JP2000019673A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance sensitivity, to lower fog and to improve storage stability and illuminance irregularity by forming at least one specified photosensitive emulsion layer and incorporating a specified compound or its oxide in at least one of photographic constituent layers. SOLUTION: One or more of the photographic constituent layers are the photosensitive silver halide emulsion layer containing silver halide grains prepared in the presence of a metal complex represented by formula I or II wherein each of Z1 and Z2 is an atomic group necessary to form an N-containing hetero ring; each of D1 and D2 is an atomic group necessary to form a poly-methine dye; M is a central metal; X is a ligand; and V is an ion necessary to neutralize a charge in the molecule. One or more constituent layers contain the compound represented by formula III: X1- C(R1)=Y}n-X2 or formula IV or its oxide. In formula III, each of X1 and X2 is an -OR3 or the like (R3 is an H or the like, Y is a C(R2) or the like, and each of R1 and R2 is an H atom or the like. In formula IV each of R6-R10 is an H atom, an alkyl group or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic emulsion having high sensitivity, low fog and / or illuminance failure and improved storage stability.

[0002]

BACKGROUND OF THE INVENTION As a dopant generally used in silver halide photographic light-sensitive materials, an octahedral hexacoordinate metal complex is generally known. Here, "dopant" refers to any compound contained in a silver halide crystal other than silver or halide ions. In particular, many studies have been made on metal complexes in which the central metal is a transition metal for the purpose of modifying silver halide emulsions as dopants.

When the reciprocity law of a photograph is satisfied (that is, when there is no reciprocity failure), the sensitivity of a photographic emulsion is constant regardless of the respective values of exposure intensity and exposure time as long as their product is the same. Become.

[0004] In the present invention, high illuminance reciprocity failure means a phenomenon that the sensitivity of a photographic emulsion becomes lower as the exposure time is shorter when the exposure amounts are the same but the exposure times are different. Similarly, low-illuminance reciprocity failure means a phenomenon in which the sensitivity of a photographic emulsion becomes lower as the exposure time is longer when the exposure amounts are the same but the exposure times are different.

[0005] Research Disclosure No. 3081
18, chapters I-D state that during grain nucleation, metals introduced during grain growth enter the grains as dopants and can alter photographic performance depending on their level and location within the grains. ing.

There is a remarkable difference in the photographic effect of the transition metal compound in the silver halide emulsion between the case where the transition metal compound is added during the formation of silver halide grains and the case where it is added after the precipitation of the silver halide grains. It has been known. In the former case, it is generally known that the transition metal compound is incorporated as a dopant into the silver halide grains and, despite its very small amount, effectively alters photographic performance. In the latter case, the transition metal compound is adsorbed on the particle surface, but often cannot interact with the peptizer due to interaction with the peptizer. In order to add the transition metal compound after grain formation and obtain the same effect as when the transition metal compound is incorporated in the silver halide grains, it is necessary to add a higher concentration of the transition metal compound. That is, it is generally recognized that when a transition metal compound is added during chemical sensitization, it is difficult to obtain a photographic effect, and the transition metal compound has been used as a dopant during grain formation.

The technical difference between the metal doping added to the emulsion during the formation of silver halide grains and the metal sensitizer due to the addition of a transition metal compound to the emulsion after the formation of the silver halide grains is discussed in detail below. The transition metal compound introduced during precipitation of the compound is described in Research Disclosure, Chapter 17643, Chapter IA, and the transition metal compound introduced during chemical sensitization is described in Chapter IIIA, Research Disclosure.

US Pat. No. 4,126,472 discloses that a silver halide emulsion is ripened in the presence of 10 ^-6 to 10 ^-4 mol of a water-soluble iridium salt per mol of silver halide, so that iridium is added to the grain surface. It is disclosed for use as a modifier. However, there is no description of a metal complex having a spectral sensitizing dye in at least one of the ligands. EP 242,190 comprises silver halide grains formed in the presence of one or more complex compounds of trivalent rhodium having 3, 4, 5 or 6 cyanide ligands. Reduction of high intensity failure in silver halide emulsions is disclosed.

US Pat. No. 3,690,888 includes a process for preparing silver halide grains containing polyvalent metal ions in the presence of a peptizer consisting mainly of an acrylic polymer. A method is disclosed. As the polyvalent metal ion, bismuth, iridium, lead, and / or osmium ion are particularly mentioned, but there is no description about a metal complex having a spectral sensitizing dye in at least one of the ligands.

In these disclosures, it is clearly shown that the ligand is incorporated into the particles together with the transition metal, and the regulation of the ligand of the transition metal compound and its effect are not described.

On the other hand, US Pat. No. 4,835,093,
Nos. 4,933,272 and 4,981,781
No. 5,037,732, No. 4,937,18
Nos. 0, 4,945,035 and the like disclose that a ligand capable of forming a coordination complex with a metal ion can enter a grain crystal structure, and a photographic performance which cannot be realized by incorporating a transition metal ion alone. It has been demonstrated that improvements can be made.

European Patent Nos. 336,425 and 33
No. 6,426, JP-A-2-20853, JP-A-2-208
No. 54 has excellent sensitivity, gradation, stability over time, and low light failure prepared in the presence of a six-coordinate rhenium, ruthenium, osmium and iridium metal complex having at least four cyano ligands. Are described.

[0013] EP-A-336,427 and JP-A-2-20852 disclose hexacoordinate vanadium, chromium, manganese containing nitrosyl or thionitrosyl ligands.
Silver halide emulsions having improved low-light reciprocity failure without lowering medium-light sensitivity by metal complexes of iron, ruthenium, osmium, rhenium and iridium are described.

Further, European Patent 336,689,
No. -20855 discloses that the ligand of the six-coordinate rhenium complex is halogen, nitrosyl, thionitrosyl, cyanine,
An emulsion is disclosed in which sensitivity is controlled by a combined metal complex of water and thiocyanine, and low light reciprocity failure is improved.

JP-A-3-118535 discloses a transition metal complex in which one ligand of a six-coordinate metal complex is carbonyl, and JP-A-3-118536 discloses two transitions of a six-coordinate metal complex. It is disclosed that an emulsion containing therein a transition metal complex whose oxygen is oxygen is effective for photographic performance.

US Pat. No. 5,132,203 discloses that a hexacoordinate Group VIII metal complex having at least four cyano ligands is contained on the subsurface, and the complex is contained in a particle surface layer of 20 to 350 °. Are disclosed as having high sensitivity. Further, EP 508,910 discloses that a sub-surface is doped with a hexacyanoiron complex to form
In addition, there is disclosed a silver halide emulsion which does not contain the iron complex in the surface layer and is color-sensitized by adding a sensitizing dye.
These patents teach that the hexacyano complex is more sensitive when present near the particle surface, but is better not to be present near the particle surface. That is, when doping a hexacoordinate cyano metal complex into a grain, the doping position is preferably on the subsurface of the silver halide grain, but when the complex is present on the surface itself, a method for obtaining high sensitivity is completely disclosed. Not.

Cyan generated by the interaction between the hexacoordinated cyano metal complex and gelatin is stable in the emulsion medium by forming a stable gold cyanide complex with gold ions. For this reason, it is difficult for gold ions to be adsorbed on the grain surface, and the photographic effect due to chemical sensitization is reduced.Therefore, hexacoordinate cyano metal complexes have been doped on the subsurface of silver halide grains. And sufficient sensitivity could not be obtained. JP-A-6-242537 discloses that in a step of doping a silver halide with a six-coordinate cyano metal complex, a part or all of the dope is adjusted to have a pH value of 7.0 or more so that the complex can be used. While maximizing its effect while allowing the particles to be present on the particle surface. JP-A-6-2895
No. 12 includes a step of doping a silver halide with a six-coordinate cyano metal complex, and a gelatin in which an amino group or a carboxyl group is invalidated thereafter (for example, phthalated gelatin, esterified gelatin), or an oxidation treatment. A method for obtaining high sensitivity by the presence of gelatin is disclosed. JP-A-8-29905 discloses that silver halide grains form particles in the presence of a compound that inhibits the reaction between gelatin and a cyano complex, for example, a salt of zinc, cesium, copper, lead, calcium, barium, or magnesium. To obtain high sensitivity.

However, these methods are not sufficient, and in the examples disclosed in Japanese Patent Application No. 9-357173, by changing to a metal complex having a spectral sensitizing dye in at least one of the ligands, the inside of the particles is reduced. A method for obtaining a high sensitivity by doping a metal compound into a photographic material was described, but there is no description of deterioration of photographic performance under high humidity.

A conventional reduction sensitization technique is disclosed in
Patents such as 191938 and JP-A-3-168632 are disclosed. However, when reduction sensitization is applied to the grains by these methods, there are problems such as high fogging in photographic properties due to storage. In particular, the problem of latent image sensitization among photographic properties from photographing to development was significant. To prevent latent image sensitization, JP-A-59-162546 discloses a method in which a curing agent having an active vinyl group and a triazine compound are used in combination. However, the above method is not sufficient in the prevention effect, and further improvement has been desired. on the other hand,
A full-color photographic material achieves the purpose of full-color photography by using a plurality of emulsions having different spectral sensitivities and a multilayer structure. Although the emulsions used have been considerably improved, fogging, intensification and regression of the latent image occur, which is not always sufficient. For example, 2-hydroxylamino-1,3,5-triazines are effective for improving the storage stability. However, 2-hydroxylamino-1,3,3
5-triazines have the disadvantage that they change the film strength and gradation and react with the hardener.

Further, Japanese Patent Application Laid-Open Nos.
No. 3,140,51 discloses a method for preventing latent image sensitization using hydroxamic acids. However, since this method is added by emulsifying together with a high boiling point solvent, the thickness of the silver halide photographic light-sensitive material is increased, leading to rapid deterioration of characteristics during development processing, and addition during silver halide emulsion production. However, there is a drawback such as an increase in fog at the time of manufacturing cannot be prevented.

[0021]

As described above, by using a silver halide emulsion prepared in the presence of a metal complex having a spectral sensitizing dye in at least one of the ligands, excellent photographic performance can be obtained. Although a photosensitive material having high sensitivity can be obtained, a technique for preventing deterioration of photographic performance under high humidity, particularly, an increase in fog is not sufficient.

Accordingly, it is an object of the present invention to provide a silver halide photographic material having high sensitivity and capable of preventing deterioration of photographic performance under high humidity, particularly preventing fog rise.

[0023]

The above objects of the present invention have been attained by the following constitutions.

(1) In a silver halide photographic light-sensitive material having a photographic constituent layer on a support, at least one of the photographic constituent layers comprises a metal complex represented by the following general formula [I] or [II]. A photosensitive silver halide emulsion layer containing silver halide grains prepared in the presence of at least one of the photographic constituent layers represented by the following general formula (1) or (2): Silver halide photographic material comprising a layer containing at least one compound or an oxidized compound thereof.

