JPH08339059A - Silver halide color photosensitive material - Google Patents

Abstract

PURPOSE: To obtain the photosensitive material high in sensitivity and superior in graininess and storage stability and processing stability by incorporating silver halide grains chemically sensitized by at least one kind of selenium or tellurium compound in at least one photosensitive layer and a specified compound in the photosensitive material. CONSTITUTION: At least one of the color photosensitive layers of the color photosensitive material having red-, green-, and blue-sensitive layers on a support contains silver halide grains chemically sensitized by at least one kind of selenium or tellurium compound and the photosensitive material contains at least one of the compounds represented by formulae I and II in which R<1> is an alkyl or alkoxy group or the like; R<2> is an alkyl or phenyl group or the like; R<3> is an H atom or a substituent; n<1> is 1, 2, or 3; Z<1> is a group releasing a development inhibitor; V is an aryl group; W is an alkyl group; and Z<2> is a group releasing a development inhibitor.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color light-sensitive material, and more particularly to a silver halide color light-sensitive material having high sensitivity, excellent graininess, storage stability and processing stability.

[0002]

2. Description of the Related Art A silver halide color photographic light-sensitive material, particularly a color light-sensitive material for photographing, is required to have a high sensitivity, excellent graininess, and good color reproducibility and sharpness. The silver halide emulsion used for the light-sensitive material is
Usually, for example, a sensitizing method using various chemical substances is performed in order to obtain desired sensitivity and gradation. As typical methods, various sensitization methods such as sulfur sensitization, selenium sensitization, noble metal sensitization such as gold, reduction sensitization, and combinations thereof are known. Various improvements have been made to these sensitizing methods in order to increase sensitivity and improve graininess.

Of the above, regarding the selenium sensitization method,
H. E. FIG. Spencer et al., Journal of
Photographic Science Magazine, 31
Volume 158 to 169 (1963), etc., and is well known in the past, and recently, JP-A-3-
111838, 3-116132, 4-258.
As described in No. 32 and No. 3-237450, the selenium sensitizer has been improved and the usage thereof has been improved. Regarding the tellurium sensitization method, Japanese Patent Laid-Open No.
No. 11381, No. 5-11385 to No. 11388, No. 5-11392, No. 5-11393 and the like show their usefulness such as high sensitivity and low fog.

Certainly, the emulsion sensitized by the selenium compound and tellurium compound described above had effects such as high sensitivity and excellent graininess, but since development progressed quickly, processing stability was difficult to obtain, and processing was difficult. Further improvements in stability are needed. With regard to graininess, it is becoming more common to enjoy photos with panoramic prints, etc.
I'm still not satisfied.

In particular, it is necessary to improve the technique for improving the graininess of a light-sensitive material using an emulsion sensitized with the above-mentioned selenium compound or tellurium compound, which has a rapid development progress and is hardly affected by so-called DIR couplers. It

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide color light-sensitive material having high sensitivity, excellent graininess, storage stability and processing stability.

[0007]

The above object of the present invention has been achieved by the following constitution.

(1) In a silver halide color light-sensitive material having at least one red light-sensitive layer, at least one green light-sensitive layer, and at least one blue light-sensitive layer on a support, at least one light-sensitive layer The layer contains silver halide grains chemically sensitized with at least one compound selected from selenium compounds and tellurium compounds, and the light-sensitive material is selected from compounds represented by the following general formulas [I] and [II]. A silver halide color light-sensitive material containing at least one compound described above.

[0009]

[Chemical 6]

[In the formula, R ¹ represents an alkyl group, an alkoxy group, a phenoxy group, or a halogen atom;
² represents an alkyl group, a phenyl group, an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, or a sulfamoyl group. R ³ is
It represents a hydrogen atom or a substituent, and n ¹ represents an integer of ¹ , 2, or 3. Z ¹ represents a development inhibitor releasing group having the following structural formula.

-(Time ₁ ) m ₁ -IN ₁ (In the formula, Time ₁ represents a Timing group capable of releasing a development inhibitor moiety by an intramolecular nucleophilic reaction or an electron transfer reaction, and m ₁ represents 1, Represents an integer of 2 or 3, IN
₁ represents a development inhibitor portion. )]

[0012]

[Chemical 7]

[In the formula, V represents an aryl group, and W is
Represents an alkyl group. Z ² represents a development inhibitor releasing group having the following structural formula.

-(Time ₂ ) m ₂ -IN ₂ (In the formula, Time ₂ represents a Timing group capable of releasing a development inhibitor moiety by an intramolecular nucleophilic reaction or an electron transfer reaction, and m ₂ represents 1, Represents an integer of 2 or 3, IN
₂ represents a development inhibitor portion. )] (2) Z ^{1 of the} compound represented by the general formula [I] is represented by the following general formula [I-Z ¹ ] and the silver halide color photosensitive material according to (1). material.

[0015]

Embedded image

[Wherein Q ₁ and Q ₂ represent an electron-withdrawing group,
R ⁴ represents a hydrogen atom, an alkyl group, or an aryl group. R ⁵ and R ⁶ represent an alkyl group or an aryl group, and R ⁷ represents a halogen atom or an alkyl group.
m ₃ represents an integer of zero or 1, and IN ₃ , IN ₄ , IN ₅ ,
IN ₆ represents a development inhibitor portion. ] (3) Z ² of the compound represented by the general formula [II] is, silver halide color photographic material as claimed in characterized by being represented by the following general formula [II-Z ^2] (1) .

[0017]

[Chemical 9]

[In the formula, Q ₃ and Q ₄ represent an electron-withdrawing group,
R ⁸ represents a hydrogen atom, an alkyl group, or an aryl group. R ⁹ and R ¹⁰ represent an alkyl group or an aryl group, and R ¹¹ represents a halogen atom or an alkyl group.
m ₄ represents an integer of 0 or 1, and IN ₇ , IN ₈ , IN ₉ ,
IN ₁₀ represents a development inhibitor portion. (4) A silver halide color light-sensitive material having at least one red light-sensitive layer, at least one green light-sensitive layer, and at least one blue light-sensitive layer on a support,
At least one photosensitive layer contains silver halide grains chemically sensitized with at least one compound selected from a selenium compound and a tellurium compound, and the photosensitive material is represented by the following general formulas [III] and [IV]. A silver halide color light-sensitive material containing at least one compound selected from the above compounds.

[0019]

[Chemical 10]

[In the formula, R ¹ represents an alkyl group, an alkoxy group, a phenoxy group, or a halogen atom;
² represents an alkyl group, a phenyl group, an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, or a sulfamoyl group. R ³ is
It represents a hydrogen atom or a substituent, and n ¹ represents an integer of ¹ , 2, or 3. V represents an aryl group, and W represents an alkyl group. Q ₁ and Q ₃ represent an electron-withdrawing group, and R ⁴ and
R ⁸ represents a hydrogen atom, an alkyl group, or an aryl group, and IN ₃ and IN ₇ represent a development inhibitor moiety. The present invention will be specifically described below. In the description, preferred embodiments of the present invention will be referred to as “preferred”, “suitable”,
Although the expression "may be used" or the like is shown, the reason why the reason is not particularly shown is that the effect of the present invention, which is excellent in sensitivity, heat-resistant storage stability and processing stability, is more remarkable. Further, the technical scope of the present invention is not limited to these preferred embodiments, but is equivalent to the invention grasped from the description of the claims.

The above general formulas [I], [II] and [I]
-Z ^1], [II-Z ^2], represented by [III] or [IV] (hereinafter also referred to as represented by the general formula [I] to [IV])
The compound will be described.

In the above general formulas [I] to [IV],
R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹
Examples of the alkyl group represented by W include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, a synlopentyl group, a hexyl group, a cyclohexyl group, an octyl group, and a dodecyl group. Etc. These alkyl groups are further halogen atoms (for example, chlorine atom, bromine atom, fluorine atom, etc.), alkoxy groups (for example, methoxy group, ethoxy group, 1,1-dimethylethoxy group, hexyloxy group,
Dodecyloxy group etc.), aryloxy group (eg phenoxy group, naphthyloxy group etc.), aryl group (eg phenyl group, naphthyl group etc.), alkoxycarbonyl group (eg methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group) , 2-ethylhexylcarbonyl group, etc.), an aryloxycarbonyl group (eg,
Phenoxycarbonyl group, naphthyloxycarbonyl group, etc.), alkenyl group (eg, vinyl group, allyl group, etc.), heterocyclic group (eg, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, morpholyl group, piperidyl group). Base,
Piperazyl group, pyrimidyl group, pyrazolyl group, furyl group etc.), alkynyl group (eg propargyl group etc.), amino group (eg amino group, N, N-dimethylamino group, anilino group etc.), hydroxyl group, cyano group , A sulfo group, a carboxyl group, a sulfonamide group (for example, a methylcarphonylamino group, an ethylsulfonylamino group,
Butylsulfonylamino group, octylsulfonylamino group, phenylsulfonylamino group, etc.) and the like.

Examples of the alkoxy group represented by R ¹ and R ² include a methoxy group, an ethoxy group, a butoxy group, an octyloxy group, a dodecyloxy group, an isopropyloxy group, a t-butyloxy group and a 2-ethylhexyloxy group. Is mentioned. These groups can be substituted with an alkyl group represented by R ¹ or R ² and a group similar to the group shown as the substituent of the alkyl group.

Examples of the phenoxy group represented by R ¹ include a phenyloxy group and a naphthyloxy group. These groups can be substituted with a group similar to the substituent represented by R ³ .

The halogen atom represented by R ¹ , R ⁷ and R ¹¹ is, for example, a chlorine atom, a bromine atom, an iodine atom or a fluorine atom.

Examples of the alkoxycarbonyl group represented by R ² include methoxycarbonyl group, ethoxycarbonyl group, isopropyloxycarbonyl group, t-butyloxycarbonyl group, 2-ethylhexyloxycarbonyl group and dodecyloxycarbonyl group. To be
These groups can be substituted with an alkyl group represented by R ¹ or R ² and a group similar to the group shown as the substituent of the alkyl group.

Examples of the aryloxycarbonyl group represented by R ² include a phenyloxycarbonyl group and a naphthyloxycarbonyl group. These groups can be substituted with a group similar to the substituent represented by R ³ .

As the carbamoyl group represented by R ² ,
Examples thereof include a methylcarbamoyl group, a propylcarbamoyl group, a t-butylcarbamoyl group, a 2-ethylhexylcarbamoyl group, a pentadecylcarbamoyl group, a dibutylaminocarbonyl group and an N-methyl-N- (2-ethylhexyl) aminocarbonyl group. These groups can be substituted with an alkyl group represented by R ¹ or R ² and a group similar to the group shown as the substituent of the alkyl group.

Examples of the sulfamoyl group represented by R ² include a methylsulfamoyl group, a propylsulfamoyl group, a t-butylsulfamoyl group, a 2-ethylhexylsulfamoyl group and a pentadecylsulfamoyl group. , Dibutylaminosulfonyl group, dioctylaminosulfonyl group, N-methyl-N- (2-ethylhexyl) aminosulfonyl group and the like. These groups can be substituted with an alkyl group represented by R ¹ or R ² and a group similar to the group shown as the substituent of the alkyl group.

V, R ² , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰
As the aryl group represented by, for example, a phenyl group,
Examples thereof include naphthyl group. These groups can be substituted with a group similar to the substituent represented by R ³ .

The substituent represented by R ³ may be any group capable of substituting on the benzene ring. For example, an alkyl group (eg, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group). Group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, octyl group, dodecyl group, etc.), alkenyl group (eg, vinyl group, allyl group, etc.), alkynyl group (eg, propargyl group, etc.), aryl group (eg, Phenyl group, naphthyl group, etc.), heterocyclic group (for example, pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group, furyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sulforanyl group, piperidinyl group, Pyrazolyl group, tetrazolyl group, etc.), halogen atom (for example, chlorine atom, Elementary atom, iodine atom, fluorine atom, etc., alkoxy group, (for example, methoxy group, ethoxy group, propyloxy group, pentyloxy group, cyclopentyloxy group, hexyloxy group, cyclohexyloxy group, octyloxy group, dodecyloxy group) Etc.), aryloxy groups (eg, phenoxy group, naphthyloxy group, etc.), alkoxycarbonyl groups (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.) , An aryloxycarbonyl group (for example, a phenyloxycarbonyl group, a naphthyloxycarbonyl group, etc.), a sulfonamide group (for example,
Methylsulfonylamino group, ethylsulfonylamino group, butylsulfonylamino group, hexylsulfonylamino group, cyclohexylsulfonylamino group, octylsulfonylamino group, dodecylsulfonylamino group, phenylsulfonylamino group, etc., sulfamoyl group (for example, aminosulfonyl group) , Methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylamino Sulfonyl group, etc.), ureido group (for example, methylureido group, erureido group, pentylureido group, cyclohexylureido group, Kuchiruureido group, dodecyl ureido group, a phenyl ureido group, Nauchiruureido group, 2
-Pyridylaminoureido group, etc.), an acyl group (for example,
Acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), carbamoyl group ( For example, an aminocarbonyl group,
Methylaminocarbonyl group, dimethylaminocarbonyl group, propylamonocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbamoyl group, dodeylaminocarbonyl group, phenylaminocarbonyl group, naphthyl Aminocarbonyl group, 2-
Pyridylaminocarbonyl group, etc., amide group (for example,
Methylcarbonylamino group, ethylcarbonylamino group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, octylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl Group, naphthylaminocarbonyl group, etc.), sulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, phenylsulfonyl group, naphthylsulfonyl group, 2- Pyridylsulfonyl group), amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2 Ethylhexyl amino group, a dodecyl group, an anilino group, naphthylamino group, 2-pyridylamino group), a cyano group, a nitro group, a carboxyl group, a hydroxyl group, a hydrogen atom or the like. These groups can be substituted with an alkyl group represented by R ¹ or R ² and a group similar to the group shown as the substituent of the alkyl group.

Examples of the development inhibitor as the development inhibitor moiety represented by IN _{1 to} IN ₁₀ include 5-mercaptotetrazole compounds (for example, 1-phenyl-5-mercaptotetrazole and 1- (4-hydroxyphenyl). )
-5-mercaptotetrazole, 1- (2-methoxycarbonylphenyl) -5-mercaptotetrazole, 1
-Ethyl-5-mercaptotetrazole and 1-propyloxycarbonylmethyl-5-mercaptotetrazole, etc., benzotriazole-based compounds (for example, 5-
(Or 6-) nitrobenzotriazole, 5- (or 6-) phenoxycarbonylbenzotriazole, etc.), 1,3,4-thiadiazole-based compound (for example,
5-methylthio-2-mercapto-1,3,4-thiadiazole, 5- (2-methoxycarbonylethylthio)
-2-mercapto-1,3,4-thiadiazole etc.),
1,3,4-oxadiazole-based compound (for example, 5-
Methyl-2-mercapto-1,3,4-oxadiazole, etc.), benzothiazole compound (eg, 2-mercaptobenzothiazole), benzimidazole compound (eg, 2-mercaptobenzimidazole), benzoxazole -Based compounds (for example, 2-mercaptobenzoxazole and the like), 1,2,4-triazole-based compounds (for example, 3- (2-furyl) -5-hexylthio-1,2,4-triazole and the like), 1,2 , 3
-Triazole compounds (for example, 4-hexylthio-
1,2,3-triazole, 4-hexyloxycarbonylmethylthio-1,2,3-triazole and the like).

The development inhibitor as the development inhibitor moiety includes a bond (eg, a bond capable of undergoing a cleavage reaction during the development process).
A compound having a substituent containing an ester bond, a urethane bond, a sulfonic acid ester bond, a carbonic acid ester bond, or the like) is preferable.

Typical compounds represented by the general formulas [I] to [IV] of the present invention are shown below, but the present invention is not limited thereto.

[0035]

[Chemical 11]

[0036]

[Chemical 12]

[0037]

[Chemical 13]

[0038]

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[0039]

[Chemical 15]

[0040]

Embedded image

[0041]

[Chemical 17]

[0042]

Embedded image

[0043]

[Chemical 19]

[0044]

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The silver halide emulsion of the present invention preferably contains tabular grains for the purpose of improving sharpness. The method well known in the art can be referred to for the method for preparing the tabular silver halide emulsion in the present invention.

For example, a tabular silver halide emulsion may be a Knack or a Chateau.
u), "Advancement of morphology of silver bromide crystals during physical ripening (Evolution of the Morphology of Silver Bromide Crystals Dualing Physical Livening)" Science & Industry * Photography, Vol. 33, No. 2 (196
2), p. 121-125, Duffin
By "Photographic Emulsion Chemistry"
"emission" Focal Press (Focal)
Press), New York, 1966, p. 66-
72, A. P. H. Tribelli,
W. F. Smith, Photographic ·
Journal (Photographic Journal
l) 80 volumes, p. 285 (1940) and, for example, JP-A-58-127921 and 58-58.
It can be easily prepared by referring to the methods described in Nos. -113927 and 58-113928.

For example, a relatively low p of pBr 1.3 or less
In a Br value atmosphere, it is desirable to add a silver and halogen solution so as to form a seed crystal in which tabular grains are present in an amount of 40% or more by weight and new crystal nuclei are not generated in the grain growth process.

The aspect ratio of tabular grains is defined as the ratio of grain diameter to grain thickness. The definition and measuring method of the aspect ratio are the same as those disclosed in JP-A-63-106746, JP-A-63-3l6847 and JP-A-2-l93138. When a tabular silver halide emulsion is used, the average aspect ratio may be 3 or more, but it is preferably 4 or more and less than 8 and particularly preferably 4.5 or more and less than 7.

As the selenium sensitizer used in the present invention, the selenium compounds disclosed in conventionally known patents can be used. That is, usually, an unstable selenium compound and / or a non-unstable selenium compound is added,
It is used by stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. As the unstable selenium compound, for example, JP-B-44-15748 and 43-134.
No. 89, Japanese Patent Application Nos. 2-130976 and 2-22930.
It is preferable to use the compounds described in No. 0. Specific examples of the unstable selenium sensitizer include isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenamides, selenocarboxylic acids (for example, 2
-Selenopropionic acid, 2-selenobutyric acid), selenoesters, diacyl selenides (for example, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, colloidal metal selenium. Can be mentioned.

Although the preferred types of labile selenium compounds are described above, these are not limiting. Stable selenium compounds as sensitizers for photographic emulsions are known to those skilled in the art, as long as selenium is unstable, the structure of the compounds is not so important, and the organic part of the selenium sensitizer molecule is not important. It is generally understood that they carry no selenium and play no role other than making them present in the emulsion in an unstable form.

In the present invention, the unstable selenium compound having such a broad concept is advantageously used.

The non-unstable selenium compounds used in the present invention include Japanese Patent Publication Nos. 46-4553 and 52-3449.
The compounds described in No. 2 and No. 52-34491 are used. Examples of non-labile selenium compounds include selenious acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenides, diaryl diselenides, dialkyl selenides, dialkyl diselenides, 2-selenazolidinediones, 2-selenooxazolidinethione and derivatives thereof are mentioned.

Of these selenium compounds, the following general formulas (1) and (2) are preferable.

[0054]

[Chemical 21]

In the formula, Z ₁ and Z ₂ may be the same or different and each is an alkyl group (eg, methyl, ethyl, t-butyl, adamantyl, t-octyl), an alkenyl group (eg, vinyl, propenyl). , Aralkyl groups (eg, benzyl, phenethyl), aryl groups (eg, phenyl, pentafluorophenyl, 4-chlorophenyl, 3-nitrophenyl, 4-octylsulfamoylphenyl, α-naphthyl), heterocyclic groups (eg,
Pyridyl, thienyl, furyl, imidazolyl), -N <
_{(R 1) (R 2)} , - it represents the OR ₃ or -SR _4.

R ₁ , R ₂ , R ₃ and R _{4, which} may be the same or different, each represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. Examples of the alkyl group, aralkyl group, aryl group or heterocyclic group include the same examples as Z ₁ . However, R ₁ and R ₂ are each a hydrogen atom or an acyl group (eg, acetyl group, propanoyl group,
Benzoyl group, heptafluorobutynol group, difluoroacetyl group, 4-nitrobenzoyl group, α-naphthoyl group, 4-trifluoromethylbenzoyl group).

In the general formula (1), Z ₁ preferably represents an alkyl group, an aryl group or -N <(R ₁ ) (R ₂ ),
Z ₂ represents _{-N <(R 5) (R} 6). R ₁ , R ₂ , R ₅ and R _{6, which} may be the same or different, each represents a hydrogen atom, an alkyl group, an aryl group or an acyl group.

In the general formula (1), more preferably N, N-
Dialkylselenourea, N, N, N'-trialkyl-
N'-acyl selenoureas, tetraalkyl selenoureas,
Represents N, N, -dialkyl-arylselenoamide, N-alkyl-N-aryl-arylselenoamide.

[0059]

[Chemical formula 22]

In the formula, Z ₃ , Z ₄ and Z ₅ may be the same or different and each is an aliphatic group, an aromatic group, a heterocyclic group, -OR ₇ , -N <(R ₈ ) (R ₉ ), -SR ₁₀ , -S
eR ₁₁ , X, represents a hydrogen atom.

R ₇ , R ₁₀ and R ₁₁ represent 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, a heterocyclic group or hydrogen. Represents an atom, and X represents a halogen atom.

In the general formula (2), Z ₃ , Z ₄ , Z ₅ ,
The aliphatic group represented by R ₇ , 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,
Propyl, isopropyl, t-butyl, butyl, octyl, decyl, hexadecyl, cyclopentyl, cyclohexyl, allyl, 2-butenyl, 3-pentenyl, propargyl, 3-pentynyl, benzyl, phenethyl).

In the general formula (2), Z ₃ , Z ₄ , Z ₅ ,
The aromatic group represented by R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a monocyclic or condensed ring aryl group (eg, phenyl, pentafluorophenyl, 4-chlorophenyl, 3-sulfophenyl, α-). Naphthyl, 4-methylphenyl).

In the general formula (2), Z ₃ , Z ₄ , Z ₅ ,
The heterocyclic group represented by R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a 3- to 10-membered saturated or unsaturated heterocyclic ring containing at least one of a nitrogen atom, an oxygen atom or a sulfur atom. Groups (eg pyridyl, thienyl, furyl, thiazolyl,
Imidazolyl, benzimidazolyl).

In the general formula (2), the cation represented by R ₇ , R ₁₀ and R ₁₁ represents an alkali metal atom or ammonium, and the halogen atom represented by X is, for example, a fluorine atom, a chlorine atom or a bromine atom. Or represents an iodine atom.

In the general formula (2), Z ₃ , Z ₄ or Z ₅ preferably represents an aliphatic group, an aromatic group or -OR ₇ , and R ₇
Represents an aliphatic group or an aromatic group.

In formula (2), a trialkylphosphine selenide, a triarylphosphine selenide, a trialkylselenophosphate or a triarylselenophosphate is more preferable.

Specific examples of the compounds represented by the general formulas (1) and (2) are shown below, but the invention is not limited thereto.

[0069]

[Chemical formula 23]

[0070]

[Chemical formula 24]

[0071]

[Chemical 25]

Next, the tellurium sensitizer used in the present invention will be described. Specific examples of preferable compounds are shown below, but the present invention is not limited thereto.

[0073]

[Chemical formula 26]

[0074]

[Chemical 27]

[0075]

[Chemical 28]

[0076]

[Chemical 29]

These selenium sensitizers and tellurium sensitizers are dissolved in water or an organic solvent such as methanol or ethanol, alone or in a mixed solvent, or disclosed in JP-A-4-1407.
No. 38, No. 4-140742, No. 5-11381,
It can be added at the time of chemical sensitization in the form described in JP-A-5-11385 or JP-A-5-11388. Preferably, it is added before the start of chemical sensitization. The selenium sensitizer and tellurium sensitizer used are not limited to one kind, and two or more kinds of the above selenium sensitizer and tellurium sensitizer can be used in combination. The unstable selenium compound and the non-unstable selenium compound may be used in combination. Moreover, you may use together at least 1 type of each of a selenium sensitizer and a tellurium sensitizer. The addition amount of the selenium sensitizer and tellurium sensitizer used in the present invention depends on the activity of the selenium sensitizer and tellurium sensitizer used, the type and size of silver halide, the temperature and time of ripening, and the like. Different, but preferably 1 × per mole of silver halide
It is 10 ^-8 mol or more. It is more preferably 1 × 10 ⁻⁷ mol or more and 3 × 10 ⁻⁵ mol or less. The temperature of chemical ripening when the selenium sensitizer and the tellurium sensitizer are used is preferably 45 ° C. or higher. More preferably 50 ° C or higher, 80 ° C
It is the following. pAg and pH are arbitrary. For example p
The effect of the present invention can be obtained in a wide range of H from 4 to 9. It is more effective to perform the selenium sensitization and the tellurium sensitization in the presence of a silver halide solvent.

The silver halide solvent which can be used in the present invention is, for example, US Pat. Nos. 3,271,157, 3,531,289, 3,574,628 and JP-A-54-54. (A) Organic thioethers described in 1019, 54-158917 and the like, JP-A-53-82.
(B) thiourea derivatives described in JP-A No. 408, 55-77737, 55-2982 and the like, JP-A-53-1.
No. 44319, (c) a silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom, (d) imidazoles described in JP-A No. 54-100717, ( Examples thereof include e) sulfite and (f) thiocyanate. Particularly preferred solvents are thiocyanate and tetramethylthiourea. Although the amount of the solvent used varies depending on the kind, for example, in the case of thiocyanate, the preferable amount is 1 × 10 ⁻⁴ mol or more and 1 × 10 ⁻² mol or less per mol of silver halide.

The silver halide photographic emulsion of the present invention can achieve higher sensitivity and lower fog by combined use of sulfur sensitization and / or gold sensitization in chemical sensitization. Sulfur sensitization usually involves adding a sulfur sensitizer,
It is carried out by stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. The gold sensitization is usually carried out by adding a gold sensitizer and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain period of time. For sulfur sensitization, known sulfur sensitizers can be used. For example, thiosulfate, thioureas, allylisothiocyanate, cystine, p-toluenethiosulfonate,
Examples include rhodanine. Other US Patent No. 1,5
74,944, 2,410,689, 2,
278,947, 2,728,668, 3,501,313, 3,656,955, German Patent 1,422,868, Japanese Patent Publication No. 56-2493.
No. 7, JP-A-55-45016 and the like can also be used. The sulfur sensitizer may be added in an amount sufficient to effectively increase the sensitivity of the emulsion. This amount varies over a considerable range under various conditions such as pH, temperature, and size of silver halide grains, but is 1 × 10 ⁻⁷ mol or more per mol of silver halide, 5 or more.
It is preferably × 10 ^-4 mol or less.

As the gold sensitizer for gold sensitization, the oxidation number of gold may be +1 valence or +3 valence, and a gold compound usually used as a gold sensitizer can be used. Representative examples include chloroauric acid salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, pyridyl trichlorogold and the like. The addition amount of the gold sensitizer varies depending on various conditions, but as a guide, it is preferably 1 × 10 ⁻⁷ mol to 1 × 10 ⁻⁷ mol of silver halide and 5 × 10 ⁻⁴ mol or less.

In chemical ripening, there are no particular restrictions on the timing and order of addition of a sulfur sensitizer and / or a gold sensitizer which can be used in combination with a silver halide solvent and a selenium sensitizer or a tellurium sensitizer. There is no need to provide it,
For example, the above compounds can be added at the same time as the initial (preferably) chemical ripening or during the progress of chemical ripening, or at different addition points. In addition, at the time of addition, the above compound may be dissolved in water or an organic solvent capable of mixing with water, for example, a single liquid or a mixed liquid of methanol, ethanol, acetone or the like and added.

In the present invention, reduction sensitization can also be used in combination. Specifically, for example, a hydrazine derivative, stannous chloride, aminoiminomethanesulfinic acid,
Examples thereof include borane compounds and polyamine compounds.

The silver halide emulsion of the present invention preferably contains a nitrogen-containing heterocyclic compound represented by the following general formula [V].

[0084]

Embedded image

In the formula, Z represents an atomic group necessary for forming an aromatic ring or a 5- or 6-membered hetero ring which may be condensed with another hetero ring, and M represents a hydrogen atom, an alkali metal atom or Represents an ammonium group.

Examples of the 5- or 6-membered hetero ring which may be condensed with the aromatic ring or other hetero ring formed by Z include imidazole, triazole, tetrazole,
Examples thereof include thiazole, oxazole, selenazole, benzimidazole, naphthimidazole, benzothiazole, naphthothiazole, benzoselenazole, pyridine, pyrimidine and quinoline, and these heterocycles include those having a substituent.

Typical examples of the compound represented by the general formula [V] (hereinafter, also referred to as compound [V]) are shown below.

[0088]

[Chemical 31]

[0089]

Embedded image

When the compound [V] is contained in the silver halide emulsion, the compound [V] is preferably added during the chemical ripening of the emulsion, at the end of the chemical ripening, or after the end of the chemical ripening and before the coating. . The addition may be carried out all at once or may be added in a plurality of times. Compound [V] is usually 1 × 10 ⁻⁹ to 1 × 1 per mol of silver halide emulsion.
It is used in an amount of 0 ⁻¹ mol, preferably 1 × 10 ⁻⁷ to 1 × 10 ⁻³ mol.

In the present invention, the silver halide emulsion is represented by Research Disclosure 308119 (hereinafter RD308).
119) can be used. The following shows the locations.

[Item] [Page of RD308119] Iodine structure 993 IA item Manufacturing method 993 I-A item and 994 E item Crystal habit (normal crystal) 993 IA item Crystal habit (twin crystal) 993 IA Item Epitaxial 993 I-A Item Halogen composition (uniform) 993 I-B Item Halogen composition (non-uniform) 993 I-B Item Halogen conversion 994 I-C Item Halogen substitution 994 I-C Metal content 994 I-D Item Monodisperse 995 I-F Item Solvent addition 995 I-F Item Latent image forming position (surface) 995 I-G item Latent image forming position (internal) 995 I-G Item Sensitive material (negative) 995 I-H item Applied Sensitive Material (Positive) 995 I-H Item Mixed Emulsion 995 I-J Desalting Item 995 II-A The silver halide emulsion of the present invention is physically ripened, chemically ripened and spectrally sensitized. It is possible to use what was done. The additive used in such a process is Research Disclosure No. 17643, No. 18716 and No.
308119 (hereinafter referred to as RD17643 and RD1
8716 and RD308119).

The description is given below.

[Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A Item 23 648 Spectral sensitizer 996 IV-AA, B, C, D, H, I, J Item 23 -24 648-9 Supersensitizer 996 IV-AE, J Item 23-24 648-9 Antifoggant 998 VI 24-25 649 Stabilizer 998 VI 24-25 649 Known photographic additives usable in the present invention Agents are also described in Research Disclosure above. Below are the relevant locations.

[Item] [Page of RD308119] [RD17643] [RD18716] Color turbidity inhibitor 1002 VII-I 25 650 Dye image stabilizer 1001 VII-J 25 Whitening agent 998 V 24 UV absorber 1003 VII- Item C, C 25 to 26 Light absorber 1003 VII-C 25 to 26 Light scattering agent 1003 VII-C Filter dye 1003 VII-C Binder 1003 IX 26 651 Antistatic agent 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer Agent 1006 XII 27 650 Lubricant 1006 〃 27 650 Activator / Coating aid 1005 XI 26 to 27 650 Matte agent 1007 XVI Developer (contained in photosensitive material) 1011 XX B Various couplers are used in the present invention. And specific examples thereof are described in Research Disclosure above. The relevant locations are shown below.

[Items] [Page of RD308119] [RD17643] Yellow coupler 1001 VII-D item VII-C to G magenta coupler 1001 VII-D item VII-C to G cyan coupler 1001 VII-D item VII-C -G item Colored coupler 1002 VII-G item VII-G item DIR coupler 1001 VII-F item VII-F item BAR coupler 1002 VII-F item Other useful residues Release coupler 1001 VII-F item Alkali-soluble coupler 1001 VII -E Item The additive used in the present invention can be added by the dispersion method described in RD308119.

In the present invention, the above-mentioned RD17643 is used.
28, RD18716, pages 647-8 and RD308.
The supports described in 119 can be used.

The light-sensitive material of the present invention includes the above-mentioned RD3081.
An auxiliary layer such as a filter layer or an intermediate layer described in the section 19-K can be provided.

The light-sensitive material of the present invention is the same as the above-mentioned RD30811.
Various layer configurations such as the forward layer, the reverse layer, and the unit configuration described in Item 9-K can be adopted.

The light-sensitive material of the present invention is applied to various color light-sensitive materials represented by color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films, and color reversal papers. be able to.

The light-sensitive material of the present invention is the above-mentioned RD17643.
28-29, RD18716, page 647 and RD30.
It can be developed by the usual method described in 8119.

[0102]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 [Production of Emulsion] <Preparation of Seed Crystal Emulsion α> JP-A-63-151618, US Pat. No. 4,797,354, West German Patent 3,70.
Referring to No. 7,135-A1, the following double-structured silver iodobromide tabular silver halide seed crystal emulsion α was prepared.

Core: 13% of total seed crystal silver Shell: 87% of total seed crystal silver: Thiourea dioxide was added to the entire seed crystal in an amount of 5 × 10 ⁻⁶ mol / mol Ag to form a shell. After that, compound A (CH ₃ CH ₂ —SO
_2- S-Na) was added to the whole seed crystal in an amount of 2 × 10 ⁻⁴ mol / mol Ag and ripened for 5 minutes.

<Preparation of EM-1> Seed crystal emulsion α maintained at 60 ° C. (containing 170 g of silver in terms of AgNO ₃ and containing gelatin 4
(Including 0 g) while stirring (1-1a liquid) and (1-1
Solution b) was added simultaneously over 5 minutes.

(1-1a solution) AgNO ₃ 8 g H ₂ O 200 ml (1-1 b solution) KBr 5 g KI 0.6 g water 200 ml While maintaining pAg at 9.0 in water (1-2 a solution) and (1 a solution).
-2b solution) were simultaneously added over 30 minutes.

[0107] (1-2a _{solution) AgNO 3 70g H 2 O 300ml} (1-2b solution) KBr 4.4 g KI 5.4 g Water 300ml Note that each solution through grain formation, Ostwald between generation and particle new nuclei It was added at an optimum rate so that the aging did not proceed. After completion of the above addition, water washing treatment was carried out at 40 ° C. using a usual flocculation method, and then gelatin was added and redispersed to adjust pAg to 8.1 and pH to 5.8.

The obtained emulsion had a grain size (equivalent sphere diameter) of 0.8.
The emulsion consisted of tabular grains having a .mu. and an average aspect ratio of 6.

Emulsions A to J were prepared by the methods described below. The ripening time was optimized for each emulsion (the best result was obtained by evaluating the fog-sensitivity). Table 1 shows the addition amounts of the selenium sensitizer, the tellurium sensitizer and the compound (V).

<Preparation of Emulsion A> After dissolution of EM-1 at 55 ° C. with dissolution, the following sensitizing dyes Sd-1 60 mg and Sd-2 were prepared.
After adding 68 mg and Sd-3 92 mg and maintaining for 20 minutes, sodium thiosulfate 4 * 10 < ^-6 > mol and chloroauric acid 1.7 * 10 were added at 55 degreeC per 1 mol of silver halides.
^-6 mol and 3.1 × 10 ^-4 mol of potassium thiocyanate were added, and the mixture was aged and subjected to gold-sulfur sensitization for an optimum time. At the end of aging, 4-hydroxy-6-methyl- (1,3,3
a, 7) Tetrazaindene is added as a stabilizer to prepare Emulsion A.
Was produced.

[0111]

[Chemical 33]

<Preparation of Emulsions B to D> In the preparation method of Emulsion A, a selenium sensitizer or a tellurium sensitizer was added as shown in Table 1 in addition to the chemicals added during the gold-sulfur sensitization. Emulsions B to D were prepared by optimally performing gold-sulfur-selenium sensitization or gold-sulfur-tellurium sensitization.

<Preparation of Emulsions E and F> In the preparation of Emulsions C and D, the compound (V) as shown in Table 1 was added in addition to the chemicals to be added, and each was optimally chemically sensitized. E and F were produced.

[0114]

[Table 1]

<Preparation of Emulsions GL> Sensitizing dye Sd-1,
Instead of Sd-2 and Sd-3, the following sensitizing dye Sd-4 1.2 × 10 ⁻⁴ mol and the following sensitizing dye Sd-5 4.0 × 10 ⁻⁵ mol were added per mol of silver halide. Emulsions G to L were prepared in the same manner as the emulsions A to F except for the above.

[0116]

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<Preparation of Photosensitive Material (Multilayer) Sample> A multilayer color photosensitive material consisting of the layers shown below (composition of photosensitive material constituting layers) was prepared on a subbed cellulose triacetate film support to prepare Sample 101. .

For silver halide and colloidal silver, the coating amount is the amount expressed in g / m ² unit in terms of metallic silver per m ² of the light-sensitive material, and for couplers and additives, the light-sensitive amount is the amounts expressed in units of g / m ² per material 1 m ^2, for Matazo sensitizing dyes exhibited mol per mol of silver halide in the same layer.

Sample 101 First layer: Antihalation layer Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.20 High boiling point solvent (OIL-1) 0.16 Gelatin 1.23 Second layer: Intermediate layer High boiling point solvent (OIL-2) 0.17 Gelatin 1.27 Third layer: low sensitivity red sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content 7 mol%) 0.50 iodine Silver bromide emulsion (average grain size 0.27 μm, silver iodide content 2.0 mol%) 0.21 Sensitizing dye (SD-1) 2.8 × 10 ⁻⁴ Sensitizing dye (SD-2) 1 1.9 × 10 ^-4 sensitizing dye (SD-3) 1.9 × 10 ^-5 sensitizing dye (SD-4) 1.0 × 10 ^-4 cyan coupler (C-1) 0.48 cyan coupler (C -2) 0.14 Colored cyan coupler (CC-1) 0.021 DIR compound (D-1) 0.020 High Point solvent (OIL-1) 0.53 Gelatin 1.30 Fourth layer: Medium-sensitive red-sensitive layer Silver iodobromide emulsion (average grain size 0.65 μm, silver iodide content 8 mol%) 0.62 Iodine Silver halide emulsion (average grain size 0.38 μm, silver iodide content 7 mol%) 0.27 Sensitizing dye (SD-1) 2.3 × 10 ⁻⁴ Sensitizing dye (SD-2) 1.2 × 10 ⁻⁴ Sensitizing dye (SD-3) 1.6 × 10 ⁻⁵ Sensitizing dye (SD-4) 1.2 × 10 ⁻⁴ Cyan coupler (C-1) 0.15 Cyan coupler (C-2) 0.18 Colored cyan coupler (CC-1) 0.030 DIR compound (D-1) 0.013 High boiling point solvent (OIL-1) 0.30 Gelatin 0.93 Fifth layer: high sensitivity red sensitive layer Iodour halide emulsion (average grain size 0.9 .mu.m, a silver iodide content of 8 mol%) 1.27 sensitizing dye (SD-1) 1.3 × 10 -4 sensitizing dye ( D-2) 1.3 × 10 ^-4 Sensitizing dye (SD-3) 1.6 × 10 -5 cyan coupler (C-2) 0.12 Colored cyan coupler (CC-1) 0.013 High boiling solvent (OIL-1) 0.14 gelatin 0.91 Sixth layer: intermediate layer High boiling point solvent (OIL-2) 0.11 gelatin 0.80 Seventh layer: low-sensitivity green sensitive layer Silver iodobromide emulsion (average grain Diameter 0.38 μm, silver iodide content 8 mol%) 0.61 Silver iodobromide emulsion (average grain size 0.27 μm, silver iodide content 2.0 mol%) 0.20 Sensitizing dye (SD- 4) 7.4 × 10 ⁻⁵ Sensitizing dye (SD-5) 6.6 × 10 ⁻⁴ Magenta coupler (M-1) 0.18 Magenta coupler (M-2) 0.44 Colored magenta coupler (CM-) 1) 0.12 DIR compound (D-2) 0.02 high boiling point solvent (OIL-2) 0.75 gelatin 1.95 8th layer: middle sensitivity green-sensitive layer Silver iodobromide emulsion (average grain size 0.65 .mu.m, a silver iodide content of 8 mol%) 0.87 Sensitizing dye (SD-7) 2.4 × 10 ^-4 Magenta coupler (M-1) 0.058 Magenta coupler (M-2) 0.13 Colored magenta coupler (CM-1) 0.070 DIR compound (D-2) 0.025 High boiling point solvent (OIL-2) ) 0.50 Gelatin 1.00 9th layer: High-sensitivity green-sensitive layer Emulsion A 1.27 Magenta coupler (M-2) 0.084 Magenta coupler (M-3) 0.064 Colored magenta coupler (CM-1) 0.012 High boiling point solvent (OIL-1) 0.27 High boiling point solvent (OIL-2) 0.012 Gelatin 1.00 10th layer: Yellow filter layer Yellow colloidal silver 0.08 Color stain inhibitor (SC-1) ) 0 15 Formalin scavenger (HS-1) 0.20 High boiling point solvent (OIL-2) 0.19 Gelatin 1.10 11th layer: Intermediate layer Formalin scavenger (HS-1) 0.20 Gelatin 0.60 12th layer: Low sensitivity blue-sensitive layer Silver iodobromide emulsion (average grain size 0.65 μm, silver iodide content 8 mol%) 0.07 Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content 7 mol) %) 0.16 Silver iodobromide emulsion (average grain size 0.27 μm, silver iodide content 2.0 mol%) Sensitizing dye (SD-8) 4.9 × 10 ⁻⁴ Yellow coupler (Y-1) ) 0.80 Comparative-1 (Comparative compound) 0.15 High boiling point solvent (OIL-2) 0.30 Gelatin 1.20 13th layer: High-sensitivity blue-sensitive layer Emulsion G 0.95 Sensitizing dye (SD-8) ) 7.3 × 10 ^-5 sensitizing dye (SD-9) 2.8 × 10 -5 yellow coupler Y-1) 0.15 high boiling point solvent (OIL-2) 0.046 gelatin 0.80 14th layer: 1st protective layer Silver iodobromide emulsion (average grain size 0.08 μm, silver iodide content 1. 0 mol%) 0.40 UV absorber (UV-1) 0.065 UV absorber (UV-2) 0.10 High boiling point solvent (OIL-1) 0.07 High boiling point solvent (OIL-3) 0. 07 Formalin scavenger (HS-1) 0.40 Gelatin 1.31 Fifteenth layer: Second protective layer Alkali-soluble matting agent (average particle size 2 μm) 0.15 Polymethylmethacrylate (average particle size 3 μm) 0.04 Sliding agent (WAX-1) 0.04 Gelatin 0.55 In addition to the above composition, a coating aid Su-1 and a dispersion aid Su.
-2, viscosity modifier V-1, hardeners H-1, H-2, stabilizer ST-1, antifoggant AF-1, dyes AI-1, A
I-2, weight average molecular weight: 10,000 and 1,10
10,000 of two AF-2 and preservative DI-1 were added. The amount of DI-1 added was 9.4 mg / m ² .

[0120]

Embedded image

[0121]

Embedded image

[0122]

Embedded image

[0123]

[Chemical 38]

[0124]

[Chemical Formula 39]

[0125]

[Chemical 40]

[0126]

Embedded image

[0127]

Embedded image

[0128]

[Chemical 43]

Comparative Example 1 (comparative compound) of Emulsion A of the ninth layer of the high-sensitivity green-sensitive layer, Emulsion G of the thirteenth layer of the high-sensitivity blue-sensitive layer and 12th layer of the low-sensitivity blue-sensitive layer of Sample 101 is shown in Table 2. Samples 102 to 1 in the same manner as Sample 101 except that
31 was produced.

The samples 101 to 131 thus produced were exposed to light as described below in accordance with the performance evaluation, and were subjected to development processing in accordance with the processing steps shown below to evaluate the performance.

(I) Photographic performance (I-1) Sensitivity Wedge exposure using white light was performed, and development processing was performed according to the processing steps shown below. From the characteristic curves of the produced yellow color image and magenta color image, the minimum was obtained. Concentration +0.3
Then, the reciprocal of the exposure amount that gives the density was calculated, and the relative sensitivity when the sample 101 was set to 100 for the blue photosensitive layer and the green photosensitive layer was calculated.

(I-2) Evaluation of storability Each sample was stored under the conditions of 40 ° C. and 80% RH for 10 days, the other sample was stored at 5 ° C. for the same period, and the same exposure was applied to these samples. At the same time, it was developed according to the following processing steps. The yellow and magenta densities of these samples were calculated, and the difference (ΔD
_min ) was calculated. The smaller the value is, the less the increase in fog is, which is preferable.

(I-3) Graininess Graininess is D _min +0.
The relative value of the standard deviation (RMS value) of the fluctuation of the density value generated when the density part of No. 5 was scanned with a microdensitometer having an opening scanning area of 250 μm ² (the value of the sample 101 was 100
And) was shown as relative granularity. The smaller this value is, the better the graininess is.

(Treatment Step) Treatment Step Treatment Time Treatment Temperature Replenishment Amount Color Development 3 minutes 15 seconds 38 ± 0.3 ° C. 780 ml Bleach 45 seconds 38 ± 2.0 ° C. 150 ml fixation 1 minute 30 seconds 38 ± 2.0 ℃ 830ml stability 60 seconds 38 ± 5.0 ℃ 830ml dry 1 minute 55 ± 5.0 ℃ − Replenishment amount is a value per 1 m ² of the light-sensitive material.

The following color developing solution, bleaching solution, fixing solution, stabilizing solution and its replenishing solution were used.

Color developer and color replenisher developer Developer replenisher Water 800 ml 800 ml Potassium carbonate 30 g 35 g Sodium hydrogen carbonate 2.5 g 3.0 g Potassium sulfite 3.0 g 5.0 g Sodium bromide 1.3 g 0.4 g Potassium iodide 1.2 mg-hydroxylamine sulfate 2.5 g 3.1 g sodium chloride 0.6 g-4-amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5 g 6.3 g diethylenetriamine Pentaacetic acid 3.0 g 3.0 g Potassium hydroxide 1.2 g 2.0 g Water is added to make 1 liter, and potassium hydroxide or 20%
The color developer is adjusted to pH 10.06 and the replenisher is adjusted to pH 10.18 using sulfuric acid.

Bleaching Solution and Bleaching Replenishing Solution Bleaching Solution Replenishing Solution Water 700 ml 700 ml 1,3-Diaminopropanetetraacetic acid iron (III) ammonium 125 g 175 g ethylenediaminetetraacetic acid 2 g 2 g sodium nitrate 40 g 50 g ammonium bromide 150 g 200 g glacial acetic acid 40 g 56 g water The pH of the bleaching solution is adjusted to pH 4.4 and the replenishing solution is adjusted to pH 4.0 using ammonia water or glacial acetic acid.

Fixing Solution and Fixing Replenishing Solution Fixing Solution Replenishing Solution Water 800 ml 800 ml Ammonium thiocyanate 120 g 150 g Ammonium thiosulfate 150 g 180 g Sodium sulfite 15 g 20 g Ethylenediaminetetraacetic acid 2 g 2 g Ammonia water or glacial acetic acid is used as a fixing solution at pH 6.2.
After adjusting the pH of the replenisher to 6.5, water is added to make 1 liter.

Stabilizer and stable replenisher water 900 ml p-octylphenol ethylene oxide 10 mol adduct 2.0 g dimethylolurea 0.5 g hexamethylenetetramine 0.2 g 1,2-benzisothiazolin-3-one 0.1 g siloxane (UCC) L-77) 0.1 g ammonia water 0.5 ml After adding water to make 1 liter, ammonia water or 50
Adjust to pH 8.5 with% sulfuric acid.

The above results are shown in Table 2.

[0141]

[Table 2]

[0142]

[Chemical 44]

*: Compounds represented by the general formulas [I] to [IV] or comparative compounds.

As is clear from Table 2, the sample using the selenium-sensitized or tellurium-sensitized emulsion without using any of the compounds of the formulas [I] to [IV] of the present invention was selenium-sensitized. Or, the sensitivity is higher than that of the sample using the emulsion not sensitized with tellurium, but the storage stability represented by ΔD _min and the granularity represented by relative granularity are inferior.

On the other hand, a sample using the compound of any one of the formulas [I] to [IV] of the present invention and using the selenium-sensitized or tellurium-sensitized emulsion has high sensitivity, storage stability and graininess. It can be seen that is significantly improved.

[0146]

According to the present invention, high sensitivity and excellent graininess,
Moreover, it was possible to provide a silver halide color light-sensitive material excellent in storage stability and processing stability.

Claims (4)

[Claims] 1. A silver halide color light-sensitive material having at least one red light-sensitive layer, at least one green light-sensitive layer, and at least one blue light-sensitive layer on a support, and at least one light-sensitive layer. Contains silver halide grains chemically sensitized with at least one compound selected from selenium compounds and tellurium compounds, and the light-sensitive material is selected from compounds represented by the following general formulas [I] and [II]. A silver halide color light-sensitive material containing at least one compound. Embedded image [In the formula, R ¹ represents an alkyl group, an alkoxy group, a phenoxy group, or a halogen atom, and R ² represents an alkyl group, a phenyl group, an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, or a sulfamoyl group. Represents a group. R ³ represents a hydrogen atom or a substituent, and n ¹ represents an integer of ¹ , 2 or 3. Z ¹ represents a development inhibitor releasing group having the following structural formula. -(Time ₁ ) m ₁ -IN ₁ (In the formula, Time ₁ represents a Timing group capable of releasing a development inhibitor moiety by an intramolecular nucleophilic reaction or an electron transfer reaction, and m ₁ represents ₁ , 2 or 3). Represents the integer of
₁ represents a development inhibitor portion. )] [Chemical 2] [In the formula, V represents an aryl group and W represents an alkyl group. Z ² represents a development inhibitor releasing group having the following structural formula. _{- (Time 2) m 2 -IN} 2 ( wherein, Time ₂ represents a releasable Timing based development inhibitor moiety by intramolecular nucleophilic reaction or electron transfer reaction, m ₂ is 1, 2 or 3 Represents the integer of
₂ represents a development inhibitor portion. )] 2. Z of the compound represented by the general formula [I]
^{1. The} silver halide color light-sensitive material according to claim 1, wherein 1 is represented by the following general formula [I-Z ¹ ]. Embedded image [In the formula, Q ₁ and Q ₂ represent an electron-withdrawing group, and R ⁴ represents a hydrogen atom, an alkyl group, or an aryl group. R ⁵ , R ⁶
Represents an alkyl group or an aryl group, and R ⁷ represents a halogen atom or an alkyl group. m ₃ represents an integer of 0 or 1, and IN ₃ , IN ₄ , IN ₅ , and IN ₆ represent development inhibitor moieties. ] 3. Z of the compound represented by the general formula [II]
^{2. The} silver halide color light-sensitive material according to claim 1, wherein ² is represented by the following general formula [II-Z ² ]. [Chemical 4] [In the formula, Q ₃ and Q ₄ represent an electron-withdrawing group, and R ⁸ represents a hydrogen atom, an alkyl group, or an aryl group. R ⁹ , R
¹⁰ represents an alkyl group or an aryl group, and R ¹¹ is
Represents a halogen atom or an alkyl group. m ₄ represents an integer of 0 or 1, and IN ₇ , IN ₈ , IN ₉ , and IN ₁₀ represent development inhibitor moieties. ] 4. A silver halide color light-sensitive material having at least one red light-sensitive layer, at least one green light-sensitive layer, and at least one blue light-sensitive layer on a support, and at least one light-sensitive layer. Contains silver halide grains chemically sensitized with at least one compound selected from selenium compounds and tellurium compounds, and the photosensitive material is selected from compounds represented by the following general formulas [III] and [IV] A silver halide color light-sensitive material containing at least one compound. Embedded image [In the formula, R ¹ represents an alkyl group, an alkoxy group, a phenoxy group, or a halogen atom, and R ² represents an alkyl group, a phenyl group, an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, or a sulfamoyl group. Represents a group. R ³ represents a hydrogen atom or a substituent, and n ¹ represents an integer of ¹ , 2 or 3. V represents an aryl group, and W represents an alkyl group. Q ₁ and Q ₃ represent an electron-withdrawing group, R ⁴ and R ⁸ represent a hydrogen atom, an alkyl group or an aryl group, and IN ₃ and
IN ₇ represents a development inhibitor portion. ]