cpd-18) 0.01
Color image stabilizer (Cpd-19) 0.02
Color image stabilizer (Cpd-20) 0.15
Color image stabilizer (Cpd-21) 0.01
Color image stabilizer (Cpd-23) 0.15
Additive (ExC-1) 0.001
Color image stabilizer (UV-A) 0.01
Solvent (Solv-4) 0.23
Solvent (Solv-6) 0.04
Solvent (Solv-9) 0.23

Second layer (color mixing prevention layer)
Gelatin 0.78
Color mixing inhibitor (Cpd-4) 0.05
Color mixing inhibitor (Cpd-12) 0.01
Color image stabilizer (Cpd-5) 0.006
Color image stabilizer (Cpd-6) 0.05
Color image stabilizer (UV-A) 0.06
Color image stabilizer (Cpd-7) 0.006
Preservative (Cpd-24) 0.006
Solvent (Solv-1) 0.06
Solvent (Solv-2) 0.06
Solvent (Solv-5) 0.07
Solvent (Solv-8) 0.07

Third layer (green photosensitive emulsion layer)
Emulsion (GH-1) 0.12
Gelatin 0.95
Magenta coupler (ExM) 0.12
UV absorber (UV-A) 0.03
Color image stabilizer (Cpd-2) 0.01
Color image stabilizer (Cpd-6) 0.08
Color image stabilizer (Cpd-7) 0.005
Color image stabilizer (Cpd-8) 0.01
Color image stabilizer (Cpd-9) 0.01
Color image stabilizer (Cpd-10) 0.005
Color image stabilizer (Cpd-11) 0.0001
Color image stabilizer (Cpd-20) 0.01
Solvent (Solv-3) 0.06
Solvent (Solv-4) 0.12
Solvent (Solv-6) 0.05
Solvent (Solv-9) 0.16

Fourth layer (color mixing prevention layer)
Gelatin 0.65
Color mixing inhibitor (Cpd-4) 0.04
Color mixing inhibitor (Cpd-12) 0.01
Color image stabilizer (Cpd-5) 0.005
Color image stabilizer (Cpd-6) 0.04
Color image stabilizer (UV-A) 0.05
Color image stabilizer (Cpd-7) 0.005
Preservative (Cpd-24) 0.005
Solvent (Solv-1) 0.05
Solvent (Solv-2) 0.05
Solvent (Solv-5) 0.06
Solvent (Solv-8) 0.06

5th layer (red photosensitive emulsion layer)
Emulsion (4: 6 mixture of RH-1 and RL-1 (silver molar ratio)) 0.10
Gelatin 1.11
Cyan coupler (ExC-1) 0.11
Cyan coupler (ExC-2) 0.01
Cyan coupler (ExC-3) 0.04
Color image stabilizer (Cpd-1) 0.03
Color image stabilizer (Cpd-7) 0.01
Color image stabilizer (Cpd-9) 0.04
Color image stabilizer (Cpd-10) 0.001
Color image stabilizer (Cpd-14) 0.001
Color image stabilizer (Cpd-15) 0.18
Color image stabilizer (Cpd-16) 0.002
Color image stabilizer (Cpd-17) 0.001
Color image stabilizer (Cpd-18) 0.05
Color image stabilizer (Cpd-19) 0.04
Color image stabilizer (UV-5) 0.10
Solvent (Solv-5) 0.19

Sixth layer (UV absorbing layer)
Gelatin 0.34
Ultraviolet absorber (UV-B) 0.24
Compound (S1-4) 0.0015
Solvent (Solv-7) 0.11

Seventh layer (protective layer)
Gelatin 0.82
Additive (Cpd-22) 0.03
Liquid paraffin 0.02
Surfactant (Cpd-13) 0.02

  The sample prepared as described above was designated as Sample 101.

(Preparation of sample 102)
In emulsion preparation, K ₂ [RhBr ₅ (H ₂ O)] was added so as to be 5 × 10 ⁻⁹ mol / mol silver with respect to the total silver amount from 83% to 88% addition of silver nitrate. did. A green sensitive emulsion GH-2 was prepared in the same manner as GH-1, except that it was added. Further, sample 102 was prepared in the same manner as in the preparation of sample 101, except that emulsion GH-1 was replaced with GH-2.