[0025]

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[In the formula, Z ¹ and Z ² each represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring, and D ¹ and D ² are required for forming a polymethine dye. Represents an atomic group. q
¹ and q ² represent an integer of 0 or 1. M represents a central metal, X represents a ligand, and m represents 3, 4 or 5. V represents an ion required to neutralize the charge in the molecule. l represents the number of ions required to neutralize the charge in the molecule. General formula (1) X _1- (C (R ₁ ) = Y) _n -X _{2 wherein} X ₁ and X ₂ are each —OR ₃ or —N (R ₄ ) R ₅
R ₃ represents a hydrogen atom or a group that can be converted to a hydrogen atom by hydrolysis, R ₄ and R ₅ are each a hydrogen atom,
Alkyl group, aryl group, heterocyclic group, sulfonyl group,
Represents an acyl group, a sulfamoyl group or a carbamoyl group. Y represents C (R ₂ ) or N, R ₁ and R ₂ each represent a hydrogen atom or another substituent, and n represents an integer of 0 or more. When n is 2 or more, a ring may be formed. ]

[0027]

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[Wherein R _{6 to} R ₁₀ are each a hydrogen atom,
Alkyl group, alkenyl group, aryl group, heterocyclic group,
Alkyloxycarbonyl group, aryloxycarbonyl group, acyl group, sulfonyl group, carboxyl group, carbamoyl group, sulfamoyl group, halogen atom, -OR
₁₁ represents -SR _12, or -N (R ₁₃₎ R _14. R _{11 to} R
₁₄ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, or a sulfonyl group. (2) In a silver halide photographic light-sensitive material having a photographic constituent layer on a support, at least one of the photographic constituent layers is in the presence of a metal complex represented by the general formula [I] or [II]. Wherein at least one of the photographic constituent layers contains a compound represented by the following general formula (3) or an oxidized product thereof. A silver halide photographic light-sensitive material, characterized in that it is a layer containing at least one species.

[0029]

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[In the formula, R ₁₅ represents a hydrogen atom, an alkali metal atom or a quaternary ammonium group, and R ₁₆ and R ₁₇ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group,
Alkoxy, aryloxy, alkylthio, acyl, acylamino, nitro, cyano, oxycarbonyl, carboxyl, sulfo, hydroxy, ureido, sulfonamide, sulfamoyl, carbamoyl, acyloxy , An amino group, a sulfonyl group, a sulfinyl group, and a heterocyclic group.
Xa represents an oxygen atom or an imino group which may be substituted. (3) In a silver halide photographic light-sensitive material having a photographic constituent layer on a support, at least one of the photographic constituent layers is in the presence of a metal complex represented by the above general formula [I] or [II]. Wherein at least one of the photographic constituent layers contains a compound represented by the following general formula (4) or an oxidized form thereof. A silver halide photographic light-sensitive material, characterized in that it is a layer containing at least one species.

[0031]

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[In the formula, R ₁₈ represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group or a sulfonyl group, and R ₁₉ represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, Represents a sulfonyl group, a sphinyl group, a carbamoyl group, a sulfamoyl group or an oxycarbonyl group, and R ₂₀ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a sphinyl group, a carbamoyl group, or a sulfamoyl group. Group or oxycarbonyl group. (4) The silver halide photographic light-sensitive material described in any one of the above items 1 to 3, wherein at least one of the emulsion layers uses a reduction-sensitized silver halide emulsion. Characteristic silver halide photographic material.

Hereinafter, the present invention will be described in detail. First, typical specific examples of the metal complex having the spectral sensitizing dye used in at least one of the ligands used in the present invention are shown, but the compounds used in the present invention are not limited thereto. .

[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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Next, the compound of the general formula (1) used in the present invention will be described. In the general formula (1), substituents represented by R ₁ and R ₂ include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group,
Alkylthio group, acyl group, acylamino group, nitro group, cyano group, oxycarbonyl group, carboxyl group,
Examples include a sulfo group, a hydroxy group, a ureido group, a sulfonamide group, a sulfamoyl group, a carbamoyl group, an acyloxy group, an amino group, a sulfonyl group, a sulfinyl group, and a heterocyclic group. When there are two or more substituents, they may be the same or different, and may be linked to each other to form a ring. The ring formed here includes cyclopentene, cyclohexadiene, cycloheptadiene,
Benzene, pyridine and the like can be mentioned, and these may further have a substituent.

The alkyl groups represented by R ₁ , R ₂ , R ₄ and R ₅ include methyl, ethyl, propyl, i-propyl,
Butyl, t-butyl, cyclohexyl, benzyl group, etc., the aryl group includes phenyl, naphthyl group, etc., and the heterocyclic group includes 4-morpholinyl,
-Piperidyl, 1-pyridinyl and the like, R ₁ ,
Examples of the sulfonyl group represented by R ₂ , R ₄ and R ₅ include methanesulfonyl, ethanesulfonyl, benzenesulfonyl, 2-hydroxybenzenesulfonyl and the like, and represented by R ₁ , R ₂ , R ₄ and R _5. Examples of the acyl group include acetyl and benzoyl groups, and R ₁ , R ₂ , R ₄
And the sulfamoyl group represented by R ₅ include dimethylsulfamoyl and dodecylsulfamoyl groups, and the carbamoyl group represented by R ₁ , R ₂ , R ₄ and R ₅ include dimethylcarbamoyl and methylphenyl And carbamoyl and dodecylcarbamoyl groups.

The halogen atom represented by R ₁ and R ₂ includes chloro, bromo and fluorine atoms, and R ₁ and R ₂
Examples of the alkoxy group represented by methoxy, ethoxy,
Butoxy, t-butoxy, cyclohexyloxy, benzyloxy, octyloxy, tridecyloxy, hexadecyloxy groups and the like, and the aryloxy groups represented by R ₁ and R ₂ include phenoxy and naphthoxy groups; the alkylthio group represented by R ₁ and _{R 2} methylthio, ethylthio, i- propylthio, butylthio, cyclohexylthio, benzylthio, t-octylthio, dodecylthio group and the like, _{R 1} and R ₂
Examples of the acylamino group represented by R include acetylamino and benzoylamino groups. Examples of the oxycarbonyl group represented by R ₁ and R ₂ include ethoxycarbonyl, hexadecyloxycarbonyl, and phenoxycarbonyl groups. Examples of the ureido group represented by ₁ and R ₂ include ureido, an N, N-dimethylureido group, and the like.
Examples of the sulfonamide group represented by R ₁ and R ₂ include a methyl sulfonamide and a phenyl sulfonamide group, and examples of the acyloxy group represented by R ₁ and R ₂ include an acetyloxy and propionyloxy group. , R ₁
And the amino group represented by R ₂ include amino, dimethylamino, anilino, diphenylamino, and the like;
Examples of the sulfinyl group represented by R ₁ and R ₂ include a methylsulfinyl group and a phenylsulfinyl group.

Specific examples of the compound represented by formula (1) of the present invention are shown below, but the compounds used in the present invention are not limited thereto.

[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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The compound of the formula (2) used in the present invention will be described. In the general formula (2), R _{6 to} R ₁₀ each represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an acyl group, a sulfonyl group, a carboxyl group, a carbamoyl group. Group, sulfamoyl group, halogen atom, —OR ₁₁ , —SR ₁₂ , or —N (R ₁₃ ) R
Represents ₁₄ . R _{11 to} R ₁₄ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, or a sulfonyl group.

The alkyl groups represented by R _{6 to} R ₁₄ include methyl, ethyl, propyl, i-propyl, butyl, t-butyl, cyclohexyl and benzyl groups, and the aryl groups include phenyl and naphthyl. And the like. Heterocyclic groups include 4-morpholinyl, 1-piperidyl, 1-pyridinyl and the like, and sulfonyl groups include methanesulfonyl, ethanesulfonyl, benzenesulfonyl and 2-hydroxybenzenesulfonyl groups. Examples of the acyl group include acetyl and benzoyl groups, and examples of the sulfamoyl group represented by R _{6 to} R ₁₀ include dimethylsulfamoyl and dodecylsulfamoyl groups, which are represented by R _{6 to} R _10. Carbamoyl groups such as dimethylcarbamoyl, methylphenylcarbamoyl, Carbamoyl group, and the like.
Examples of the halogen atom represented by R _{6 to} R ₁₀ include chloro, bromo and fluorine atoms.

Specific examples of the compound represented by the general formula (2) of the present invention are shown below, but the compounds used in the present invention are not limited thereto.

[0057]

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[0058]

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The compound of the formula (3) used in the present invention will be described. In the general formula (3), R ₁₅ represents a hydrogen atom, an alkali metal atom or a quaternary ammonium group,
R ₁₆ and R ₁₇ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an acyl group, an acylamino group, a nitro group,
Cyano group, oxycarbonyl group, carboxyl group, sulfo group, hydroxy group, ureido group, sulfonamide group,
Sulfamoyl group, carbamoyl group, acyloxy group,
Represents an amino group, a sulfonyl group, a sulfinyl group, and a heterocyclic group.

Here, examples of the alkali metal atom represented by R ₁₅ include Li ⁺ , Na ⁺ , K ^{+ and the} like. Examples of the quaternary ammonium group include NH ₄ ⁺ , N ⁺ (CH ₃ ) ₄ , N
⁺ (C ₄ H ₉ ) ₄ , N ⁺ (CH ₃ ) ₃ nC ₁₂ H ₂₅ , N ⁺ (C
H ₃ ) ₃ nC ₁₆ H ₃₃ and N ⁺ (CH ₃ ) ₃ HCH ₂ C ₆ H ₅ .

The halogen atoms represented by R ₁₆ and R ₁₇ include chloro, bromo and fluorine atoms, and the alkyl groups include methyl, ethyl, propyl, i-propyl, butyl, t-butyl, cyclohexyl, benzyl and the like. Examples of the aryl group include phenyl and naphthyl groups, and the alkoxy group includes methoxy, ethoxy,
Butoxy, t-butoxy, cyclohexyloxy, benzyloxy, octyloxy, tridecyloxy, hexadecyloxy group, etc., the aryloxy group includes phenoxy and naphthoxy groups, and the alkylthio group includes methylthio, ethylthio, i -Propylthio, butylthio, cyclohexylthio, benzylthio,
t-octylthio, dodecylthio group and the like; acyl group includes acetyl and benzoyl group; acylamino group includes acetylamino and benzoylamino group; and oxycarbonyl group as ethoxycarbonyl and hexadecyloxy. Carbonyl, phenoxycarbonyl group and the like; ureido group includes ureido and N, N-dimethylureido group; sulfonamide group includes methylsulfonamide and phenylsulfonamide group; and sulfamoyl group; Sulfamoyl, N, N-dimethylsulfamoyl, monophorinosulfonyl, piperidinosulfonyl, and the like. Examples of the carbamoyl group include carbamoyl,
N, N-dimethylcarbamoyl, monophorinocarbonyl, piperidinocarbonyl group and the like, acyloxy group includes acetyloxy and propionyloxy group, and amino group include amino, dimethylamino, anilino, diphenylamino And the like.Examples of the sulfonyl group include methylsulfonyl, propylsulfonyl, and phenylsulfonyl groups.Examples of the sulfinyl group include methylsulfinyl and phenylsulfinyl groups. Piperidyl, 1-pyridinyl and the like.

