JP2816610B2 - Silver halide photographic material - Google Patents

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 high-speed silver halide photographic material having a high sensitivity and a small change in sensitivity due to a change in humidity during exposure.
Further, the present invention relates to a silver halide photographic material in which the fog density does not increase much even if the photographic material is stored for a long time.

[0002]

2. Description of the Related Art At present, commercially available silver halide photographic light-sensitive materials and image forming methods using the same are widely used in various fields. The halogen composition of silver halide emulsions used in many of these light-sensitive materials is often silver iodobromide mainly containing silver bromide for the purpose of achieving high sensitivity, particularly in the case of photographic light-sensitive materials. . On the other hand, in products used in markets where there is a strong demand for finishing large quantities of prints in a short delivery time, such as photosensitive materials for color photographic paper, bromide containing substantially no silver iodide is required due to the need to increase the development speed. Silver or silver chlorobromide is used. In recent years, there has been an increasing demand for rapid processing performance improvement of color photographic paper, and much research has been conducted.
It is known that increasing the silver chloride content of the silver halide emulsion used results in a dramatic improvement in development speed. It is known that silver chloride emulsions generally have a drawback of low sensitivity, and various techniques for overcoming this drawback have been disclosed for increasing the sensitivity of silver halide emulsions having a high silver chloride content. ing.

[0003] Selenium sensitization is known as a technique for increasing the sensitivity of silver halide emulsions. The present inventors have also applied selenium sensitization to silver halide emulsions having a high silver chloride content, and found Confirmed the effect. However, a photosensitive material for color photographic paper is required to have a small change in photographic performance even if the photosensitive material is stored for a long period of time. In the case of a light-sensitive material using a silver emulsion, the fog density tends to increase due to long-term storage, which proved to be a problem. Further, it is desirable that the photographic performance of color photographic paper does not change in response to a change in humidity when printing in a laboratory. This is very important for maintaining a constant quality. In a light-sensitive material using a selenium-sensitized high silver chloride emulsion, selenium sensitization needs to be performed sparingly in order to reduce the increase in fog density due to the long-term storage described above. However, it has also been found that such a modest selenium sensitization causes a problem that a change in sensitivity due to a change in humidity at the time of exposure increases.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a high-speed, high-speed, high-sensitivity, little change in sensitivity due to fluctuations in humidity at the time of exposure. An object of the present invention is to provide a silver halide photographic material in which an increase in fog density is suppressed.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic material having at least one photosensitive emulsion layer containing a silver halide emulsion on a support. (I), the compounds represented by the general formulas (II) and (III) and the compounds represented by the following I
II-14, III-15, III-18, III-2
And silver halide grains substantially containing no silver iodide and having a silver chloride content of 90 mol% or more, and chemically sensitized with a selenium compound. This was achieved by a silver halide photographic material characterized by containing a silver emulsion. General formula (I)

[0006]

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Wherein X ¹ is —NR ¹⁵ R ¹⁶ or —NH
Represents SO ₂ R ¹⁷ , and Y ¹ represents a hydroxyl group or a group having the same meaning as X ¹ . R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each represent a hydrogen atom or an arbitrary substituent, and R ¹¹ and R ¹² , R ¹³ and R ¹⁴
May together form a carbocycle. R ¹⁵ and R ¹⁶ each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ¹⁵ and R ¹⁶ may together form a nitrogen-containing heterocyclic ring. R ¹⁷ represents an alkyl group, an aryl group, an amino group or a heterocyclic group. General formula (II)

[0008]

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In the formula, X ² and Y ² each represent a hydroxyl group, —N
It represents a R ²³ R ²⁴ or -NHSO ₂ R ^25. R ²¹ , R ²²
Each represents a hydrogen atom or an arbitrary substituent, R ²¹
And R ²² may together form a carbocyclic or heterocyclic ring. R ²³ and R ²⁴ each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ²³ and R ²⁴ may form a nitrogen-containing heterocyclic ring together. R ²⁵ represents an alkyl group, an aryl group, an amino group or a heterocyclic group. General formula (III)

[0010]

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In the formula, X ³ represents a hydroxyl group or —NR ³² R ³³ , and Y ³ represents —CO— or —SO ₂ —. R
³¹ represents a hydrogen atom or an arbitrary substituent, and n is 0 or 1. R ³² and R ³³ each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ³¹ and R ³² ,
R ³² and R ³³ may together form a nitrogen-containing heterocyclic ring.

The general formulas (I), (II) and (I
In order to incorporate the compound represented by (II) into the silver halide emulsion layer, they may be directly dispersed in the emulsion, or may be dissolved in a solvent such as water or methanol alone or in a mixed solvent and added to the emulsion. May be. The timing of addition to the emulsion may be any stage from preparation of the emulsion to immediately before coating, but it is preferable to add the emulsion during preparation of the coating solution. The amount of the compound represented by the general formula (I), the general formula (II) or the general formula (III) is 1 to 1 mol per mol of silver halide.
It is preferably from × 10 ^-5 to 1 mol, and from 1 × 10 ^-3 to 1 mol.
More preferably, it is 5 × 10 ⁻¹ mol. Among the compounds represented by the general formula (I), the general formula (II) and the general formula (III), a change in sensitivity due to a change in humidity at the time of exposure and an increase in fog density when the photosensitive material is stored for a long period of time. The inhibitory effect is greatest for the compound represented by the general formula (III), and most preferably contains at least one compound represented by the general formula (III).