(Preparation of sample 103)
A green sensitive emulsion GH-3 was prepared in the same manner as GH-1, except that selenium compound SE3-9 was used instead of sodium thiosulfate pentahydrate. Further, Sample 103 was prepared in the same manner as in the preparation of Sample 101 except that emulsion GH-1 was replaced with GH-3.

(Preparation of sample 104)
In emulsion preparation, K ₂ [RhBr ₅ (H ₂ O)] was added so as to be 5 × 10 ⁻⁹ mol / mol silver with respect to the total silver amount from 83% to 88% addition of silver nitrate. Except for the above, a green sensitive emulsion GH-4 was prepared in the same manner as GH-3. Further, Sample 104 was prepared in the same manner as in the preparation of Sample 101 except that emulsion GH-1 was replaced with GH-4.

(Preparation of sample 105)
In the preparation of the emulsion, in the same manner as GH-3 except that potassium iodide (0.2 mol% per mol of the finished silver halide) was added with vigorous stirring when the addition of silver nitrate was 90% to 100%. A green sensitive emulsion GH-5 was prepared. Further, sample 105 was prepared in the same manner as in the preparation of sample 101 except that emulsion GH-1 was replaced with GH-5.

(Preparation of sample 106)
In emulsion preparation, K ₂ [RhBr ₅ (H ₂ O)] was added so as to be 5 × 10 ⁻⁹ mol / mol silver with respect to the total silver amount from 83% to 88% addition of silver nitrate. Except for the above, a green sensitive emulsion GH-6 was prepared in the same manner as GH-5. Further, sample 106 was prepared in the same manner as in the preparation of sample 101 except that emulsion GH-1 was replaced with GH-6.

(Preparation of sample 107)
In emulsion preparation, K ₂ [RhBr ₅ (H ₂ O)] was added to 1 × 10 ⁻⁵ mol / mol silver with respect to the total silver amount from 83% to 88% addition of silver nitrate. Except for the above, a green sensitive emulsion GH-7 was prepared in the same manner as GH-5. Further, Sample 107 was prepared in the same manner as in the preparation of Sample 101 except that the emulsion GH-1 was replaced with GH-7.

Each coated sample was subjected to 1 × 10 ^{−4 second} gradation exposure for sensitometry through a green filter using a high-illuminance exposure photometer (HIE type manufactured by Yamashita Denso Co., Ltd.). The exposed sample was subjected to the rapid color development rapid processing (Processing A) shown below 6 seconds after the exposure.

(Rapid processing)
Sample 101 was processed into a roll having a width of 127 mm, and a standard photographic image was exposed using Digital Minilab Frontier 330 (manufactured by Fuji Photo Film Co., Ltd.). Thereafter, continuous processing (running) was performed in the following processing steps until the volume of the color developer replenisher became twice the volume of the color developer tank. The treatment using this running treatment liquid was designated as treatment A.

Processing temperature Temperature Time Replenishment amount *
Color development 45.0 ℃ 17 seconds 35mL
Bleach fixing 40.0 ℃ 17 seconds 30mL
Rinse 1 45.0 ° C. 4 seconds −
Rinse 2 45.0 ° C. 4 seconds −
Rinse 3 ** 45.0 ° C 3 seconds-
Rinse 4 ** 45.0 ° C 5 seconds 121mL
Drying 80 ° C 15 seconds (Note)
* The photosensitive material 1 m ² per replenishment amount ** manufactured by Fuji Photo Film Co., Ltd. rinse cleaning system RC50D attached to rinse 3 sends from the rinse 3, and the rinse solution was taken out to the reverse osmosis module (RC50D) by a pump. The permeated water sent in the tank is supplied to the rinse 4 and the concentrated solution is returned to the rinse 3. The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 mL / min, and the temperature was circulated for 10 hours per day. The rinsing was a 4-tank counterflow system from 1 to 4.