Specific examples of the compound represented by formula (3) of the present invention are shown below, but the compounds used in the present invention are not limited thereto.

[0063]

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[0064]

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Further, the compound of the general formula (4) used in the present invention will be described. In the general formula (4), R ₁₈ represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group,
Represents an acyl group or a sulfonyl group, R ₁₉ is an alkyl group,
An alkenyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a sphinyl group, a carbamoyl group, a sulfamoyl group or an oxycarbonyl group, and R ₂₀ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, As the alkyl group represented by R _{18 to} R ₂₀ representing an acyl group, a sulfonyl group, a sphinyl group, a carbamoyl group, a sulfamoyl group or an oxycarbonyl group, methyl, ethyl, propyl, i-propyl, butyl, t-butyl, cyclohexyl , Benzyl group, etc., alkenyl group, allyl, vinyl group, etc., aryl group, phenyl, naphthyl group, etc., and heterocyclic group, 4-morpholinyl, 1-piperidyl, 1-pyridinyl. And acyl groups such as acetyl and benzoyl groups. Gerare, methanesulfonyl As the sulfonyl group, ethanesulfonyl, benzenesulfonyl, 2
- hydroxybenzene sulfonyl group and the like, R ₁₉
And a sulfinyl group represented by R ₂₀ include methylsulfinyl, phenylsulfinyl group, and the like; carbamoyl groups include dimethylcarbamoyl, methylphenylcarbamoyl, dodecylcarbamoyl group, and the like; and sulfamoyl groups include dimethylsulfamoyl; A dodecylsulfamoyl group and the like can be mentioned, and as the oxycarbonyl group, an ethoxycarbonyl, hexadecyloxycarbonyl, phenoxycarbonyl group and the like can be mentioned.

Specific examples of the compound represented by formula (4) of the present invention are shown below, but the compounds used in the present invention are not limited thereto.

[0067]

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[0068]

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In order to incorporate the compounds represented by formulas (1) to (4) used in the present invention into the silver halide emulsion of the present invention, they may be dispersed directly in the emulsion. Alternatively, it may be added to the emulsion by dissolving it in a solvent such as water, methanol, ethanol, propanol, methyl cellosolve, 2,2,3,3-tetrahydrofluoropropanol, alone or in a mixed solvent. In addition, Japanese Unexamined Patent Publication No.
No. 23389, No. 44-27555, No. 57-22
No. 089, etc. to make an aqueous solution by coexisting with an acid or a base, or to coexist with a surfactant as described in U.S. Pat. Nos. 3,822,135 and 4,006,025. An aqueous solution or a colloidal dispersion may be added to the emulsion. After dissolving in a substantially water-immiscible solvent such as phenoxyethanol, a dispersion in water or a hydrophilic colloid may be added to the emulsion. As described in JP-A-53-102733 and JP-A-58-105141, the dispersion may be directly dispersed in a hydrophilic colloid, and the dispersion may be added to the emulsion. The compounds represented by the general formulas (1) to (4) may be dissolved using ultrasonic vibration described in U.S. Pat. No. 3,485,634. In addition, as a method of dissolving or dispersing the compounds represented by the general formulas (1) to (4) and adding them to the emulsion, US Pat. Nos. 3,482,981 and 3,585, U.S. Pat. 19
No. 5, No. 3,469,987, No. 3,425,8
No. 35, No. 3,342,605 and British Patent Nos. 1,2.
No. 71,329, No. 1,038,029, No. 1,
121,174; U.S. Patent No. 3,660,101;
No. 3,658,546 can be used.

The compound represented by the general formula (1) to the general formula (4) used in the present invention may be added in any of a grain forming step (including physical ripening), a desalting water washing step and a chemical sensitizing step. It may be time.

The general formulas (1) to (4) used in the present invention
Is 1 × 10 5 per mole of silver halide.
^-5 to 1 × 10 mol, preferably 1 × 10 ^-4 to 1 mol, is contained in the silver halide photographic emulsion.

The compounds represented by formulas (1) to (4) used in the present invention may be contained anywhere in the light-sensitive material, but are preferably added to a silver halide emulsion layer. . Alternatively, it is preferably added to a non-photosensitive hydrophilic colloid layer which is a layer adjacent thereto. The non-photosensitive hydrophilic colloid layer comprises a protective layer, an intermediate layer,
There are a color mixing prevention layer, an antihalation layer and the like.

In the light-sensitive material of the present invention, the effect is more remarkable when the emulsion used is reduction-sensitized. Hereinafter, the reduction sensitization of the present invention will be described. In the present invention, examples of the reduction sensitization method that can be used include, for example, Photographic Sensitive.
(Tadaaki Tani, Oxford University)
y Press 1995), page 180, describes various reduction sensitization methods. However, various methods of reduction sensitization are known and are not limited thereto. That is, a method of adding a known reducing agent to a silver halide emulsion,
A method of growing or ripening in an atmosphere having a low pAg of pAg 1 to 7, which is called silver ripening.
PH 8 called high pH aging as shown in No. 0
Methods of growing or ripening in a high pH atmosphere of up to 11 are known, and two or more methods can be used in combination. The method of adding a reduction sensitizer is a preferable method because the level of reduction sensitization can be finely adjusted.

As reduction sensitizers, stannous salts, amine and polyamic acids, hydrazine derivatives, formamidinesulfinic acid, silane compounds, borane compounds and the like are known. In the present invention, these known compounds can be selected and used. Two or more compounds can be used in combination. Stannous chloride, thiourea dioxide as reduction sensitizer,
Dimethylamine borane is a preferred compound. More preferably, the alkynylamine compounds described in US Pat. No. 5,389,510 can be selected. The addition amount of the reduction sensitizer is the addition amount needs to be selected depends on emulsion manufacturing conditions, per mol of silver halide ^10-7
A range of ^-3 moles is suitable.

Ascorbic acid and its derivatives can also be used as the reduction sensitizer of the present invention. Specific examples of ascorbic acid and its derivatives (hereinafter, referred to as “ascorbic acid compound”) include the following.

(A-1) L-ascorbic acid (A-2) Sodium L-ascorbate (A-3) Potassium L-ascorbate (A-4) DL-ascorbic acid (A-5) D-ascorbic acid Sodium (A-6) L-ascorbic acid-6-acetate (A-7) L-ascorbic acid-6-palmitate (A-8) L-ascorbic acid-6-benzoate (A-9) L-ascorbic acid- 5,6-Diacetate (A-10) L-ascorbic acid-5,6-O-isopropylidene The ascorbic acid compound used in the present invention is compared with the amount of the conventional reduction sensitizer which is preferably used. It is desirable to use a large amount. For example, JP-B-57-33572
No. "The amount of reducing agent is usually 0.75 × g per silver ion.
Does not exceed 10 ^-2 meq (8 × 10 ^-4 mol / AgX mol). An amount of 0.1 to 10 mg per kg of silver nitrate (10 ^-7 to 10 ^-5 mol / AgX mol as ascorbic acid) is often effective. (The converted value is based on the inventors). U.S. Pat. No. 2,487,850
No. describes "1.times.10.sup.- ⁷ to 4.times.10.sup.- ⁶ mol as an addition amount in which a tin compound can be used as a reduction sensitizer". Japanese Patent Application Laid-Open No. Sho 57-179835 discloses that the amount of thiourea dioxide added is about 0.1 per mole of silver halide.
01mg to about 2mg, about 0.01mg as stannous chloride
It is stated that it is appropriate to use from about 3 mg.
The ascorbic acid compound used in the present invention includes the grain size of the emulsion, the halogen composition, the temperature for preparing the emulsion, pH, pAg
Although the preferable addition amount depends on factors such as the above, it is desirable to select from the range of 5 × 10 ^-5 to 1 × 10 ^-1 mol per mol of silver halide. More preferably, it is preferably selected from the range of 5 × 10 ⁻⁴ mol to 1 × 10 ⁻² mol. It is particularly preferable to select from a range of 1 × 10 ⁻³ mol to 1 × 10 ⁻² mol.

The reduction sensitizer can be dissolved in water or a solvent such as alcohols, glycols, ketones, esters and amides and added during grain formation, before or after chemical sensitization. The compound may be added during any step of the emulsion production process, but a particularly preferable method is to add the compound during grain growth. It may be added to the reaction vessel in advance, but it is more preferable to add it at an appropriate time during particle formation. Alternatively, a reduction sensitizer may be added in advance to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide, and particles may be formed using these aqueous solutions. It is also a preferred method to add the solution of the reduction sensitizer in several portions as the grains are formed, or to add the solution continuously for a long time.

Next, the silver halide grains used in the present invention will be described. The silver halide grains of the present invention include silver bromide, silver chloride, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide,
It is silver chloroiodobromide. Other silver salts, such as rodin silver,
Silver sulfide, silver selenide, silver carbonate, silver phosphate, and organic acid silver may be contained as separate grains or as a part of silver halide grains. When rapid development, desilvering and (bleaching, fixing and bleach-fixing) steps are desired, silver halide grains having a high silver chloride content are desirable. In order to appropriately suppress development, it is preferable to contain silver iodide. The preferred silver iodide content depends on the intended light-sensitive material. For example, the preferred range is 0.1 to 15 mol% for X-ray photographic materials and 0.01 to 5 mol% for graphic arts and micro photographic materials. In the case of a photographic light-sensitive material represented by a color negative, silver halide grains containing 0.1 to 3% of silver iodide are preferred, more preferably 0.5 to 2.0% by mole, and particularly preferably 0.5 to 2.0% by mole. 0.8 to 1.5 mol%. It is preferable that silver iodobromide grains contain silver chloride in order to reduce lattice strain.

The silver halide grains of the present invention preferably have a distribution or a structure with respect to the halogen composition in the grains. A typical example is JP-B-43-1316.
No. 2, JP-A-61-215540 and JP-A-60-22284
No. 5, No. 60-143331, No. 61-75337, etc. are core-shell type or double structure type particles having a halogen composition in which the inside and the surface of the grains have different halogen compositions. Also, it is not a simple double structure.
It is possible to form a triple structure as disclosed in JP-A-222844 or a multilayer structure thereof or more, or to apply a thin silver halide having a different composition to the surface of a core-shell double structure grain. .

