JP2005309395A - Silver halide emulsion and silver halide color photosensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide emulsion and a silver halide color photosensitive material having little fogging, excellent gradation properties, high sensitivity and excellent rapid processability. <P>SOLUTION: The silver halide emulsion containing silver halide grains with a silver chloride content of ≥95 mol% contains at least two compounds each having a function of oxidizing metallic silver clusters and is sensitized with selenium and gold. The silver halide color photosensitive material contains the silver halide emulsion. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a silver halide emulsion and a silver halide color photographic light-sensitive material. More specifically, the present invention relates to a silver halide emulsion and a silver halide color photographic light-sensitive material capable of obtaining a high gradation, low fog and high gradation.

In recent years, with the spread of digital cameras and personal computers, silver halide photographic light-sensitive materials are increasingly used as print materials for digital image information. As print materials for digital image information, there are widespread use of image output materials other than silver halide photographic light-sensitive materials typified by inkjet printers, etc., and silver halides such as color photographic paper are used to compete with these materials. In the field of photographic light-sensitive materials, there are increasing demands for rapid development processing, high image quality, and stable processing.
The silver halide emulsion used for color photographic paper is mainly a silver halide emulsion with a high silver chloride content because of the above-mentioned demand for speeding up. It is desired. In particular, there is a great demand for reducing the size of the yellow dye-forming silver halide emulsion having the largest silver halide grain size in color photographic paper and the silver halide emulsion grains in the emulsion layer closest to the support having a slow development progress. Usually, for a spectrally sensitized emulsion, the sensitivity of the emulsion is proportional to the surface area of the silver halide grains. Therefore, decreasing the silver halide grain size causes a decrease in sensitivity. Various improvements such as chemical sensitization and silver halide emulsion grain formation have been made to further increase the sensitivity of silver halide emulsions.

Typical methods for chemical sensitization in silver halide emulsions include sulfur sensitization, selenium sensitization, tellurium sensitization, sensitization of noble metals such as gold, reduction sensitization, and various sensitizing methods based on a combination thereof. It has been. Among the above sensitizing methods, it is known that selenocarboxylic acid esters, that is, selenoesters, can be used as selenium sensitizers in selenium sensitizing methods (see, for example, Patent Documents 1 to 3).
Although selenium sensitization may exhibit a greater sensitizing effect than sulfur sensitization performed in the industry, fogging is large and softening tends to occur. Moreover, when gold sensitization is used in combination with selenium sensitization, a significant increase in sensitivity can be obtained, but at the same time, the rise of fog is large and softening tends to occur. It was strongly desired.

In silver chloride emulsion, it has been proposed in Patent Document 4 to chemically sensitize with a selenium compound for high sensitivity and low fog at 1/10 second exposure. It has been desired to develop a method that achieves high sensitivity with high concentration, low fog, and high sensitivity.
On the other hand, Patent Documents 5, 6, 7, and 8 propose specific disulfide compounds, sulfinate compounds, combinations of specific disulfide compounds and sulfinate or seleninate compounds, or combinations of specific selenium compounds and radical scavengers. However, it does not deal with fogging problems in selenium sensitization.

U.S. Pat. No. 3,297,446 US Pat. No. 3,297,447 Japanese Patent Publication No.57-22090 JP 7-140579 A European regional patent No. 627657 JP-A-6-35147 JP-A-6-202265 JP-A-10-31279

  The problem to be solved by the present invention is to provide a silver halide emulsion and a silver halide photographic light-sensitive material which have less fogging, excellent gradation characteristics (particularly high contrast), high sensitivity and excellent rapid processing. That is.

As a result of intensive studies, the present inventors have focused on the action of oxidizing metal silver clusters and found that the above-described problems can be achieved by the following means.
(1) A silver halide emulsion containing silver halide grains having a silver chloride content of 95 mol% or more, containing at least two kinds of compounds having an action of oxidizing metal silver clusters, and comprising selenium and gold A silver halide emulsion characterized by being sensitized.
(2) A silver halide emulsion containing silver halide grains having a silver chloride content of 95 mol% or more, containing at least two compounds selected from the following groups A to F, and sensitized with selenium and gold A silver halide emulsion characterized by
Group A
Compound group B represented by the following general formula (I)
Compound group C represented by the following general formula (II)
Compound group D represented by the following general formula (III)
Hydrogen peroxide or hydrogen peroxide adduct group E
Chlorous acid group F
Inorganic sulfur

(Wherein R ¹ , R ² and R ³ each independently represents an aliphatic group, an aromatic group or a heterocyclic group, and M represents a cation. Here, R ² and R ³ are bonded to each other). R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, alkoxy group, hydroxy group, halogen atom, aryloxy group, Represents an alkylthio group, an arylthio group, an acyl group, a sulfonyl group, an acyloxy group, a carboxyl group, a cyano group, a nitro group, a sulfo group, an alkyl sulfoxide or a trifluoroalkyl group, wherein any of R ⁴ , R ⁵ and R ⁶ May be bonded to each other to form a 5-membered or 6-membered ring or a polycyclic system, R ⁷ represents a carboxylate or O ⁻ , X ⁻ represents an anion counter ion, and w represents 0 Or 1 Be provided that when ^{R 6} is a carboxyl group or a sulfo group, w is a 0, ^{R 7} is O ^-. A it).

(3) The silver halide emulsion as described in (2), wherein at least one of the at least two compounds is a compound selected from the group A.
(4) The silver halide emulsion as described in (2), wherein at least one of the at least two compounds is a compound selected from the group B.
(5) The silver halide emulsion as described in (2), wherein at least one of the at least two compounds is a compound selected from the group C.
(6) The silver halide emulsion as described in (2), wherein at least one of the at least two compounds is a compound selected from the group D.
(7) The silver halide emulsion as described in (2), wherein at least one of the at least two compounds is a compound selected from the group E.
(8) The silver halide emulsion as described in (2), wherein at least one of the at least two compounds is a compound selected from the group F.
(9) The silver halide emulsion as described in (2), wherein the at least two compounds are compounds selected from different groups among the groups A to F.

(10) Of the at least two compounds, at least one compound is a compound selected from the group A, and the remaining at least one compound is a compound selected from the groups B to F. The silver halide emulsion as described in (9), wherein
(11) Of the at least two compounds, at least one compound is a compound selected from the group B, and at least one remaining compound is selected from the groups A and C to F The silver halide emulsion as described in (9), which is a compound.
(12) Of the at least two compounds, at least one compound is a compound selected from the group C, and the remaining at least one compound is selected from the groups A, B, and D to F (9) The silver halide emulsion as described in (9) above.
(13) Of the at least two compounds, at least one compound is a compound selected from the group D, and the remaining at least one compound is selected from the groups A to C, E, and F. (9) The silver halide emulsion as described in (9) above.
(14) Of the at least two compounds, at least one compound is a compound selected from the group E, and the remaining at least one compound is selected from the groups A to D and F. The silver halide emulsion as described in (9), which is a compound.
(15) Of the at least two compounds, at least one compound is a compound selected from the group F, and the remaining at least one compound is a compound selected from the groups A to E. The silver halide emulsion as described in (9), wherein
(16) The silver halide emulsion as described in any one of (1) to (15), wherein an average side length of the silver halide grains is from 0.10 μm to 0.60 μm.

(17) A silver halide color light-sensitive material comprising a yellow dye-forming silver halide emulsion layer, a magenta dye-forming silver halide emulsion layer, and a cyan dye-forming silver halide emulsion layer on a support, wherein at least one halogen layer A silver halide color photographic light-sensitive material comprising the silver halide emulsion described in any one of (1) to (16) in a silver halide emulsion layer.
(18) A silver halide color light-sensitive material comprising a yellow dye-forming silver halide emulsion layer, a magenta dye-forming silver halide emulsion layer, and a cyan dye-forming silver halide emulsion layer on a support, the yellow dye-forming halogenated material A silver halide color photographic light-sensitive material comprising the silver halide emulsion described in any one of (1) to (16) in a silver emulsion layer.
(19) A silver halide color light-sensitive material comprising a yellow dye-forming silver halide emulsion layer, a magenta dye-forming silver halide emulsion layer, and a cyan dye-forming silver halide emulsion layer on a support, the closest to the support A silver halide color photographic light-sensitive material comprising the silver halide emulsion described in any one of (1) to (16) in a silver halide emulsion layer.