The composition of each treatment liquid is as follows.
[Color developer] [Tank solution] [Replenisher]
800 ml of water 800 ml
Optical brightener (FL-3) 4.0g 8.0g
Residual color reducing agent (SR-1) 3.0 g 5.5 g
Triisopropanolamine 8.8g 8.8g
Sodium p-toluenesulfonate 10.0 g 10.0 g
Ethylenediaminetetraacetic acid 4.0 g 4.0 g
Sodium sulfite 0.10g 0.10g
Potassium chloride 10.0 g ―
4,5-dihydroxybenzene-
Sodium 1,3-disulfonate 0.50 g 0.50 g
Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 8.5 g 14.0 g
4-Amino-3-methyl-N-ethyl-N-
(Β-Methanesulfonamidoethyl) aniline, 3/2 sulfate, monohydrate 7.0 g 19.0 g
Potassium carbonate 26.3g 26.3g
Add water for a total volume of 1000 mL 1000 mL
pH (adjusted with sulfuric acid and KOH at 25 ° C.) 10.25 12.6

[Bleaching fixer] [Tank solution] [Replenisher]
Water 800mL 300mL
Ammonium thiosulfate (750 g / L) 107 mL 214 mL
Succinic acid 29.5g 59.0g
Ethylenediaminetetraacetic acid iron (III)
Ammonium 47.0g 94.0g
Ethylenediaminetetraacetic acid 1.4 g 2.8 g
Nitric acid (67%) 17.5g 35.0g
Imidazole 14.6g 29.2g
Ammonium sulfite 16.0 g 32.0 g
Potassium metabisulfite 23.1g 46.2g
Add water for a total volume of 1000 mL 1000 mL
pH (adjusted with 25 ° C, nitric acid and aqueous ammonia) 6.00 6.00

[Rinse solution] [Tank solution] [Replenisher solution]
Chlorinated isocyanurate sodium 0.02g 0.02g
Deionized water (conductivity 5 μS / cm or less) 1000 mL 1000 mL
pH (25 ° C.) 6.5 6.5

The magenta color density of each sample after treatment A was measured to obtain a characteristic curve of 1 × 10 ⁻⁴ second exposure. The high illuminance sensitivity of each emulsion was read from the logarithm of the exposure amount E required to give a color density of 0.2 for each sample. A relative value with the sensitivity of the sample 101 is represented by logE, and is defined as a relative high illuminance sensitivity SH. The higher the value, the higher the sensitivity. Further, from the exposure amount required to give a color density of 0.3, the color density D at an exposure amount 0.5 higher by logE was read, and (D−0.3) /0.5 was obtained as the gradation γ. In the case of digital exposure by laser scanning exposure, this value is preferably in the range of 2.2 ± 0.2, more preferably 2.2 ± 0.1. The results are shown in Table 2 below.

When the compound represented by the general formula (D1) is used, the contrast becomes hard but desensitization is accompanied. It was found that the degree of desensitization can be reduced by using a selenium sensitizer together. That is, the sensitization effect of the selenium compound becomes significant when the compound represented by the general formula (D1) is used in combination. By using a high-contrast metal complex in combination with selenium sensitization, a high-sensitivity and highly sensitive photosensitive material was obtained. It was also found that the effect of reducing desensitization was great when a silver iodide layer was introduced. As described in JP-A-8-95184, when a large amount of metal complex was used (sample 107), it was greatly desensitized and the effect of the present invention was not obtained.
A coated sample was prepared in the same manner as Samples 103 to 106 except that SE3-9 was changed to SE1-2 or SE2-12, and the same evaluation was performed. A light-sensitive material with less feeling was obtained.

Example 2
(Preparation of sample 108)
In the preparation of the emulsion, K ₂ [IrCl ₅ (H ₂ O)] was added so as to be 8 × 10 ⁻⁶ mol / mol silver with respect to the total silver amount when the addition of silver nitrate was 90% to 100%. Prepared green sensitive emulsion GH-8 in the same manner as GH-1. Further, sample 108 was prepared in the same manner as in the preparation of sample 101 except that emulsion GH-1 was replaced with GH-8.