When two or more silver halides are present as mixed crystals or with a structure, it is important to control the halogen composition distribution between grains. Regarding the method of measuring the halogen composition distribution between grains, see JP-A-60-1985.
No. 254032. Uniform halogen distribution between grains is a desirable property. In particular, a highly uniform emulsion having a coefficient of variation of 20% or less is preferable. Another preferred form is an emulsion having a correlation between the grain size and the halogen composition. As an example, large-sized particles have a high iodine content,
On the other hand, there is a case where the smaller the size, the lower the iodine content. Depending on the purpose, an inverse correlation or a correlation with another halogen composition can be selected. For this purpose, it is preferable to mix two or more emulsions having different compositions.

It is important to control the halogen composition near the surface of the silver halide grains. Increasing the silver iodide content near the surface or increasing the silver chloride content can be selected according to the purpose because the dye adsorbability and the developing speed are changed. When changing the halogen composition in the vicinity of the surface, either a structure that wraps the entire grain or a structure that adheres only to a part of the grain can be selected. For example, (10
This is a case where the halogen composition is changed only on one side of the tetrahedral grain composed of the (0) plane and the (111) plane, or one of the main plane and the side face of the tabular grain is changed.

The silver halide grains of the present invention can be made of a normal crystal having no twin planes. 163, such as a single twin with one twin plane, a parallel multiple twin with two or more parallel twin planes, a non-parallel with two or more non-parallel twin planes It can be selected from multiple twins or the like depending on the purpose. An example of mixing particles having different shapes is disclosed in U.S. Pat. No. 4,865,964, but this method can be selected as necessary. In the case of a normal crystal, a cube consisting of (100) planes, an octahedron consisting of (111) planes, Japanese Patent Publication No. 55-42737,
A dodecahedral particle having a (110) plane disclosed in JP-A-222842 can be used. Furthermore, Jour
nalof Imaging Science, 30
Volume, pp. 247, (hll) plane particles represented by the (211) plane as reported in 1986, (33
(1) The (hhl) -plane particles represented by the plane, the (hk0) -plane particles represented by the (210) plane, and the (hkl) -plane particles represented by the (321) plane also require devising the preparation method. Can be selected for use. (100) face and (1)
11) a tetrahedral particle whose plane coexists in one particle, (10
Particles in which two planes or many planes coexist, such as particles in which the (0) plane and the (110) plane coexist, can be selected and used according to the purpose. The value obtained by dividing the circle equivalent diameter of the photographing area of the particle by the particle thickness is called an aspect ratio, and defines the shape of the tabular particle. Tabular grains having an aspect ratio of greater than 1 can be used as the silver halide grains of the present invention. Tabular grains are described in "Theory and Practice of Photography" by Cleeve (Clev
e, Photography Thory and P
Lactice (1930)), p. 131;
Photographic Science and Engineering (Gutoff, PhotographicSc)
issue Engineering), No. 14
248-257 (1970); U.S. Pat.
No. 434,226, 4,414,310, 4,433,048, 4,439,520 and British Patent No. 2,112,157. Can be. When tabular grains are used, there are advantages such as an increase in covering power and an increase in color sensitization efficiency by a sensitizing dye.
No. 34,2265. The average aspect ratio of 80% or more of the total projected area of the grains is preferably 1 or more and 100 or less. It is more preferably 2 or more and 20 or less, and particularly preferably 3 or more and 10 or less. An excessively high aspect ratio is not preferable because a pressure drop or the like occurs. Triangular, hexagonal,
You can choose a circle or the like. U.S. Pat. No. 4,797,
A regular hexagon having substantially equal lengths of six sides as described in Japanese Patent No. 354 is a preferred form.

As the grain size of the tabular grains, a circle equivalent diameter of the projected area of the grains is often used, and grains having an average diameter of 0.6 μm or less as described in US Pat. No. 4,748,106 are used. Is preferable for high image quality.
It is preferable to limit the thickness of the tabular grains to 0.5 μm or less, more preferably 0.3 μm or less, in order to increase sharpness. Further, JP-A-63-16345
The particles described in No. 1 which define the thickness of the particles and the distance between twin planes are also preferable.

When monodisperse tabular grains having a narrow grain size distribution are used, more preferable results may be obtained. U.S. Pat. No. 4,797,354 and JP-A-2-8
No. 38 describes a method for producing monodisperse hexagonal tabular grains having a high tabularization ratio. In addition, European Patent No. 514, 74
No. 2 describes a method for producing tabular grains having a coefficient of variation in grain size distribution of less than 10% using a polyalkylene oxide block copolymer. It is preferable to use these tabular grains in the present invention. Further, a particle having a high uniformity of thickness having a variation coefficient of the particle thickness of 30% or less is also preferable.

In the case of tabular grains, dislocation lines can be observed with a transmission electron microscope. It is preferable to select a particle containing no dislocation line, a particle containing several dislocations, or a particle containing many dislocations according to the purpose. It is also possible to select dislocations or dislocations that are introduced linearly with respect to a specific direction of the crystal orientation of the grains, or to introduce them all over the grains, or to introduce them only into specific portions of the grains,
For example, dislocations can be introduced only in the fringe portion of the particles. The introduction of dislocation lines is preferable not only in the case of tabular grains but also in the case of irregular grains typified by normal crystal grains or potato grains. Also in this case, it is a preferable embodiment to limit to a specific portion such as a vertex or a ridge of the particle.

The silver halide grains of the present invention are described in European Patent No. 9
No. 6,727B1, No. 64,412B1, etc., a treatment for imparting roundness to particles, or West German Patent No. 2,306,447C2, JP-A-60-22.
The surface may be modified as disclosed in No. 1320.

A structure having a flat particle surface is generally used.
It is preferable in some cases to form irregularities intentionally.
JP-A-58-106532 and JP-A-60-221320 disclose a method of forming a hole in a part of a crystal, for example, a vertex or a center of a plane, or U.S. Pat.
Raffle particles described in No. 966 are examples.

The grain size of the silver halide grains of the present invention and the finally obtained grains are as follows: a circle equivalent diameter of a projected area using an electron microscope, a sphere equivalent diameter of a grain volume calculated from the projected area and the grain thickness, or a Coulter counter. It can be evaluated by the sphere equivalent diameter of the volume by the method. It can be used by selecting from ultrafine particles having a sphere equivalent diameter of 0.05 μm or less and coarse particles exceeding 10 μm. Preferably, particles having a size of 0.1 μm or more and 3 μm or less are used as photosensitive halogenated particles.

The silver halide grains of the present invention or the grains finally obtained can be selected depending on the purpose, whether they are polydisperse emulsions having a wide grain size distribution or monodisperse emulsions having a narrow size distribution. In some cases, a variation coefficient of a diameter equivalent to a projected area of a particle or a diameter equivalent to a sphere of a volume is used as a scale representing a size distribution. When using a monodisperse emulsion,
It is preferable to use an emulsion having a size distribution with a variation coefficient of 25% or less, more preferably 20% or less, and still more preferably 15% or less.

The monodisperse emulsion may be defined as having a grain size distribution such that 80% or more of all grains fall within ± 30% of the average grain size by number or weight of grains. In order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodispersed silver halide emulsions having different grain sizes are mixed in the same layer or different layers in an emulsion layer having substantially the same color sensitivity. Can be applied in layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion can be used as a mixture or as a mixture.

The silver halide grains of the present invention can be obtained by the method described in "Physics and Chemistry of Photography" by Grafkid, published by Paul Montell (P.G.
lafkides, Chimie et Physiq
uePhotographique Paul Mon
tel., 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Phot).
ographic Emulsion Chemistr
y, Focal Press, 1966), "Manufacture and Coating of Photographic Emulsions", by Zeligman et al., published by Focal Press (VL Zelikman et al., Makin).
g and Coating Photographic
Emulsion, FocalPress, 196
It can be prepared using the method described in 4). That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halide may be any one of a one-side mixing method, a simultaneous mixing method, and a combination thereof. Good. A method in which grains are formed in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one type of the double jet method, a method of maintaining a constant pAg in a liquid phase in which silver halide grains are formed, that is, a so-called controlled double jet method can be used. According to this method, silver halide grains having a regular crystal form and a nearly uniform grain size can be obtained.

A method of adding previously precipitated silver halide grains to a reaction vessel for preparing an emulsion, US Pat. Nos. 4,334,012, 4,301,241, and 4,150,994. Are preferably used in some cases, and these can be used as seed crystals, and are also effective when supplied as silver halide for growth. In the latter case, it is preferable to add an emulsion having a small grain size, and the addition method can be selected from the method of adding the whole amount at once, adding a plurality of times, or adding continuously. It is also effective in some cases to add particles of various halogen compositions to modify the surface.

A method for converting most or only a part of the halogen composition of silver halide grains by a halogen conversion method is disclosed in US Pat. Nos. 3,477,852 and 4,14.
No. 2,900, European Patent Nos. 273,429 and 27
No. 3,430, West German Patent No. 3,819,241, etc., which are effective particle forming methods. A solution of a soluble halogen or silver halide grains can be added to convert the silver salt into a more insoluble silver salt. It can be selected from methods such as converting at once, converting into a plurality of times, or converting continuously.

In addition to the method of adding a soluble silver salt and a halogen salt at a constant concentration and a constant flow rate for grain growth, British Patent No. 1
469,480; U.S. Pat. No. 3,650,757;
The particle formation method in which the concentration is changed or the flow rate is changed as described in US Pat. No. 4,242,445 is a preferred method. By increasing the concentration or increasing the flow rate, the amount of silver halide to be supplied can be changed by a linear function, a quadratic function, or a more complicated function of the addition time. It is also preferable in some cases to reduce the amount of silver halide supplied as necessary. Further, when adding a plurality of soluble silver salts having different solution compositions, or when adding a plurality of soluble halide salts having different solution compositions,
An addition method in which one is increased and the other is decreased is also an effective method.

A mixer for reacting a solution of a soluble silver salt and a soluble halide salt is disclosed in US Pat. No. 2,996,287.
No. 3,342,605 and No. 3,415,65
No. 0, No. 3,785,777, West German Patent No. 2,
556,885 and 2,555,364.

A silver halide solvent is useful for the purpose of accelerating ripening. For example, it is known to have an excess of halogen ions in the reactor to promote ripening. Other ripening agents can also be used. These ripening agents can be incorporated in their entirety in the dispersion medium in the reactor before adding the silver and halide salts, or can be added together with the halide salts, silver salts or peptizers, and added to the reactor. Can also be introduced. As another variant, the ripening agent can be introduced independently during the silver halide and silver salt addition steps.

