JP2002193942A - Disulfide compound and its production method, method of producing gold complex, silver halide emulsion, and silver halide photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a disulfide compound useful for medicines, agricultural chemicals, and additives for photography, to provide a method for producing the disulfide compound and a gold complex, and to provide a silver halide emulsion as well as a silver halide photosensitive material having supersensitivity, high contrast, small change of sensitivity even when humidity condition varies at exposure, and excellent characteristic of reciprocity law at high intensity of illumination. SOLUTION: The disulfide compound represented by formula (I) and/or the gold complex are/is produced by reacting a mesoionic compound having a thiolate structure and/or a mesoionic compound having a protonated thiolate structure with a Au (III) compound. In formula (I), f represents sulfur atom, e represents carbon atom, a, b, c and d represent a non-substituted or substituted atom or group which form five-membered ring of the mesoionic compound, and x represents an anion which neutralizes the electric charge of the molecule. The silver halide emulsion as well as the silver halide photosensitive material contain the disulfide compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a disulfide compound useful as a pharmaceutical, agrochemical, and a photographic additive, a method for producing the same, and a method for producing a gold complex. More specifically, the present invention relates to a mesoionic compound having a thiolate structure, and / or ,
The present invention relates to a disulfide compound using a mesoionic compound having a protonated thiolate structure as a raw material, a method for producing the same, and a method for producing a gold complex. Further, the present invention relates to a silver halide emulsion containing the disulfide compound and a gold complex, and a silver halide photographic light-sensitive material containing the silver halide emulsion, in particular, high sensitivity and high contrast, at the time of exposure The present invention relates to a silver halide emulsion and a silver halide photographic light-sensitive material which exhibit little sensitivity fluctuation due to a difference in humidity conditions and have excellent reciprocity characteristics at high illuminance.

[0002]

2. Description of the Related Art In the fields of medicines, agricultural chemicals, photographic additives and the like, development of useful and novel disulfide compounds has been desired. As for the method for producing a disulfide compound, a simple and efficient production method is desired. In general, various methods for synthesizing a disulfide compound are known. For example, Maruzen Co., Ltd. 4th edition Experimental Chemistry Lecture 24 Organic Synthesis IV
As described in the general synthesis method on page 330, a method of oxidizing a thiol compound with an oxidizing agent is general. Various metal complexes are known as the oxidizing agent, but there are few examples of synthesizing a disulfide using a gold compound (particularly, an Au (III) compound). Further, there is no example of application to a mesoionic compound having a thiolate structure and / or a mesoionic compound having a protonated thiolate structure, and a disulfide compound derived therefrom is not known. Regarding the synthesis of a gold complex, for example, JP-A-4-267249 discloses a synthesis example of a mesoionic gold compound. However, a multistep process has been required, and a simpler production method has been demanded in terms of yield and purity.

[0003] In recent years, there has been an increasing demand for high sensitivity, high image quality, and performance such as toughness during processing in color photographic paper. Emulsions with little photographic fluctuation are desired.

In order to achieve high sensitivity of the color photographic paper, gold sensitization is an effective means. As the gold compound used for the gold sensitization, an Au (I) compound containing a meso-ion ligand having a thiolate structure is known, and JP-A-4-267249 discloses that it is useful for producing a high-sensitivity, high-contrast emulsion. Is disclosed.

Further, a specific compound having a disulfide structure is disclosed in JP-A-10-123658 and the like. When the disulfide compound is used together with an Au (III) compound (gold sensitizer), there is a problem that the sensitivity is slightly lowered due to the disulfide compound and adversely affects the disulfide compound.

Therefore, it is extremely important in organic synthetic chemistry to simply and efficiently synthesize a disulfide compound and a gold complex from a mesoionic compound having a thiolate structure and / or a mesoionic compound having a protonated thiolate structure. That is. Further, particularly in the field of silver halide photography, as described above, there is a strong demand for the development of a compound capable of preparing a silver halide emulsion having high sensitivity and high contrast.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems and achieve the following objects. That is, first, an object of the present invention is to provide a novel disulfide compound which is useful in the fields of medicines, agricultural chemicals, photographic additives and the like. Second, the present invention relates to a mesoionic compound having a thiolate structure, and / or
Alternatively, it is an object of the present invention to provide a simple and efficient method for producing a disulfide compound and a method for producing a gold complex, using a mesoionic compound having a protonated thiolate structure as a raw material. Third, the present invention uses the disulfide compound, the gold complex, or a mixed solution thereof, has high sensitivity and high contrast, and has a small sensitivity variation due to a difference in humidity conditions at the time of exposure, and a high illuminance. It is an object of the present invention to provide a silver halide emulsion having excellent reciprocity characteristics and a silver halide photographic material containing the silver halide emulsion.

[0008]

Means for solving the above problems are as follows. That is, <1> a disulfide compound represented by the following general formula (I).

[0009]

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In the general formula (I), f represents a sulfur atom. e represents a carbon atom. a, b, c, and d are unsubstituted or substituted atoms or groups forming a 5-membered ring of the mesoionic compound, and each independently represents a C—R group, N
—R ′ represents a group, an oxygen atom or a sulfur atom. R and R ′ each independently represent a hydrogen atom or a substituent. X represents an anion that neutralizes the charge of the molecule.

<2> A mesoion compound having a thiolate structure represented by the following general formula (II-1) and / or a mesoion compound having a protonated thiolate structure represented by the following general formula (II-2) The disulfide compound according to <1>, which is synthesized from the compound by an oxidation reaction.

[0012]

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The general formula (II-1) and the general formula (II-
In 2), f represents a sulfur atom. e represents a carbon atom. a, b, c and d are unsubstituted or substituted atoms or groups forming a 5-membered ring of the mesoionic compound, each independently being a C—R group, an N—R ′ group, an oxygen atom, or Represents a sulfur atom. R and R ′ each independently represent a hydrogen atom or a substituent. Y represents an anion that neutralizes the charge of the molecule.

<3> In the oxidation reaction, Au (II
I) The disulfide compound according to <2>, wherein the compound is a compound.

<4> Mesoionic compound having a thiolate structure represented by the following general formula (II-1) and / or mesoion having a protonated thiolate structure represented by the following general formula (II-2) A method for producing a disulfide compound represented by the following general formula (I), which comprises using a compound.

[0016]

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In the general formula (I), f represents a sulfur atom. e represents a carbon atom. a, b, c, and d are unsubstituted or substituted atoms or groups forming a 5-membered ring of the mesoionic compound, and each independently represents a C—R group, N
—R ′ represents a group, an oxygen atom or a sulfur atom. R and R ′ each independently represent a hydrogen atom or a substituent. X represents an anion that neutralizes the charge of the molecule.

[0018]

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The formulas (II-1) and (II-)
In 2), f represents a sulfur atom. e represents a carbon atom. a, b, c and d are unsubstituted or substituted atoms or groups forming a 5-membered ring of the mesoionic compound, each independently being a C—R group, an N—R ′ group, an oxygen atom, or Represents a sulfur atom. R and R ′ each independently represent a hydrogen atom or a substituent. Y represents an anion that neutralizes the charge of the molecule.

<5> A method for producing a disulfide compound represented by the following general formula (I), characterized by using an Au (III) compound.

[0021]

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In the general formula (I), f represents a sulfur atom. e represents a carbon atom. a, b, c, and d are unsubstituted or substituted atoms or groups forming a 5-membered ring of the mesoionic compound, and each independently represents a C—R group, N
—R ′ represents a group, an oxygen atom or a sulfur atom. R and R ′ each independently represent a hydrogen atom or a substituent. X represents an anion that neutralizes the charge of the molecule.

<6> A method for producing a gold complex represented by the following general formula (III), comprising a Au (III) compound and a mesoionic compound having a thiolate structure represented by the following general formula (II-1) And / or a mesoionic compound having a protonated thiolate structure represented by the following general formula (II-2).

[0024]

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The general formula (II-1) and the general formula (II-
In 2), f represents a sulfur atom. e represents a carbon atom. a, b, c and d are unsubstituted or substituted atoms or groups forming a 5-membered ring of the mesoionic compound, each independently being a C—R group, an N—R ′ group, an oxygen atom, or Represents a sulfur atom. R and R ′ each independently represent a hydrogen atom or a substituent. Y represents an anion that neutralizes the charge of the molecule.

[0026]

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In the above general formula (III), a to f are
It is synonymous with the general formulas (II-1) and (II-2). Z represents an anion. m represents an integer of 1 or 2.
n represents an integer of 1 to 4.

<7> A silver halide emulsion containing the disulfide compound represented by formula (I) according to any one of <1> to <3>. <8> The silver halide emulsion according to <7>, containing the gold complex represented by the general formula (III) produced by the method for producing a gold complex according to <6>. <9> A silver halide photographic material comprising the silver halide emulsion according to <7> or <8>.

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. First, the disulfide compound of the present invention, a method for producing the same, and a method for producing a gold complex will be described.

(Disulfide compound and method for producing the same,
And a method for producing a gold complex) The disulfide compound of the present invention is characterized by being represented by the following general formula (I).

[0031]

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In the general formula (I), f represents a sulfur atom. e represents a carbon atom. a, b, c, and d are unsubstituted or substituted atoms or groups forming a 5-membered ring of the mesoionic compound, and each independently represents a C—R group, N
—R ′ represents a group, an oxygen atom or a sulfur atom. R and R ′ each independently represent a hydrogen atom or a substituent.

In the above a, b, c and d, further adjacent groups may be bonded to each other to form a ring. Also,
Examples of the substituent represented by R and R ′ include an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an alkynyl group, an aralkyl group, a heterocyclic group, a halogen atom, an alkoxy group, an aryloxy group, an amino group, Ureido group, urethane group, sulfonyl group, sulfinyl group,
Sulfonamide group, sulfamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy group, alkylthio group, arylthio group, cyano group, hydroxy group, mercapto group, carboxy group, phosphono group, nitro group, sulfo group, Preferable examples include a sulfino group, an ammonium group, and a silyl group.

Among the above alkyl groups, those having 1 to 20 carbon atoms
Are preferable, and a linear or branched alkyl group having 1 to 10 carbon atoms is more preferable. Among them, for example,
Methyl, ethyl, i-propyl, t-butyl, n-octyl are particularly preferred. Among the cycloalkyl groups,
A cycloalkyl group having 3 to 20 carbon atoms is preferable, and a cycloalkyl group having 3 to 10 carbon atoms is more preferable. Among them, for example, a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group are particularly preferable. Among the aryl groups, an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 carbon atoms is preferable.
A monocyclic or condensed aryl group of 10 to 10 is more preferable, and among them, for example, a phenyl group, a naphthyl group, and a 4-methylphenyl group are particularly preferable.

Among the alkenyl groups, those having 2 to 2 carbon atoms
An alkenyl group of 0 is preferable, and an alkenyl group having 2 to 10 carbon atoms is more preferable. Among them, for example, an allyl group, a 2-butenyl group, and a 3-pentenyl group are particularly preferable. Among the alkynyl groups, an alkynyl group having 2 to 20 carbon atoms is preferable, an alkynyl group having 2 to 10 carbon atoms is more preferable, and among them, for example, a propargyl group,
A 3-pentynyl group is particularly preferred. Among the aralkyl groups, an aralkyl group having 7 to 20 carbon atoms is preferable, an aralkyl group having 7 to 10 carbon atoms is more preferable, and among them, for example, a benzyl group and a phenethyl group are particularly preferable.