(Preparation of sample 109)
In emulsion preparation, K ₂ [RhBr ₅ (H ₂ O)] was added so as to be 5 × 10 ⁻⁹ mol / mol silver based on the total silver amount from 83% to 88%. Except for the above, a green sensitive emulsion GH-9 was prepared in the same manner as GH-8. Further, Sample 109 was prepared in the same manner as in the preparation of Sample 101 except that the emulsion GH-1 was replaced with GH-9.

(Preparation of sample 110)
A green sensitive emulsion GH-10 was prepared in the same manner as GH-8 except that selenium compound SE3-9 was used instead of sodium thiosulfate pentahydrate. Further, Sample 110 was prepared in the same manner as in the preparation of Sample 101 except that emulsion GH-1 was replaced with GH-10.

(Preparation of sample 111)
In emulsion preparation, K ₂ [RhBr ₅ (H ₂ O)] was added so as to be 5 × 10 ⁻⁹ mol / mol silver based on the total silver amount from 83% to 88%. Except for the above, a green sensitive emulsion GH-11 was prepared in the same manner as GH-10. Further, Sample 111 was prepared in the same manner as in the preparation of Sample 101 except that emulsion GH-1 was replaced with GH-11.

  Samples 101 to 104 and 108 to 111 were exposed in the same manner as in Example 1, and high illuminance sensitivity and gradation were measured. In addition, after 60 minutes, the process A was performed, and the sensitization width ΔS with respect to the case where the process A was performed 6 seconds after the exposure was measured. Furthermore, SP-1 filter was attached to each coated sample using a sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd.), and after 10 seconds of low illumination exposure, the treatment A was started after 6 seconds. The characteristic curve of low illuminance was obtained. The low illuminance gradation γL was obtained from the low illuminance characteristic curve in the same manner as in Example 1. The results are shown in Table 3 below.

  As shown in Table 3, the compound represented by the general formula (D2) is desired to be used because the gradation in the high-illuminance exposure of the sample is in a preferable region. When the compound represented by the general formula (D2) was used in combination, it was found that the stability of the latent image was particularly high in the sample of the present invention. However, it has been found that when the compound represented by the general formula (D2) is used in combination, there is a problem that the gradation of low illuminance is softened. In this regard, it was found that the aspect of the present invention is excellent without softening. Further, when the compound represented by the general formula (D2) was used in combination, sensitization was performed. It was found that the effect of the present invention is unique when the compound represented by the general formula (D1) and the selenium compound are used in combination.

Example 3
(Preparation of sample 112)
In the preparation of the emulsion, from the time when the addition of silver nitrate is 83% to the time when it is 88%, K ₂ [RhBr ₅ (H ₂ O)] becomes 1.8 × 10 ⁻⁸ mol / mol silver with respect to the total silver amount. A green sensitive emulsion GL-1 was prepared in the same manner as GH-10 except for the above addition. Further, Sample 112 was prepared in the same manner as in the preparation of Sample 101 except that emulsion GH-1 was replaced with GL-1.

(Preparation of sample 113)
Sample 113 was prepared in the same manner except that emulsion GH-1 was replaced with a mixture of emulsions GH-11 and GL-1 (mixed at a silver ratio of 1: 1) in the preparation of sample 101.

  Samples 112 to 113 were processed in the same manner as in Example 1 to determine SH and γ. The results are shown in Table 4 below. The sensitivity was obtained in the same manner as in Example 1, but in this example, it was expressed as a relative value to the sensitivity of the sample 111, not the sample 101.

As shown in Table 4, it was possible to make the gradation most favorable by using two types of emulsions.

Claims (20)

In a silver halide color photographic light-sensitive material having a red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layer on a support, at least one of the silver halide emulsion layers has a silver chloride content of 95 mol% or more. A silver halide color photographic light-sensitive material containing a silver halide emulsion, wherein the silver halide emulsion contains an Se compound and at least one metal complex represented by the following general formula (D1).
General formula (D1)
[M ^D1 X ^D1 _n L ^D1 _(6-n) ] ^m
In the general formula (D1), M ^D1 represents Cr, Mo, Re, Fe, Ru, Os, Co, Rh, Pd, or Pt, and X ^D1 represents a halogen ion. L ^D1 represents an arbitrary ligand different from X ^D1 . n represents 3, 4, 5 or 6, m represents the charge of the metal complex, and represents 4-, 3-, 2-, 1-, 0 or 1+. Here, a plurality of X ^D1 may be the same or different from each other, and when a plurality of L ^D1 are present, these may be the same or different. However, the metal complex represented by the general formula (D1) does not have or has one CN ion as a ligand. 2. The metal complex represented by the general formula (D1) is contained in silver halide grains in an amount of 1 × 10 ⁻¹⁰ to 1 × 10 ⁻⁶ mol per mol of silver. Silver halide color photographic material. The silver halide color photographic material according to claim 1 or 2, wherein the silver halide emulsion containing a Se compound further contains at least one metal complex represented by the following general formula (D2). .
General formula (D2)
[IrX ^D2 _n L ^D2 _(6-n) ] ^m
In general formula (D2), X ^D2 represents a pseudohalogen ion other than a halogen ion or a cyanate ion, and L ^D2 represents an arbitrary ligand different from X ^D2 . n represents 3, 4 or 5, m is the charge of the metal complex, and represents 5-, 4-, 3-, 2-, 1-, 0 or 1+. Here, a plurality of X ^D2 may be the same as or different from each other, and when a plurality of L ^D2 are present, these may be the same or different.   The silver halide emulsion containing a Se compound contains 0.05 to 1.0 mole of silver iodide per mole of silver and has a silver iodide-containing phase having a higher silver iodide concentration than the surroundings. The silver halide color photographic light-sensitive material according to claim 1, wherein the silver halide color photographic light-sensitive material is formed.   The halogenated halide according to any one of claims 1 to 4, wherein an average equivalent sphere diameter of silver halide grains contained in the silver halide emulsion layer containing a Se compound is 0.6 µm or less. Silver color photographic light-sensitive material.   The amount of coupler contained in the silver halide emulsion layer containing a Se compound is 0.6 to 1 equivalent per 1 mol of silver. Silver halide color photographic light-sensitive material. The silver halide color photographic light-sensitive material according to any one of claims 1 to 6, wherein the total coating設銀weight of 0.2 g / ^{m 2} or more 0.45 g / ^{m 2} or less. The silver halide color photographic light-sensitive material according to any one of claims 1 to 7, wherein the total coated gelatin amount is 3 g / m ² or more and 6 g / m ² or less.   The rapid processing halogen in which the silver halide color photographic light-sensitive material starts a color development process within 9 seconds after imagewise exposure, and the color development process is performed within 28 seconds. 9. The silver halide color photographic light-sensitive material according to claim 1, which is a silver halide color photographic light-sensitive material.   The silver halide color photographic light-sensitive material according to any one of claims 1 to 9, wherein the exposure is a silver halide color photographic light-sensitive material for digital exposure that is imagewise exposed by laser scanning exposure. material.   At least one of the silver halide emulsion layers contains the silver halide emulsion according to any one of claims 1 to 10, and the layer is further different in sensitivity from the silver halide emulsion, The silver halide color photographic light-sensitive material according to any one of claims 1 to 10, comprising a silver halide emulsion having a silver chloride content of 95 mol% or more.   In the two types of silver halide emulsions having different sensitivities, the desensitization due to at least one selected from the metal complex represented by the general formula (D1) is lower in the emulsion on the lower sensitivity side than in the emulsion on the higher sensitivity side. The silver halide color photographic light-sensitive material according to claim 11, wherein   In the two types of silver halide emulsions having different sensitivities, the content per mole of at least one silver halide selected from the metal complex represented by the general formula (D1) is higher than that of the emulsion on the high sensitivity side. The silver halide color photographic light-sensitive material according to claim 11 or 12, wherein the emulsion on the low-sensitivity side is more. The silver halide color according to any one of claims 1 to 13, wherein the metal complex represented by the general formula (D1) is a metal complex represented by the following general formula (D1A). Photosensitive material.