Ammonia, thiocyanates (for example, rhodacali, rhodamonium ammonium), and organic thioether compounds (for example, US Pat. Nos. 3,574,628, 3,021,215, and 3,057,724) No. 3,038,805, No. 4,276,374,
Nos. 4,297,439 and 3,704,130
No. 4,782,013, JP-A-57-1049.
No. 26 etc.), thione compounds (for example,
Tetrasubstituted thioureas described in JP-A-53-82408 and JP-A-55-77737, U.S. Pat. No. 4,782,013, and compounds described in JP-A-53-144319), Mercapto compounds and amine compounds capable of accelerating the growth of silver halide grains described in JP-A-57-202531 (for example, JP-A-52-25331).
No. 100717).

Gelatin is advantageously used as a protective colloid used in preparing the emulsion of the present invention and as a binder for other hydrophilic colloid layers, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates, sodium alginate and starch derivatives Sugar derivative; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone,
Various kinds of synthetic hydrophilic high molecular substances such as a single or copolymer such as polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylvirazole can be used.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Ph
oto. Japan. No. 16 P30 (1966)
Enzyme-treated gelatin as described in may be used,
In addition, a hydrolyzate or enzymatic decomposition product of gelatin can also be used.

The emulsion of the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid. The temperature of water washing can be selected according to the purpose, but is preferably selected in the range of 5 ° C to 50 ° C. The pH at the time of washing can be selected according to the purpose, but is preferably selected from 2 to 10. More preferably, it is in the range of 3 to 8. The pAg at the time of washing can be selected according to the purpose, but is preferably selected from 5 to 10. The method for washing can be selected from noodle washing, dialysis using a semipermeable membrane, centrifugal separation, coagulation sedimentation, and ion exchange. In the case of the coagulation sedimentation method, a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative, and the like can be selected.

A method of adding a chalcogenide compound during the preparation of an emulsion as described in US Pat. No. 3,772,031 is sometimes useful. In addition to S, Se, Te, cyanide, thiocyanate, selenocyanic acid, carbonate,
Phosphates and acetates may be present.

The silver halide grains of the present invention may be subjected to at least one of sulfur sensitization, selenium sensitization, gold sensitization, palladium sensitization or noble metal sensitization in any step of the production process of a silver halide emulsion. Can be. It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are a type in which a chemical sensitization nucleus is embedded in the inside of a grain, a type in which a chemical sensitization nucleus is embedded in a position shallow from the particle surface, and a type in which a chemical sensitization nucleus is formed on the surface. In the emulsion of the present invention, the location of the chemical sensitization nucleus can be selected according to the purpose. Generally, it is preferable to form at least one type of chemical sensitization nucleus near the surface.

One of the chemical sensitizations which can be preferably carried out in the present invention is a chalcogenide sensitization and a noble metal sensitization alone or in combination, and is described by TH (James), The Photographic Process, No. 4 Edition, Macmillan, 1977, (TH James, The Th
eory of the PhotographicP
process, 4th ed, Makmi11an, 1
977) pages 67-76, and can be performed using active gelatin, and can also be performed by Research Disclosure 120, April 1974, 12008; Research Disclosure 34, June 1975.
Moon, 13452, U.S. Pat. Nos. 2,642,361, 3,297,446, and 3,773,031,
No. 3,857,711, No. 3,901,714
No. 4,226,018 and No. 3,904,
415 and pAg 5-10, pH 5-8 and temperature 3 as described in GB 1,315,755.
At 0 to 80 ° C, sulfur, selenium, tellurium, gold, platinum,
It can be palladium or a combination of several of these sensitizers. In noble metal sensitization, for example, gold, platinum,
Noble metal salts of palladium can be used, and among them, gold sensitization, palladium sensitization and a combination of both are preferred. In the case of gold sensitization, for example, known compounds of chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, and gold selenide can be used. The palladium compound means a divalent salt or a tetravalent salt of palladium. Preferred palladium compounds are M ₂ PdX ₆ or M ₂
Represented by PdX _4. Here, M represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom, and represents a chlorine, bromine or iodine atom.

More specifically, for example, K ₂ PdCl ₄ , (N
H ₄ ) ₂ PdCl ₆ , Na ₂ PdCl ₄ , (NH ₄ ) ₂ PdC
l ₄ , Li ₂ PdCl ₄ , Na ₂ PdCl ₆ or K ₂ PdBr
₄ is preferred. The gold compound and the palladium compound are preferably used in combination with a thiocyanate or a selenocyanate.

As sulfur sensitizers, hypo, thiourea compounds, rhodanine compounds and US Pat. No. 3,857,7
No. 11, No. 4,226,018 and No. 4,05
Sulfur-containing compounds described in US Pat. No. 4,457 can be used. Chemical sensitization can also be performed in the presence of a so-called chemical sensitizer. Useful chemical sensitization aids include compounds known to suppress fog in the course of chemical sensitization and increase sensitivity, such as azaindene, azapyridazine and azapyrimidine. Examples of chemical sensitization aid modifiers are described in U.S. Pat.
Nos. 411,914 and 3,554,757, JP-A-58-126526 and the aforementioned "Photographic Emulsion Chemistry" by Duffin, pp. 138-143.

The emulsion of the present invention is preferably used in combination with gold sensitization. The preferred amount of the gold sensitizer is 1 × 10 ^-4 to 1 × 10 ^-7 mol, more preferably 1 × 10 ^{-5 to} 5 × 10 ^-7 mol, per mol of silver halide. The preferred range of the palladium compound is from 1 × 10 ⁻³ to 5 × 10 ⁻⁷ . The preferred range of the thiocyan compound or selenocyan compound is from 5 × 10 ⁻² to 1 × 10 ⁻⁶ .

The preferred amount of sulfur sensitizer used for the silver halide grains of the present invention is 1 × per mole of silver halide.
10 ^-4 to 1 × 10 ^-7 mol, more preferably 1 × 10 ^-7 mol.
10 ^{-5 to} 5 × 10 ^-7 mol.

Selenium sensitization is a preferred sensitizing method for the emulsion of the present invention. In the selenium sensitization, a known unstable selenium compound is used, and specifically, for example, colloidal metal selenium, selenoureas (for example, N, N-dimethylselenourea, N, N-diethylselenourea, etc.),
Selenium compounds such as selenoketones and selenamides can be used. Selenium sensitization may be preferably used in combination with sulfur sensitization or noble metal sensitization or both.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material or stabilizing photographic performance. . That is, thiazoles, for example, benzothiazolium salts, nitroimidazoles,
Nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, Mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines;
Thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a,
7) Many compounds known as antifoggants or stabilizers, such as tetraazaindenes and pentaazaindenes, can be added. For example, U.S. Pat.
954, 474, 3,982,947, and JP-B-52-28660 can be used. One of the preferred compounds is disclosed in JP-A-63-21293.
There are compounds described in No. 2. An antifoggant and a stabilizer are used before the particle formation, during the particle formation, after the particle formation, a washing step,
It can be added according to the purpose at various times during dispersion after washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. In addition to exhibiting the original antifogging and stabilizing effects by adding during emulsion preparation, control the crystal wall of the grains, reduce the grain size, reduce the solubility of the grains, control the chemical sensitization, It can be used for various purposes such as controlling the arrangement of dyes.

The spectral sensitizing dyes adsorbed on the silver halide grains of the present invention include methine dyes. Therefore, the photographic emulsion finally obtained is also spectrally sensitized by methine dyes and the like. It is preferable to exhibit the effect. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine chords. Any of nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, for example, a pyrroline nucleus, an oxazoline nucleus, a thiozoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; A nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, that is, for example, an indolenine nucleus, a benzoindolenine nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselena A sol nucleus, a benzimidazole nucleus, and a quinoline nucleus can be applied. These nuclei may be substituted on carbon atoms. In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, for example, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,
5- to 6-membered heterocyclic nuclei such as 4-dione nuclei, thiazolidine-2,4-dione nuclei, rhodanine nuclei and thiobarbituric acid nuclei can be applied.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Representative examples are U.S. Pat. Nos. 2,688,545 and 2,972.
No. 7,229, No. 3,397,060, No. 3,5
No. 22,052, No. 3,527,641, No. 3,
Nos. 617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703,377,
Nos. 3,769,301 and 3,814,609
No. 3,837,862, No. 4,026,70
7, UK Patent Nos. 1,344,281 and 1,50
7,803, JP-B-43-4936, 53-12
No. 375, JP-A-52-110618, JP-A-52-10
No. 9925.

In addition to the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

The addition time of the spectral sensitizing dye of the present invention is preferably after the formation of silver halide grains and before the addition of fine grains. Most commonly, it is carried out after completion of chemical sensitization but before coating, but as described in US Pat. Nos. 3,628,969 and 4,225,666, chemical sensitizers are used. At the same time as the above, spectral sensitization can be performed at the same time as chemical sensitization, or can be performed prior to chemical sensitization as described in JP-A-58-113928. It can be added before the completion of the formation to start spectral sensitization. No. 4,255,6.
It is also possible to add these compounds separately as taught in No. 66, i.e. to add some of these compounds prior to chemical sensitization and the remainder after chemical sensitization. At any time during the formation of silver halide grains, including the method disclosed in U.S. Pat. No. 4,183,756.

The addition amount was 4 × / mol of silver halide.
It can be used in an amount of from 10 ^-6 to 8 × 10 ^-3 mol. In the case of a more preferable silver halide grain size of 0.2 to 1.2 μm, about 5 × 10 ^-5 to 2 × 10 ^-3 mol is more effective. It is. When the emulsion obtained in the present invention is used as a light-sensitive material, the above-mentioned various additives are used. In addition, various additives can be used according to the purpose.

These additives are described in more detail in Research Disclosure Item 17643 (1978).
December 18), Item 18716 (November 1979)
Monday) and Item 308119 (December 1989)
Month).

The novel silver halide emulsion of the present invention can be used in any ordinary photographic light-sensitive material. Alternatively, the emulsion can be included in any photographic material having one or more silver halide emulsion layers. In one embodiment, the novel emulsions of the present invention are contained in a single emulsion layer of a photographic material intended to produce a silver or dye photographic image after photography or scanning exposure. In one simple embodiment, the photographic material can be a black and white (e.g., silver image forming) photographic material in which the underlying (first) emulsion layer is orthochromatic or panchromatic sensitized. In another embodiment, the photographic light-sensitive material is a multicolor photographic material that includes blue recording (yellow dye image formation), green recording (magenta dye image formation) and red (cyan dye image formation) layer units in any coating order. It can be a photosensitive material.