Formula (I) will be described in more detail. Where X
¹ -NR ¹⁵ R ^16, represents -NHSO ₂ R ^17, Y ¹ represents a hydroxyl group or X ¹ group having the same meaning. R ¹¹ , R ¹² , R
¹³ and R ¹⁴ each represent a hydrogen atom or an arbitrary substituent. As the optional substituent, for example, an alkyl group (C 1
To 20 are preferable, for example, methyl, ethyl, octyl, hexadecyl, t-butyl), an aryl group (preferably having 6 to 20 carbon atoms, for example, phenyl and p-tolyl), and an amino group (0 to 20 carbon atoms) Are preferred,
For example, amino, diethylamino, diphenylamino, hexadecylamino), amide group (having preferably 1 to 20 carbon atoms, for example, acetylamino, benzoylamino, octadecanoylamino, benzenesulfonamide), and alkoxy group (having 1 to carbon atoms) 20 are preferred, for example, methoxy, ethoxy, hexadecyloxy),
Alkylthio group (preferably having 1 to 20 carbon atoms, for example, methylthio, butylthio, octadecylthio), acyl group (preferably having 1 to 20 carbon atoms, for example, acetyl, hexadecanoyl, benzoyl, benzenesulfonyl), carbamoyl group (C1-20 are preferable, for example, carbamoyl, N-hexylcarbamoyl, N, N-diphenylcarbamoyl), alkoxycarbonyl group (C2-20 is preferable, for example, methoxycarbonyl, octyloxycarbonyl, etc.) ,
Examples include a hydroxyl group, a halogen atom (F, Cl, Br, etc.), a cyano group, a nitro group, a sulfo group, a carboxyl group, and the like. These substituents may be further substituted by another substituent (for example, those described as R ¹¹ ). Also,
R ¹¹ and R ¹² and R ¹³ and R ¹⁴ may form a carbon ring (preferably a 5- to 7-membered ring) together. R ¹⁵ and R ¹⁶ are preferably a hydrogen atom or an alkyl group (having 1 to 10 carbon atoms,
For example, ethyl, hydroxyethyl, octyl), an aryl group (having 6 to 10 carbon atoms is preferable, for example, phenyl or naphthyl) or a heterocyclic group (having 2 to 10 carbon atoms is preferable, for example, 2-furanyl, 4-pyridyl) ), Which may be further substituted with a substituent (for example, those described as R ¹¹ ). R ¹⁵ and R ¹⁶ may form a heterocyclic ring (preferably a 5- to 7-membered ring).
R ¹⁷ is preferably an alkyl group (having 1 to 20 carbon atoms,
For example, ethyl, octyl, hexadecyl) and an aryl group (having 6 to 20 carbon atoms are preferable, for example, phenyl,
p-tolyl, 4-dodecyloxyphenyl), an amino group (preferably having 0 to 20 carbon atoms, for example, N, N-diethylamino, N, N-diphenylamino, morpholino) or a heterocyclic group (having 2 to 2 carbon atoms) 20 is preferable, for example, 3-pyridyl), which may be further substituted.

In the formula (I), X ¹ is preferably -NHSO
₂ represents R ¹⁷ , and R ¹¹ , R ¹² , R ¹³ and R ¹⁴ preferably represent a hydrogen atom, an alkyl group, an amide group, a halogen atom, a sulfo group or a carboxyl group. Formula (II) will be described in more detail. In the formula, X ² and Y ² each represent a hydroxyl group,
It represents a R ²³ R ²⁴ or -NHSO ₂ R ^25. R ²¹ , R ²²
Represents a hydrogen atom or an optional substituent. The optional substituents and the like substituents exemplified in the description of the example R ^11. R ²¹ and R ²² may form a carbon ring or a heterocyclic ring (each preferably a 5- to 7-membered ring). R ²³ , R
Each ²⁴ hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, their details are the same as R ^15.
R ²³ and R ²⁴ are jointly used as a nitrogen-containing heterocyclic ring (preferably 5 to 7).
A ring). R ²⁵ represents an alkyl group, an aryl group, an amino group or a heterocyclic group, the details of which are the same as those of R ¹⁷ .

In the formula (II), X ² is preferably -NR ²³ R ²⁴
Or represents _{^{-NHSO 2 R 25, R 21,}} R 22 is preferably a hydrogen atom, an alkyl group, an aryl group, jointly form a carbocyclic or heterocyclic ring. Details of these groups can be found in R
^Same as ¹⁵ . Formula (III) will be described in more detail. In the formula, X ³ represents a hydroxyl group or —NR ³² R ³³ , and Y ³ represents —
CO- or -SO ₂ - represent. R ³¹ represents a hydrogen atom or an optional substitution (for example, those described in the description of R ¹¹ ), and n is 0 or 1. R ³² and R ³³ represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and the details thereof are the same as those of R ¹⁵ . R ³¹ and R ³² and R ³² and R ³³ may form a heterocyclic ring (preferably a 5- to 7-membered ring). In the formula (III), X ³ is preferably -NR
Represents ³² R ³³ and Y ³ preferably represents -CO-.
R ³¹ is preferably a hydrogen atom, an alkyl group, an aryl group,
Alkoxy group, an aryloxy group, an amino group, they may be substituted by further optional substituents (e.g. those described for R ^11). R ³² and R ³³ preferably represent a hydrogen atom or an alkyl group.

In the following, formula (I) used in the present invention,
Specific examples of the compounds represented by (II) and (III) and III-14, III-15, III-18, III
-25 compounds are listed, but the present invention is not limited thereto.

[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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The average halogen composition of the silver halide grains contained in at least one emulsion used in the present invention needs to have a silver chloride content of 90 mol% or more.
Further, it is preferable that the average halogen composition of all silver halides constituting the silver halide grains of the emulsion is 95 mol% or more of silver chloride and substantially contains no silver iodide. Here, the phrase "contains substantially no silver iodide" means that the silver iodide content is 1.
It is preferably at most 0 mol%. A more preferred halogen composition of the silver halide grains is silver chlorobromide or silver chloride, wherein 98 mol% or more of all silver halide constituting the silver halide grains is silver chloride and contains substantially no silver iodide. .