General formula (D1A)
[M ^D1A X ^D1A _n L ^D1A _(6-n) ] ^m
In the general formula (D1A), M ^D1A represents Re, Ru, Os, or Rh, and X ^D1A represents a halogen ion. L ^D1A represents NO or NS when M ^D1A is Re, Ru or Os, and represents H ₂ O, OH or O when M ^D1A is Rh. n represents 3, 4, 5 or 6, m represents the charge of the metal complex, and represents 4-, 3-, 2-, 1-, 0 or 1+. Here, a plurality of X ^D1A may be the same or different from each other, and when a plurality of L ^D1A are present, these may be the same or different. The silver halide color photographic light-sensitive material according to claim 1, wherein M ^D1 is Rh in the metal complex represented by the general formula (D1). The silver halide color according to any one of claims 3 to 15, wherein the metal complex represented by the general formula (D2) is a metal complex represented by the following general formula (D2A). Photosensitive material.
General formula (D2A)
[IrX ^D2A _n L ^D2A _(6-n) ] ^m
In the general formula (D2A), X ^D2A represents a halogen ion or a pseudohalogen ion (excluding a cyanate ion), and L ^D2A represents an arbitrary inorganic ligand different from X ^D2A . n represents 3, 4 or 5, m is the charge of the metal complex, and represents 5-, 4-, 3-, 2-, 1-, 0 or 1+. Here, a plurality of X ^D2A may be the same or different from each other, and when a plurality of L ^D2A are present, these may be the same or different. The silver halide color according to any one of claims 3 to 15, wherein the metal complex represented by the general formula (D2) is a metal complex represented by the following general formula (D2B). Photosensitive material.
General formula (D2B)
[IrX ^D2B _n L ^D2B _(6-n) ] ^m
In the general formula (D2B), X ^D2B represents a halogen ion or a pseudohalogen ion (excluding a cyanate ion), and L ^D2B has a base structure of a chain or cyclic hydrocarbon, or a base structure thereof Represents a ligand in which some carbon or hydrogen atoms are replaced with other atoms or atomic groups. n represents 3, 4 or 5, m is the charge of the metal complex, and represents 5-, 4-, 3-, 2-, 1-, 0 or 1+. Here, a plurality of X ^D2B may be the same or different from each other, and when a plurality of L ^D2B are present, these may be the same or different. The silver halide color according to any one of claims 3 to 15, wherein the metal complex represented by the general formula (D2) is a metal complex represented by the following general formula (D2C). Photosensitive material.
General formula (D2C)
[IrX ^D2C _n L ^D2C _(6-n) ] ^m
In the general formula (D2C), X ^D2C represents a halogen ion or a pseudohalogen ion (excluding a cyanate ion). L ^D2C is a 5-membered ring ligand which represents a ligand containing at least one nitrogen atom and at least one sulfur atom in the ring skeleton, and has an arbitrary substituent on a carbon atom in the ring skeleton. You can. n represents 3, 4 or 5, m is the charge of the metal complex, and represents 5-, 4-, 3-, 2-, 1-, 0 or 1+. Here, the plurality of X ^D2Cs may be the same or different from each other, and when there are a plurality of L ^D2Cs , these may be the same or different. The silver halide color according to any one of claims 3 to 15, wherein the metal complex represented by the general formula (D2) is a metal complex represented by the following general formula (D2D). Photosensitive material.
General formula (D2D)
[IrX ^D2D _n L ^D2D _(6-n) ] ^m
In the general formula (D2D), X ^D2D represents a halogen ion or a pseudohalogen ion (excluding a cyanate ion). L ^D2D is a 5-membered ring ligand which represents a ligand containing at least two nitrogen atoms and at least one sulfur atom in the ring skeleton, and has an arbitrary substituent on a carbon atom in the ring skeleton. It's okay. n represents 3, 4 or 5, m is the charge of the metal complex, and represents 5-, 4-, 3-, 2-, 1-, 0 or 1+. Here, the plurality of X ^D2Ds may be the same or different from each other, and when there are a plurality of L ^D2Ds , these may be the same or different. The silver halide color photographic light-sensitive material comprises at least a yellow dye-forming coupler-containing silver halide emulsion layer, a magenta dye-forming coupler-containing silver halide emulsion layer, and a cyan dye-forming coupler-containing silver halide emulsion layer on a reflective support. The silver halide photographic light-sensitive material according to any one of claims 1 to 19, which is a silver halide color photographic light-sensitive material having one layer at a time.