[0118]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. The invention can be better understood by reference to the following examples of emulsion preparation, emulsion and photographic elements that satisfy the requirements of the invention. The sensitivity is represented by the relative value of the logarithm of the reciprocal of the exposure amount E (E is expressed in units of lux-second) giving a density of fog + 0.2.

Example 1 (Color negative photosensitive material) (Preparation of seed emulsion T-1) Seed emulsion T-1 having two parallel twin planes was prepared by the following method.

(A-1 solution) Ossein gelatin 38.0 g Potassium bromide 11.7 g 34.0 L with water (B-1 solution) Silver nitrate 810.0 g with water 3815 ml (C-1 solution) Potassium bromide 567. 315 ml with 3 g of water (D-1 solution) Ossein gelatin 163.4 g of HO (CH ₂ CH ₂ O) _m (CH ₂ CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) 10% methanol solution 5.5ml 3961ml with water (E-1 solution) Sulfuric acid (10%) 91.1ml (F-1 solution) 56% acetic acid aqueous solution Required amount (G-1 solution) Ammonia water (28%) 105. 7 ml (H-1 solution) Potassium hydroxide aqueous solution (10%) Required amount Using a stirring device described in JP-A-62-160128, 3
Solution E-1 was added to solution A-1 which was vigorously stirred at 0 ° C. Then, 279 ml each of solution B-1 and solution C-1 were added at a constant rate for 1 minute by a double jet method to obtain silver halide nuclei. Was generated.

Thereafter, the solution D-1 was added, the temperature was raised to 60 ° C. over 31 minutes, the solution G-1 was further added, the pH was adjusted to 9.3 with the solution H-1, and 6.5 minutes. Aging was performed. Thereafter, the pH was adjusted to 5.8 with the F-1 solution, and then the remaining B-1 solution and the C-1 solution were acceleratedly added by the double jet method in 37 minutes, and immediately desalted by the usual method. went. When this seed emulsion was observed with an electron microscope, the ECD (projected area circle converted particle size) having two twin planes parallel to each other was 0.7.
This was a monodisperse tabular seed emulsion having a particle size distribution of 2 μm and a COV (particle size distribution) of 16%.

(Preparation of Reduction-Sensitized Tabular Grain Emulsion Em-1) Emulsion Em-1 was prepared using Seed Emulsion T-1 and the following solution.
-1 was prepared.

(A-2 solution) Ossein gelatin 519.9 g HO (CH ₂ CH ₂ O) _m (CH ₂ CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) % Methanol solution 4.5 ml Seed emulsion T-1 5.3 mol equivalent Water 18.0 L (solution B-2) 3.5N silver nitrate aqueous solution 2787 ml (solution C-2) potassium bromide 1020 g potassium iodide 29.1 g water 2500 ml (D-2 solution) Potassium bromide 618.5 g Potassium iodide 8.7 g Water 1500 ml (E-2 solution) Potassium bromide 208.3 g Water 1000 ml (F-2 solution) 56% acetic acid aqueous solution (Solution H-2) A fine grain emulsion composed of 3.0% by weight of gelatin and silver iodide fine grains (ECD = 0.05 μm) equivalent to 0.672 mol The preparation method is described below.

4. containing 0.254 mol of potassium iodide
To 9942 ml of 0% gelatin solution, 3092 ml of an aqueous solution containing 10.59 mol of silver nitrate and 10.59 mol of potassium iodide were added at a constant speed over 35 minutes to form fine particles. The temperature during the formation of fine particles is controlled at 40 ° C, pH,
The EAg was established.

(I-2 solution) 10 ml of an aqueous solution containing 1.4 × 10 ⁻⁶ mol of thiourea dioxide per mol of silver halide (J-2 solution) 1. Sodium ethylthiosulfonate per mol of silver halide. Aqueous solution containing 3 × 10 ^-5 mol 100 ml (K-2 solution) 10% aqueous potassium hydroxide solution Required amount Add the A-2 solution into the reaction vessel and add the I-2 solution while stirring vigorously at 75 ° C. After that, solution B-2, solution C-2
Solution D-2 and Solution D-2 were added by the simultaneous mixing method in accordance with the combinations shown in Table 1, seed crystals were grown, and Comparative Emulsion Em-1 was prepared. Here, B-2 solution, C-2 solution, D
-2 The addition rate of the liquid is changed in a function-wise manner with respect to the addition time in consideration of the critical growth rate, and the generation of small particles other than the seed particles growing and the particle size distribution due to Ostwald ripening between the growing particles. To prevent deterioration.

First, the first growth was carried out by controlling the solution temperature in the reaction vessel to 75 ° C., the pAg to 8.9, and the pH to 5.8. In the first addition, 6 of solution B-2 was used.
5.8% was added. Thereafter, the solution J-2 was added, the solution temperature in the reaction vessel was lowered to 40 ° C. in 30 minutes, and the pAg was raised to 1
The solution was adjusted to 0.3, the entire amount of the H-2 solution was added at a constant speed for 2 minutes, and the second addition was immediately performed. The second addition was performed while controlling the solution temperature in the reaction vessel to 40 ° C., the pAg to 10.3, and the pH to 5.0, and added all the rest of the B-2 solution. For controlling pAg and pH, E-2 solution, F-2 solution and K-2 solution were added as needed.

After the particles are formed, desalting is performed according to the method described in JP-A-5-72658, and then gelatin is added and dispersed, and at 40 ° C., pAg 8.06, pH 5.0.
8 were obtained.

When the silver halide grains in this emulsion were observed with an electron microscope, they were hexagonal tabular monodisperse silver halide grains having an ECD of 1.50 μm, a particle size distribution of 14% and an average aspect ratio of 7.0. Was.

[0129]

[Table 1]

(Preparation of Unreduced Sensitized Tabular Grain Emulsion Em-2) Em-2 was prepared by changing the conditions for producing Em-1 as follows.

In the preparation of Em-1, the same amount of water was added instead of I-2 and J-2. Other steps are performed using Em-
Performed identically to 1.

(Preparation of Em-3 and Em-4) Em-3 and Em-4 were prepared by changing the conditions for producing Em-2 as follows.
Was prepared. In the production of Em-2, the total amount of added silver was 50%.
% Of the compound of the present invention I-2, I-11
Was performed in the same manner as in the preparation of Em-2, except that 1 × 10 ⁻⁵ mol / mol Ag was added as an aqueous solution. These emulsions are named Em-3 and 4, respectively.

(Preparation of Em-5 and Em-6) Em-5 and Em-6 were prepared by changing the conditions for producing Em-1 as follows.
Was prepared. In the production of Em-1, the total amount of added silver was 50%.
% Of the compound of the present invention I-2, I-11
Was performed in the same manner as in the preparation of Em-1, except that 1 × 10 ⁻⁵ mol / mol Ag was added as an aqueous solution. These emulsions are named Em-5 and 6, respectively.

Sensitization Next, each of the emulsions Em-1 to Em-6 was sensitized as follows. 0.5 mol of an emulsion sample was melted at 40 ° C., and sensitizing dye 1, dye 2 and dye 3 shown below were added at a ratio of 1: 1: 1 so that the total coverage was about 70%. Thereafter, triphosphine selenide, sodium thiosulfate, chloroauric acid and potassium thiocyanate were added, and after optimal chemical sensitization according to a conventional method, 4-hydroxy-6 was added.
-Methyl-1,3,3a, 7-tetraazaindene (T
AI), 1-phenyl-5-mercaptotetrazole (PMT) was added.

Preparation of Single Layer Sensitive Material Samples The sensitized emulsions Em-1 to Em-6 were prepared according to the general formulas (1) to (4) of the present invention by the addition method and amount shown in Table 2 below.
Is added to the cellulose acetate film support coated with a gray silver antihalation layer, and the emulsion layer is coated with a surfactant and bis (vinylsulfonyl) methane hardener (gelatin). It was overcoated with 4.3 g / m ² gelatin layer containing 1.75 wt%) and the total weight. The coating amount of the emulsion (in terms of silver) was 0.646 g / m ² .
A total amount of surfactant and gelatin of 1.08 g / m ² was also included. Thus, samples 101 to 108 were produced.

[0136]

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[0137]

[Table 2]

Evaluation Each of the samples 101 to 108 thus obtained was exposed to a wedge with white light for 0.01 second, developed in accordance with the following processing steps, and then subjected to an optical densitometer (PD manufactured by Konica).
A-65) was used to measure the sensitivity and fog. Table 3 shows the relative sensitivity and fog density of the sample 102 with the fog taken as 100. At the same time, the results of sensitivity and fogging evaluations for each of those subjected to post-storage processing under the following condition A after exposure are also shown.

Condition A: 7 days at 40 ° C. and 80% RH Processing: Processing step Processing time Processing temperature Color development 2 minutes and 50 seconds 38 ± 0.3 ° C. Bleaching 45 seconds 38 ± 2.0 ° C. Fixed 1 minute 30 seconds 38 ± 2.0 ° C. Stability 60 seconds 38 ± 5.0 ° C. Drying 1 minute 55 ± 5.0 ° C. The following color developing solution, bleaching solution, fixing solution and stabilizing solution were used.

Color developer water 800 cc Potassium carbonate 30 g Sodium bicarbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-amino- 3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Add water to make 1 liter, and add potassium hydroxide or 20%
Adjust to pH 10.06 with sulfuric acid.

Bleaching solution water 700 cc Ammonium iron (III) 1,3-diaminopropanetetraacetate 125 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 40 g Ammonium bromide 150 g Glacial acetic acid 40 g Add water to make 1 liter and use ammonia water or glacial acetic acid. And adjust to pH 4.4.

Fixing solution water 800 cc Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.2 using aqueous ammonia or glacial acetic acid, add water to make 1 liter.

Stabilized water 900 cc Paraoctylphenyl polyoxyethylene ether (n = 10) 2.0 g Dimethylol urea 0.5 g Hexamethylenetetramine 0.2 g 1,2-Benzoisothiazolin-3-one 0.1 g Siloxane (manufactured by UCC) L-77) 0.1 g ammonia water 0.5 cc Add water to make 1 liter, then add ammonia water or 50 liters.
Adjust to pH 8.5 with% sulfuric acid.

[0144]

[Table 3]

As is evident from Table 3, a metal complex represented by the general formula [I] or [II] of the present invention having at least one ligand having an adsorptive group to silver halide was added. ,
General formula (1) of the present invention to metal-doped silver halide
Samples 105 to 10 to which the compounds represented by (4) were added
In No. 8, a photographic emulsion having an unprecedented high sensitivity, in which the sensitivity was remarkably improved and the fog was reduced and the storage stability was improved, could be obtained.