  According to the present invention, it is possible to provide a silver halide emulsion and a silver halide photographic light-sensitive material with less fogging, excellent gradation characteristics (particularly high contrast), high sensitivity, and excellent rapid processing.

Details of the present invention will be described below.
The silver halide emulsion of the present invention is a silver halide emulsion containing silver halide grains having a silver chloride content of 95 mol% or more, and is a metal silver cluster (aggregation of silver atoms, and a grain formation process). Or at least two kinds of compounds having an action of oxidizing (which may occur in the post-ripening process and cause fogging), and is sensitized with selenium and gold.

Here, the compound having an action of oxidizing metal silver clusters is a silver halide emulsion (silver coating amount 1.5 × 10 ⁻³ mol / m) together with a protective film of gelatin (gelatin coating amount 1.0 g / m ² ). ² ) Before the development process, apply the coated sample in a gold intensifying solution having the following composition at 20 ° C. for 3 minutes, wash with water for 1 minute, and suppress fogging that occurs when normal development is performed. It is a compound that can be

Gold booster solution 0.1% H [AuCl ₄ ] 4 ml
88 ml of H ₂ O
1.0% KSCN 5ml
1.2% NaCl 3ml

Any compound that exhibits such properties may be used. For example, halogen elements such as hydrogen peroxide, nitric acid, nitrous acid, bromine and iodine, oxyacid salts such as permanganate (eg, KMnO ₄ ), chromate (eg, K ₂ CrO), and perhalogenates Commonly known oxidizing agents such as (for example, potassium periodate), high-valent metal salts (for example, potassium ferricyanide) and the like may be used.
In the present invention, as such a compound, at least two kinds of compounds are preferably selected from the following groups A to F. At this time, it is preferable not to use a sulfinic acid compound in combination.

Group A
Compound group B represented by the following general formula (I)
Compound group C represented by the following general formula (II)
Compound group D represented by the following general formula (III)
Hydrogen peroxide or hydrogen peroxide adduct group E
Chlorous acid group F
Inorganic sulfur

In the formula, R ¹ , R ² and R ³ each independently represents an aliphatic group, an aromatic group or a heterocyclic group, and M represents a cation. Here, R ² and R ³ may be bonded to each other to form a ring. R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, alkoxy group, hydroxy group, halogen atom, aryloxy group, alkylthio group, arylthio group, acyl group, A sulfonyl group, an acyloxy group, a carboxyl group, a cyano group, a nitro group, a sulfo group, an alkyl sulfoxide, or a trifluoroalkyl group is represented. Here, any two groups of R ⁴ , R ⁵ and R ⁶ may be bonded to each other to form a 5-membered or 6-membered ring or a polycyclic system. R ⁷ represents a carboxylate or O ⁻ , X ⁻ represents an anion counter ion, and w represents 0 or 1. However, when R ⁶ is a carboxyl group or a sulfo group, w is 0 and R ⁷ is O ⁻ .

Below, each compound of group AF is demonstrated.
First, the compound represented by formula (I) in group A will be described.
In the thiosulfonic acid compound represented by the general formula (I), R ¹ represents an aliphatic group, an aromatic group or a heterocyclic group, and M represents a cation. The aliphatic group for R ¹ includes a linear, branched or cyclic alkyl group, alkenyl group and alkynyl group, and the number of carbon atoms is not particularly limited, but water, lower alcohols such as methanol and ethanol, ethyl acetate, etc. The number of carbons is such that it can be dissolved in the organic solvent or a mixed solvent thereof, more preferably an aliphatic group having 1 to 8 carbon atoms. Examples of the aliphatic group include a methyl group and an ethyl group. The aromatic group in R ¹ includes a phenyl group and a naphthyl group, and the heterocyclic group is preferably a 5- to 7-membered ring containing at least one of a nitrogen atom, an oxygen atom or a sulfur atom as a hetero atom, This ring may be saturated or unsaturated. Moreover, what condensed other rings, such as a benzene ring, may be used. An example is an indole ring. The number and type of substituents that can be substituted on these aliphatic groups, aromatic groups, and heterocyclic groups are not particularly limited, but are soluble in water, organic solvents, or mixed solvents as mentioned above. Those that promote, or at least not interfere with are preferred.
Specific examples of the substituent include an alkoxy group, aryl group, alkyl group, halogen atom, amino group, acylamino group, carboxyl group, hydroxyl group, and heterocyclic group.
R ¹ is preferably an aliphatic group or an aromatic group, and more preferably an aromatic group.
Examples of the cation represented by M include alkali metals (for example, Li ⁺ , Na ⁺ , K ⁺ ), ammonium ions (NH ₄ ⁺ , tetraethylammonium ions) and the like.
The typical example of the thiosulfonic acid compound used for this invention below is given.

The amount of Group A compound used is preferably 1 × 10 ⁻⁷ to 1 × 10 ⁻¹ mol per mol of silver halide. Furthermore, the addition amount of 1 × 10 ⁻⁶ to 1 × 10 ⁻² , particularly 1 × 10 ⁻⁵ to 1 × 10 ⁻³ mol / mol Ag is preferable.

The disulfide compound represented by the general formula (II), which is a group B compound in the present invention, will be described.
R ² and R ³ each independently represents an aliphatic group, an aromatic group or a heterocyclic group. Here, R ² and R ³ may be bonded to each other to form a ring.
The aliphatic group in R ² and R ³ represents an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, or an aralkyl group, preferably having 1 to 18 carbon atoms, such as methyl, ethyl, n -Propyl, i-propyl, i-butyl, t-pentyl, n-hexyl, n-decyl, allyl, 3-pentenyl, propargyl, cyclohexyl, cyclohexenyl, benzyl, phenethyl and the like. The aromatic group in R ² and R ³ is a monocyclic or condensed aryl group, preferably having 6 to 20 carbon atoms, and examples thereof include phenyl and naphthyl. The heterocyclic group in R ² and R ³ preferably has 3 to 10 carbon atoms, and examples thereof include morpholino and pyridyl. R ² and R ³ may be bonded to each other to form a ring, and those that form a 5- to 6-membered ring with —SS— are preferred.

Each group represented by R ² and R ³ may be further substituted with a substituent, and examples of these substituents include the following. In addition, a plurality of these substituents may be substituted. Typical substituents include a carboxyl group, an alkoxycarbonyl group (for example, ethoxycarbonyl), an aryloxycarbonyl group (for example, phenoxycarbonyl group), an amino group, a substituted amino group (for example, ethylamino, dimethylamino, methylphenyl). Amino), hydroxyl group, alkoxy group (for example, methoxy), aryloxy group (for example, phenoxy), acyl group (for example, acetyl), acylamino group (for example, acetamide), ureido group (for example, N, N-dimethylureido) ), Nitro group, sulfonyl group (for example, methylsulfonyl, phenylsulfonyl), sulfo group, mercapto group, alkylthio group (for example, methylthio), cyano group, phosphonyl group, sulfamoyl group (for example, unsubstituted sulfamoyl, N, N- The Tilsulfamoyl), carbamoyl group (eg unsubstituted carbamoyl, N, N-diethylcarbamoyl), alkyl group (eg ethyl), aryl group (eg phenyl), heterocyclic group (eg morphonyl, pyrazolyl), halogen Atoms (for example, chlorine, bromine) and the like. These substituents may be further substituted.
R ² and R ³ are preferably an aliphatic group or an aromatic group, and more preferably an aliphatic group.
Specific examples represented by the general formula (II) of the present invention are shown below, but the present invention is not limited thereto.

The amount of Group B compound used is preferably 1 × 10 ⁻⁷ to 1 × 10 ⁻¹ mol per mol of silver halide. Furthermore, the addition amount of 1 × 10 ⁻⁶ to 1 × 10 ⁻² , particularly 1 × 10 ⁻⁵ to 1 × 10 ⁻³ mol / mol Ag is preferable.

Below, the aryl iodonium compound represented by general formula (III) in group C in the present invention will be described in detail.
In the general formula (III), R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, alkoxy group, hydroxy group, halogen atom, aryloxy group, alkylthio group. Represents a group, arylthio group, acyl group, sulfonyl group, acyloxy group, carboxyl group, cyano group, nitro group, sulfo group, alkyl sulfoxide or trifluoroalkyl group. Here, any two groups of R ⁴ , R ⁵ and R ⁶ may be bonded to each other to form a 5-membered or 6-membered ring or a polycyclic system. In addition, each of these groups and the ring formed by combining R ^{4 to} R ⁵ may further have a substituent.
The aliphatic group for R ^{4 to} R ⁶ is preferably an alkyl group having 1 to 22 carbon atoms, or an alkenyl or alkynyl group having 2 to 22 carbon atoms. More preferably, they are a C1-C10 alkyl group, or a C3-C5 alkenyl or alkynyl group. Most preferably they are alkyl groups having 1 to 5 carbon atoms. These groups may or may not have a substituent. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-hexylhexyl, decyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, isopropyl, and t-butyl. Examples of the alkenyl group include allyl, Examples include butenyl, and examples of the alkynyl group include propargyl and butynyl.

The aromatic group in R ^{4 to} R ⁶ is preferably an aromatic group having 6 to 20 carbon atoms, and examples thereof include phenyl and naphthyl. More preferred is an aromatic group having 6 to 10 carbon atoms, and most preferred is phenyl. These groups may or may not be substituted.
The heterocyclic group in R ^{4 to} R ⁶ is preferably a 3- to 15-membered heterocyclic group having at least one atom selected from nitrogen, oxygen, sulfur, selenium and tellurium, and includes nitrogen, oxygen, sulfur, selenium, and A 5- or 6-membered heterocyclic group having at least one atom selected from tellurium is more preferable. Examples of the heterocyclic ring include pyrrolidine, piperidine, pyridine, tetrahydrofuran, thiophene, oxazole, thiazole, imidazole, benzothiazole, benzoxazole, benzimidazole, selenazole, benzoselenazole, tellurazole, triazole, benzotriazole, tetrazole, Examples include oxadiazole or thiadiazole rings.
R ^{4 to} R ⁶ are further alkoxy groups (for example, methoxy, ethoxy, octyloxy), hydroxy groups, halogen atoms, aryloxy groups (for example, phenoxy), alkylthio groups (for example, methylthio, butylthio), arylthio groups (for example, Phenylthio), acyl groups (eg acetyl, propionyl, butyryl, valeryl), sulfonyl groups (eg methylsulfonyl, phenylsulfonyl), acyloxy groups (eg acetoxy, benzoxy), carboxyl groups, cyano groups, nitro groups, sulfo groups Represents an alkyl sulfoxide group (for example, methane sulfoxide, benzene sulfoxide) or a trifluoroalkyl group (for example, trifluoromethyl).
The ring that any two groups of R ^{4 to} R ⁶ may be bonded to each other may be monocyclic, polycyclic, alicyclic, aromatic, or heterocyclic. There may be.

Of the above groups in R ^{4 to} R ^6, a group that does not hinder the reciprocity improving activity of the aryl iodonium compound is preferable.
Of the groups represented by R ^{4 to} R ⁶ , in one preferred embodiment, R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. In another preferred embodiment, R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group or a heterocyclic group (heterocyclic group), and R ⁶ is a sulfo group or a carboxyl group It is a group.

R ⁷ represents a carboxylate (for example, acetate, formate, benzoate, trifluoroacetate) or O ⁻ . w represents 0 or 1; Provided that when ^{R 6} is a sulfo group or a carboxyl group, w is 0, and ^{R 7} is O ^-.

X ⁻ represents an anion counter ion, and the anion counter ion preferably does not interfere with the reciprocity law improving effect of the compound. The anion counter ion is more preferably water-soluble.
X ⁻ includes, for example, CH ₃ CO ₂ ⁻ , Cl ⁻ , CF ₃ SO ₃ ⁻ , PF ₆ ⁻ , Br ⁻ , BF ₄ ⁻ , AsF ₆ ⁻ , CH ₃ SO ₃ ⁻ , CF ₃ CO ₂ ⁻ , CH ^{_{3 C 6 H 4 SO 3 -}} , HSO 4 -, SbF 6 -, HCO 2 -, or _CCl 3 CO ₂ ^- and the like. Particularly _{^{preferably, CH 3 CO 2 -, CH}} 3 SO 3 -, or PF ₆ ^- is.

Each group of R ^{4 to} R ⁷ may further have a substituent. Examples of such a substituent include an alkyl group (for example, methyl, ethyl, hexyl), an alkoxy group (for example, methoxy, ethoxy, Octyloxy), aryl groups (eg phenyl, naphthyl, tolyl), hydroxy groups, halogen atoms, aryloxy groups (eg phenoxy), alkylthio groups (eg methylthio, butylthio), arylthio groups (eg phenylthio), acyl Groups (eg, acetyl, propionyl, butyryl, valeryl), sulfonyl groups (eg, methylsulfonyl, phenylsulfonyl), acylamino groups, sulfonylamino groups, acyloxy groups (eg, acetoxy, benzoxy), carboxyl groups, cyano groups, sulfo groups , And amino groups (including al Arylamino group, an arylamino group, heterocyclic amino group). Of these, preferred are an alkyl group (lower alkyl group, that is, one having 1 to 4 carbon atoms (for example, methyl) is more preferred) and a halogen atom (for example, chlorine).

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

The amount of Group C compound used is preferably 1 × 10 ⁻⁷ to 1 × 10 ⁻¹ mol per mol of silver halide. Furthermore, the addition amount of 1 × 10 ⁻⁶ to 1 × 10 ⁻² , particularly 1 × 10 ⁻⁵ to 1 × 10 ⁻³ mol / mol Ag is preferable.

The adducts of hydrogen peroxide and peroxide in group D will be described below.
Peroxide adducts are, for example, NaBO ₂ .H ₂ O ₂ .3H ₂ O, 2NaCO ₃ .3H ₂ O ₂ , Na ₄ P ₂ O ₇ .2H ₂ O ₂ , 2Na ₂ SO ₄ .H ₂ O _And 2.2H ₂ O. The amount used is preferably 1 × 10 ⁻⁷ to 1 × 10 ⁻¹ mol per mol of silver halide. Furthermore, the addition amount of 1 × 10 ⁻⁶ to 1 × 10 ⁻² , particularly 1 × 10 ⁻⁵ to 1 × 10 ⁻³ mol / mol Ag is preferable.

Group E in the present invention is chlorous acid, and the amount used is preferably 1 × 10 ⁻⁷ to 1 × 10 ⁻¹ mol per mol of silver halide. Furthermore, the addition amount of 1 × 10 ⁻⁶ to 1 × 10 ⁻² , particularly 1 × 10 ⁻⁵ to 1 × 10 ⁻³ mol / mol Ag is preferable.

The inorganic sulfur of group F in the present invention refers to a simple substance, elemental sulfur, and α-sulfur that exists stably in a solid state at room temperature is preferable. The amount of inorganic sulfur used is preferably 1 × 10 ⁻⁷ to 1 × 10 ⁻¹ mol per mol of silver halide. Furthermore, the addition amount of 1 × 10 ⁻⁶ to 1 × 10 ⁻² , particularly 1 × 10 ⁻⁵ to 1 × 10 ⁻³ mol / mol Ag is preferable.
In the present invention, the at least two compounds are preferably selected from different groups among groups A to F, preferably selected from groups A and B, respectively.

Next, the selenium compound will be described in detail.
The selenium compound is not particularly limited as long as it sensitizes a silver halide emulsion, but a compound represented by the following general formula (SE1), (SE2) or (SE3) is preferable.

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. 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.

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 to} J ³ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.

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.

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

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 a substituted or unsubstituted phenyl group and naphthyl group having 6 to 20 carbon atoms (for example, unsubstituted phenyl, unsubstituted naphthyl, 3,5-dimethylphenyl, 4 -Butoxyphenyl, 4-dimethylaminophenyl, etc.), etc., and the heterocyclic group has at least one hetero atom (preferably a nitrogen atom, oxygen atom, sulfur atom) having 0 to 20 carbon atoms as a ring atom. A 3- to 12-membered heterocyclic group contained as 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. Is preferably an alkoxy group having 1 to 30 carbon atoms, such as methoxy, ethoxy, n-butyloxy, cyclohexyloxy, n-octyloxy, n-decyloxy, etc. The carbamoyl group is a carbamoyl having 1 to 30 carbon atoms. Groups are preferred, for example unsubstituted carbamoyl, N, N-die Carbamoyl, N- phenylcarbamoyl, and the like.
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, sulfonamido 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) 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. Examples of the salt include cations such as alkali metals, alkaline earth metals, and heavy metals, and organic cations such as ammonium ions and phosphonium ions. 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, or an acyl group, wherein Q is 1 to 6 substituted or unsubstituted linear or branched alkyl groups, substituted or unsubstituted cyclic alkyl groups having 3 to 6 carbon atoms, alkenyl groups having 2 to 6 carbon atoms, substituted or unsubstituted groups having 6 to 10 carbon atoms A phenyl group, or NM ⁴ M ⁵ , and each of M ⁴ and M ⁵ independently represents a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 6 carbon atoms, or a substitution having 3 to 6 carbon atoms Or unsubstituted ring 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.
Although the specific example of a compound represented by general formula (SE1) below is given, this invention is not limited to these.

  The compound represented by the general formula (SE1) of the present invention can be prepared 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 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 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 prepared by a known method, for example, Organic Phosphorus Compounds (Vol. 4, pages 1 to 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), etc. It can be easily synthesized by the method described in 1) or a method analogous thereto.

Next, the compound represented by general formula (SE3) is demonstrated.
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 phenoxycarbonyl and naphthoxycarbonyl. The carbamoyl group is preferably a carbamoyl group having 1 to 30 carbon atoms such as an unsubstituted carbamoyl group. Yl, 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 general formula (SE3) is selected from the group represented by any one of E ¹ and E ² represented by the following general formulas (T1) to (T4). 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 ¹¹ or NR ¹² R ¹³ , and R ^{11 to} R ¹³ 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 ¹⁷ , and R ^{14 to} R ¹⁷ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. Represent. R ¹⁵ and R ¹⁶ 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 ²¹ , R ¹⁸ 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 ¹⁹ to to R ²¹ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. R ¹⁹ and R ²⁰ may be bonded to each other to form a ring. Z represents a substituent, and k represents an integer of 0 to 4. When k is 2 or more, 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 ¹¹ or NR ¹² R ¹³ , and R ^{11 to} R ¹³ 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 General Formula (T1), 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 includes a cycloalkylene group, and those represented by the following general formula (L1) or general formula (L2), and more preferably those represented by the following general formula (L1) or 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 _m value, preferably σ _m value is 0.12 or more, and the upper limit is 1.0 or less. Represents a substituent of Specific examples of the electron withdrawing group having a positive σ _m value include an alkoxy group, an alkylthio group, an acyl group, a formyl group, an acyloxy group, an acylthio group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, and a nitro group. Group, dialkylphosphono group, diarylphosphono group, dialkylphosphinyl group, diarylphosphinyl group, phosphoryl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, A 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, an aryloxy group, an arylthio group, Acylami Group, an alkylamino group, sigma _p value is an aryl group substituted with 0.2 or more other electron-withdrawing group, a heterocyclic group, a halogen atom, an azo group, and selenocyanate group.

In the present invention, EWG is preferably an alkoxy group, alkylthio group, acyl group, formyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkylphosphono group, diarylphosphono group, dialkylphosphine group. Finyl group, diarylphosphinyl 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 an salt thereof), an alkyl group substituted with at least 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 alkoxy group, an alkyl group Thio group, acyl group, formyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, alkylsulfonyl group, arylsulfonyl group, carboxy group, alkyl substituted with at least two halogen atoms More preferably an alkoxy group, an alkylthio group, an acyl group, a 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 ^{14 to} R ¹⁷ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. 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 M ^{1 to} M ⁵ and Q in the general formula (SE1), respectively. The preferable range is also the same.

In the present invention, R ¹⁴ is preferably an alkyl group. R ¹⁵ and R ¹⁶ 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 ¹⁷ 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 General Formula (T3), A ¹ represents an oxygen atom, a sulfur atom, or NR ^{17. 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 ^{18 to} R ²¹ has the same meaning as 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. Examples of the acyl group represented by R ¹⁸ include acetyl, formyl, benzoyl, pivaloyl, caproyl, n-nonanoyl and the like.

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).

  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) sulfonyl group, ( Archi 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), 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, heterocyclic thio group , A sulfo group (including a salt thereof) and the like, and 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 hetero Ring) amino group, ureido group, alkylthio group, arylthio (Including and salts thereof) a sulfo group and the like.

In General Formula (T4), k represents an integer of 0 to 4. In the present invention, k preferably represents 0 to 2, more preferably 0 or 1.
In General Formula (T4), A ² represents an oxygen atom, a sulfur atom, or NR ²¹ , 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 Formula (T3), E ¹ is General Formula (T1), E ² is General Formula (T4), E ¹ is General Formula (T2), E ² is General Formula (T3), and E ¹ is 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 the general formula (T2), and E ² is the general formula (T3).

  Specific examples of the selenium compound represented by formula (SE3) in the present invention 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 described in the following literature, S.I. Patai, Z .; The Rapport ed., The Chemistry of Organic Selenium and Tellurium Compounds, Volume 1 (1986), Volume 2 (1987), D. It can be easily synthesized by the method described in Liotta, Organo-selenium Chemistry, (1987), or a similar method.

  In the present invention, as other selenium compounds, JP-B Nos. 43-13489, 44-15748, JP-A-4-25832, JP-A-4-109240, JP-A-4-271341, JP-A-5-40324, 5-11385, 6-51415, 6-175258, 6-180478, 6-208186, 6-208184, 6-317867, 7-92599, 7- 98083, 7-140579, 7-301879, 7-301880, 8-114882, 9-138475, 9-197603, 10-10666, etc. Selenium compounds, specifically colloidal metal selenium, selenoketones (eg selenobenzophenone), isoselenocyanene DOO acids, such 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 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 generally 1 × 10 ⁻⁸ to 1 × 10 ⁻⁴ mol per mol of silver halide. Preferably, about 1 × 10 ⁻⁷ to 1 × 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.
In addition, the selenium compound used in the present invention can be added at any stage from immediately after grain formation until immediately before completion of chemical sensitization. A preferable addition time is between the chemical sensitization process after the desalting.

In the present invention, the selenium sensitization by the above selenium compound is sensitized by gold.
As the gold sensitizer, colloidal gold sulfide or a gold sensitizer having a gold complex stability constant log β ₂ of 21 or more and 35 or less can be preferably used. 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.) It can be preferably used.
The amount of the gold sensitizer used in the present invention varies depending on the gold compound used, silver halide grains, chemical ripening conditions, etc., but is generally 1 × 10 ⁻⁴ to 1 × 10 ⁻⁸ mol per mol of silver halide. Preferably, about 1 × 10 ⁻⁴ to 1 × 10 ⁻⁷ mol is used.
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.

  In addition to selenium sensitization and gold sensitization, sulfur sensitization, tellurium sensitization or other noble metal sensitization can be used in combination. Further, a reduction sensitizer can be used in combination, and specific examples include stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives, borane compounds, silane compounds, polyamine compounds, and the like.

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), thioether compound (for example, US Pat. Nos. 3,021,215 and 3,271,157). The compounds described in the description, Japanese Patent Publication No. 58-30571, Japanese Patent Application Laid-Open No. 60-136736, etc., in particular, 3,6-dithia-1,8 octanediol, etc., tetrasubstituted thiourea compounds (for example, No. 59-11892, US Pat. No. 4,221,863, etc., especially tetramethylthiourea, etc.), and thione compounds described in JP-B-60-11341, JP-B-63. No. 29727, a mercapto compound described in JP-A-60-163042, a mesoionic compound described in US Pat. No. 4,782,013 Selenoether compound of the mounting, 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 1 × 10 ⁻⁵ to 1 × 10 ⁻² mole per mole of silver halide.

  The average side length of the silver halide grains constituting the silver halide emulsion of the present invention is not particularly limited, but is generally from 0.1 μm to 0.6 μm, preferably from 0.1 μm to 0.5 μm. It is more preferably 1 μm or more and 0.45 μm or less, and most preferably 0.1 μm or more and 0.4 μm or less. The variation coefficient of the average side length is preferably 10% to 20%. Furthermore, it is preferable that the projected area of the silver halide grains having a side length of 0.1 μm or more and 0.6 μm or less occupy 50% or more of the total of the projected areas of all the silver halide grains constituting the silver halide emulsion, It is more preferable to occupy 80% or more, and it is particularly preferable to occupy 90% or more. The side length of silver halide grains can be determined from the electron micrograph, and the side length of a cube having the same volume as the silver halide grains is taken as the grain side length. The average side length can be obtained by measuring the side length of a statistically meaningful number (for example, 600 or more) of silver halide grains and calculating the average value.

  The silver halide emulsion of the present invention must have a silver chloride content of 95 mol% or more, preferably 98 mol% or more. The grain shape of the silver halide grains is not particularly limited, but is substantially a cubic or tetradecahedral crystal grain having {100} faces (these grains have rounded vertices and have higher-order faces. In other words, octahedral crystal grains, and tabular grains having a main surface of {100} planes or {111} planes and having an aspect ratio of 2 or more are preferable. 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, cubic or tetrahedral particles are more preferable.

  The silver halide emulsion of the present invention preferably has a silver bromide-containing phase and / or a silver iodide-containing phase. When the silver halide emulsion of the present invention has a silver bromide-containing phase, the silver bromide content is preferably from 0.1 to 4 mol%, more preferably from 0.5 to 2 mol%. When the silver halide emulsion of the present invention has a silver iodide-containing phase, the silver iodide content is preferably 0.02-1 mol%, more preferably 0.05-0.50 mol%, and 0.07- 0.40 mol% is more preferable.

  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, and silver iodobromochloride grains having the above-mentioned halogen composition are particularly preferable. 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 3 mol% or more, more preferably 5 to 40 mol%, and most preferably 5 to 25 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 provided in the form of layers in each grain, and the silver bromide or silver iodide content may be different.

  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.

  It is preferable to concentrate the functions of the silver bromide-containing phase and silver iodide-containing phase that control photographic action close to the surface in the grain. Therefore, 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 measured from the inside and formed at any position of 50% to 100% of the grain volume, 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 of 70% to 95% of the grain volume, and the silver iodide-containing phase is further formed at any position of 90% to 100% of the grain volume. preferable.

  When the silver halide emulsion of the present invention has a silver bromide-containing phase, another preferred embodiment of the silver bromide-containing phase has a silver bromide content of 0. 0 in a depth within 20 nm from the grain surface. It is a silver halide emulsion having a region of 5 to 20 mol%. It is preferable to have a silver bromide-containing phase within 10 nm from the grain surface, preferably a silver bromide-containing phase having a silver bromide content of 0.5 to 10 mol%, and 0.5 to 5 mol More preferably, it has a silver bromide-containing phase. In this case, the silver bromide-containing phase does not necessarily have to be formed in layers. However, in order to further enhance the effect of the present invention, it is preferable that a silver bromide-containing phase is formed in a layered manner so as to surround the grains.

  When the silver halide emulsion of the present invention has a silver iodide-containing phase, another preferable embodiment of the silver iodide-containing phase has a silver iodide content of 0. 0 in a depth within 20 nm from the grain surface. It is a silver halide emulsion having a region of 3 to 10 mol%. The silver iodide-containing phase preferably has a silver iodide-containing phase within 10 nm from the grain surface, and preferably has a silver iodide-containing phase having a silver iodide content of 0.5 to 10 mol%, preferably 0.5 to 5 mol. % Of silver iodide containing phase is more preferred. In this case, the silver iodide-containing phase is not necessarily formed in a layer form. However, in order to further enhance the effects of the present invention, it is preferable that a silver iodide-containing phase is formed in a layered manner so as to surround the grains.

  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 using, for example, 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.

  The specific silver halide grains in the silver halide emulsion of the present invention preferably contain an iridium complex. As the iridium complex, a hexacoordinate complex having Ir as a central metal having at least two different ligands in the same complex is particularly preferable. Examples of such iridium complexes include 6-coordination complexes having Ir as a central metal containing a halogen ligand (including a pseudohalogen ligand) and an organic ligand in the same complex. Among them, hexacoordinate complexes containing Ir as a central metal and containing an inorganic ligand other than halogen in the same complex are preferable. Hexacoordination complex containing halogen ligand and organic ligand in the same complex with Ir as the central metal, and Ir containing halogen ligand and inorganic ligand other than halogen in the same complex as the central metal It is more preferred to have both hexacoordinate complexes.

  The hexacoordination complex having Ir as a central metal, which is preferably used in the present invention, is a metal complex represented by the following general formula (1).

General formula (1)
^{_{[IrX I n L I (6}} -n)] m

In the general formula (1), X ^I represents a pseudohalogen ion other than a halogen ion or a cyanate ion, and L ^I represents an arbitrary ligand different from X ^I. 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, 3-5 X ^I may be the same or different from each other. When L ^I there are a plurality, a plurality of L ^I may be the same or different from each other.
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.
^XI 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 ^I is not particularly limited to, it may be an organic compound be an inorganic compound, that charge may be also uncharged have a, but an inorganic compound or organic compound uncharged preferable.

  Among the metal complexes represented by the general formula (1), a metal complex represented by the following general formula (1A) is preferable.

General formula (1A)
[IrX ^IA _n L ^IA _(6-n) ] ^m

In the general formula ^{(1A), X IA} represents a pseudohalogen ion other than halide ion or cyanide ^{ion, L IA} represent different any inorganic ligand and ^{X IA.} n represents 3, 4 or 5, m is the charge of the metal complex, and represents 5-, 4-, 3-, 2-, 1-, 0 or 1+.
^{Incidentally, X IA} has the same meaning as ^{X I} of the general formula (1), and the preferred range is also the same. ^LIA is preferably water, OCN, ammonia, phosphine, or carbonyl, and particularly preferably water.
Here, three to five X ^IA may be the same or different from each other. When L ^IA there are a plurality, a plurality of L ^IA may be the same or different from each other.

  Among the metal complexes represented by the general formula (1), a metal complex represented by the following general formula (1B) is more preferable.

General formula (1B)
[IrX ^IB _n L ^IB _(6-n) ] ^m

In the general formula (1B), X ^IB represents a pseudohalogen ion other than halide ion or cyanide ion, L ^IB is a part of Kusarishiki or cyclic or a hydrocarbon as a matrix structure, or parent structure Represents a ligand in which a carbon or hydrogen atom is replaced by another atom or atomic group. n represents 3, 4 or 5, m is the charge of the metal complex, and represents 5-, 4-, 3-, 2-, 1-, 0 or 1+.
X ^IB has the same meaning as X ^{I in} formula (1), and the preferred range is also the same. L ^IB represents an Kusarishiki or cyclic or a hydrocarbon as a matrix structure, or a part carbon or hydrogen atoms of the parent structure is replaced by another atom or atomic group ligand, cyanide Ions are not included. ^LIB 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. Here, three to five X ^IB may be the same or different from each other. When L ^IB there are a plurality, a plurality of L ^IB may be the same or different from each other.

  Among the metal complexes represented by the general formula (1B), the metal complex represented by the following general formula (1C) is more preferable.

General formula (1C)
[IrX ^IC _n L ^IC _(6-n) ] ^m

In the general formula (1C), X ^IC represents a pseudohalogen ion other than a halogen ion or a cyanate ion, L ^IC has a 5-membered ring ligand, and at least one nitrogen atom and at least one nitrogen atom in the ring skeleton It is a ligand containing a sulfur atom. An arbitrary substituent may be present on a carbon atom in the ring skeleton. n represents 3, 4 or 5, m is the charge of the metal complex, and represents 5-, 4-, 3-, 2-, 1-, 0 or 1+.
X ^IC has the same meaning as X ^{I in} formula (1), and the preferred range is also the same. L The substituent on the carbon atoms of the ring skeleton in ^IC, is preferably a substituent having a smaller volume than 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.
Here, three to five X ^IC may be the same or different from each other. When L ^IC there are a plurality, a plurality of L ^IC may be the same or different from each other.

  Although the preferable specific example of a metal complex represented by General formula (1) 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 ] ^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 ] ⁻

More preferably, the specific silver halide grains in the silver halide emulsion of the present invention have a six-coordinate complex in which all six ligands are composed of Cl, Br or I and whose center metal is Ir. In this case, Cl, Br, or I may be mixed in the hexacoordination complex. It is particularly preferable that a hexacoordinate complex containing Ir as a central metal having Cl, Br or I as a ligand is contained in a silver bromide-containing phase in order to obtain a high gradation in high-illuminance exposure.
Specific examples of the 6-coordination complex in which all six ligands are composed of Cl, Br or I and having Ir as a central metal are given below, but iridium in the present invention is not limited to these.
[IrCl ₆ ] ^2-
[IrCl ₆ ] ^3-
[IrBr ₆ ] ^2-
[IrBr ₆ ] ^3-
[IrI ₆ ] ^3-

When the metal complex mentioned above is an anion and forms a salt with a cation, what is easy to melt | dissolve 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. These iridium complexes are preferably added in an amount of 1 × 10 ⁻¹⁰ mol to 1 × 10 ⁻³ mol per mol of silver during grain formation, and may be added in an amount of 1 × 10 ⁻⁸ mol to 1 × 10 ⁻⁵ mol. Most preferred.

  In the present invention, the above-mentioned iridium complex is added directly to the reaction solution at the time of silver halide grain formation, added to an aqueous halide solution for forming silver halide grains, or to 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 iridium complex is 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 complexes are incorporated into silver halide grains, they can be uniformly present inside the grains, but they are disclosed in JP-A-4-208936, JP-A-2-125245, and JP-A-3-188437. As described above, it is also preferable to be present only in the particle surface layer, and it is also preferable to add a layer containing only the complex 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.

  In the present invention, in addition to iridium, 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, or rhodium 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 the iridium complex in combination with these complex compounds. 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 of the complex having a cyanide ion as a ligand per mol of silver during grain formation, and 1 × 10 ⁻⁶ mol to 5 × 10 ⁶ It is most preferable to add ^-4 mol. When ruthenium and osmium are used as the central metals, it is also preferable to use nitrosyl ions, thionitrosyl ions, or water molecules and chloride ions together as ligands. More preferably, a pentachloronitrosyl complex, a pentachlorothionitrosyl complex, or a pentachloroaqua complex is formed, and a hexachloro complex is also preferably formed. These complexes are preferably added in an amount of 1 × 10 ⁻¹⁰ mol to 1 × 10 ⁻⁶ mol, and more preferably 1 × 10 ⁻⁹ mol to 1 × 10 ⁻⁶ mol, per 1 mol of silver during grain formation. That is.

  To the silver halide emulsion used in the present invention, various compounds or precursors thereof are 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, a 5-arylamino-1,2,3,4-thiatriazole compound (the aryl residue has at least one electron-withdrawing group) described in EP 0447647 is 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 11 column 22 line description is preferably applied to the present invention 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 used in 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 the range of 1.0 * 10 < ^-6 > mol-5.0 * 10 < ^-3 > mol.
The silver halide emulsion of the present invention is contained in at least one silver halide emulsion layer. It is preferably contained in the yellow dye-forming silver halide emulsion layer, and is also preferably contained in the silver halide emulsion layer closest to the support.

Next, the silver halide color photographic light-sensitive material relating to the present invention will be described.
As described above, the silver halide color photographic light-sensitive material of the present invention comprises a yellow-colored blue-sensitive silver halide emulsion layer, a magenta-colored green-sensitive silver halide emulsion layer, and a cyan-colored red light sensitive material on a support. A silver halide emulsion layer. The yellow-colored blue-sensitive silver halide emulsion layer is a yellow-colored layer containing a yellow dye-forming coupler, the magenta-colored green-sensitive silver halide emulsion layer is a magenta-colored layer containing a magenta dye-forming coupler, and a cyan-colored red light-sensitive layer The silver halide emulsion layer functions as a cyan color forming layer containing a cyan dye forming coupler. 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). Have.
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 is used in place of the water-soluble dye or in combination with the water-soluble dye. 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, solids such as dyes described in JP-A-2-282244, page 3, upper right column to page 8, and JP-A-3-7931, page 3, upper right column to page 11, lower left column. 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 photosensitive material of the present invention is used for color negative film, color positive film, color reversal film, color reversal photographic paper, color photographic paper display photosensitive material, digital color proof, movie color positive, movie color negative, etc. Materials, digital color proofs, color positives for movies, color reversal photographic papers, and color photographic papers are preferred, and particularly preferred as color photographic papers. As described above, the color photographic paper has at least one yellow-colored blue-sensitive silver halide emulsion layer, magenta-colored green-sensitive silver halide emulsion layer, and cyan-colored red-sensitive silver halide emulsion layer. In general, these silver halide emulsion layers are arranged in the order from the support to the yellow-colored blue-sensitive silver halide emulsion layer, the magenta-colored green-sensitive silver halide emulsion layer, and the cyan-colored red-sensitive halogen halide. It is a silver halide emulsion layer.

However, a different layer structure may be used.
The blue-sensitive silver halide emulsion layer may be disposed at any position on the support. However, when the blue-sensitive silver halide emulsion layer contains tabular grains of green halide, It is preferably coated at a position farther from the support than at least one of the silver halide emulsion layer or the red-sensitive silver halide emulsion layer. In addition, from the viewpoint of promoting color development, desilvering, and reducing residual color by sensitizing dye, the blue-sensitive silver halide emulsion layer is coated at the position farthest from the support than the other silver halide emulsion layers. It is preferable to be provided. Further, from the viewpoint of reducing Blix fading, the red-sensitive silver halide emulsion layer is preferably the center layer of other silver halide emulsion layers, and from the viewpoint of reducing photobleaching, the red-sensitive silver halide emulsion layer is preferred. Is preferably the lowermost layer. Further, each of the coloring 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 the general formulas (II) and (III) of WO 98/33760 and the general formula (D) of JP-A-10-221825 may be added.

  As a cyan dye-forming coupler that can be used in the present invention (sometimes simply referred to as “cyan coupler”), a pyrrolotriazole-based coupler is preferably used, and the general formula (I) or (II) described in JP-A-5-313324 is used. ), 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 as they are to the present invention 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 invention as they are, It is incorporated 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 with a loadable latex polymer (eg, US Pat. No. 4,203,716) in the presence (or absence) of a high boiling organic solvent, or water insoluble and It is preferable to dissolve together with an organic solvent-soluble polymer and emulsify and disperse it 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 photosensitive 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.

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 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.

  The photosensitive material of the present invention is preferably imagewise exposed with coherent light of a blue laser 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), a semiconductor laser (oscillation wavelength: About 470 nm of blue laser and semiconductor laser (oscillation wavelength: about 1060 nm) extracted by wavelength conversion with LiNbO ₃ SHG crystal having a waveguide-like inversion domain structure and having a waveguide-like inversion domain structure Preferably, a green laser with a wavelength of about 530 nm, a red semiconductor laser with a wavelength of about 685 nm (Hitachi type No. HL6738MG), a red semiconductor laser with a wavelength of about 650 nm (Hitachi type No. HL6501MG), which is extracted by converting the wavelength with an SHG crystal of LiNbO ₃ is used. Used.

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 300 dpi, the preferable exposure time is 1 × 10 ⁻⁴ seconds or less, more preferably 1 × 10 ⁻⁶ seconds. It is as follows.

  The silver halide color photographic light-sensitive material of the present invention can be preferably used in combination with the exposure and development system described in the following known documents. 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 JP 2000-310822 A.

  Preferred scanning exposure methods applicable to the present invention are described in detail in the patents listed in the table above.

  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. Further, as the preservative used in the developer, compounds described in the patents listed in the above table are preferably used.

  The photosensitive material of the present invention is preferably applied as a photosensitive material having rapid processing suitability. When rapid processing is performed, the color development 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. 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 shorter, more preferably 40 seconds or shorter and 6 seconds or longer.

  The color development time is 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 and is bleach-fixed in the next processing step. The total of both the time during which air is conveyed toward the bath (so-called air time) is called 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.

  In the light-sensitive material of the present invention, the color development time is particularly preferably 20 seconds or less (preferably 6 to 20 seconds, more preferably 6 to 15 seconds). Here, in the present invention, color development processing with a color development time of 20 seconds or less means that the color development time described above is 20 seconds or less (not the entire time of color development processing).

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 B-1)
High silver chloride cubic particles were prepared by simultaneously adding silver nitrate and sodium chloride to deionized distilled water containing deionized gelatin and mixing. In the course of this preparation, K ₄ [Ru (CN) ₆ ] was added from 80% to 90% addition of silver nitrate. Potassium bromide (2 mol% per mole of finished silver halide) was added from the point where the addition of silver nitrate was 80% to 100%. K ₂ [IrCl ₆ ] and K ₂ [RhBr ₅ (H ₂ O)] were added from 83% to 88% addition of silver nitrate. When 90% of the addition of silver nitrate was completed, potassium iodide (0.1 mol% per mol of the 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 grains having a side length of 0.50 μm and a coefficient of variation of 8.0%. 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, Compound I-22, dimethylthiourea as a sulfur sensitizer, and sodium tetrachloroaurate as a gold sensitizer were added and ripened to optimize chemical sensitization. Thereafter, a mixture of compounds represented by 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound-2, compound-3, wherein n is 2 or 3 as a main component (terminal X ₁ and X ₂ are Hydroxyl group), compound-4 and potassium bromide were added to terminate the chemical sensitization. The emulsion thus obtained was designated as Emulsion B-1.

(Preparation of emulsion B-2)
In preparation of Emulsion B-1, the temperature and the addition speed of the step of adding and mixing silver nitrate and sodium chloride are changed, and the amount of various metal complexes added during the addition of silver nitrate and sodium chloride is changed. Thus, emulsion grains were obtained. The emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.40 μm and a coefficient of variation of 9.0%. After redispersing this emulsion, Emulsion B-2 was prepared in the same manner as B-1, except that the amount of various compounds added was changed.
(Preparation of emulsion B-3)
In the preparation of emulsion B-2, an emulsion was prepared by adding 6 × 10 ⁻⁶ mol of selenium compound (SE3-9) per mol of silver halide instead of dimethylthiourea which is a sulfur sensitizer. It was set as B-3.
(Preparation of emulsion B-4)
In the preparation of Emulsion B-2, an emulsion was prepared by adding Compound I-22 and Compound II-8 instead of Compound I-22, and this was designated as Emulsion B-4.

(Preparation of emulsion B-5)
In the preparation of Emulsion B-2, Compound I-22 and Compound II-8 were added instead of Compound I-22, and selenium compound (SE3-9) was halogenated instead of dimethylthiourea, which is a sulfur sensitizer. An emulsion was prepared by adding 6 × 10 ⁻⁶ mol per mol of silver, and this was designated as Emulsion B-5.
(Preparation of emulsion B-6)
In preparing Emulsion B-5, Compound III-1 was added instead of Compound II-8, and this was designated Emulsion B-6.
(Preparation of emulsion B-7)
In preparing Emulsion B-5, inorganic sulfur was added instead of Compound I-22, and this was designated Emulsion B-7.
(Preparation of emulsion B-8)
In the preparation of Emulsion B-5, sodium p-toluenesulfinate was added instead of Compound II-8, and this was designated as Emulsion B-8.
(Preparation of emulsion B-9)
In preparing the emulsion B-5, a selenium compound (SE3-29) was added instead of the selenium compound (SE3-9), and this was designated as emulsion B-9.

(Preparation of green-sensitive layer emulsion G-1)
High silver chloride cubic particles were prepared by simultaneously adding silver nitrate and sodium chloride to deionized distilled water containing deionized gelatin and mixing. In the course of this preparation, K ₄ [Ru (CN) ₆ ] was added from 80% to 90% addition of silver nitrate. Potassium bromide (2 mol% per mole of finished silver halide) was added from the point where the addition of silver nitrate was 80% to 100%. K ₂ [IrCl ₆ ] and K ₂ [RhBr ₅ (H ₂ O)] were added from 83% to 88% addition of silver nitrate. When 90% of the addition of silver nitrate was completed, potassium iodide (0.1 mol% per mol of the 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 grains having a side length of 0.42 μm and a coefficient of variation of 8.0%. This emulsion was subjected to precipitation desalting and redispersion in the same manner as described above.

  This emulsion was dissolved at 40 ° C. and compound I-22, sodium thiosulfate pentahydrate as a sulfur sensitizer and bis (1,4,5-trimethyl-1,2,4-triazolium as a gold sensitizer -3-thiolate) orate (I) tetrafluoroborate) was added 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 G-1.

(Preparation of emulsion RH-1 for red-sensitive layer)
High silver chloride cubic particles were prepared by simultaneously adding silver nitrate and sodium chloride to deionized distilled water containing deionized gelatin and mixing. 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 R-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 with 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 emulsion B-1 were mixed and dissolved, and a first layer coating solution was prepared so as to have the 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. (H-1), (H-2), and (H-3) were used as gelatin hardeners for each layer. Also, Ab-1 to each layer, Ab-2, Ab-3 , and Ab-4 the total amount respectively ^{14.0mg / m 2, 62.0mg / m} 2, 5.0mg / m 2 and 10.0 mg / m ² was added.

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 (B-1) 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
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 (G-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
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 (R-1) 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 obtained as described above was designated as Sample 101. Further, the emulsion B-1 in the blue-sensitive emulsion layer in Sample 101 was changed to the emulsions described in B-2 to B-9, and Samples 102 to 109 were obtained, respectively.

  In order to examine the photographic characteristics of these samples, the following experiment was conducted. Using a sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd.) for each coated sample, an SP-1 filter was attached and exposed for 10 seconds with low illuminance. After the exposure, the following color development processing A was performed.

Processing A
The sample 101 was processed into a 127 mm wide roll, and a standard photographic image was exposed using a digital minilab frontier 350 (trade name, manufactured by Fuji Photo Film Co., Ltd.). Thereafter, continuous processing (running test) 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 process Temperature Time Replenishment color development 38.5 ° C 45 seconds 45 mL
Bleach fixing 38.0 ° C 45 seconds 35 mL
Rinse 1 38.0 ° C. 20 seconds −
Rinse 2 38.0 ° C 20 seconds-
Rinse 3 38.0 ° C. 20 seconds −
Rinse 4 38.0 ° C 20 seconds 121mL
Dry 80 ° C
(note)
* Replenishment amount per 1 m ^{2 of} photosensitive material ** A rinsing screening system RC50D manufactured by Fuji Photo Film Co., Ltd. is attached to the rinsing 3, and the rinsing liquid is taken out from the rinsing 3 and sent 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-1) 2.2g 5.1g
Optical brightener (FL-2) 0.35 g 1.75 g
Triisopropanolamine 8.8g 8.8g
Polyethylene glycol (average molecular weight 300)
10.0g 10.0g
Ethylenediaminetetraacetic acid 4.0 g 4.0 g
Sodium sulfite 0.10g 0.20g
Potassium chloride 10.0 g −
Sodium 4,5-dihydroxybenzene-1,3-disulfonate
0.50g 0.50g
Disodium-N, N-bis (sulfonate ethyl) hydroxylamine
8.5g 14.0g
4-Amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline, 3/2 sulfate, monohydrate
4.8g 14.0g
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 ℃)
10.15 12.40

[Bleaching Fixer] [Tank Solution] [Replenisher]
Water 800mL 300mL
Ammonium thiosulfate (750 g / L) 107 mL 214 mL
m-Carboxybenzenesulfinic acid 8.3 g 16.5 g
Ethylenediamine tetraacetate iron (III) ammonium
47.0g 94.0g
Ethylenediaminetetraacetic acid 1.4 g 2.8 g
Nitric acid (67%) 16.5g 33.0g
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 nitric acid and ammonia water at 25 ° C)
6.5 6.5

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

The following experiment was performed on each sample thus obtained.
(Experiment 1)
The yellow color density of each sample after the treatment was measured to obtain a characteristic curve of 10 second low illumination exposure. The sensitivity (S) is a true value of the reciprocal of the exposure amount giving a color density 1.0 higher than the minimum color density, and is expressed as a relative value with the sensitivity of the sample 101 as 100. Higher values are preferred for higher sensitivity. The gradation (γ) is the difference between the sensitivity of density 0.5 and density 1.5, and is expressed as a relative value where the gradation of sample 101 is 100. The smaller the value, the better the contrast. The fog density (Dmin) represents a value obtained by subtracting the base density from the yellow density of the unexposed area, and the smaller the value, the better the white background. The shoulder concentration (Dmax) of the characteristic curves was compared. The higher the value, the higher the concentration. The results of sensitivity (S), gradation (γ), fog density (Dmin), and shoulder density (Dmax) are shown in Table 2 below.

  From Table 2, samples 105 to 107 and 109, which are silver halide emulsions of the present invention, have almost the same or slightly higher sensitivity than the sample 101 subjected to sulfur sensitization, and the gradation is more hard or equivalent. It can be seen that the fog value is equivalent and Dmax is high. It can be seen that the sensitivity is very high and preferable as compared with the sample 102 sulfur-sensitized with the side length of the same emulsion grain. Further, it can be seen that the fog value is greatly improved as compared with the sample 103 sensitized with selenium and the sample 108 using the compound outside the group as in the samples 105 to 107 and 109. It can also be seen that the effect of selenium sensitization is greater than that of applying the present invention to a sulfur sensitized emulsion as compared with sample 104.

(Experiment 2)
In order to evaluate the change in whiteness due to natural radiation during storage of each sample, each sample was uniformly irradiated with X-rays (120 KV, 1/10 second), and then the samples and X-rays irradiated with X-rays The sample which was not irradiated was similarly subjected to color processing by the processing A, and the preference of the white background after the processing was evaluated. The degree of whiteness represents a value obtained by subtracting the concentration of the sample not irradiated with X-rays from the concentration of the sample irradiated with X-rays. These results are shown in Table 3 below.

  From Table 3, it can be seen that Samples 105 to 107 and 109 using the silver halide emulsion of the present invention have lower fog density after X-ray irradiation and higher whiteness natural radiation resistance than Sample 101.

<Example 2>
In order to examine the photographic characteristics in the ultra-rapid processing of each of the samples 101 to 109, the following experiment was conducted.
Each sample was subjected to gradation exposure for giving gray in the following color development processing B shown below with the following exposure apparatus, and color development processing was performed in processing B 5 seconds after the exposure was completed. As a laser light source, a semiconductor laser (oscillation wavelength of about 940 nm) is obtained by converting a wavelength of a semiconductor laser (oscillation wavelength of about 940 nm) with a LiNbO ₃ SHG crystal having a waveguide inversion domain structure, and a blue laser of about 470 nm and a semiconductor laser (oscillation wavelength of about 1060 nm). A green laser with a wavelength of about 530 nm and a red semiconductor laser with a wavelength of about 650 nm (Hitachi type No. HL6501MG) extracted by wavelength conversion using a LiNbO ₃ SHG crystal having a waveguide-like inversion domain structure were used. The laser beams of the three colors are moved in the direction perpendicular to the scanning direction by the polygon mirror so that the sample can be sequentially scanned and exposed. Variation in the amount of light due to the temperature of the semiconductor laser is suppressed by keeping the temperature constant using a Peltier element. The effective beam diameter was 80 μm, the scanning pitch was 42.3 μm (600 dpi), and the average exposure time per pixel was 1.7 × 10 ⁻⁷ seconds. The temperature of the semiconductor laser was made constant by using a Peltier element in order to suppress the change in light quantity due to temperature.

Process B
The sample 101 was processed into a roll having a width of 127 mm, and a standard photographic image was exposed using a digital minilab frontier 330 (manufactured by Fuji Photo Film Co., Ltd.). Thereafter, continuous processing (running test) 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 B.

Processing process 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)
* Replenishment amount per 1 m ^{2 of} photosensitive material ** A rinsing screening system RC50D manufactured by Fuji Photo Film Co., Ltd. is mounted on the rinsing 3, and the rinsing liquid is taken out from the rinsing 3 and sent 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
Ethylenediamine tetraacetate 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 nitric acid and ammonia water at 25 ° C)
6.00 6.00

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

The yellow color density of each sample after processing was measured, and the same experiment as in Example 1 was performed. As a result, Samples 105 to 107 and 109 of the present invention obtained the same results as in Example 1, and were subjected to laser scanning exposure. It was found that it is also suitable for image formation for ultra-rapid processing.

Claims (7)

  A silver halide emulsion containing silver halide grains having a silver chloride content of 95 mol% or more, containing at least two kinds of compounds having an action of oxidizing metal silver clusters, and sensitized by selenium and gold A silver halide emulsion characterized by A silver halide emulsion containing silver halide grains having a silver chloride content of 95 mol% or more, containing at least two compounds selected from the following groups A to F, and sensitized with selenium and gold A silver halide emulsion characterized by that.
Group A
Compound group B represented by the following general formula (I)
Compound group C represented by the following general formula (II)
Compound group D represented by the following general formula (III)
Hydrogen peroxide or hydrogen peroxide adduct group E
Chlorous acid group F
Inorganic sulfur

(Wherein R ¹ , R ² and R ³ each independently represents an aliphatic group, an aromatic group or a heterocyclic group, and M represents a cation. Here, R ² and R ³ are bonded to each other). R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, alkoxy group, hydroxy group, halogen atom, aryloxy group, Represents an alkylthio group, an arylthio group, an acyl group, a sulfonyl group, an acyloxy group, a carboxyl group, a cyano group, a nitro group, a sulfo group, an alkyl sulfoxide or a trifluoroalkyl group, wherein any of R ⁴ , R ⁵ and R ⁶ May be bonded to each other to form a 5-membered or 6-membered ring or a polycyclic system, R ⁷ represents a carboxylate or O ⁻ , X ⁻ represents an anion counter ion, and w represents 0 Or 1 Be provided that when ^{R 6} is a carboxyl group or a sulfo group, w is a 0, ^{R 7} is O ^-. A it).   The silver halide emulsion according to claim 2, wherein the at least two compounds are compounds selected from different groups among the groups A to F.   4. The silver halide emulsion according to claim 1, wherein an average side length of the silver halide grains is from 0.10 μm to 0.60 μm.   A silver halide color light-sensitive material comprising a yellow dye-forming silver halide emulsion layer, a magenta dye-forming silver halide emulsion layer, and a cyan dye-forming silver halide emulsion layer on a support, and comprising at least one silver halide emulsion A silver halide color photographic light-sensitive material comprising the silver halide emulsion according to any one of claims 1 to 4 in a layer.   A silver halide color light-sensitive material comprising a yellow dye-forming silver halide emulsion layer, a magenta dye-forming silver halide emulsion layer, and a cyan dye-forming silver halide emulsion layer on a support, the yellow dye-forming silver halide emulsion layer A silver halide color photographic material comprising the silver halide emulsion according to any one of claims 1 to 4. A silver halide color light-sensitive material comprising a yellow dye-forming silver halide emulsion layer, a magenta dye-forming silver halide emulsion layer, and a cyan dye-forming silver halide emulsion layer on a support, the silver halide closest to the support A silver halide color photographic light-sensitive material comprising the silver halide emulsion according to any one of claims 1 to 4 in an emulsion layer.