The silver halide grains of the present invention preferably have a localized phase in which the silver bromide content exceeds at least 10 mol%. Such an arrangement of the localized phase having a high silver bromide content needs to be in the vicinity of the grain surface in order to exhibit the effects of the present invention and further from the viewpoint of the pressure property, the processing solution composition dependency and the like. Here, “near the grain surface” means a position within 1/5 of the grain size of the silver halide grains to be used, as measured from the outermost surface. The position is preferably within 1/10 of the grain size of the silver halide grains to be used, as measured from the outermost surface. The most preferable arrangement of the localized phase having a high silver bromide content is that a localized phase having a silver bromide content of at least more than 10 mol% is epitaxially grown at a corner of a cubic or tetradecahedral silver chloride particle.

The silver bromide content of the localized phase having a high silver bromide content is preferably more than 10 mol%, but if the silver bromide content is too high, it decreases when pressure is applied to the light-sensitive material. In some cases, characteristics unfavorable for a photographic light-sensitive material, such as causing a sense of sensation or a large change in sensitivity and gradation due to a change in the composition of the processing solution, may be imparted. Taking these points into consideration, the silver bromide content of the localized phase having a high silver bromide content is preferably in the range of 10 to 60 mol%, and 2
The range of 0 to 50 mol% is most preferred. The silver bromide content of the localized phase having a high silver bromide content is determined by an X-ray diffraction method (for example,
"The Chemical Society of Japan, New Experimental Chemistry Course 6, Structural Analysis" Maruzen,
, Etc.).

The localized phase having a high silver bromide content is 0.1% of the total silver constituting the silver halide grains contained in the emulsion of the present invention.
Preferably composed of 1 to 20% silver,
More preferably, it is comprised of 0.5 to 7% silver. The interface between the localized phase having a high silver bromide content and other phases may have a clear phase boundary, or may have a transition region in which the halogen composition changes gradually. Good. Various methods can be used to form such a localized phase having a high silver bromide content. For example, a localized phase can be formed by reacting a soluble silver salt and a soluble halogen salt by a one-side mixing method or a simultaneous mixing method. Further, a localized phase can be formed by using a conversion method for converting already formed silver halide grains into silver halide having a lower solubility product. For example, a water-soluble bromide solution is added to cubic or tetradecahedral silver halide host grains, or silver bromide or salt odor having a smaller average grain size than the silver halide host grains and a higher silver bromide content. By mixing and ripening the silver halide fine particles, a localized phase having a high silver bromide content can be formed.

The formation of a localized phase having a high silver bromide content is preferably carried out in the presence of an iridium compound. Here, the formation of the localized phase in the presence of an iridium compound means that
This means that the iridium compound is supplied simultaneously with, immediately before, or immediately after the supply of silver or halogen for forming a localized phase. For example, when a localized phase having a high silver bromide content is formed by adding a water-soluble bromide solution, the solution may contain an iridium compound in advance, or another solution containing the iridium compound at the same time. The addition is preferably performed. After mixing silver halide fine grains having a smaller average grain size than the silver halide host grains and having a high silver bromide content,
When a localized phase having a high silver bromide content is formed by ripening, it is also preferable to previously contain an iridium compound in silver halide fine grains having a high silver bromide content. The iridium compound may be present during the phase formation other than the formation of the localized phase having a high silver bromide content, but the localized phase having a high silver bromide content is formed together with at least 50% of the total iridium to be added. Is preferred. Most preferably, it is formed with at least 80% of the total iridium added.

The silver halide grains of the present invention may have (100) planes, (111) planes, or both on the outer surface. May further include a higher-order plane, but is preferably a cube mainly composed of a (100) plane or a tetrahedron. The size of the silver halide grains of the present invention may be within the range usually used, but preferably the average grain size is from 0.1 μm to 1.5 μm. The particle size distribution may be polydisperse or monodisperse, but is preferably monodisperse. The particle size distribution representing the degree of monodispersion is preferably 0.2 or less in a ratio (s / d) between the statistical standard deviation (s) and the average particle size (d).
0.15 or less is more preferable. It is also preferable to use a mixture of two or more monodisperse emulsions.

The silver halide emulsion of the present invention is subjected to selenium sensitization. As the selenium sensitizer used in the present invention, a selenium compound disclosed in a conventionally known patent can be used. Selenium sensitization is usually performed by adding an unstable selenium compound and / or a non-unstable selenium compound to a silver halide emulsion and stirring the emulsion at a high temperature, preferably at 40 ° C. or higher for a certain period of time. As the unstable selenium compound, the compounds described in JP-B-44-15748, JP-B-43-13489, JP-A-2-130976, JP-A-2-229300 and the like are preferably used. Specific labile selenium sensitizers include:
Isoselenocyanates (eg, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenoamides, selenocarboxylic acids (eg, 2-selenopropionic acid, 2-selenobutyric acid), selenoesters , Diacyl selenides (eg, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, colloidal metal selenium, and the like.

Although the preferred types of unstable selenium compounds have been described above, they are not intended to be limiting. Those skilled in the art will note that an unstable selenium compound as a sensitizer for a photographic emulsion is not very important as long as selenium is unstable, and the structure of the selenium sensitizer molecule is not important. It is generally understood that the moieties carry selenium and have no role other than to make them present in the emulsion in an unstable manner. In the present invention, an unstable selenium compound having such a broad concept is advantageously used. The non-labile selenium compound used in the present invention is disclosed in
No. 4553, Japanese Patent Publication No. 52-34492 and Japanese Patent Publication No. 5
The compound described in 2-34491 is used. Examples of the non-labile selenium compound include selenous acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenide, diaryl diselenide, dialkyl selenide, dialkyl diselenide, 2-selenazolidinedione, 2-selenooxazolidinethione and derivatives thereof. Among these selenium compounds, the following general formulas (IV) and (V) are preferred. General formula (IV)

[0035]

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In the formula, Z ₁ and Z ₂ may be the same or different and each represents an alkyl group (eg, methyl, ethyl, t-butyl, adamantyl, t-octyl), an alkenyl group (eg, vinyl, propenyl) Aralkyl group (eg, benzyl, phenethyl), aryl group (eg, phenyl, pentafluorophenyl, 4-chlorophenyl, 3-nitrophenyl, 4-octylsulfamoylphenyl, α-naphthyl), heterocyclic group (eg, Pyridyl, chenyl, furyl, imidazolyl),-
NR ₁ (R _2), - represents the OR ₃ or -SR _4.
R ₁ , R ₂ , R ₃ and R ₄ may be the same or different and each represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. Alkyl group, an aralkyl group, the same examples as Z ₁ is exemplified as an aryl group or a heterocyclic group. However, R ₁ and R ₂ are a hydrogen atom or an acyl group (eg, acetyl, propanoyl, benzoyl,
Heptafluorobutanoyl, difluoroacetyl, 4-
Nitrobenzoyl, α-naphthoyl, 4-trifluoromethylbenzoyl).

In the general formula (IV), preferably, Z ₁ represents an alkyl group, an aryl group or —NR ₁ (R ₂ ), and Z ₂ represents —NR ₅ (R ₆ ). R ₁ , R ₂ , R ₅ and R ₆
May be the same or different, and represent a hydrogen atom, an alkyl group, an aryl group, or an acyl group. General formula
In (IV), more preferably N, N-dialkylselenourea, N, N, N′-trialkyl-N′-acylselenourea, tetraalkylselenourea, N, N-dialkyl-arylselenoamide, N-alkyl Represents -N-aryl-arylselenoamide. General formula (V)

[0038]

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In the formula, Z ₃ , Z ₄ and Z ₅ may be the same or different, and each represents an aliphatic group, an aromatic group, a heterocyclic group, —OR ₇ , —NR ₈ (R ₉ ), —SR ₁₀ , -Se
R ₁₁ represents —X or a hydrogen atom. R ₇ , R ₁₀ and R
₁₁ represents an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation, and R ₈ and R ₉ represent an aliphatic group, an aromatic group,
X represents a heterocyclic group or a hydrogen atom, and X represents a halogen atom. In the general formula (V), Z ₃ , Z ₄ , Z ₅ , R ₇ ,
The aliphatic group represented by R ₈ , R ₉ , R ₁₀ and R ₁₁ is a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group, aralkyl group (for example, methyl, ethyl, n
-Propyl, isopropyl, t-butyl, n-butyl,
n-octyl, n-decyl, n-hexadecyl, cyclopentyl, cyclohexyl, allyl, 2-butenyl, 3
-Pentenyl, propargyl, 3-pentynyl, benzyl, phenethyl). In the general formula (V),
Z ₃ , Z ₄ , Z ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁
Represents a monocyclic or condensed-ring aryl group (for example, phenyl, pentafluorophenyl, 4-chlorophenyl, 3-sulfophenyl, α-naphthyl, 4-methylphenyl).

In the general formula (V), Z ₃ , Z ₄ ,
The heterocyclic group represented by Z ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a saturated or unsaturated 3- to 10-membered ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. (For example, pyridyl, phenyl, phenyl, furyl, thiazolyl, imidazolyl, benzimidazolyl).
In the general formula (V), cations represented by R ₇ , R ₁₀ and R ₁₁ represent an alkali metal atom or ammonium, and a halogen atom represented by X is, for example, a fluorine atom,
Represents a chlorine atom, bromine atom or iodine atom. In formula (V), preferably, Z ₃ , Z ₄ or Z ₅ represents an aliphatic group, an aromatic group or —OR ₇ , and R ₇ represents an aliphatic group or an aromatic group. In formula (V), more preferably, it represents a trialkylphosphine selenide, a triarylphosphine selenide, a trialkylselenophosphate or a triarylselenophosphate. The general formula below
Specific examples of the compounds represented by (IV) and (V) are shown below.
The present invention is not limited to this.

[0041]

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[0042]

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[0043]

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[0046]

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[0047]

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[0048]

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The amount of the selenium sensitizer used depends on the selenium compound to be used and the silver halide grains (kind and content of halogen,
Grain size, crystal form, etc.), chemical ripening conditions and the like, but generally 10 ^-8 to 10 ^-4 mol, preferably about 10 ^-7 to 10 ^-5 mol per mol of silver halide. The conditions for chemical sensitization in the present invention are not particularly limited, but the pAg is generally 5 to 10, preferably 5.5 to 10.
8, more preferably 6 to 7.5, and the temperature is generally 30 to 80 ° C, preferably 40 to 70 ° C. p
H is generally 4 to 10, preferably 5 to 8.
The temperature is generally 30 to 80 ° C, preferably 40 to 70 ° C.
° C. In the present invention, it is preferable to sensitize the surface with selenium after forming a localized phase having a high silver bromide content. As chemical sensitization other than selenium sensitization, sulfur sensitization is preferably used in combination, but gold sensitization, reduction sensitization and the like are also preferably used in combination. The chemical sensitization with sulfur used in the present invention is performed using a compound containing sulfur that can react with active gelatin or silver (for example, thiosulfate, thioureas, mercapto compounds, rhodanines). Specific examples thereof are described in U.S. Patent Nos. 1,574,944 and 2,27.
No. 8,947, No. 2,410,689, No. 2,7
28,668 and 3,656,955.

In the photographic material according to the present invention, the hydrophilic colloid layer can be decolorized by the processing described in EP 0,337,490A2, pp. 27-76, for the purpose of improving the sharpness of the image. Dyes (among which are oxonol dyes) are added so that the optical reflection density at 680 nm of the photosensitive material becomes 0.70 or more, and dihydric alcohols (2 to 4) are added to the water-resistant resin layer of the support. Titanium oxide surface-treated with, for example, trimethylolethane)
It is preferable to contain 2% by weight or more (more preferably 14% by weight or more).

The photographic additives such as cyan, magenta and yellow couplers which can be used in the present invention are preferably used by dissolving them in a high-boiling organic solvent. The high-boiling organic solvent has a melting point of 100 ° C. or less and a boiling point of 140 ° C. Any of the above water-immiscible compounds and a good solvent for the coupler can be used. The melting point of the high boiling organic solvent is preferably 80 ° C. or lower. The boiling point of the high-boiling organic solvent is preferably 160 ° C. or higher,
More preferably, it is 170 ° C. or higher. Details of these high-boiling organic solvents are described in JP-A-62-215272, page 137, lower right column to page 144, upper right column. Alternatively, cyan, magenta or yellow couplers can be impregnated with a loadable latex polymer (eg, U.S. Pat. No. 4,203,716) in the presence or absence of the high boiling organic solvent described above, or with a water-insoluble and organic solvent. It can be dissolved together with a solvent-soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution. Preferably, columns 7 to 15 of U.S. Pat. No. 4,857,449.
And WO 12/723 of WO 88/00723.
The homopolymers or copolymers described on pages 30 to 30 are used, and the use of methacrylate or acrylamide polymers, particularly the use of acrylamide polymers, is preferred for stabilizing the color image.

In the light-sensitive material according to the present invention, it is preferable to use a color image preservability improving compound as described in EP 0,277,589 A2 together with a coupler. In particular, combination use with a pyrazoloazole coupler is preferred. That is, the compound (F) which forms a chemically inert and substantially colorless compound by chemically bonding with the aromatic amine-based developing agent remaining after the color developing process and / or the aromatic compound remaining after the color developing process. The compound (G) which forms a chemically inert and substantially colorless compound by chemically bonding with an oxidized form of an aromatic amine color developing agent can be used simultaneously or alone, for example, in storage after processing. It is preferable in order to prevent the generation of stains and other side effects due to the formation of a coloring dye due to the reaction between the color developing agent or its oxidized product and the coupler remaining in the film.

The light-sensitive material according to the present invention is provided with a fungicide such as that described in JP-A-63-271247 in order to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image. It is preferred to add an agent.

As a support for use in the light-sensitive material according to the present invention, a white polyester-based support or a layer containing a white pigment was provided on a support having a silver halide emulsion layer for a display. A support may be used. In order to further improve the sharpness, an antihalation layer is preferably provided on the support on the side where the silver halide emulsion layer is coated or on the back surface. In particular, the transmission density of the support is set to 0.3 so that the display can be viewed with both reflected light and transmitted light.
It is preferable to set in the range of 5 to 0.8.

The light-sensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low-illuminance exposure or high-illuminance short-time exposure. In the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ^-4 seconds is preferred.

Further, upon exposure, US Pat.
It is preferable to use the band stop filter described in U.S. Pat. This removes light mixing,
The color reproducibility is significantly improved.

The exposed light-sensitive material can be subjected to conventional black-and-white or color development processing. In the case of a color light-sensitive material, bleach-fix processing is preferably performed after color development for the purpose of rapid processing. In particular, when the high silver chloride emulsion is used, the pH of the bleach-fixing solution is adjusted to about 6.5 for the purpose of accelerating desilvering.
Or less, more preferably about 6 or less.

The silver halide emulsion and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied to the light-sensitive material according to the present invention, and processing methods applied for processing this light-sensitive material As the additives for treatment and processing, those described in the following patent gazettes, in particular, EP 0,355,660 A2 (JP-A-2-139544) are preferably used.

[0059]

[Table 1]

[0060]

[Table 2]

[0061]

[Table 3]

[0062]

[Table 4]

[0063]

[Table 5]

Further, as a cyan coupler, JP-A-Hei 2-
In addition to the diphenylimidazole cyan couplers described in US Pat. No. 33,144, EP 0,333,185 A2
3-hydroxypyridine-based cyan couplers described in (1), (4) couplers of the couplers (42) listed as specific examples, which have been converted to 2-equivalent couplers with a chlorine leaving group, and couplers (6) and (9) Are particularly preferred) and the use of cyclic active methylene cyan couplers described in JP-A-64-32260 (in particular, coupler examples 3, 8, and 34 listed as specific examples) are also preferred.

As for the processing method of the color light-sensitive material, the method described in JP-A-2-207250, page 27, upper left column to page 34 can be used.
The method described in the upper right column of the page is particularly preferably applied.

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EXAMPLES The present invention will be described below in detail with reference to Examples, but the present invention is not limited thereto. Example 1 32 g of lime-processed gelatin was added to 800 cc of distilled water.
After dissolution at 0 ° C., 5.76 g of sodium chloride was added,
The temperature was raised to 75C. To this solution was added N, N'-dimethylimidazolidin-2-thione (1% aqueous solution).
8 cc was added. Subsequently, 100 g of silver nitrate was added to 400 cc of distilled water.
And 34.4 g of sodium chloride in distilled water 40
The solution dissolved in 0 cc was added to and mixed with the above solution over a period of 53 minutes while maintaining 75 ° C. Next, a solution obtained by dissolving 60 g of silver nitrate in 200 cc of distilled water and a solution obtained by dissolving 17.4 g of sodium chloride in 200 cc of distilled water were added and mixed over 18 minutes while maintaining the temperature at 75 ° C. After desalting and washing at 40 ° C., 90 g of lime-processed gelatin was added, and pAg was further increased with sodium chloride and sodium hydroxide.
5, and the pH was adjusted to 6.5. After heating to 58 ° C,
The following blue-sensitizing sensitizing dye was added in an amount of 3 × 10 ^-4 mol per mol of silver halide, and further, sulfur sensitization was optimally performed using triethylthiourea at 6 × 10 ^-6 mol per mol of silver halide. gave. The silver chloride emulsion thus obtained was named Emulsion A.

Emulsion A was prepared by changing the pH adjusted to 5.8 before adding the blue-sensitive sensitizing dye to 5.8, and optimizing sulfur sensitization with triethylthiourea instead of dimethylselenourea. A silver chloride emulsion differing only in optimum selenium sensitization was prepared using 6 × 10 ^-6 mol per mol of silver halide, and this was designated as Emulsion B. 32 g of lime-processed gelatin was added to 800 cc of distilled water, dissolved at 40 ° C., and 5.76 g of sodium chloride was added to raise the temperature to 75 ° C. N, N'-dimethylimidazolidin-2 was added to this solution.
1.8 cc of thione (1% aqueous solution) was added. Subsequently, a solution obtained by dissolving 100 g of silver nitrate in 400 cc of distilled water and a solution obtained by dissolving 34.4 g of sodium chloride in 400 cc of distilled water were used.
The mixture was added to and mixed with the above solution over a period of 53 minutes while maintaining the temperature at 75 ° C. Next, a solution in which 59.2 g of silver nitrate was dissolved in 200 cc of distilled water and a solution in which 17.1 g of sodium chloride was dissolved in 200 cc of distilled water were added and mixed over 18 minutes while maintaining the temperature at 75 ° C. After cooling to 40 ° C., the following blue-sensitive sensitizing dye was added in an amount of 3 × 10 ^-4 mol per mol of silver halide, and then a solution prepared by dissolving 0.8 g of silver nitrate in 100 cc of distilled water and 0.1 ml of potassium bromide. A solution obtained by dissolving 56 g in 100 cc of distilled water was added and mixed over 8 minutes while maintaining 40 ° C. After desalting and washing with water, add 90 g of lime-processed gelatin, and further add sodium chloride and sodium hydroxide.
Ag was adjusted to 7.5 and pH was adjusted to 6.5. After the temperature was raised to 58 ° C., sulfur sensitization was optimally performed using the same amount of triethylthiourea as in Emulsion A. The silver chlorobromide emulsion (containing 0.5 mol% of silver bromide) thus obtained was designated as Emulsion C.

Emulsion C was prepared by changing the pH adjusted to 5.8 before adding the blue-sensitizing sensitizing dye to 5.8, and optimizing sulfur sensitization with triethylthiourea. A silver chlorobromide emulsion differing only in that selenium was optimally sensitized using dimethylselenourea was prepared, and this emulsion was used as emulsion D. Emulsions A, B, C and D thus prepared
For, the particle shape, particle size, and particle size distribution were determined from electron micrographs. The particle size was represented by the average value of the diameter of a circle equivalent to the projected area of the particle, and the particle size distribution was obtained by dividing the standard deviation of the particle size by the average particle size. Emulsions A, B, C and D were all cubic grains having a grain size of 0.82 μm and a grain size distribution of 0.10. Electron micrographs of Emulsions C and D showed that the corners of the cube were sharper than those of Emulsions A and B. The X-ray diffraction of Emulsions C and D showed weak diffraction at a portion corresponding to a silver bromide content of 10 mol% to 30 mol%. From the above, emulsions C and D
Can be said that a localized phase having a silver bromide content of 10 mol% to 30 mol% is epitaxially grown at the corners of cubic silver chloride substrate grains.

After a corona discharge treatment was applied to the surface of the paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further coated to form a layer structure shown below. Was prepared (sample A). The coating solution was prepared as follows. Preparation of First Layer Coating Solution 19.1 g of yellow coupler (ExY), 4.1 g of color image stabilizer (Cpd-1) and color image stabilizer (Cpd-)
7) To 0.7 g, 27.2 cc of ethyl acetate and solvent (S
olv-3) and 4.1 g of a solvent (Solv-7) were added and dissolved, and this solution was dissolved in a 10% aqueous gelatin solution containing 8 cc of sodium dodecylbenzenesulfonate.
After adding to 85 cc, the mixture was emulsified and dispersed by an ultrasonic homogenizer. The resulting dispersion was mixed and dissolved with the silver chloride emulsion A to prepare a first layer coating solution. Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. The total amount of Cpd-10 and Cpd-11 was 2 in each layer.
It was added to a 5.0 mg / m ² and 50.0 mg / m ^2.
The following were used as spectral sensitizing dyes for each layer.

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The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

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In order to prevent irradiation, the following dyes were added to the emulsion layer.

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(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver. Support Polyethylene laminated paper [The first layer side polyethylene contains a white pigment (TiO ₂ ) and a bluish dye (ultra blue)] First layer (blue-sensitive yellow coloring layer) Silver chloride emulsion A 0.30 Gelatin 22 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-3) 0.18 Solvent (Solv-7) 0.18 Color image stabilizer (Cpd-7) 06

Second layer (color mixture preventing layer) Gelatin 0.64 Color mixture inhibitor (Cpd-5) 0.10 Solvent (Solv-1) 0.16 Solvent (Solv-4) 0.08 Third layer (green light sensitive) Color magenta color-forming layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of large-size emulsion B having an average grain size of 0.55 μm and small-size emulsion B having an average grain size of 0.39 μm (Ag molar ratio), grain size distribution) Are 0.10 and 0.08, respectively, and 0.8 mol% of AgBr is locally contained in a part of the grain surface in each emulsion.) 0.12 Gelatin 1.28 Magenta coupler (ExM) 23 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-3) 0.16 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-9) 0.02 Solvent (Solv-2) 0.40 fourth layer (ultraviolet light Absorbing layer) Gelatin 1.41 Ultraviolet absorber (UV-1) 0.47 Color mixture inhibitor (Cpd-5) 0.05 Solvent (Solv-5) 0.24

Fifth layer (red-sensitive cyan coloring layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of large-size emulsion C having an average grain size of 0.58 μm and small-size emulsion C having a size of 0.45 μm ( (Ag mole ratio) The variation coefficient of the grain size distribution was 0.09 and 0.11, and 0.6 mol% of AgBr was locally contained in a part of the grain surface in each size emulsion.) 0.23 Gelatin 1.04 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-6) 0.18 Color image stabilizer (Cpd) -7) 0.40 Color image stabilizer (Cpd-8) 0.05 Solvent (Solv-6) 0.14 Sixth layer (ultraviolet absorbing layer) Gelatin 0.48 Ultraviolet absorbing agent (UV-1) 0.16 Color mixture inhibitor (Cpd-5) 0.02 Solvent (Solv- 5) 0.08 Seventh layer (protective layer) Gelatin 1.10 Acrylic-modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Liquid paraffin 0.03

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For the sample A obtained as described above, the emulsion of the first layer (blue-sensitive layer) was replaced as shown in Table 6, and the compounds shown in Table 6 were further added to the coating solution for the first layer. Photosensitive materials differing only in the above were prepared, and these were designated as Samples B to W. In order to examine the sensitivity of the photosensitive material and the range of photographic sensitivity variation due to changes in humidity during exposure, 25 ° C.-55%
The photosensitive material was kept in an atmosphere of RH and 25 ° C.-85% RH, exposed to light for 0.1 second through an optical wedge and a blue filter, and subjected to color development using the following processing steps and processing solutions. The sensitivity (S) was determined by calculating the reciprocal of the amount of exposure required to give a density 0.5 higher than the fog density when exposed at 25 ° C.-55% RH, and setting the sensitivity of Sample A to 100.
And expressed as relative values. The change in sensitivity (ΔS humidity) was represented by the difference between the logarithmic value of the exposure amount required to give a density 0.5 higher than the fog density. Negative values represent desensitization under high humidity exposure. In order to evaluate the change in photographic performance due to long-term storage of the photosensitive material, the sample was stored for 2 days in an atmosphere of 60 ° C. and 40% RH, and then subjected to the above exposure and treatment. The fog density change (△ D storage) was measured. Table 7 shows the results.

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[Table 6]

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[Table 7]

(Development Processing) The exposed samples were used after being subjected to continuous processing (running) using a paper processor until continuous replenishment of twice the tank capacity of color development in the next processing step. Processing process Temperature Time Replenisher ^* tank capacity Color development 35 ° C 45 seconds 161 ml 17 liter Bleach-fix 30-35 ° C 45 seconds 215 ml 17 liter Rinse 30-35 ° C 20 seconds -10 liter Rinse 30-35 ° C 20 seconds -10 l rinse 30 to 35 ° C. 20 seconds 350 ml 10 liter drying 70 to 80 ° C. 60 seconds * replenishment rate (set to 3 tank countercurrent system to rinse →.) per photosensitive material 1 m ² of the following composition each processing solution It is on the street.

Color developer tank liquid Replenisher water 800 ml 800 ml ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 1.5 g 2.0 g potassium bromide 0.015 g-triethanolamine 8.0 g 12. 0 g sodium chloride 1.4 g-potassium carbonate 25 g 25 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-amino aniline sulfate 5.0 g 7.0 g N, N-bis (carboxymethyl ) Hydrazine 4.0 g 5.0 g N, N-di (sulfoethyl) hydroxylamine.1Na 4.0 g 5.0 g Fluorescent whitening agent (WHITEX 4B, manufactured by Sumitomo Chemical) 1.0 g 2.0 g 1000ml pH (25 ° C) 10.05 10.45

Bleach-fix solution (same as tank solution and replenisher) Water 400 ml Ammonium thiosulfate (700 g / l) 100 ml Sodium sulfite 17 g Ammonium iron (III) ethylenediaminetetraacetate 55 g Disodium ethylenediaminetetraacetate 5 g Ammonium bromide 40 g Water is added. 1000ml pH (25 ℃) 6.0 Rinse solution (same as tank solution and replenisher) Deionized water (Calcium and magnesium are each 3ppm or less)

As is clear from the results in Table 7, selenium sensitization is effective for increasing the sensitivity of high silver chloride emulsions, but has a large desensitization upon exposure to high humidity and a fog density during long-term storage. (Sample E). The samples (F, G, H, and N to W) containing the selenium-sensitized high silver chloride emulsion and the compound of the present invention have high sensitivity, low desensitization upon exposure to high humidity, and long-term storage. Has a characteristic that sensitization is small. In addition, these effects can be seen by the fact that the sample (N to W) used in combination with the emulsion having a localized phase having a high silver bromide content near the surface of the silver halide grains has no localized phase (F).
To H), it is more remarkable. Example 2 32 g of lime-processed gelatin was added to 1000 cc of distilled water.
After dissolution at 40 ° C., 3.3 g of sodium chloride was added and the temperature was raised to 70 ° C. To this solution was added N, N'-dimethylimidazolidin-2-thione (1% aqueous solution).
8 cc was added. Subsequently, 32.0 g of silver nitrate was added to 200 parts of distilled water.
cc and 11.0 g of sodium chloride in distilled water 2
The solution dissolved in 00 cc was added to and mixed with the above solution over 14 minutes while maintaining 70 ° C. Furthermore, silver nitrate 128.0
g in 560 cc of distilled water and sodium chloride 4
A solution of 4.0 g dissolved in 560 cc of distilled water was added and mixed over 40 minutes while maintaining 70 ° C. After desalting and washing at 40 ° C, lime-treated gelatin 90.0 g
Was added, and the pAg was adjusted to 7.5 and the pH was adjusted to 5.8 with sodium chloride and sodium hydroxide. Subsequently, the same blue-sensitive sensitizing dye as used in Example 1 was added in an amount of 4 × 10 ^-4 mol per mol of silver halide.
Selenium sensitization was optimally performed at 60 ° C. using the same amount of dimethylselenourea. The silver chloride emulsion thus obtained was named Emulsion E. 32 g of lime-processed gelatin was added to 1000 cc of distilled water, dissolved at 40 ° C., and 3.3 g of sodium chloride was added to raise the temperature to 70 ° C. To this solution was added 2.0 cc of N, N'-dimethylimidazolidin-2-thione (1% aqueous solution). Then silver nitrate 3
2.0 g dissolved in 200 cc of distilled water and 10.9 g of sodium chloride and 0.22 g of potassium bromide in distilled water 2
The solution dissolved in 00 cc was added to and mixed with the above solution over 15 minutes while maintaining 70 ° C. Furthermore, silver nitrate 128.0
g in 560 cc of distilled water and sodium chloride 4
3.6 g and 0.90 g of potassium bromide were added to 560 of distilled water.
The solution dissolved in cc was added and mixed over 40 minutes while maintaining 70 ° C. After desalting and washing at 40 ° C., 90.0 g of lime-processed gelatin was added, and the pAg was further adjusted to 7.5 with sodium chloride and sodium hydroxide.
The pH was adjusted to 5.8. Subsequently, the same blue-sensitive sensitizing dye as used in Example 1 was added in an amount of 4 per mole of silver halide.
After adding ^10-4 mol, selenium sensitization was optimally performed at 60 ° C using the same amount of dimethylselenourea as in Example 1. The silver chlorobromide emulsion (containing 1 mol% of silver bromide) thus obtained was designated as emulsion F. Emulsion G is an ultrafine silver bromide emulsion (particle size: 0.05 μm, potassium hexachloroiridate (IV) at 7.0 × 10 ⁻⁶ mol per mol of silver bromide) at 60 ° C. before selenium sensitization. Was added in an amount containing 0.4 mol% of silver bromide with respect to silver chloride.
After ripening for 2 minutes, a silver chlorobromide emulsion was prepared which was different only in that selenium sensitization was optimized. With respect to the three types of emulsions E, F, and G thus prepared, the shape, the particle size, and the particle size distribution of the particles were determined from electron micrographs. The particle size was represented by the average value of the diameter of a circle equivalent to the projected area of the particle, and the particle size distribution was obtained by dividing the standard deviation of the particle size by the average particle size. All three types of emulsions E, F and G were cubic grains having a grain size of 0.69 μm and a grain size distribution of 0.09. For sample A obtained in Example 1,
Photosensitive materials were prepared by replacing the emulsion of the first layer (blue-sensitive layer) as shown in Table 8 and further adding the compounds shown in Table 8 to the coating solution for the first layer, and these were designated as samples a to i. .
For these samples, the effect of humidity during exposure and the change in fog density due to long-term storage of the photosensitive material were examined in the same manner as in Example 1. Table 8 shows the results.

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[Table 8]

As is clear from the results shown in Table 8, the effect of the present invention is particularly remarkable in emulsions having a localized phase having a high silver bromide content near the surface of silver halide grains.

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EFFECTS OF THE INVENTION The present invention provides a halogenated compound which is excellent in rapid processing property, has high sensitivity, has little variation in sensitivity due to changes in humidity at the time of exposure, and suppresses an increase in fog density even when the photosensitive material is stored for a long period of time. A silver photographic light-sensitive material is obtained.

Claims (2)

(57) [Claims] 1. A silver halide photographic material having at least one light-sensitive emulsion layer containing a silver halide emulsion on a support, wherein the light-sensitive emulsion layer contains a compound represented by the general formula (I):
Compounds represented by the general formulas (II) and (III) and III-14, III-15, III-1
8, at least one compound selected from the group consisting of III-25, and a silver chloride content of 90 mol% substantially free of silver iodide.
A silver halide photographic material comprising the silver halide grains described above and a silver halide emulsion chemically sensitized with a selenium compound. General formula (I) In the formula, X ¹ represents —NR ¹⁵ R ¹⁶ or —NHSO ₂ R
^And Y ¹ represents a hydroxyl group or a group having the same meaning as X ¹ . R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ each represent a hydrogen atom or an arbitrary substituent, and R ¹¹ , R ¹² , R
¹³ and R ¹⁴ may together form a carbocyclic ring.
R ¹⁵ and R ¹⁶ each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ¹⁵ and R ¹⁶ may together form a nitrogen-containing heterocyclic ring. R ¹⁷ represents an alkyl group, an aryl group, an amino group or a heterocyclic group. Formula (II) In the formula, X ² and Y ² each represent a hydroxyl group, —NR ²³ R ²⁴
Or it represents a -NHSO ₂ R ^25. Each R ^{21, R 22} represents a hydrogen atom or an arbitrary ^{substituent, R 21}
And R ²² may together form a carbocyclic or heterocyclic ring. R ^{23, R 24} are each a hydrogen atom, an alkyl group, an aryl group or a heterocyclic ^{group, R 23} and R
²⁴ may together form a nitrogen-containing heterocycle. R
²⁵ represents an alkyl group, an aryl group, an amino group or a heterocyclic group. General formula (III) In the formula, X ³ represents a hydroxyl group or —NR ³² R ³³ ;
Y ³ is -CO- or -SO ₂ - represent. R ³¹ represents a hydrogen atom or an optional substituent, and n is 0 or 1. R ^{32, R 33} are each a hydrogen atom, an alkyl group, an aryl group or a heterocyclic ^{group, R 31} and R
³² , R ³² and R ³³ may form a nitrogen-containing heterocyclic ring together. 2. A silver bromide content of at least 1 in the vicinity of the surface of silver halide grains contained in a silver halide emulsion.
2. The halogen according to claim 1, wherein the emulsion is a silver chlorobromide emulsion substantially free of silver iodide, wherein 95 mol% or more of the silver bromide having a localized phase exceeding 0 mol% is silver chloride. Silver halide photographic material.