Example 2 (Photosensitive Material for Medical Use) Preparation of Em-7 (reduction-sensitized silver iodobromide tabular grain emulsion) (A1 solution) 56.6 g of ossein gelatin 10% of surfactant (a) Ethanol aqueous solution 0.36 ml Potassium bromide 48.2 g Make up to 8083 ml with water.

(B1 solution) 2.01 A silver nitrate aqueous solution 1791 ml (C1 solution) 3.5 N silver nitrate aqueous solution 11505 ml (D1 solution) 4.0 N potassium bromide aqueous solution 10962 ml (E1 solution) 2.0 N potassium bromide aqueous solution The following silver potential control Amount (F1 solution) Ossein gelatin 245 g 10% aqueous solution of surfactant (a) in ethanol 14.12 ml Make up to 2264 ml with water.

(Solution G1) 0.171 g of thiourea dioxide Distilled to 170 ml with water.

(H1 solution) Ethyl thiosulfonic acid 1.556 g Finished with water to 156 ml.

(I1 solution) Fine grain emulsion composed of 3% by weight of gelatin and silver iodide grains (ECD = 0.05 μm) Equivalent to 0.088 mol Surfactant (a): HO (CH ₂ CH ₂ O) _{n - [CH (CH 3) CH} 2 O] 17 - (CH 2 CH 2 O) m H (m + n = 5~7) a fine emulsion in the I1 solution is as follows.
To 6.64 liters of a 5.0% by weight aqueous gelatin solution containing 0.06 mol of potassium iodide, 2 liters of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide were each applied for 10 minutes. Was added. During the formation of fine particles, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the particles are formed, the pH is adjusted using an aqueous sodium carbonate solution.
Was adjusted to 6.0.

Japanese Patent Publication Nos. 58-58288 and 58-58
No. 289, the total amount of the solution (B1) and 895 ml of the solution (D1) were added to the solution (A1) at 55 ° C.
The mixture was added by a simultaneous mixing method over 3 minutes and 5 seconds to form nuclei.

After the addition of the solution (B1) and the solution (D1), the solution (F1) was added, and the temperature was raised to 70 ° C. for 30 minutes to ripen. Subsequently, the solution (C1) 907 m
was added over 11 minutes, an aqueous 28% ammonia solution was added, the mixture was aged at pH = 8.2 for 10 minutes, and then the pH was returned to 6.0 with 56% acetic acid.
1) was added in its entirety. Then, while maintaining the total amount of the solution (C1) and the solution (D1) at pAg = 7.8,
Simultaneous addition and mixing were performed over 134 minutes while gradually increasing the addition rate so that the initial flow rate of 1) was 23 ml / min and the final flow rate was 154 ml / min. On the way, the remaining amount of the solution (C1) is 63
At the time when the volume reached 60 ml, a 56% acetic acid aqueous solution was added, and p was added.
H was adjusted to 4.4. Further, the remaining amount of the solution (C1) is 38
When the volume reached 50 ml, the entire solution (H1) was added. The addition of the solution (I1) was started at 122 minutes after the start of the addition of the solution (C1), and the solution (I1) was added over 12 minutes.
Was added. The addition of the solution (I1) was completed at the same time as the addition of the solution (C1). After stirring for 10 minutes, the temperature was lowered to 40 ° C., and soluble salts were desalted and removed by a sedimentation method. Thereafter, the pH was adjusted to 5.8.

In this emulsion, 90% or more of the total projected area of the silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0, and the average thickness of the hexagonal tabular grains is 0.18.
It was confirmed by an electron microscope that the μm and ECD were 0.81 μm and the average aspect ratio was 4.5. The distribution of the circle equivalent diameter was 15%.

(Preparation of Unreduced Sensitized Tabular Grain Emulsion Em-8) An unreduced sensitized emulsion Em-8 was prepared by replacing G1 and H1 with water under the same conditions as for Em-7.

(Preparation of Em-9 and 10) Under the conditions for producing Em-7, the compound I-14 of the present invention was prepared at the stage where G1 and H1 were substituted with water and 50% of the total silver added was consumed.
The same operation as in the preparation of Em-7 was carried out except that 1 × 10 ⁻⁵ mol / mol Ag was added to each of I-15. These emulsions are named Em-9 and 10, respectively.

(Preparation of Em-11 and 12) Under the conditions for producing Em-7, the compounds I-18 and I-19 of the present invention were each added in an amount of 1 × 10 at the stage when 50% of the total added silver was consumed.
The same operation as in the preparation of Em-7 was performed except that ^-5 mol / mol Ag was added. These emulsions were each named Em-1
1, 12.

The above Em-7 to 12 are divided into predetermined amounts,
The temperature was set to 55 ° C., and spectral sensitization and chemical sensitization were performed by the following sensitization prescription. That is, after a predetermined amount of adenine was added as a compound adsorbed on silver halide, the following spectral sensitizing dye, an aqueous solution of ammonium thiocyanate and chloroauric acid, sodium thiosulfate, and triphenylphosphine selenide were added. Twenty minutes later, 0.2 mol% of a silver iodide fine grain emulsion was added, and ripening was performed for a total of 2 hours.

At the end of ripening, 1-phenyl-5-mercaptotetrazole (PMT) and TA
I was added. The sensitizing dye used was sensitizing dye (A): 5,5'-dichloro-9-ethyl-
3,3'-di- (3-sulfopropyl) oxacarbocyanine sodium salt anhydride, sensitizing dye (B): 5,5'-di- (butoxycarbonyl) -1,1'diethyl-3,3 ' -Di (4-sulfobutyl) -benzimidazocarbocyanine-sodium salt anhydride.

The amounts of the compounds added (per mole of silver halide) are shown below.

Spectral sensitizing dye (A) 450 mg Spectral sensitizing dye (B) 5 mg Adenine 10 mg Ammonium thiocyanate 145 mg Chloroauric acid 18.5 mg Sodium thiosulfate 3 mg Triphenylphosphine selenide 3 mg Silver iodide fine particles 0.2 mol% PMT (added as a stabilizer at the end of chemical ripening) 10 mg TAI (added as a stabilizer at the end of chemical ripening) 100 mg Note that the spectral sensitizing dye is a solid fine particle dispersion, and a predetermined amount of the spectral sensitizing dye is previously set at 27 ° C. In addition to the temperature-controlled water, one obtained by stirring with a high-speed stirrer (dissolver) at 3,500 rpm for 30 to 120 minutes was used.

Then, the additives described below were added to the obtained emulsion to prepare an emulsion layer coating solution. At the same time, a coating solution for a protective layer described below was prepared. Using two slide hopper coaters at a speed of 80 m / min so that the amount of silver per surface is 1.6 g / m ² and the amount of gelatin is 2.5 g / m ² using both coating solutions. Simultaneous coating on both sides of the support
After drying for 20 minutes, samples 201 to 208 were obtained. As a support, glycidyl methacrylate 50 wt%, methyl acrylate 10 wt%, butyl methacrylate 40 wt%
% Of the copolymer composed of three kinds of monomers is 10 wt%
A mixture of an aqueous dispersion of a copolymer and a dispersion of colloidal tin oxide obtained by dilution to give
A polyethylene terephthalate film base colored blue to a concentration of 0.15 for a μm X-ray film was used. The additives used in the emulsion are as follows. The amount of addition was shown in an amount per m ² .

First Layer (Dye Layer) Solid Fine Particle Dispersion Dye (AH) 180 mg Gelatin 0.2 g Sodium dodecylbenzenesulfonate 5 mg Compound (I) 5 mg 2,4-dichloro-6-hydroxy-1,3,5- Triazine Na salt 5 mg Colloidal silica (ECD = 0.014 μm) 10 mg Second layer (emulsion layer) The following various additives were added to each emulsion obtained above.

Compound (G) 0.5 mg 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg t-butyl-catechol 130 mg polyvinylpyrrolidone (average molecular weight 10,000) 35 mg styrene- Maleic anhydride copolymer 80 mg Sodium polystyrene sulfonate 80 mg Trimethylolpropane 350 mg Diethylene glycol 50 mg Nitrophenyl-triphenyl-phosphonium chloride 20 mg 500 mg ammonium 1,3-dihydroxybenzene-4-sulfonate 500 mg 2-Mercaptobenzimidazole-5-sulfonic acid sodium 5mg compound _{(H) 0.5mg n-C 4} H 9 OCH 2 CH (OH) CH 2 n (CH 2 COOH) 2350mg compound (M) 5mg compound N) 5 mg Colloidal silica 0.5 g Latex (L) 0.2 g Dextrin (average molecular weight: about 1,000) 0.1 g Dextran (average molecular weight: about 40,000) 0.1 g However, the coating amount of gelatin is 0.8 g. / M ² .

Third layer (protective layer) Solid fine particle dispersion dye (AH) 50 mg Gelatin 0.8 g Matting agent composed of polymethyl methacrylate (ECD = 7.0 μm) 50 mg Formaldehyde 20 mg 2,4-dichloro-6-hydroxy- 1,3,5-triazine Na salt 10 mg bis (vinylsulfonylmethyl) ether 36 mg latex (L) 0.2 g polyacrylamide (average molecular weight 10,000) 0.1 g sodium polyacrylate 30 mg polysiloxane (SI) 20 mg compound ( I) 12 mg Compound (J) 2 mg Compound (S-1) 7 mg Compound (K) 15 mg Compound (O) 50 mg Compound (S-2) 5 mg C ₉ F ₁₉ -O- (CH ₂ CH ₂ O) ₁₁ H 3 mg C _{8 F 17 SO 2 N- (C} 3 H 7) (CH 2 CH 2 O) 1 _{5 H 2mg C 8 F 17 SO} 2 N- (C 3 H 7) (CH 2 CH 2 O) shows _{4 (CH 2) 4 SO 3 Na} 1mg structure of the compounds used in the sample below.

[0165]

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[0166]

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[0167]

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The photographic characteristics were evaluated using the obtained samples 201 to 208. First, the sample was sandwiched between two fluorescent intensifying screens (KO-250, manufactured by Konica Corporation) and exposed to X-rays at a tube voltage of 80 kVp and a tube current of 100 mA for 0.05 seconds through an aluminum wedge for exposure. Then, the film was treated with a developing solution and a fixing solution having the following formulation using an automatic developing machine (model SRX-502 manufactured by Konica Corporation).

The method for preparing the solid processing agent of the developer according to the present invention will be described below.