Among the above heterocyclic groups, those having 0 to 20 carbon atoms
Is preferably a heterocyclic group having 0 to 10 carbon atoms, and has at least one heteroatom as a ring-constituting atom, and includes an oxygen atom, a sulfur atom, a nitrogen atom, and a carbon atom. Heterocyclic groups composed of selected atoms are more preferred, among which, for example, a pyridyl group,
Furyl, imidazolyl, piperidyl and morpholino groups are particularly preferred. Among the halogen atoms, for example, a fluorine atom, a chlorine atom, and a bromine atom are preferable. Among the alkoxy groups, an alkoxy group having 1 to 20 carbon atoms is preferable, and an alkoxy group having 1 to 10 carbon atoms is more preferable. Among them, for example, a methoxy group, an ethoxy group,
Butoxy groups are particularly preferred. Among the aryloxy groups, an aryloxy group having 6 to 20 carbon atoms is preferable,
An aryloxy group having 6 to 10 carbon atoms is more preferable, and among them, for example, a phenoxy group and a 2-naphthyloxy group are particularly preferable.

Among the above amino groups, an amino group having 0 to 20 carbon atoms is preferable, and an amino group having 0 to 10 carbon atoms is more preferable. Among them, for example, an unsubstituted amino group, a dimethylamino group, an ethylamino group, Anilino groups are particularly preferred. Among the ureido groups, a ureido group having 1 to 20 carbon atoms is preferable, and a ureido group having 1 to 10 carbon atoms is more preferable. Among them, for example, an unsubstituted ureido group, N-
A methylureide group and an N-phenylureide group are particularly preferred. Among the urethane groups, a urethane group having 1 to 20 carbon atoms is preferable, and a urethane group having 1 to 10 carbon atoms is more preferable. Among them, for example, a methoxycarbonyl group, an amino group, and a phenoxycarbonylamino group are particularly preferable.

Among the sulfonyl groups, those having 1 to 2 carbon atoms
A sulfonyl group of 0 is preferable, and a sulfonyl group having 1 to 10 carbon atoms is more preferable. Among them, for example, a mesyl group and a tosyl group are particularly preferable. Among the sulfinyl groups, a sulfinyl group having 1 to 20 carbon atoms is preferable, a sulfinyl group having 1 to 10 carbon atoms is more preferable, and among them, for example, a methylsulfinyl group and a phenylsulfinyl group are particularly preferable. Among the sulfonamide groups, a sulfonamide group having 1 to 20 carbon atoms is preferable.
To 10 to 10 sulfonamide groups are more preferable, and among them, for example, a methanesulfonamide group is particularly preferable. Among the sulfamoyl groups, a sulfamoyl group having 1 to 20 carbon atoms is preferable, a sulfamoyl group having 1 to 10 carbon atoms is more preferable, and among them, for example, an N-methylsulfamoyl group is particularly preferable.

Among the above alkyloxycarbonyl groups, an alkyloxycarbonyl group having 2 to 20 carbon atoms is preferable, and an alkyloxycarbonyl group having 2 to 10 carbon atoms is more preferable. Among them, for example, a methoxycarbonyl group and an ethoxycarbonyl group are preferable. Is particularly preferred. Among the aryloxycarbonyl groups, an aryloxycarbonyl group having 6 to 20 carbon atoms is preferable, and an aryloxycarbonyl group having 6 to 1 carbon atoms is preferable.
An aryloxycarbonyl group of 0 is more preferable, and among them, for example, a phenoxycarbonyl group is particularly preferable. Among the acyl groups, an acyl group having 1 to 20 carbon atoms is preferable, and an acyl group having 1 to 10 carbon atoms is more preferable. Among them, for example, an acetyl group, a benzoyl group,
A formyl group and a pivaloyl group are particularly preferred.

Among the above acyloxy groups, those having 1 to 1 carbon atoms
An acyloxy group of 20 is preferable, and an acyloxy group having 1 to 10 carbon atoms is more preferable. Among them, for example, an acetoxy group and a benzoyloxy group are particularly preferable. Among the alkylthio groups, an alkylthio group having 1 to 20 carbon atoms is preferable, an alkylthio group having 1 to 10 carbon atoms is more preferable, and among them, for example, a methylthio group and an ethylthio group are particularly preferable. Among the arylthio groups, an arylthio group having 6 to 20 carbon atoms is preferable, an arylthio group having 6 to 10 carbon atoms is more preferable, and among them, for example, a phenylthio group is particularly preferable. Among the above ammonium groups, for example, a trimethylammonio group is preferable. Among the silyl groups, for example, a trimethylsilyl group is preferable.

Among the groups represented by R and R ', a hydrogen atom, an alkyl group and an aryl group are preferred, a hydrogen atom and an alkyl group are more preferred, and an alkyl group is most preferred.

The groups represented by R and R 'may be further substituted with a substituent.
And the substituents exemplified as the groups represented by R ′. When there are two or more substituents represented by R and R ′, they may be the same or different.

In the general formula (I), X represents an anion for neutralizing the electric charge of the molecule. X is preferably, for example, a chloride ion, a halogen ion such as a bromine ion, an inorganic anion such as a tetrafluoroborate anion, or an organic anion such as an acetate ion. Among them, a chlorine ion and a tetrafluoroborate anion are more preferable. preferable.

The disulfide compound represented by formula (I) preferably has a total of 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and more preferably 2 to 1
Most preferably, it is 2.

Preferred specific examples (I-1 to 15) of the disulfide compound represented by the general formula (I) of the present invention are shown below, but the present invention is not limited thereto.

[0046]

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[0047]

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[0048]

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The disulfide compound represented by the general formula (I) of the present invention is a mesoionic compound having a thiolate structure represented by the following general formula (II-1):
Alternatively, it is preferably synthesized by an oxidation reaction from a mesoionic compound having a protonated thiolate structure represented by the following general formula (II-2).

[0050]

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The formulas (II-1) and (II-)
In 2), f represents a sulfur atom. e represents a carbon atom. a, b, c and d are unsubstituted or substituted atoms or groups forming a 5-membered ring of the mesoionic compound, each independently being a C—R group, an N—R ′ group, an oxygen atom, or Represents a sulfur atom. R and R ′ each independently represent a hydrogen atom or a substituent. Y represents an anion that neutralizes the charge of the molecule.

The formulas (II-1) and (II-)
In 2), the description of a, b, c and d, R and R ′, and specific examples of preferred groups are the same as those in the disulfide compound represented by the general formula (I).

In the general formula (II-2), Y represents an anion for neutralizing the electric charge of the molecule, and the anion includes an inorganic anion such as a chloride ion and a halogen ion such as a bromine ion; A conjugate base of an organic acid such as an acetate ion or a trifluoroacetate ion is preferably used.

The mesoionic compound having a protonated thiolate structure represented by the general formula (II-2) is
F of the mesoionic compound having a thiolate structure represented by the general formula (II-1), that is, a compound in which the thiolate group is protonated. Protonated thiolate groups are designated SH groups. The pKa of the SH group is low, and in a neutral aqueous solution, almost all of the protons of the SH group dissociate to form a mesoionic compound having a thiolate structure.
In the present invention, a mesoionic compound having a thiolate structure represented by the general formula (II-1), and / or
Although a mesoionic compound having a protonated thiolate structure represented by the general formula (II-2) can be used, a mesoionic compound having a thiolate structure represented by the general formula (II-1) can be used. Is preferred.

Examples of the mesoionic compound having a thiolate structure represented by the general formula (II-1) include, for example,
1,3-diazolium-4-thiolates, 1,3-thiazolium-5-thiolates, 1,2,3-oxadiazolium-5-thiolates, 1,3,4-oxadiazolium-2-thiolate , 1,2,3-triazolium-4-thiolate, 1,2,4-triazolium-3-thiolate, 1,2,3-thiadiazolium-5-thiolate, 1,3,4-thiarate Diazolium
2-thiolates, 1,2,3,4-oxatriazolium-5-thiolates, 1,2,3,4-tetrazolium-5-thiolates, 1,2,3,4-thiatriazolium -5-thiolates, 1,2-dithiolium-
4-thiolates are preferred.

In the present invention, the compound represented by the general formula (II-1)
Among the examples of the mesoionic compound having a thiolate structure represented by 1,3-diazolium-4-thiolates, 1,3-thiazolium-5-thiolates, 1,
2,3-oxadiazolium-5-thiolates, 1,
3,4-oxadiazolium-2-thiolates, 1,
2,3-triazolium-4-thiolates, 1,2,2
4-triazolium-3-thiolates, 1,2,3-
Thiadiazolium-5-thiolates and 1,3,4-thiadiazolium-2-thiolates are preferred, and among them, 1,3-diazolium-4-thiolates,
3-Thiazolium-5-thiolates, 1,2,3-triazolium-4-thiolates, and 1,2,4-triazolium-3-thiolates are more preferred.

Among the more preferred examples of the mesoionic compound having a thiolate structure represented by the general formula (II-1), 1,3-diazolium-4-thiolates,
3-Thiazolium-5-thiolates and 1,2,4-triazolium-3-thiolates are more preferred, and among them, 1,2,4-triazolium-3-thiolates are most preferred.

Specific examples of the meso-ionic compound having a thiolate structure represented by the general formula (II-1) of the present invention (II
Specific examples of the mesoionic compound (II-2-1) having a protonated thiolate structure represented by the following general formula (II-2) are shown below. It is not limited to these.

[0059]

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[0060]

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The mesoionic compound having a thiolate structure represented by the general formula (II-1) and the mesoionic compound having a protonated thiolate structure represented by the general formula (II-2) according to the present invention are: Can be synthesized according to a synthesis method described in the following known documents. For example, tetrahedron (Te) such as Ramsden
Trahedron), Volume 38, pp. 2965-301.
1 page, 1982, Vol. 33, 3203-3232
Page, 1977, Advances in Hete
rocyclic Chemistry, Vol. 19, 1
Pp. 122, published in 1976.

The disulfide compound represented by the general formula (I) of the present invention may be a mesoionic compound having a thiolate structure represented by the general formula (II-1) and / or
It is preferably synthesized from a mesoionic compound having a protonated thiolate structure represented by the general formula (II-2) by an oxidation reaction. In the oxidation reaction,
It is more preferable to use an Au (III) compound.

The Au (II) used in the above oxidation reaction
Examples of the compound (I) include chloroauric acid, potassium tetrachloroaurate, ammonium tetrabromoaurate, gold (II) chloride, gold (II) bromide, gold (II) iodide, potassium gold (II) iodide, and gold ( III) Hydroxide and the like are preferable, and among them, chloroauric acid, potassium tetrachloroaurate and ammonium tetrabromoaurate are more preferable, and chloroauric acid is particularly preferable.

The solvent used for producing the disulfide compound represented by the above general formula (I) of the present invention includes water,
Alcohols are preferred, and among them, water is more preferred. In the production of the disulfide compound represented by the general formula (I) of the present invention, the compound represented by the general formula (II-
Molar mixing of a mesoionic compound having a thiolate structure represented by 1) and / or a mesoionic compound having a protonated thiolate structure represented by the general formula (II-2) and an Au (III) compound The ratio is from 1: 1 to 2
It is preferably 0: 1, more preferably 2: 1 to 10: 1, and most preferably 4: 1 to 6: 1. In the production of the disulfide compound represented by the general formula (I) of the present invention, the reaction temperature is from 0 ° C to 80 ° C.
C is preferable, 10C to 60C is more preferable, and 20C
~ 50 ° C is most preferred.

The method for producing a gold complex represented by the following general formula (III) according to the present invention comprises the steps of: preparing an Au (III) compound; a mesoionic compound having a thiolate structure represented by the general formula (II-1); And / or a mesoionic compound having a protonated thiolate structure represented by the general formula (II-2).

[0066]

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In the general formula (III), a to f are
It has the same meaning as that of the general formulas (II-1) and (II-2). The description of a, b, c and d, R and R ′, and specific examples of preferred groups are the same as those in the disulfide compound represented by the general formula (I). In the general formula (III), Z represents an anion. As the anion, a chloride ion, a bromine ion, a tetrafluoroborate anion, and an acetate ion are preferable, and among them, a chloride ion and a tetrafluoroborate anion are more preferable. The general formula (II
In I), m represents an integer of 1 or 2. n represents an integer of 1 to 4.

Specific examples (III-1 to III-1) of the gold complex represented by the general formula (III) obtained by the method for producing a gold complex of the present invention.
14) is shown below, but the present invention is not limited to these.

[0069]

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[0070]

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The Au (III) compound, the mesoionic compound having a thiolate structure represented by the above general formula (II-1), and the mesoionic compound having a thiolate structure represented by the above general formula (II-2) used in the method for producing a gold complex of the present invention. Examples of the mesoionic compound having a protonated thiolate structure represented by the above include those preferably used in the production of the disulfide compound represented by the above general formula (I). Preferred solvents, molar mixing ratios, reaction temperatures And so on. That is, in the method for producing a disulfide compound and the method for producing a gold complex according to the present invention, an Au (III) compound and a compound represented by the general formula (II-
By using a mesoionic compound having a thiolate structure represented by 1) and a mesoionic compound having a protonated thiolate structure represented by the general formula (II-2), the compound represented by the general formula (I) is used. And the gold complex represented by the general formula (III) can be obtained at the same time.

When the disulfide compound represented by the general formula (I) of the present invention and the gold complex represented by the general formula (III) are produced at the same time, they can be easily separated. These compounds may be generally used after being isolated and purified, or may be used as they are without taking out those produced in the medium used. This means that in the present invention, "synthesis" or "production" and "production" are used synonymously. For example, a compound represented by the general formula (II-1): And / or the general formula (II
In the presence of the compound represented by -2) and / or the Au (III) compound, the product is "formed" as a "synthesized" or "manufactured" of the present invention.

Next, the silver halide emulsion of the present invention and a silver halide photographic light-sensitive material containing the silver halide emulsion will be described in detail.

(Silver Halide Emulsion) The silver halide emulsion of the present invention is characterized by containing the disulfide compound represented by the above formula (I), and further comprises the above formula (II)
It preferably contains the gold complex represented by I).

<Gold Sensitization> The silver halide emulsion of the present invention comprises:
Gold sensitization was performed using various Au (III) compounds. Examples of the Au (III) compound include chloroauric acid, potassium tetrachloroaurate, ammonium tetrachloroaurate, potassium tetrabromoaurate, gold (II) chloride, gold (II) bromide, gold (II) iodide, and metal iodide. Potassium gold fluoride, gold (III) hydroxide and the like can be used.

In the present invention, the Au (III) compound used as a gold sensitizer is a mesoionic compound having a thiolate structure represented by the general formula (II-1), and / or
Alternatively, a mesoionic compound having a protonated thiolate structure represented by the above general formula (II-2) (hereinafter sometimes simply referred to as “mesoionic compound”) is separately added to a silver halide emulsion. And may be added simultaneously. In the present invention, the mesoionic compound and the Au (III) compound can be added to a silver halide emulsion after the silver halide grains are formed and before the completion of chemical sensitization. It is preferably added during ripening.

The mesoionic compound and the Au (II
I) The addition ratio (molar ratio) to the compound is 20/1
To 0.5 / 1, but 15/1 to 1/1.
Is preferred, and 10/1 to 2/1 is more preferred, and 8/1
４4/1 is most preferred. Further, the Au (III) compound and the mesoionic compound may be mixed in a solvent and then added to the silver halide emulsion. As a solvent for mixing them, water, alcohol and the like are preferably exemplified, and among them, water is preferred. The pH of the solvent can be adjusted by adding an acid or an alkali to the solvent, and the pH of the solvent is preferably from 2 to 11, and more preferably from 3 to 8. From the viewpoint of the stability of the mixed solution, the time after mixing the Au (III) compound and the mesoionic compound is preferably within 3 days, more preferably within 1 day, and most preferably within 6 hours. As a method for adding the Au (III) compound and the mesoionic compound, a method in which both are mixed in a solvent in advance and then added to a silver halide emulsion is preferable.

The amount of the Au (III) compound added can vary widely depending on the case, but is preferably from 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol per mol of silver halide, preferably from 5 × 10 ⁻³ mol.
^{-6 to} 5 × 10 ^-4 mol is more preferred.

In the present invention, gold sensitization is combined with other sensitization methods such as sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization, and noble metal sensitization using a compound other than a gold compound. You may. In the present invention, a combination of gold sensitization and sulfur sensitization is preferred.

The mesoionic compound and the Au (II
When the compound (I) and the compound are mixed with each other, a disulfide compound which is an oxidized dimer thereof is formed. In particular, by mixing the mesoionic compound and the Au (III) compound before adding them to the silver halide emulsion, Au (II)
A molar number of disulfide compounds approximately equal to I) can be generated. The present invention also differs from the sensitization method using a mesoionic gold (I) compound described in JP-A-4-267249 in that the present invention includes this disulfide compound.

A specific compound having a disulfide structure is disclosed in JP-A-10-123658 and the like. The disulfide compound represented by the above general formula (I) of the present invention has a positive charge. It has a structure completely different from the above-mentioned disulfide compound in that it has an aromatic heterocycle. Further, when the disulfide compound described in JP-A-10-123658 is used together with an Au (III) compound (gold sensitizer), the disulfide compound has an adverse effect of slightly lowering the sensitivity. The disulfide compound represented by the general formula (I) is Au (II)
I) There is an advantage that the sensitivity is not reduced even when used together with the compound.

Further, the silver halide photographic light-sensitive material containing the silver halide emulsion of the present invention has high sensitivity in both low illuminance and high illuminance, and has good toughness against humidity change during exposure. Has the advantage of photographic properties.

<Silver Halide Grains> The silver halide grains in the silver halide emulsion according to the present invention are substantially $ 10.
Cubes with 0 ° planes, tetrahedral crystal grains (these may have rounded particle vertices and have higher planes), or octahedral crystal grains, or 5 of the total projected area
Tabular grains having an aspect ratio of 2 or more in which 0% or more are composed of {100} planes or {111} planes are preferred. Here, the aspect ratio is a value obtained by dividing a diameter of a circle corresponding to a projection area by a thickness of a particle. In the present invention, a cube or $ 10
Tabular grains having a main plane of the {0} plane or tabular grains having a main plane of the {111} plane are more preferred.

As the silver halide emulsion used in the present invention, silver chloride, silver bromide, silver iodobromide, silver chloro (iodo) bromide emulsion and the like can be used. Silver chloride, silver chlorobromide, silver chloroiodide having a content of 95 mol% or more,
Alternatively, a silver chlorobromoiodide emulsion is preferable, and a silver chloride, silver chlorobromide, silver chloroiodide, or silver chlorobromoiodide emulsion having a silver chloride content of 98 mol% or more is more preferable. Among such silver halide emulsions, 0.01 to 0.50 mol%, more preferably 0.05 to 0.40 mol% of iodine is preferably added to the shell portion of the silver halide grains per mol of total silver. Those having a silver chloride phase are more preferred because they provide high sensitivity and are excellent in high illuminance exposure suitability. Here, the "shell portion" refers to a portion having a volume ratio of 0 to 30% in the outer shell portion of the silver halide grain. Further, those having a silver bromide localized phase of preferably 0.2 to 5 mol%, more preferably 0.5 to 3 mol%, based on the total silver mol, on the surface of silver halide grains,
It is particularly preferable because high sensitivity can be obtained and photographic performance can be stabilized.

The silver halide emulsion of the present invention preferably contains silver iodide. As a method for introducing iodide ions, a method of adding an iodide salt solution alone or a method of adding an iodide salt solution in combination with the addition of a silver salt solution and a high chloride salt solution may be adopted. In the latter case, a method of adding the iodide salt solution and the high chloride salt solution separately or as a mixed solution of the iodide salt and the high chloride salt may be adopted. The iodide salt is added in the form of a soluble salt, such as an alkali iodide salt or an alkaline earth iodide salt. Alternatively, as described in US Pat. No. 5,389,508,
It is also possible to adopt a method of introducing iodide by cleaving iodide ions from organic molecules. Also, fine silver iodide grains can be used as another iodide ion source.

The addition of the iodide salt solution may be carried out intensively at one stage of grain formation, or may be carried out over a certain period of time. The position at which iodide ions are introduced into a high chloride emulsion is limited in order to obtain an emulsion having high sensitivity and low fogging. As the introduction of iodide ions is made deeper into the emulsion grains, the increase in sensitivity is smaller. Thus, the addition of the iodide salt solution is preferably from outside 50% of the particle volume, more preferably from outside 70%, most preferably from outside 80%. Further, the addition of the iodide salt solution is preferably completed within 98% of the particle volume, and particularly preferably completed within 96% of the particle volume. When the addition of the iodide salt solution is completed slightly inward from the grain surface, an emulsion with higher sensitivity and lower fogging can be obtained.

The distribution of iodide ion concentration in the depth direction in the grain is determined by etching / TOF-SIMS (Timeo
f Flight-Secondion Ion
Mass Spectrometry) method, for example, TRIFII type TOF-S manufactured by Phi Evans
It can be measured using IMS. The TOF-SIMS method is specifically described in “Surface Analysis Technology Selection Secondary Ion Mass Spectrometry” edited by The Surface Science Society of Japan, Maruzen Co., Ltd. (1999). Etching / TOF-SIMS
When the emulsion grains are analyzed by the method, even if the addition of the iodide salt solution is completed inside the grains, it can be analyzed that the iodide ions are seeping out toward the grain surface. When the silver halide emulsion of the present invention contains silver iodide, etching / TOF-
In the analysis by the SIMS method, it is preferable that the iodide ion has a concentration maximum on the particle surface and the iodide ion concentration is attenuated inward.

The silver halide emulsion of the present invention preferably has a silver bromide localized layer. When the silver halide emulsion of the present invention contains a silver bromide localized phase, it is more preferable that the silver bromide content is at least 10 mol% or more by epitaxially growing a silver bromide localized phase on the grain surface. It is more preferable to have an outermost shell portion having a silver bromide content of 1 mol% or more near the surface layer. The silver bromide content of the silver bromide localized phase is preferably from 1 to 80 mol%, more preferably from 5 to 70 mol%. The silver bromide localized phase is preferably composed of silver in an amount of 0.1 to 30 mol% of the total silver constituting the silver halide grains in the present invention, and is preferably composed of silver in an amount of 0.3 to 20 mol%. More preferably, it is constituted. In the silver bromide localized phase, first iridium (III) chloride, first bromide
Iridium (III), iridium (II) chloride, sodium hexachloroiridate (III), potassium hexachloroiridium (IV), hexaammineiridium (IV) salt, trioxalatoiridium (III) salt,
It is preferable to contain a Group VIII metal complex ion such as a trioxalatoiridium (IV) salt. The addition amount of these compounds varies widely depending on the purpose, but is preferably from 10 ^-9 to 10 ^-2 mol per mol of silver halide.

In the present invention, a transition metal ion is added during the process of forming and / or growing silver halide grains,
Metal ions can be incorporated inside and / or on the surface of the silver halide grains. As the metal ion to be used, a transition metal ion is preferable, and among them, iron, ruthenium, iridium, osmium, lead, cadmium, or zinc is preferable. Furthermore, these metal ions are more preferably used as a hexacoordinate octahedral complex with a ligand. When an inorganic compound is used as the ligand, cyanide ion, halide ion, thiocyanate, hydroxide ion, peroxide ion, azide ion, nitrite ion, water, ammonia, nitrosyl ion, or thiol ion Nitrosyl ions are preferably used as ligands, and the iron, ruthenium, iridium, osmium,
It is preferable to use by coordinating with any metal ion among lead, cadmium and zinc, and it is also preferable to use plural kinds of ligands in one complex molecule. In addition, an organic compound can be used as the ligand. Preferred examples of the organic compound include a chain compound having 5 or less carbon atoms in the main chain and / or a 5- or 6-membered heterocyclic compound. be able to. Among them, the nitrogen atom in the molecule,
A compound having a phosphorus atom, an oxygen atom, or a sulfur atom as a coordinating atom to a metal is more preferable, and furan, thiophene, oxazole, isoxazole, thiazole,
Most preferred are isothiazole, imidazole, pyrazole, triazole, furazane, pyran, pyridine, pyridazine, pyrimidine, and pyrazine. Compounds having these compounds as a basic skeleton and further introducing a substituent into them are also preferable.

Combination of the metal ion and the ligand
These include iron ions, cyanide ions, ruthenium ions
A combination of on and cyanide ions is preferred. This
In these combinations, the cyanide ion has a central
The majority of the coordination numbers to the iron or ruthenium metal
Preferably, the remaining coordination sites are thiocyan,
Ammonia, water, nitrosyl ion, dimethyl sulfoxy
Sid, pyridine, pyrazine, and 4,4'-bipyridine
More preferably. center
All six coordination sites of metal are occupied by cyanide ions
Hexacyanoiron complex or hexacyanoruthenium complex
Most preferably, the body is formed. These cyanide a
The complex having on as a ligand was equivalent to 1 mole of silver during grain formation.
1 × 10^-81 x 10 from mole^-2It is preferable to add
Better 1 × 10^-65 × 10 from mole^-FourAdd mole
Is more preferable. Using iridium as the central metal
In this case, the ligands are fluoride ion, chloride ion
, Bromide ions and iodide ions are preferred.
But chloride or bromide ions are more preferred
No. Complexes using iridium as the central metal (hereinafter referred to as
It may be called "iridium complex". Preferred)
As a specific example, [IrCl₆]^3-, [IrCl₆]^2-,
[IrCl_Five(H_TwoO)]^2-, [IrCl_Five(H
_TwoO)]^-, [IrCl_Four(H_TwoO)_Two]^-, [IrCl
_Four(H_TwoO)_Two]⁰, [IrCl_Three(H_TwoO)_Three]⁰, [IrC
l_Three(H_TwoO)_Three]⁺, [IrBr₆]^3-, [IrB
r₆]^2-, [IrBr_Five(H_TwoO)]^{Two -}, [IrBr_Five(H
_TwoO)]^-, [IrBr_Four(H_TwoO)_Two]^-, [IrBr
_Four(H_TwoO)_Two]⁰, [IrBr_Three(H_TwoO)_Three]⁰, And [I
rBr_Three(H_TwoO)_Three]⁺Are preferably mentioned. Said iris
During the formation of silver halide grains, the indium complex was converted to 1 mol
1 × 10 ^-Ten1 x 10 from mole^-3Mole addition
Is preferably 1 × 10^-81 x 10 from mole^-FiveAdd mole
Is most preferred. Ruthenium and osmium inside
When the core metal is used, the ligand is nitrosyl ion
Thionitrosyl ion, water molecule, or chloride ion
Are preferably used together. For example, pentachloroni
Trosyl complex, pentachlorothionitrosyl complex, or
More preferred to form pentachloroaqua complex
In addition, it is more preferable to form a hexachloro complex.
As complexes with ruthenium and osmium as central metals
Is 1 × 1 per mole of silver during silver halide grain formation.
0^-Ten1 x 10 from mole^-6Molar addition is preferred
1 × 10^-91 x 10 from mole^-6Can be added in moles
More preferred.

In the present invention, the complex is added directly to the reaction solution when forming silver halide grains, or in an aqueous halide solution for forming silver halide grains, or in another solution. It is preferable to incorporate into silver halide grains by adding it to the grain forming reaction solution. Further, it is also preferable that these methods be combined and contained in silver halide grains.

When these complexes are incorporated into silver halide grains, it is preferable that they are uniformly present in the grains. However, JP-A-4-208936 and JP-A-2-12524 are also preferable.
No. 5, JP-A-3-18837, it is also preferable that the complex is present only on the particle surface layer, and a complex is present only inside the particle and a layer containing no complex is added on the particle surface. It is also preferable to do so. Further, as disclosed in U.S. Pat. Nos. 5,252,451 and 5,256,530, it is also possible to physically ripen the complex with fine particles in which the complex is incorporated in the particles to modify the particle surface phase. preferable. Further, these methods may be used in combination, and plural kinds of complexes may be incorporated in one silver halide grain. There is no particular limitation on the halogen composition at the position where the complex is contained, and a silver chloride layer, a silver chlorobromide layer,
It is also preferred that any of the silver bromide, silver iodochloride and silver iodobromide layers contain a complex.

The average grain size of the silver halide grains contained in the silver halide emulsion of the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grain and the number average thereof is taken) is 0. .1 μm to 2 μm is preferred. The particle size distribution has a coefficient of variation (standard deviation of particle size distribution divided by average particle size) of 20.
% Or less, more preferably 15% or less, and particularly preferably 10% or less, so-called monodispersed one. At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the monodispersed emulsion by blending it in the same layer, or to perform multi-layer coating.

The silver halide emulsion of the present invention may contain various compounds or compounds thereof for the purpose of preventing fog during the production process, storage or photographic processing of the silver halide photographic material, or stabilizing photographic performance. Can be added. As specific examples of these compounds, those described on page 39 to page 72 of JP-A-62-215272 are preferably used. Furthermore, EP0447
No. 647, 5-arylamino-1,
A 2,3,4-thiatriazole compound (the aryl residue having at least one electron-withdrawing group) is preferably used.

In the silver halide emulsion of the present invention, the hydroxamic acid derivatives described in JP-A-11-109576 and JP-A-11-3270 are described in order to enhance the storage stability.
No. 94, cyclic ketones having a double bond, both ends of which are substituted with an amino group or a hydroxyl group (in the general formula (S1) described in Paragraph Nos. 0036 to 0071). Represented compounds), JP-A-1
The sulfo-substituted catechols and hydroquinones (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), US Pat. No. 5,556,741 Hydroxylamines represented by the general formula (A) described in the specification (US Pat. No. 5,556,741;
The description on line 22 from line 6 to column 11 is preferably applied also in the present application. ), And water-soluble reducing agents represented by the general formulas (I) to (III) in JP-A-11-102045 are preferably used.

(Silver halide photographic light-sensitive material)
The silver halide photographic light-sensitive material of the present invention (hereinafter sometimes simply referred to as "light-sensitive material") will be described. The silver halide photographic light-sensitive material of the present invention is characterized by containing the silver halide emulsion according to the present invention. In the silver halide photographic material of the present invention, the silver halide emulsion of each layer is subjected to spectral sensitization for the purpose of imparting spectral sensitivity to a desired light wavelength region. In the silver halide photographic light-sensitive material of the present invention, the spectral sensitizing dye used for spectral sensitization in the blue, green and red regions includes, for example, F.I. M. Harm
er Heterocyclic compound
s-Cyanine dyes and related
d compounds (John Wiley & S
ons [New York, London] 196
4 years). Specific examples of compounds and spectral sensitization methods are described in
The ones described in the upper right column on page 22 to page 38 of JP-A-2-215272 are preferably used. In particular, as the red-sensitive spectral sensitizing dye for silver halide emulsion grains having a high silver chloride content, spectral sensitizing dyes described in JP-A-3-123340 are useful in terms of stability, strength of adsorption and exposure. It is particularly preferable from the viewpoint of the temperature dependence of the compound.

The addition amount of these spectral sensitizing dyes may vary over a wide range depending on the case, and may be in the range of 0.1 to 1 mol per mol of silver halide.
The range of 5 × 10 ^{−6 to} 1.0 × 10 ⁻² mol is preferable,
The range is more preferably from 1.0 × 10 ^{−6 to} 5.0 × 10 ⁻³ mol.

The silver halide emulsion of the present invention is usually subjected to chemical sensitization. As the chemical sensitization method, sulfur sensitization represented by addition of an unstable sulfur compound, noble metal sensitization represented by gold sensitization, reduction sensitization, or the like can be used alone or in combination. Compounds used for chemical sensitization are described in JP-A-62-215272, 18th.
Those described in the lower right column of the page to the upper right column of page 22 are preferably used. Among these, it is more preferable that the metal is subjected to gold sensitization. This is because, by performing gold sensitization, fluctuations in photographic performance when scanning exposure is performed using a laser beam or the like can be further reduced.

In the silver halide photographic light-sensitive material of the present invention,
Conventionally known photographic materials and additives can be used. As the photographic support, for example, a transmission type support or a reflection type support can be used. Examples of the transmission type support include transparent films such as cellulose nitrate film and polyethylene terephthalate, and further include 2,6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG).
And a polyester of NDCA, terephthalic acid and EG provided with an information recording layer such as a magnetic layer is preferably used. The reflection type support is preferably laminated with a plurality of polyethylene layers or polyester layers, and such a water-resistant resin layer (laminate layer)
It is preferable that at least one of these contains a white pigment such as titanium oxide.

In the present invention, more preferred reflective supports include those having a polyolefin layer having micropores on a paper substrate on which a silver halide emulsion layer is provided. The polyolefin layer may be composed of multiple layers, in which case the polyolefin layer, which is preferably adjacent to the gelatin layer on the side of the silver halide emulsion layer, does not have micropores (eg, polypropylene, polyethylene) and may be on a paper substrate. More preferably, it is made of a polyolefin (for example, polypropylene or polyethylene) having micropores on the side close to. The density of the multilayer or one polyolefin layer located between the paper substrate and the photographic component layer is preferably 0.40 to 1.0 g / ml, more preferably 0.50 to 0.70 g / ml. Further, the thickness of the multilayer or one polyolefin layer located between the paper substrate and the photographic component layer is 10 to 10.
100 μm is preferable, and 15 to 70 μm is more preferable. Further, the ratio of the thickness of the polyolefin layer to the thickness of the paper substrate is preferably from 0.05 to 0.2, and more preferably from 0.1 to 0.15.
Is more preferred.

It is also preferable to provide a polyolefin layer on the opposite side (back side) of the photographic constituent layer of the paper substrate from the viewpoint of increasing the rigidity of the reflective support. In this case, as the polyolefin layer on the back surface, polyethylene and polypropylene with matte surface are preferable, and among them, polypropylene is more preferable. The thickness of the polyolefin layer on the back surface is preferably 5 to 50 μm, and 10 to 30 μm.
m is more preferred. Further, the density of the polyolefin layer on the back surface is preferably 0.7 to 1.1 g / ml. In the reflection support of the present invention, a preferred embodiment relating to a polyolefin layer provided on a paper substrate is described in
-333277, 10-333278, 11-
Nos. 52513, 11-65024, EP0
Examples described in the specifications of JP 880065 and EP 088066 are described.

Further, the water-resistant resin layer (laminate layer) preferably contains a fluorescent whitening agent. The fluorescent whitening agent may be dispersed in a hydrophilic colloid layer of a silver halide photographic material. As the fluorescent whitening agent, it is preferable to use a benzoxazole-based, coumarin-based, or pyrazoline-based one, and among them, a benzoxazolylnaphthalene-based or benzooxazolylstilbene-based fluorescent whitening agent is more preferable. The amount of the fluorescent whitening agent used,
Although not particularly limited, 1 to 100 mg / m ² is preferable. The mixing ratio when mixed with the water-resistant resin layer is preferably 0.0005 to 3% by mass relative to the resin,
The content is more preferably from 01 to 0.5% by mass.

The reflective support used in the silver halide photographic light-sensitive material of the present invention may be a transmissive support,
Alternatively, a hydrophilic colloid layer containing a white pigment may be provided on the reflective support. Further, a support having a mirror-reflective or second-class diffuse-reflective metal surface may be used.

As the support used in the silver halide photographic light-sensitive material of the present invention, a white polyester-based support or a layer containing a white pigment for a display is provided on the support having a silver halide emulsion layer. You may use what was done. Further, in order to improve sharpness, it is preferable to coat an antihalation layer on the side of the support on which the silver halide emulsion layer is coated or on the back surface. 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 both reflected light and transmitted light.

In the silver halide photographic light-sensitive material of the present invention,
For the purpose of improving image sharpness and the like, a dye (particularly an oxonol-based dye) which can be decolorized by a treatment described in pages 27 to 76 of EP 0,337,490 A2 is applied to the hydrophilic colloid layer. , 68 of photosensitive material
Oxidation that is added so that the optical reflection density at 0 nm becomes 0.70 or more, or is surface-treated with a divalent or tetravalent alcohol (for example, trimethylolethane) in the water-resistant resin layer of the support. It is preferable to contain titanium in an amount of 12% by mass or more (more preferably, 14% by mass or more).

In the silver halide photographic light-sensitive material of the present invention,
For the purpose of preventing irradiation and halation, and improving safelight safety, etc., the hydrophilic colloid layer is coated on the hydrophilic colloid layer in EP 2733790 A2, No. 27.
It is preferable to add dyes (of which oxonol dyes and cyanine dyes) can be decolorized by the treatment described on pages 76 to 76. Further, dyes described in European Patent EP 0819977 are preferably added to the light-sensitive material of the present invention. Some of these water-soluble dyes deteriorate color separation and safelight safety when used in an increased amount. Dyes that can be used without deteriorating color separation are described in JP-A-5-127324, JP-A-5-127325, and JP-A-5-127325.
Water-soluble dyes described in each of the publications of No. 16185 are more preferable.

In the present invention, a colored layer that can be decolorized is used instead of or in combination with the water-soluble dye. The colored layer that can be decolorized by the processing used may be in direct contact with the emulsion layer, or may be arranged so as to be in contact with an intermediate layer containing a processing color mixture inhibitor such as gelatin or hydroquinone. This colored layer is preferably provided below (on the side of the support) the emulsion layer 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 arbitrarily select only some of them. It is also possible to provide a colored layer that is colored corresponding to a plurality of primary color gamuts. The optical reflection density of the colored layer is within the wavelength range used for exposure (400 ppm in ordinary printer exposure).
In the case of scanning exposure, this refers to the wavelength of the scanning exposure light source used. )), The optical density value at the wavelength having the highest optical density is preferably 0.2 or more and 3.0 or less.
It is more preferably from 5 to 2.5, particularly preferably from 0.8 to 2.0.

In order to form the colored layer, a conventionally known method can be applied. For example, Japanese Patent Application Laid-Open No. 2-282244
The dyes described on page 3 from the upper right column of page 3 to page 8;
A method in which a solid colloidal dispersion is contained in a hydrophilic colloid layer, such as a dye described in the upper right column of page 3 to the lower left column of page 11 of JP-A-3-7931, and an anionic dye is a cationic polymer. A method in which a dye is adsorbed on fine particles such as silver halide and fixed in a layer, and a method using colloidal silver as described in JP-A-1-239544. As a method of dispersing the fine powder of the dye 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 lower, but is substantially water-soluble at least at pH 8 or higher is particularly preferred. No. 4 of JP-A-2-308244
-13 pages. Further, as a method of mordanting the anionic dye to a cationic polymer, Japanese Patent Application Laid-Open No.
No. 84637, pages 18 to 26. About the preparation method of colloidal silver as a light absorber,
U.S. Pat. Nos. 2,688,601 and 3,459,56
No. 3 is shown in each specification. Among these methods, a method of incorporating a fine powder dye and a method of using colloidal silver are preferred.

The silver halide photographic light-sensitive material of the present invention is used for a color negative film, a color positive film, a color reversal film, a color reversal photographic paper, a color photographic paper and the like. Particularly, it is preferably used as a color printing paper. The color photographic paper is a yellow coloring silver halide emulsion layer,
It is preferable to have at least one layer each of a magenta color-forming silver halide emulsion layer and a cyan color-forming silver halide emulsion layer. It is preferable that the silver halide emulsion layer is a water-soluble silver halide emulsion layer, a magenta color-forming silver halide emulsion layer, and a cyan color-forming silver halide emulsion layer. However, a different layer configuration may be adopted.

The silver halide emulsion layer containing the yellow coupler may be arranged at any position on the support. However, when the yellow coupler containing layer contains silver halide tabular grains, magenta The coating is preferably provided at a position farther from the support than at least one of the coupler-containing silver halide emulsion layer and the cyan coupler-containing silver halide emulsion layer. Further, from the viewpoint of accelerating color development, accelerating desilvering, and reducing residual color by the sensitizing dye, the silver halide emulsion layer containing the yellow coupler is located farthest from the support than the other silver halide emulsion layers. More preferably, it is coated. Further, from the viewpoint of reduction of Blix fading, the cyan coupler-containing silver halide emulsion layer is preferably a layer at the center of the other silver halide emulsion layers. The lowermost layer of the emulsion layer is preferred. Further, each of the color forming layers of yellow, magenta and cyan may be composed of two or three layers. For example, JP-A-4-75055,
As described in JP-A-9-114035 and JP-A-10-246940 and U.S. Pat. No. 5,576,159, a coupler layer containing no silver halide emulsion is used.
It is also preferable to provide a color-forming layer provided adjacent to the silver halide emulsion layer.

The silver halide emulsion used in the present invention, other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) and the silver halide photographic light-sensitive material of the present invention can be used for processing. Japanese Patent Application Laid-Open No. Sho 62-215272 and Japanese Patent Application Laid-Open No. 2-3314
4, each of which is described in the specification of EP 0,355,660 A2, in particular, EP 0,3
What is described in the specification of 55,660A2 is preferably used. Furthermore, JP-A-5-34889, JP-A-4-359249, JP-A-4-313753, and JP-A-4-23753
No. 70344, No. 5-66527, No. 4-34548
Nos. 4-145433, 2-854, 1-1
No. 58431, No. 2-90145, No. 3-19453
9 and 2-93641, European Patent Publication No. 0
The silver halide photographic light-sensitive material described in 520457A2 and the like and the processing method thereof are also preferable.

In particular, in the silver halide photographic light-sensitive material of the present invention, storage of the above-mentioned reflective support, silver halide emulsion, different metal ion species doped in silver halide grains, and silver halide emulsion. Stabilizers or antifoggants,
Chemical sensitization method (sensitizer), spectral sensitization method (spectral sensitizer), cyan, magenta, yellow couplers and their emulsifying and dispersing methods, color image preservability improvers (stain inhibitors and anti-fading agents), dyes Regarding the (colored layer), the kind of gelatin, the layer constitution of the photosensitive material, the coating pH of the photosensitive material, and the like, those described in the patents in Table 1 below are particularly preferably applicable.

[0113]

[Table 1]

The cyan, magenta and yellow couplers used in the present invention include those described in
No.-215272, page 91, upper right column, lines 4 to 121
Line 6 in the upper left column of the page, line 14 in the upper right column of page 3 to page 18 in the upper left column of page 18, and line 6 in the upper right column of page 30 to line 11 in the lower right column of JP-A-2-33144. EP0355,660
From page 15, lines 15 to 27, page 5, line 30 to page 28, page 45, lines 29 to 31, page 47, line 23 to page 63, page 50 of the specification of A2 The couplers described are also useful. In the present invention, a compound represented by formulas (II) and (III) described in WO-98 / 33760 and a compound represented by formula (D) described in JP-A-10-221825 may be added. preferable.

Hereinafter, the cyan, magenta and yellow couplers will be described more specifically. As the cyan coupler usable in the present invention, a pyrrolotriazole coupler is preferably used.
No. 24, a coupler represented by formula (I) or (II), a coupler represented by formula (I) described in JP-A-6-347960, and a coupler described in these publications. Illustrative couplers are particularly preferred. Also,
Phenol-based and naphthol-based cyan couplers are also preferable. For example, a cyan coupler represented by the general formula (ADF) described in JP-A-10-333297 is preferable. Other cyan couplers include the European Patent EP
No. 4,488,248 and EP0491197A1, pyrroloazole-type cyan couplers described in U.S. Pat. No. 5,888,716, 2,5-diacylaminophenol couplers described in U.S. Pat. No. 5,888,716, U.S. Pat.
Pyrazoloazole-type cyan couplers having an electron-withdrawing group and a hydrogen bonding group at the 6-position described in the specifications of JP-A Nos. 3,183 and 4,916,051.
No. 185, No. 8-313360, No. 8-339060
Pyrazoloazole-type cyan couplers having a carbamoyl group at the 6-position described in each of the above publications are also preferred.

In addition to the diphenylimidazole cyan couplers described in JP-A-2-33144, 3-hydroxypyridine cyan couplers described in European Patent No. EP 0333185A2 (among them, specific examples are given below). 4-equivalent coupler of coupler (42) having a chlorine leaving group to give 2 equivalents, couplers (6) and (9) are particularly preferred), and JP-A-64-322.
No. 60, and cyclically active methylene cyan couplers (of which coupler examples 3, 8, and 34 listed as specific examples are particularly preferred), and EP 0456.
Pyrrolopyrazole cyan couplers described in 226A1 and pyrroleimidazole cyan couplers described in EP 0484909 can also be used.

Among these cyan couplers, pyrroloazole-based cyan couplers represented by the general formula (I) described in JP-A-11-282138 are particularly preferred, and the description in paragraphs 0012 to 0059 of the publication is given. Is applied to the present application as it is, including the exemplified cyan couplers (1) to (47).

Examples of the magenta coupler usable in the present invention include those described in the publicly known documents listed in Table 1 above.
Pyrazolone-based magenta couplers and pyrazoloazole-based magenta couplers are used. A pyrazolotriazole coupler having a group directly bonded to the 2, 3 or 6-position of the pyrazolotriazole ring; a pyrazoloazole coupler containing a sulfonamide group in the molecule described in JP-A-61-65246; No. 61-147254, pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group, EP 226,84.
It is more preferable to use a pyrazoloazole coupler having an alkoxy group or an aryloxy group at the 6-position described in JP 9A and JP 294,785A.
Particularly, as a magenta coupler, JP-A-8-1229
No. 84, a pyrazoloazole coupler represented by the general formula (MI) is preferred, and paragraph No. 00 of the publication is preferable.
09 to 0026 are applied to the present application as they are. In addition, pyrazoloazole couplers having a sterically hindered group at both the 3-position and the 6-position described in European Patent Nos. 854,384 and 844,640 are also preferably used.

The yellow couplers usable in the present invention include, in addition to the compounds shown in Table 1, acyl couplers having a 3- to 5-membered cyclic structure in the acyl group described in European Patent EP 0 474 969 A1. Acetamide-type yellow coupler, a malondianilide-type yellow coupler having a cyclic structure described in European Patent EP 0 482 552 A1, European Patent Nos. 954874A1, No. 9
Pyrrole-2 described in each specification such as 53875A1
Or 3-yl or indol-2 or 3-ylcarbonylacetic acid anilide-based couplers, US Pat.
Acylacetamide type yellow couplers having a dioxane structure described in JP-A-8,599 are preferably used. Among them, it is particularly preferable to use an acylacetamide type yellow coupler in which the acyl group is a 1-alkylcyclopropane-1-carbonyl group and a malondianilide type yellow coupler in which one of the anilides forms an indoline ring. These couplers can be used alone or in combination.

The couplers used in the present invention may be prepared by loading a loadable latex polymer (for example, US Pat. No. 4,2,100) in the presence (or absence) of a high-boiling organic solvent shown in Table 1 above.
No. 03,716) or dissolved together with a water-insoluble and organic solvent-soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution. As the water-insoluble and organic solvent-soluble polymer that can be preferably used, US Pat.
Preferred are homopolymers or copolymers described in columns 7 to 15 of 857,449 and pages 12 to 30 of WO 88/00723, and among them,
Methacrylate-based or acrylamide-based polymers are more preferred, and acrylamide-based polymers are particularly preferred in view of color image stability and the like.

In the present invention, known color mixing inhibitors can be used, and among them, those described in the following patents are preferable. For example, JP-A-5-333501
Patent Publication No. WO98
/ 33760, U.S. Pat. No. 4,923,787, etc., phenidone and hydrazine compounds, JP-A-5-249637, JP-A-10-282615, and German Patent No. 19629142A1. And the like can be used. Also,
In particular, when increasing the pH of the developer to speed up the development, German Patent No. 196187786A1 and European Patent No. 8
39623 A1, EP 842975 A1, DE 198 06 846 A1 and French patent 2760
It is also preferable to use the redox compound described in each specification of 460A1.

In the present invention, it is preferable to use a compound having a triazine skeleton having a high molar extinction coefficient as an ultraviolet absorber. For example, compounds described in the following known documents can be used. These may be photosensitive layers or /
And non-photosensitive. JP 46-33A
No. 35, No. 55-152776, JP-A-5-1970
No. 74, No. 5-232630, No. 5-307232
Nos. 6-211813, 8-53427 and 8
-234364, 8-239368, 9-31
Nos. 067, 10-11598 and 10-1475
No. 77, 10-182621, German Patent No. 19739797A, European Patent No. 711804A, and Japanese Patent Application Laid-Open No. 8-501291.

As a binder or a protective colloid which can be used in the silver halide photographic light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic colloids are used alone or together with gelatin. be able to. Gelatin preferably contains 5 ppm or less of heavy metals contained as impurities such as iron, copper, zinc, and manganese, and more preferably 3 ppm or less.
The amount of calcium contained in the silver halide photographic light-sensitive material is preferably 20 mg / m ² or less, more preferably 10 mg / m ² or less.
g / m ² or less is more preferable, and 5 mg / m ² or less is most preferable. In the present invention, in order to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image, a bactericidal / fungicide as described in JP-A-63-271247 is added. Is preferred. Further, the coating pH of the silver halide photographic light-sensitive material is preferably from 4.0 to 7.0, more preferably from 4.0 to 6.5.

In the present invention, a surfactant can be added to the silver halide photographic light-sensitive material from the viewpoint of improving the coating stability of the silver halide photographic light-sensitive 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.
JP-A-333492. As the surfactant used in the present invention, a fluorine atom-containing surfactant is preferable, and a fluorine atom-containing surfactant is particularly preferably used.

The amount of the surfactant added to the silver halide photographic light-sensitive material is not particularly limited, but is generally 1 × 10 ^{−5 to} 1 g / m ² , and 1 × 10 ^{− 4} to 1
× 10 ^-1 g / m ² is preferred, and 1 × 10 ^-3 to 1 × 10 ^-2.
g / m ² is more preferred. The fluorine atom-containing surfactant may be used alone or in combination with other conventionally known surfactants, but is preferably used in combination with other conventionally known surfactants.

The silver halide photographic light-sensitive material of the present invention is suitable for a scanning exposure method using a cathode ray (CRT) in addition to being used for a printing system using a normal negative printer. A cathode ray tube exposure apparatus is simpler, more compact, and lower in cost than an apparatus using a laser. Further, adjustment of the optical axis and color is also easy. For the cathode ray tube used for image exposure, various luminous bodies that emit light in a spectral region are used as necessary. For example, any one of a red light emitter, a green light emitter, and a blue light emitter, or a mixture of two or more thereof is used. The spectral region is not limited to the above red, green, and blue, and a phosphor that emits light in a yellow, orange, purple, or infrared region is also used. In particular,
A cathode ray tube which emits white light by mixing these light emitters is often used.

In the case where the silver halide photographic material has a plurality of photosensitive layers having different spectral sensitivity distributions and the cathode tube also has a phosphor which emits light in a plurality of spectral regions, a plurality of colors can be used at once. , The image signals of a plurality of colors may be input to the cathode ray tube to emit light from the tube surface. A method of sequentially inputting image signals for each color to sequentially emit light of each color, and exposing through a film that cuts a color other than that color (plane sequential exposure) may be employed. However, since a high-resolution cathode ray tube can be used, it is preferable from the viewpoint of high image quality.

The silver halide photographic light-sensitive material of the present invention can be obtained by a second harmonic combining a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser, or a solid-state laser using a semiconductor laser as an excitation light source and a nonlinear optical crystal. A digital scanning exposure method using monochromatic high-density light such as a wave light source (SHG) is preferably used. In order to make the system compact and inexpensive, it is preferable to use a semiconductor laser, a semiconductor laser or a second harmonic generation light source (SHG) combining a solid-state laser and a nonlinear optical crystal. In particular, in order to design an apparatus that is compact, inexpensive, and has a long life and high stability, it is preferable to use a semiconductor laser, and it is preferable to use a semiconductor laser as at least one of the exposure light sources.

In the case of using such a scanning exposure light source,
Maximum spectral sensitivity wavelength of the silver halide photographic material of the present invention
Can be set arbitrarily according to the wavelength of the scanning exposure light source used.
Can be Using a semiconductor laser as the excitation light source
Laser or semiconductor laser and nonlinear optical crystal
In the SHG light source obtained by combining
Can reduce the vibration wavelength by half, so blue light and green light can be obtained.
You. Therefore, the spectral sensitivity maximum of the photosensitive material is normal blue, green,
It is possible to give it to the three wavelength regions of red. this
The exposure time in such scanning exposure is such that the pixel density is 400
The pixel size in the case of dpi is defined as the exposure time.
In essence, 10^-FourIs preferably 10 seconds or less. ^-6Less than a second
Is more preferable.

Preferred scanning exposure methods applicable to the silver halide photographic light-sensitive material of the present invention are described in detail in the documents shown in Table 1 above. In order to process the silver halide photographic light-sensitive material of the present invention, a method described in JP-A No. 2-20
No. 7250, 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, line 17 to page 18, lower right column, line 20. The processing materials and processing methods described above are preferably applicable. As the preservative used in the developer, compounds described in the literature shown in Table 1 are preferably used.

The silver halide photographic light-sensitive material of the present invention is preferably applied as a light-sensitive material having rapid processing suitability. The color development time refers to the time from when the photosensitive material enters the color developing solution to when it enters the bleach-fix solution in the next processing step. For example, when processing is performed by an automatic developing machine or the like, the time during which the photosensitive material is immersed in the color developing solution (so-called in-solution time) and the time when the photosensitive material leaves the color developing solution and is bleached and fixed in the next processing step The sum of the time during which it is transported in the air toward the bath (the so-called air time) is referred to as the color development time. Similarly, the bleach-fixing time refers to the time from when the photosensitive material enters the bleach-fixing solution to when it enters the next washing or stabilizing bath. The term “washing or stabilizing time” refers to the time during which the photosensitive material is in the washing or stabilizing solution and is in the solution for the drying step (so-called in-solution time).

When rapid processing is performed in the present invention, the color development time is preferably 60 seconds or less, more preferably 50 seconds or more and 6 seconds or more, and most preferably 30 seconds or less and 6 seconds or more. Similarly, the bleach-fixing time is preferably 60 seconds or less, more preferably 50 seconds or less and 6 seconds or more, and most preferably 30 seconds or less and 6 seconds or more. Further, the washing or stabilizing time is preferably 150 seconds or less, and 130 seconds or less.
Seconds or more are more preferable.

The silver halide photographic light-sensitive material of the present invention can be developed after exposure by a conventional method of developing with a developer containing an alkali agent and a developing agent, by incorporating the developing agent into the photographic material, In addition to a wet method such as a method of developing with an activator solution such as an alkali solution containing no (hereinafter, referred to as an "activator method"), a thermal development method without using a processing solution can be used. In particular, the activator method is a preferable method in that the processing agent is not contained in the processing solution, so that the management and handling of the processing solution is easy, and the load at the time of processing the waste solution is small, and from the viewpoint of environmental conservation. In the activator method, as a developing agent or a precursor thereof incorporated in the photosensitive material, for example,
JP-A-8-234388, JP-A-9-152686, JP-A-9-152693, JP-A-9-212814, JP-A-9-291814
The hydrazine-type compounds described in each of JP-A-60193 are preferred.

A developing method in which the amount of silver applied to the light-sensitive material is reduced and image amplification processing (intensification processing) using hydrogen peroxide is preferably used. It is particularly preferred to use this method for the activator method. Specifically, an image forming method using an activator solution containing hydrogen peroxide described in JP-A-8-297354 and JP-A-9-152699 is preferably used. In the above-described activator method, desilvering processing is usually performed after processing with an activator solution.However, in the image amplification processing method using a low-silver amount photosensitive material, desilvering processing is omitted, and simple processing such as water washing or stabilization processing is performed. Method can be performed. Further, in a method of reading image information from a photosensitive material by a scanner or the like, a processing mode that does not require desilvering processing can be adopted even when a photosensitive material having a high silver content such as a photosensitive material for photography is used.

As the activator solution, desilvering solution (bleaching / fixing solution), water washing and stabilizing solution used in the activator method, known materials and processing methods can be used. Preferably, Research Disclosure I
tem 36544 (September 1994), pages 536 to 541 and JP-A-8-234388 can be used.

When the silver halide photographic light-sensitive material of the present invention is exposed to a printer, it is preferable to use a band stop filter described in US Pat. No. 4,880,726. As a result, light color mixing is removed, and color reproducibility is significantly improved. In the present invention, European Patent EP0
As described in the specifications of JP-A-789270A1 and EP0789480A1, before applying image information, a yellow microdot pattern may be pre-exposed in advance to control copying.

The silver halide photographic light-sensitive material of the present invention can be preferably used in combination with an exposure and development system described in the following known materials. An automatic printing and developing system described in JP-A-10-333253; a photosensitive material conveying device described in JP-A-2000-10206; a recording system including an image reading device described in JP-A-11-21512; JP-A-11-88619 and JP-A-10-202
Exposure system comprising a color image recording method described in each publication of No. 950 ・ Digital photo print system including a remote diagnosis method described in JP-A-10-210206 ・ Image recording described in Japanese Patent Application No. 10-159187 Photo printing system including device

[0138]

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

[0139] (Example 1) chloroauric acid _{(HAuCl 4 · 4H 2 O)} 10.0g at room temperature <Exemplified Compound (I-1) and (III-2) Synthesis of> was dissolved in water 200 mL, there Illustrative compound (II-1-1)
A solution in which 13.9 g was dissolved in 30 mL of water was added dropwise.
The solution immediately turned reddish brown. Next, slowly 42
When 10.9 mL of a 1% aqueous HBF ₄ solution was added dropwise, white crystals precipitated immediately. This white crystal was measured by NMR and IR, and was confirmed to be Exemplified Compound (III-2). The precipitate is collected by filtration at 10 ° C. or lower,
Washed several times with water. The filtrate was concentrated, and 100 mL of ethanol was added to the residue, whereupon a white precipitate was immediately formed. This was collected by filtration and washed several times with ethanol. The compound thus obtained was confirmed to be Exemplified Compound (I-1) by NMR, IR, elemental analysis, and X-ray crystal structure analysis.

[0140] - spectrum of Exemplified Compound ^{(III-2) - [1} H-NMR (dmso-d 6, δ: Ref.TM
S)]; 3.80 (s, 3H), 3.65 (s, 3
H), 2.60 (s, 3H) [IR (cm ^-1 )]; 3450, 1590, 1540,
1435, 1350, 1160, 1100, 1060,
1040, 800

-Spectrum of Exemplified Compound (I-1)-[ ¹ H-NMR (dmso-d ⁶ , δ: Ref.TM
S)]; 4.00 (s, 6H), 3.80 (s, 6).
H), 2.75 (s, 6H) [IR (cm ^-1 )]; 3400, 1080, 800, 7
35, 530, 520

[0142] (Example 2) <exemplified compound (I-2) and (III-1) solution [A] Preparation of containing> chloroauric acid at room temperature (HAuCl ₄ · 4H ₂
O) 10.0 g was dissolved in 200 mL of water, and a solution of 13.9 g of the exemplary compound (II-1-1) dissolved in 30 mL of water was added dropwise thereto. The solution immediately turned reddish brown. NMR and UV analysis of the reaction solution revealed that Exemplified Compounds (I-2) and (III-1) were present as the main components in a molar ratio of about 1: 1. The solution thus obtained was added to the emulsion as it was, and subjected to a photographic test described in Examples described later.

In the following, as shown in Table 2 below, the disulfide compound represented by the general formula (I) was synthesized in the same manner as in Example 1 except that the type of the mesoionic compound was changed.
And the yield of the gold complex represented by the general formula (III).

[0144]

[Table 2]

Example 3 <Preparation of Emulsion A Used for Blue-Sensitive Emulsion Layer> A cubic large-sized emulsion A1 having an average particle size of 0.70 μm, and 0.5
Emulsion A was prepared as a 1: 1 mixture (silver molar ratio) with 0 μm small size emulsion A2. The variation coefficients of the grain size distributions of emulsions A1 and A2 were 0.09 and 0.11, respectively.
Met. In each size emulsion, 0.5 mol% of silver bromide was used.
Silver chloride was locally contained on a part of the surface of the grain.
In a portion corresponding to 10% by volume from the outermost layer of this grain, 0.1 mol% of iodide ion is present with respect to all halogens, and 1 × 10 ⁻⁶ mol of 1 mol of silver halide is present. K ₄ Ru (CN) ₆ , 1 × 1 per mole of silver halide
^0-7 mol of yellow blood salt, 1 × 1 per mol of silver halide
^0-8 moles of K ₂ IrCl ₅ (H ₂ O) were present. In this emulsion, the following blue-sensitive sensitizing dyes A and B were added in an amount of 3.2 × 10 ^-4 mol per mol of silver per mol of silver.
4.4 × 10 ^-4 mol was added to each of No. 2 and spectral sensitization was performed.

[0146]

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<Preparation of Emulsion B Used for Green-Sensitive Emulsion Layer> A cubic emulsion B having an average particle size of 0.40 μm was prepared. The coefficient of variation of the particle size distribution was 0.09.
Each size emulsion contained 0.1 mol% of silver iodide near the grain surface and 0.4 mol% of silver bromide localized on the grain surface. Similarly to Emulsion A, K ₄ Ru (C
N) ₆ , yellow blood salt, K ₂ IrCl ₅ (H ₂ O) were present.
Sensitizing dye D was used in an amount of 3.3 × 10 ^-4 per mol of silver halide.
Mole of sensitizing dye E per mole of silver halide.
× 10 ⁻⁵ mol, and 2.3 × 10 ⁻⁴ mol of sensitizing dye F per mol of silver halide.

[0148]

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<Preparation of Emulsion C used for Red-Sensitive Emulsion Layer> A large-sized emulsion C1 having a cubic shape and an average grain size of 0.40 μm
And a 1: 1 mixture (silver molar ratio) of E.C. and 0.30 .mu.m small size emulsion C2. The coefficient of variation of the particle size distribution was 0.09 and 0.11, respectively. In each size emulsion, 0.1 mol% of silver iodide was contained in the vicinity of the grain surface, and 0.8 mol% of silver bromide was locally contained in the grain surface. Similarly to Emulsion A, K ₄ R
u (CN) ₆ , yellow blood salt, K ₂ IrCl ₅ (H ₂ O) were present. Sensitizing dyes G and H were used in an amount of 8.0 × 10 ^-5 mol per mol of silver halide per mol of silver halide emulsion, respectively.
10.7 × 10 ^-5 mol was added to the small size emulsion. Further, the following compound I was added to the red-sensitive emulsion layer in an amount of 3.0 × 10 ⁻³ mol per mol of silver halide.

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<Preparation of color photographic light-sensitive material and coated sample> The surface of a support having both sides of paper coated with a polyethylene resin is subjected to a corona discharge treatment, and then a gelatin undercoat containing sodium dodecylbenzenesulfonate is performed. The layers were provided, and the first to seventh photographic constituent layers were sequentially coated to prepare a comparative sample (101) of a silver halide photographic light-sensitive material having the following layer structure. The coating solution for each photographic constituent layer was prepared as follows.

Preparation of Coating Solution for First Layer 57 g of yellow coupler (ExY), color image stabilizer (Cp
d-1) 7 g, color image stabilizer (Cpd-2) 4 g, color image stabilizer (Cpd-3) 7 g, color image stabilizer (Cpd-8) 2
g of solvent (Solv-1) 21 g and ethyl acetate 80 m
1 g of a 23.5% by weight aqueous gelatin solution containing 4 g of sodium dodecylbenzenesulfonate.
In 0 g, the mixture was emulsified and dispersed by a high-speed stirring emulsifier (dissolver), and water was added to prepare 900 g of emulsified dispersion A. Separately, the emulsified dispersion A and the emulsion A were mixed and dissolved to prepare a coating solution for the first layer so as to have the composition described below. The emulsion coating amount indicates a coating amount in terms of silver amount.

The coating solution for the second to seventh layers is also the first layer coating solution.
It was prepared in the same manner as described above. As a gelatin hardener for each layer
Is sodium (2,4-dichloro-6-oxide-1,
3,5-triazine) (H-1), (H-2), (H-
3) at a total amount of 100 mg / m ^TwoUsing. In addition, A
b-1, Ab-2, Ab-3 and Ab-4 respectively
The total amount is 15.0 mg / m^Two, 60.0 mg / m^Two, 5.0
mg / m^TwoAnd 10.0 mg / m^TwoAnd add
Was.

[0155]

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[0156]

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-Chemical Sensitization Step- The above emulsion was heated to 40 ° C., and optimal amounts of sodium thiosulfate pentahydrate and chloroauric acid were added. After heating at 60 ° C. for 40 minutes, the sensitizing dye was added to the emulsion. In addition, after cooling to 40 ° C, 1-
(3-Methylureidophenyl) -5-mercaptotetrazole was added in an amount of 3.3 × per mol of silver halide.
10 ^-4 mol, 1.0 × 10 ^-3 mol and 5.9 × 10 ^-4 mol were added.

Also, 1- (3-methylureidophenyl) -5-mercaptotetrazole was added to the second, fourth, sixth, and seventh layers in an amount of 0.2 mg / mg each.
m ² , 0.2 mg / m ² , 0.6 mg / m ² , 0.1 mg
/ M ² .

In addition, the blue-sensitive emulsion layer and the green-sensitive emulsion layer
And 4-hydroxy-6-methyl-1,3,3a, 7-
Tetrazaindene was applied per mole of silver halide.
1 × 10^-FourMole, and 2 × 10^-FourMole was added. Ma
In the red-sensitive emulsion layer, methacrylic acid and butyl acrylate
Copolymer latex (weight ratio 1: 1, average molecular weight 20)
0000-400000) to 0.05 g / m ^TwoAdd
Was. In the second, fourth and sixth layers, catechol-
Disodium 3,5-disulfonate at 6 mg /
m^Two, 6mg / m^Two, 18mg / m^TwoAnd add
Was. The following dyes are used to prevent irradiation.
(The amount in parentheses indicates the amount of coating).

[0160]

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-Layer Structure- The structure of each layer is shown below. The number is the coating amount (g / m ² )
Represents The silver halide emulsion represents a coating amount in terms of silver. Support Polyethylene resin laminated paper [A white pigment (TiO ₂ ; content: 16% by mass, ZnO: content: 4% by mass) and a fluorescent whitening agent (4,4′-bis (5 -Methylbenzooxosazolyl) stilbene, containing 0.03% by mass) and a bluish dye (ultramarine)] First layer (blue-sensitive emulsion layer) Emulsion A 0.24 Gelatin 1.25 Yellow coupler (ExY) 0.57 Color image stabilizer (Cpd-1) 0.07 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.07 Color image stabilizer (Cpd-8) 02 Solvent (Solv-1) 0.21

Second layer (color mixture prevention layer) Gelatin 0.99 Color mixture prevention agent (Cpd-4) 0.09 Color image stabilizer (Cpd-5) 0.018 Color image stabilizer (Cpd-6) 13 Color image stabilizer (Cpd-7) 0.01 Solvent (Solv-1) 0.06 Solvent (Solv-2) 0.22

Third layer (green-sensitive emulsion layer) Emulsion B 0.14 Gelatin 1.36 Magenta coupler (ExM) 0.15 Ultraviolet absorber (UV-A) 0.14 Color image stabilizer (Cpd-2) 0.02 Color image stabilizer (Cpd-4) 0.002 Color image stabilizer (Cpd-6) 0.09 Color image stabilizer (Cpd-8) 0.02 Color image stabilizer (Cpd-9) 03 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-11) 0.0001 Solvent (Solv-3) 0.11 Solvent (Solv-4) 0.22 Solvent (Solv-5) 0 .20

Fourth layer (color mixture prevention layer) Gelatin 0.71 Color mixture prevention layer (Cpd-4) 0.06 Color image stabilizer (Cpd-5) 0.013 Color image stabilizer (Cpd-6) 10 Color image stabilizer (Cpd-7) 0.007 Solvent (Solv-1) 0.04 Solvent (Solv-2) 0.16

Fifth layer (red-sensitive emulsion layer) Emulsion C 0.12 Gelatin 1.11 Cyan coupler (ExC-2) 0.13 Cyan coupler (ExC-3) 0.03 Color image stabilizer (Cpd-1) ) 0.05 Color image stabilizer (Cpd-6) 0.06 Color image stabilizer (Cpd-7) 0.02 Color image stabilizer (Cpd-9) 0.04 Color image stabilizer (Cpd-10) 0 0.01 Color image stabilizer (Cpd-14) 0.01 Color image stabilizer (Cpd-15) 0.12 Color image stabilizer (Cpd-16) 0.03 Color image stabilizer (Cpd-17) 0.09 Color image stabilizer (Cpd-18) 0.07 Solvent (Solv-5) 0.15 Solvent (Solv-8) 0.05

Sixth layer (ultraviolet absorbing layer) Gelatin 0.46 Ultraviolet absorber (UV-B) 0.45 Compound (S1-4) 0.0015 Solvent (Solv-7) 0.25 Seventh layer ( Protective layer) Gelatin 1.00 Acrylic-modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-13) 0.01

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Similarly, instead of the emulsion B of the comparative sample (101), compounds shown in Table 3 (gold sensitizer, disulfide compound represented by (I), etc.) were used in the chemical sensitization step.
Using the emulsions (D to L) shown in Table 3 to which
Nos. 02 to 110 were produced. Emulsion D (Comparative sample 102)
In Emulsion I (Comparative Sample 107), not the disulfide compound represented by the general formula (I) of the present invention,
Comparative compound A (p-glutaramidophenyl disulfide disodium salt) described in -267249 was used. Emulsion L (Sample 110) contains chloroauric acid and (II
Aqueous solution a obtained by mixing -1) was added to the emulsion. The mixing method was the same as the method for preparing the reaction solution A described in Example 2. Therefore, in the aqueous solution a, as the main components, the exemplified compound (I-2) and the exemplified compound (III-1)
Are present at about 1: 1 (molar ratio).

<Evaluation of Photographic Properties> The following experiments were conducted to examine the photographic properties of these samples. -Experiment 1 Sensitometry (low illuminance and high illuminance)-Each of the coated samples was subjected to gradation exposure for sensitometry using a sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd.). With an SP-2 filter attached, exposure 200
Exposure was performed for 10 seconds at a low illuminance at lx · sec. In addition, a high-illumination exposure sensitometer (H
(IE type) to give sensitometric gradation exposures. An SP-2 filter was attached, and exposure was performed at a high illuminance of ^10-4 seconds. After the exposure, the following color development processing A was performed.

The processing steps will be described below. [Processing A] The above sample was processed into a roll having a width of 127 mm, and was imagewise exposed using a minilab printer processor PP1258AR manufactured by Fuji Photo Film Co., Ltd. , Continuous processing (running test). The processing using the running liquid was referred to as processing A. Processing process Temperature Time Replenishment amount ^* Color development 38.5 ° C 45 seconds 45 ml Bleaching and 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 for 20 seconds-Rinse (4) ** 38.0 ° C for 30 seconds 121 ml * Replenishment amount per 1 m ^{2 of} photographic material ** Rinse phosphorus screening system RC50D manufactured by Fuji Photo Film Co., Ltd. Install in (3), take out the rinse liquid from rinse (3) and send it to reverse osmosis membrane module (RC50D) by pump. The permeated water obtained in the tank is supplied to the rinse (4), and the concentrated water 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 a day. (Rinsing was carried out in a tank countercurrent system from (1) to (4).)

The composition of each processing solution is as follows. [Color developer] [Tank solution] [Replenisher] Water 800 ml 800 ml Dimethylpolysiloxane-based surfactant 0.1 g 0.1 g (Silicone KF351A / Shin-Etsu Chemical Co., Ltd.) Tri (isopropanol) amine 8.8 g 8 8.8 g Ethylenediaminetetraacetic acid 4.0 g 4.0 g Polyethylene glycol (molecular weight 300) 10.0 g 10.0 g Sodium 4,5-dihydroxybenzene-1,3-disulfonate 0.5 g 0.5 g Potassium chloride 10.0 g-odor Potassium iodide 0.040 g 0.010 g Triazinylaminostilbene-based fluorescence 2.5 g 5.0 g Brightener (Hakor FWA-SF / Showa Chemical Co., Ltd.) Sodium sulfite 0.1 g 0.1 g Disodium-N, N- 7. bis (sulfonatoethyl) hydroxylamine g 11.1 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-amino-4-aminoaniline / 3/2 sulfuric acid monohydrate 5.0 g 15.7 g potassium carbonate 26.g 3g 26.3g Water was added to add 1000ml 1000ml pH (25 ° C / adjusted with potassium hydroxide and sulfuric acid) 10.15 12.50

[Bleach-fixing solution] [Tank solution] [Replenisher] Water 700 ml 600 ml ammonium ethylenediaminetetraacetate (III) ammonium 47.0 g 94.0 g ethylenediaminetetraacetic acid 1.4 g 2.8 g m-carboxybenzenesulfinic acid 8.3 g 16.5 g nitric acid (67%) 16.5 g 33.0 g imidazole 14.6 g 29.2 g ammonium thiosulfate (750 g / l) 107.0 ml 214.0 ml ammonium sulfite 16.0 g 32.0 g ammonium bisulfite 23.1 g 46.2 g Water was added to add 1000 ml 1000 ml pH (adjusted at 25 ° C./acetic acid and ammonia) 6.0 6.0

[Rinse solution] [Tank solution] [Refill solution] 0.02 g 0.02 g of chlorinated sodium isocyanurate Deionized water (conductivity of 5 μS / cm or less) 1000 ml 1000 ml pH 6.5 6.5

The magenta color density of each sample after processing was measured, and emulsions B (sample 101) and D to L (samples 102 to 11) were prepared.
0) 10 seconds exposure low illuminance sensitivity and 10 ^-4 seconds exposure high illuminance sensitivity were determined. The sensitivity was defined as the reciprocal of the exposure amount giving a color density 1.5 higher than the minimum color density, and expressed as a relative value when the developed sensitivity of the comparative sample (101) was set to 100. The gradation is expressed by a difference between a logarithm of an exposure amount giving a color density of 0.5 and a logarithm of an exposure amount giving a color density of 1.8. The smaller this value is, the higher the contrast is.

-Experiment 2 Exposure Humidity Dependence of Sensitivity- The relative humidity (RH) at which each coated sample was exposed to light was 5
Set to 5% and 80%. After the exposure for 1/10 seconds, the processing A was performed, and the magenta color density of each sample was measured.
The sensitivity is defined as the reciprocal of the exposure amount that gives a color density 0.5 higher than the minimum color density, and is expressed as a relative value when the developed sensitivity of the comparative sample (101) is set to 100, and the sensitivity is 55%. 80 from relative sensitivity
% (Hereinafter referred to as dS)
Is shown).

The results of Experiments 1 and 2 are summarized in Table 3 below.

[0187]

[Table 3]

From the results in Table 3, it is found that the samples 103, 1
Nos. 04 and 105 have higher sensitivity at low illuminance exposure and higher sensitivity at high illuminance exposure than the comparative sample 101 using only the gold sensitizer, chloroauric acid, and have high contrast. Further, when the exposure humidity is high, there is a problem that the sensitivity is lower than when the exposure humidity is medium, but such a problem is remarkably reduced in the sample of the present invention. Such an effect was not observed when Comparative Compound A was used. In addition, from the results of Samples 108, 109, and 110 of the present invention, the exemplified compound (III
When -1) and (III-2) were used as gold sensitizers,
It was confirmed that the same effect as above was obtained. In addition, the result of the sample 110 shows that the exemplary compound (I-2) of the present invention represented by the general formula (I) can be used without isolation.

(Example 4) When preparing the samples 101 to 110, the UV-absorbers UV-A and UV-B used in each sample were used as one of the constituent mixtures thereof. UV-A ′ and UV-B ′ were obtained by replacing only 4 with the same mass by UV-8, and each sample was prepared by replacing the corresponding mass with the corresponding UV-A and UV-B, and the same as above. As a result, the same results as those described above were confirmed.

[0190]

First, according to the present invention, medicines, pesticides,
It is useful in the field of photographic additives and the like, and can provide a novel disulfide compound. Second, according to the present invention, a simple and efficient method for producing a disulfide compound and a gold complex using a mesoionic compound having a thiolate structure and / or a mesoionic compound having a protonated thiolate structure as a raw material Can be provided. Third, according to the present invention, using the disulfide compound, the gold complex, or a mixed solution thereof, the sensitivity is high, the contrast is high, and the sensitivity variation due to the difference in humidity conditions at the time of exposure is small. And a silver halide photographic light-sensitive material containing the silver halide emulsion.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C07D 271/10 C07D 271/10 273/00 273/00 285/125 339/04 339/04 G03C 1/09 G03C 1 / 09 1/34 1/34 C07D 285/12 DF term (reference) 2H023 CA02 CC02 4C023 MA04 4C036 AA05 AA07 AA11 AA17 AA18 4C056 AA01 AB03 AB10 AC07 AC10 AD01 AE03 AF06 FA04 FB07 FC02 4H006 AA01 AB76 TA04

Claims (9)

[Claims] 1. A disulfide compound represented by the following general formula (I). Embedded image In the general formula (I), f represents a sulfur atom. e represents a carbon atom. a, b, c and d are unsubstituted or substituted atoms or groups forming a 5-membered ring of the mesoionic compound, each independently being a C—R group, an N—R ′ group, an oxygen atom, or Represents a sulfur atom. R and R ′ each independently represent a hydrogen atom or a substituent. X represents an anion that neutralizes the charge of the molecule. 2. A mesoionic compound having a thiolate structure represented by the following general formula (II-1) and / or a mesoionic compound having a protonated thiolate structure represented by the following general formula (II-2): 2. The disulfide compound according to claim 1, which is synthesized from the compound by an oxidation reaction. Embedded image In the general formulas (II-1) and (II-2),
f represents a sulfur atom. e represents a carbon atom. a, b, c
And d are unsubstituted or substituted atoms or groups forming a 5-membered ring of the mesoionic compound, and each independently represents
Represents a C—R group, an N—R ′ group, an oxygen atom, or a sulfur atom. R and R ′ each independently represent a hydrogen atom or a substituent. Y represents an anion that neutralizes the charge of the molecule. 3. The disulfide compound according to claim 2, wherein an Au (III) compound is used in the oxidation reaction. 4. A mesoionic compound having a thiolate structure represented by the following general formula (II-1) and / or a mesoionic compound having a protonated thiolate structure represented by the following general formula (II-2): A method for producing a disulfide compound represented by the following general formula (I): Embedded image In the general formula (I), f represents a sulfur atom. e represents a carbon atom. a, b, c and d are unsubstituted or substituted atoms or groups forming a 5-membered ring of the mesoionic compound, each independently being a C—R group, an N—R ′ group, an oxygen atom, or Represents a sulfur atom. R and R ′ each independently represent a hydrogen atom or a substituent. X represents an anion that neutralizes the charge of the molecule. Embedded image In the general formulas (II-1) and (II-2),
f represents a sulfur atom. e represents a carbon atom. a, b, c
And d are unsubstituted or substituted atoms or groups forming a 5-membered ring of the mesoionic compound, and each independently represents
Represents a C—R group, an N—R ′ group, an oxygen atom, or a sulfur atom. R and R ′ each independently represent a hydrogen atom or a substituent. Y represents an anion that neutralizes the charge of the molecule. 5. A method for producing a disulfide compound represented by the following general formula (I), wherein an Au (III) compound is used. Embedded image In the general formula (I), f represents a sulfur atom. e represents a carbon atom. a, b, c and d are unsubstituted or substituted atoms or groups forming a 5-membered ring of the mesoionic compound, each independently being a C—R group, an N—R ′ group, an oxygen atom, or Represents a sulfur atom. R and R ′ each independently represent a hydrogen atom or a substituent. X represents an anion that neutralizes the charge of the molecule. 6. A method for producing a gold complex represented by the following general formula (III), comprising: an Au (III) compound; and a mesoionic compound having a thiolate structure represented by the following general formula (II-1): And / or a mesoionic compound having a protonated thiolate structure represented by the following general formula (II-2): Embedded image In the general formulas (II-1) and (II-2),
f represents a sulfur atom. e represents a carbon atom. a, b, c
And d are unsubstituted or substituted atoms or groups forming a 5-membered ring of the mesoionic compound, and each independently represents
Represents a C—R group, an N—R ′ group, an oxygen atom, or a sulfur atom. R and R ′ each independently represent a hydrogen atom or a substituent. Y represents an anion that neutralizes the charge of the molecule. Embedded image In the general formula (III), a to f represent the general formula (I
It is synonymous with I-1) and general formula (II-2). Z represents an anion. m represents an integer of 1 or 2. n is 1 to 4
Represents an integer. 7. A silver halide emulsion containing the disulfide compound represented by the general formula (I) according to any one of claims 1 to 3. 8. The silver halide emulsion according to claim 7, which contains the gold complex represented by the general formula (III) produced by the method for producing a gold complex according to claim 6. 9. A silver halide photographic light-sensitive material comprising the silver halide emulsion according to claim 7 or 8.