(1) Preparation of solid developer using hydroquinone as a developing agent (Preparation of 100 liter amount as developing solution) [Preparation of granulated product (A)] Hydroquinone 3, a developing agent
000 g, phenidone 400 g, boric acid 1,000 g,
10 g of N-acetyl-D, L-penicillamine and 500 g of glutaraldehyde sodium bisulfite are ground in a commercially available bantam mill until ECD = 10 μm.
The fine powder was mixed with Na salt 500 of Exemplified Compound III-1 of the present invention.
g, sodium sulfite 700 g and a binder D-sorbite 200 g were added and mixed in a mill for 30 minutes. After granulating by adding 30 ml of water at room temperature for about 5 minutes in a commercially available stirring granulator, the granulated product is subjected to 40 ° C. in a fluidized bed drier.
And dried for 2 hours to remove almost completely the moisture of the granulated material.
A granulated product (A) was obtained.

[Preparation of Solid Developer A] The granulated product (A) thus obtained was mixed with 100 g of sodium 1-octanesulfonate in a room conditioned at 25 ° C. and 40% RH or less. The mixture was mixed uniformly for 10 minutes, and the resulting mixture was used as a tough press collect 1527 manufactured by Kikusui Seisakusho Co., Ltd.
Filling amount per tablet is 10g using a tableting machine with modified HU
To obtain a solid developer A in a cylindrical shape having a diameter of 30 mm.

[Preparation of Granulated Material (B)] Potassium carbonate 1
000g, sodium bicarbonate 1,000g, KBr
200 g each in a commercially available bantam mill with ECD = 1
Grind to 0 μm. LiOH ・ H for each fine powder
The ₂ O 200g, DTPA · 5H (diethylenetriaminepentaacetic acid) and 250 g, 1-phenyl-5-mercaptotetrazole 5g, sodium sulfite 4,000 g, the compound (N) 40 g, compound (O) 8 g and binding agent mannitol 1, Add 000 g, mix in a mill for 30 minutes, granulate by adding 30 ml of water at room temperature for about 15 minutes in a commercial stirring granulator, and then granulate to 40 ° C. with a fluidized drier. After drying for 2 hours, the water content of the granulated product was almost completely removed to obtain a granulated product (B).

[Preparation of Solid Developer B] The granulated product (B) thus obtained was mixed with 200 g of sodium 1-octanesulfonate in a room conditioned at 25 ° C. and 40% RH or less using a mixer. After the mixture was uniformly mixed for 10 minutes, the obtained mixture was subjected to compression tableting using a tableting machine similar to the above with a filling amount of 10 g per tablet to prepare an alkali-developed tablet.

Both the solid developers A and B obtained as described above were sealed and packaged in 4.0-liter portions in a pillow bag containing aluminum for moisture prevention.

A solid fixing agent having a volume of 100 liters was prepared by the following operation.

[Preparation of Granulated Material (C)] Ammonium thiosulfate / sodium thiosulfate (90/10 weight ratio)
000 g are ground in a commercial bantam mill until ECD = 10 μm. Add 500 mg of sodium sulfite to this fine powder.
g, Na ₂ S ₂ O ₅ 750 g, binder pine flow 1
Agitation granulation was performed with 300 g added and water added to 50 ml, and the granulated product was dried at 40 ° C. with a fluidized bed drier to remove water almost completely, thereby obtaining a granulated product (C).

[Granulated product (D)] 400 g of boric acid, 1,200 g of aluminum sulfate octahydrate, 1,200 g of succinic acid, and 300 g of tartaric acid were ECD = 10 μm in a commercially available bantam mill.
Crush until it becomes D-Mannit 250 is added to this fine powder.
g, D-Sorbit 120 g, PEG # 4,000 1
60 g was added thereto, and the amount of water added was 30 ml, and the mixture was stirred and granulated, and the granulated product was dried at 40 ° C. using a fluidized bed drier to completely remove water to obtain a granulated product (D).

[Preparation of solid fixing agents (C) and (D)] 3,000 g of β-alanine was added to the granulated product (C) obtained above.
Sodium acetate (4,330 g) and sodium 1-octanesulfonate were added to make up 1.5% of the total weight, and 750 g of sodium metabisulfite and 1-octane were added to the granules (D) obtained above. Sodium sulfonate was added to make up 1.0% of the total weight,
After uniformly mixing for 10 minutes using a mixer in a room humidified to 0% RH or less, the obtained mixture was subjected to a tableting machine similar to the above to give a filling amount per tablet (C) of 10.2 g. ,
(D) Compress tableting with 11.2g, diameter 30m
m of cylindrical fixing tablets were prepared. Each of the tablets was packed in a pillow bag containing aluminum for moisture proofing in an amount of 4.0 liters.

<Processing method> The automatic developing machine is SRX-502.
(Konica Corporation) was modified and used. The developer in the developing tank at the start is prepared by mixing solid developers A and B using a chemical mixer and diluting and dissolving with diluting water. The tablet was completely dissolved, and no precipitate was observed. 16 liters of this developing solution was put into SRX-502, a starter described later was added, and the solution was put into a developing tank as a starting solution to start processing. The starter addition amount was 33 ml / liter.

The fixing agent is prepared by diluting the solid fixing agents (C) and (D) with dilution water using a chemical mixer. The tablets were completely dissolved, and no precipitate was observed. 10 liters of the prepared fixing solution was put into the fixing processing tank of the automatic developing machine.

Starter formulation KBr 5.5 g HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ OH 0.05 g N-acetyl-D, L-penicillamine 0.10 g sodium metabisulfite Starting solution as above Amount to become pH Water finish 35ml The pH of the developer was 10.4 when the starter was added.
Fine adjustment was made with acetic acid and / or KOH to give a pH of 5. The pH of the fixing solution was 4.80.

The photosensitive material prepared above was exposed to light so that the optical density after development processing was 1.0, and the photosensitive material was run. For the running, an automatic developing machine SRX-502 equipped with a charging member for a solid processing agent and modified so as to be capable of continuous processing at a processing speed of 15 seconds was used.

Processing conditions Condition A: 7 days at 40 ° C., 80% RH Development 39 ° C. 6.0 seconds Fixing 36 ° C. 4.5 seconds Rinsing 35 ° C. 4.5 seconds Squeeze 1.5 seconds Drying 50 ° C. 2.5 Seconds Total 19 seconds (Evaluation of fog and sensitivity) In addition, the fog is the sample No. treated immediately after exposure. The sensitivity is a relative value when the optical density of the sample 202 is 100, and the sensitivity is the reciprocal of the amount of received light that gives a density of fog + 0.1.
o. The relative values are shown assuming that the blue sensitivity of 202 is 100. At the same time, the results of sensitivity and fogging evaluations of each of those subjected to post-exposure storage and treatment under condition A are also shown.

[0184]

[Table 4]

From Table 4, it can be seen that Sample No. 205-20
Sample No. 8 exhibited excellent sensitivity and fog immediately after exposure or after storage under high humidity with respect to the comparative emulsion.

[0186]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material having high sensitivity and capable of preventing deterioration of photographic performance under high humidity, particularly preventing fog rise.

Claims (4)

[Claims] 1. A silver halide photographic light-sensitive material having a photographic constituent layer on a support, wherein at least one of the photographic constituent layers contains a metal complex represented by the following general formula [I] or [II]. A photosensitive silver halide emulsion layer containing silver halide grains prepared below, and at least one of the photographic constituent layers is represented by the following general formula (1) or (2). A silver halide photographic material comprising a layer containing one or more compounds or oxidized compounds thereof. Embedded image [In the formula, Z ¹ and Z ² each represent an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring, and D ¹ and D ² represent an atom group necessary for forming a polymethine dye. Represent. q ¹ and q ² each represent an integer of 0 or 1. M represents a central metal, X represents a ligand, and m represents 3, 4 or 5. V represents an ion required to neutralize the charge in the molecule. l represents the number of ions required to neutralize the charge in the molecule. General formula (1) X _1- (C (R ₁ ) = Y) _n -X _{2 wherein} X ₁ and X ₂ are each —OR ₃ or —N (R ₄ ) R ₅
R ₃ represents a hydrogen atom or a group that can be converted to a hydrogen atom by hydrolysis, R ₄ and R ₅ are each a hydrogen atom,
Alkyl group, aryl group, heterocyclic group, sulfonyl group,
Represents an acyl group, a sulfamoyl group or a carbamoyl group. Y represents C (R ₂ ) or N, R ₁ and R ₂ each represent a hydrogen atom or another substituent, and n represents an integer of 0 or more. When n is 2 or more, a ring may be formed. [Chemical formula 2] [Wherein, R _{6 to} R ₁₀ each represent a hydrogen atom, an alkyl group,
Alkenyl group, aryl group, heterocyclic group, alkyloxycarbonyl group, aryloxycarbonyl group, acyl group, sulfonyl group, carboxyl group, carbamoyl group,
Sulfamoyl group, halogen atom, -OR ₁₁ , -S
R ₁₂ represents —N (R ₁₃ ) R ₁₄ . R _{11 to} R ₁₄ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, or a sulfonyl group. ] 2. In a silver halide photographic material having a photographic component layer on a support, at least one of the photographic component layers contains a metal complex represented by the above general formula [I] or [II]. A photosensitive silver halide emulsion layer containing silver halide grains prepared below, and at least one of the photographic constituent layers contains a compound represented by the following general formula (3) or an oxidized compound thereof. A silver halide photographic light-sensitive material, which is a layer containing at least one kind. Embedded image [Wherein, R ₁₅ represents a hydrogen atom, an alkali metal atom or a quaternary ammonium group, and R ₁₆ and R ₁₇ each represent a hydrogen atom,
Halogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, acyl group, acylamino group, nitro group, cyano group, oxycarbonyl group, carboxyl group, sulfo group, hydroxy group, ureido group, sulfonamide group , A sulfamoyl group, a carbamoyl group, an acyloxy group, an amino group, a sulfonyl group, a sulfinyl group, and a heterocyclic group. Xa represents an oxygen atom or an imino group which may be substituted. ] 3. In a silver halide photographic light-sensitive material having a photographic constituent layer on a support, at least one of the photographic constituent layers contains a metal complex represented by the above general formula [I] or [II]. A light-sensitive silver halide emulsion layer containing silver halide grains prepared below, and at least one of the photographic constituent layers contains a compound represented by the following general formula (4) or an oxidized compound thereof. A silver halide photographic light-sensitive material, which is a layer containing at least one kind. Embedded image [Wherein, R ₁₈ represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group or a sulfonyl group;
₁₉ represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a sphinyl group, a carbamoyl group, a sulfamoyl group or an oxycarbonyl group, and R ₂₀ represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group. , A heterocyclic group, an acyl group, a sulfonyl group, a sphinyl group, a carbamoyl group, a sulfamoyl group or an oxycarbonyl group. ] 4. The silver halide photographic light-sensitive material according to claim 1, wherein at least one of said emulsion layers uses a reduction-sensitized silver halide emulsion. A silver halide photographic light-sensitive material, characterized in that: