JPH09197603A - Silver halide photographic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a highly sensitive silver halide photographic material with less fogging. SOLUTION: A silver halide photographic material is composed of a substrate and at least one silver halide emulsion layer formed on the substrate and exhibited by the following formula: R1 -Ch-M-NR R2 R3 where R1 , R2 , R3 are a fat group hydrocarbon radial, an aromatic group hydrocarbon radical, an acyl radical, an oxycarbonyl radical, a carbamoyl, a sulfonyl radical, sulfomoyl radical or a sulfinyl radical, R2 and R3 being sometime a hydrogen atom, Ch is Se or Te, and M is a methylane chain. When selenium-sensitization is made with the use of the above-mentioned compound, it exhibits a high sensitivity equal to or higher than that of a conventional compound, and a remarkably low fogging.

Description

Detailed Description of the Invention

[0001]

[0001] The present invention relates to a silver halide photographic material. In particular, the present invention relates to a silver halide photographic material using a silver halide emulsion having improved fog, sensitivity, gradation and the like.

[0002]

2. Description of the Related Art A silver halide emulsion used in a silver halide photographic light-sensitive material is usually subjected to chemical sensitization using various chemical substances in order to obtain a desired sensitivity, gradation and the like. Typical methods include sulfur sensitization, selenium sensitization, tellurium sensitization,
Various sensitization methods are known, such as sensitization of noble metals such as gold, reduction sensitization, and combinations thereof. In recent years, there has been a strong demand for high sensitivity, excellent graininess and high sharpness in silver halide photographic light-sensitive materials, as well as rapid processing with a rapid development progress, and various improvements of the above sensitization method have been made. .

Among them, selenium sensitization and tellurium sensitization may show a larger sensitizing effect than sulfur sensitization which is carried out in the art, but fogging is large, and a soft tone is easily generated, which causes a problem in storage. There is a tendency that there is a large change in sensitivity.
Many of the patents disclosed so far improve these drawbacks, but the results are still unsatisfactory, and in particular, a basic improvement to further suppress fogging has been eagerly desired. . In addition, especially sulfur sensitization, selenium sensitization,
When gold sensitization is used in combination with tellurium sensitization, a marked increase in sensitivity is obtained, but at the same time, fog also increases. Compared with gold-sulfur sensitization, gold-selenium sensitization and gold-tellurium sensitization have a particularly large increase in fog and tend to soften, so a hard selenium sensitizer with less fog and tellurium sensitization. The development of agents has been strongly desired.

On the other hand, it is known that certain selenium compounds and tellurium compounds exhibit antifogging effect, stabilizing effect, and properties as a silver halide solvent. Such compounds are often not useful as selenium sensitizers and tellurium sensitizers. The selenium sensitizer and tellurium sensitizer exhibit a sensitizing action by reacting with silver halide in the emulsion to form silver selenide and silver telluride. On the other hand, a selenium compound and a tellurium compound exhibiting an antifogging effect, a stabilizing effect, and a property as a silver halide solvent are often compounds having a stable carbon-selenium (or tellurium) bond. It is believed that silver telluride cannot be formed and cannot function as a sensitizer. As such selenium compounds and tellurium compounds having antifoggant and stabilizing effects and properties as a silver halide solvent, selenides are disclosed in JP-A-2-132434 and telluride are disclosed in JP-A-2-118566. Classes are disclosed. The compounds specifically disclosed in these publications do not exhibit properties as chemical sensitizers when added alone at the time of post-ripening. Therefore, these are not selenium sensitizers or tellurium sensitizers. In addition, Japanese Patent Laid-Open No. 6-1
Japanese Patent No. 75258 discloses a chain telluride compound. Although the telluride showed the effect of tellurium sensitization, its effect was insufficient.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a high-sensitivity silver halide photographic light-sensitive material with less fog and excellent gradation.

[0006]

SUMMARY OF THE INVENTION The above objects of the present invention are as follows.
The means (1) to (3) summarized below makes it possible to fully utilize the sensitizing effect of selenium sensitization and tellurium sensitization, which has been difficult with conventional techniques. (1) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers contains at least one compound represented by the following general formula (I). A silver halide photographic light-sensitive material, characterized by containing the general formula (I) R ₁ -Ch-M-NR ₂ R ₃ (wherein R ₁ , R ₂ , and R ₃ are aliphatic hydrocarbon groups, aromatic Group represents a hydrocarbon group, a heterocyclic group, an acyl group, an oxycarbonyl group, a carbamoyl group, a sulfonyl group, a sulfamoyl group, a sulfinyl group, and R ₂ and R ₃ may represent a hydrogen atom (either one of which is hydrogen. is preferably atoms), R ₂ and R ₃ may form a nitrogen-containing heterocyclic ring bonded to, Ch represents Se, a Te, M represents a methylene chain). (2) A silver halide photographic light-sensitive material comprising a silver halide emulsion chemically sensitized with at least one compound represented by the general formula (I).

(3) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers is at least one represented by the following general formula (II). A silver halide photographic light-sensitive material as described in (1), which contains a compound of formula (II) R ₁ -Ch-M-NR ₂ R ₃ (wherein R ₁ is an acyl group or oxy group). Represents a carbonyl group, a carbamoyl group, a sulfonyl group, a sulfamoyl group, R
₂ and R ₃ are a hydrogen atom (not simultaneously a hydrogen atom), an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, an acyl group, an oxycarbonyl group, a carbamoyl group,
Represents a sulfonyl group, a sulfamoyl group or a sulfinyl group, R ₂ and R ₃ may combine with each other to form a nitrogen-containing heterocycle, Ch represents Se and Te, and M represents a methylene chain).

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The general formula (I) will be described in detail below. In the general formula (I), R ₁ , R ₂ and R ₃
The aliphatic group represented by is preferably an aliphatic group having 1 to 30 carbon atoms, and particularly a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group or aralkyl group having 1 to 20 carbon atoms. Here, the branched ones may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Examples of the alkyl group, alkenyl group, alkynyl group and aralkyl group include methyl group, ethyl group, isopropyl group, t-butyl group, n
-Octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, allyl group, 2-butenyl group, 3-pentenyl group, propargyl group, 3-pentynyl group, benzyl group, etc. .

In the general formula (I), R ₁ , R ₂ and R
_The aromatic group represented by ₃ is preferably an aromatic group having 5 to 30 carbon atoms, particularly a monocyclic or condensed aryl group having 6 to 20 carbon atoms, such as a phenyl group or a naphthyl group. . In the general formula (I), the heterocyclic group represented by R ₁ , R ₂ and R ₃ is a saturated or unsaturated heterocyclic 3- to 10-membered ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. It is a cyclic group. These may be monocyclic or may form a condensed ring with another aromatic ring. The heterocyclic group is preferably a 5- or 6-membered aromatic heterocyclic group, pyridyl group, imidazolyl group, quinolyl group, benzimidazolyl group, pyrimidyl group, pyrazolyl group, isoquinolinyl group, thiazolyl group, thienyl group, Examples thereof include furyl group and benzothiazolyl group.

In the general formula (I), R ₁ , R ₂ and R
_{As the} acyl group represented by ₃ , for example, formyl group, acetyl group, propionyl group, isobutyryl group, valeryl group, pivaloyl group, octanoyl group, acryloyl group,
Pyruvoyl group, benzoyl group, 1-naphthoyl group, m-
Examples thereof include a toluoyl group, an anisoyl group and a cinnamoyl group. Examples of the carbamoyl group include an unsubstituted carbamoyl group, an N-methylcarbamoyl group, an N-ethylcarbamoyl group, an N, N-dimethylcarbamoyl group and an N, N-
Examples thereof include a diethylcarbamoyl group and an N-phenylcarbamoyl group. Examples of the sulfamoyl group include an unsubstituted sulfamoyl group, an N-methylsulfamoyl group, and an N-methylsulfamoyl group.
-Ethylsulfamoyl group, N, N-dimethylsulfamoyl group, N, N-diethylsulfamoyl group, N-phenylsulfamoyl group and the like can be mentioned. Examples of the sulfonyl group include a mesyl group and a tosyl group. , A tauryl group, and the like, and examples of the sulfinyl group include a methylsulfinyl group, a phenylsulfinyl group, and the like.

In the general formula (I), R ₁ , R ₂ and R
Examples of the oxycarbonyl group represented by ₃ include an alkoxycarbonyl group and an aryloxycarbonyl group, and examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a benzyloxycarbonyl group and an isopropoxycarbonyl group. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group and a naphthyloxycarbonyl group. In the general formula (I), R ₂ and R
_It may represent ₃ hydrogen atoms, and one of them is preferably a hydrogen atom.

In the general formula (I), the methylene chain represented by M and each group represented by R ₁ , R ₂ and R ₃ may be substituted. Examples of the substituent include the following. Halogen atom (for example, fluorine atom, chlorine atom,
Bromine atom, etc.), alkyl group (for example, methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group,
n-octyl group, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (eg, allyl group, 2-butenyl group, 3-pentenyl group), alkynyl group (eg, propargyl group, 3-pentynyl group, etc.), aralkyl group (eg, , Benzyl group, phenethyl group, etc.), aryl group (eg, phenyl group, naphthyl group, 4-methylphenyl group, etc.), heterocyclic group (eg, pyridyl group, furyl group, imidazolyl group, piperidyl group, morpholino group, etc.) , An alkoxy group (eg, methoxy group, ethoxy group, butoxy group, etc.), an aryloxy group (eg, phenoxy group, 2
-Naphthyloxy group, etc.), amino group (for example, unsubstituted amino group, dimethylamino group, ethylamino group, anilino group, etc.), acylamino group (for example, acetylamino group,
Benzoylamino group, etc.), ureido group (eg, unsubstituted ureido group, N-methylureido group, N-phenylureido group, etc.), urethane group (eg, methoxycarbonylamino group, phenoxycarbonylamino group, etc.), sulfonylamino group (For example, methylsulfonylamino group, phenylsulfonylamino group, etc.), sulfamoyl group (for example, unsubstituted sulfamoyl group, N, N-dimethylsulfamoyl group, N-phenylsulfamoyl group, etc.), carbamoyl group (for example, Unsubstituted carbamoyl group, N, N
-Dimethylcarbamoyl group, N-phenylcarbamoyl group, etc.), sulfonyl group (eg, mesyl group, tosyl group, etc.), sulfinyl group (eg, methylsulfinyl group, phenylsulfinyl group, etc.), alkyloxycarbonyl group (eg, methoxycarbonyl group) Group, ethoxycarbonyl group etc.), aryloxycarbonyl group (eg phenoxycarbonyl group etc.), acyl group (eg
Acetyl group, benzoyl group, formyl group, pivaloyl group etc.), acyloxy group (eg acetoxy group, benzoyloxy group etc.), phosphoric acid amide group (eg N, N-
Diethylphosphoric acid amide group etc.), alkylthio group (eg methylthio group, ethylthio group etc.), arylthio group (eg phenylthio group etc.), cyano group, sulfo group,
Carboxy group, hydroxy group, mercapto group, phosphono group, nitro group, sulfino group, ammonio group (eg trimethylammonio group etc.), phosphonio group, hydrazino group, silyl group (eg trimethylsilyl group, triethylsilyl group, t-butyldimethyl group) Silyl group, t-butyldiphenylsilyl group, etc.) and the like. These groups may be further substituted. When there are two or more substituents, they may be the same or different.

Further, in the general formula (I), R ₂ and R
₃ may combine with each other to form a nitrogen-containing heterocycle, and examples of the nitrogen-containing heterocycle include 5- and 6-membered saturated and unsaturated heterocycles. Specific examples thereof include a pyrrole ring and an imidazole ring. Examples thereof include a ring, a triazole ring, an indole ring, a pyrrolidine ring, an imidazoline ring, a pyrazoline ring, a piperidine ring, a piperazine ring and a morpholine ring.

In the general formula (I), it is preferable to use the compound represented by the general formula (II). General formula (II) in _{R 1 -Ch-M-NR 2} R 3 ( wherein, R ₁ represents an acyl group, an oxycarbonyl group, a carbamoyl group, a sulfonyl group, a sulfamoyl radical, R
₂ and R ₃ represent a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, an acyl group, an oxycarbonyl group, a carbamoyl group, a sulfonyl group, a sulfamoyl group and a sulfinyl group, and R ₂ and R ₃ May combine with each other to form a nitrogen-containing heterocycle, Ch represents Se, Te, and M represents a methylene chain).

More preferably in the general formula (II), R
₁ represents an acyl group, an oxycarbonyl group, a carbamoyl group, a sulfonyl group, a sulfamoyl group, R ₂ and R ₃ are an acyl group, an oxycarbonyl group, a carbamoyl group, a sulfonyl group, a sulfamoyl group, and Ch ₃ is Se. There is something. Most preferably, in the general formula (II), R ₁ , R ₂ and R ₃ are an acyl group or a carbamoyl group, and Ch is Se.

Specific examples of the compound of the present invention are shown below.
The compound of the present invention is not limited to this.

[0017]

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[0018]

Embedded image

The compound represented by the general formula (I) is already known, and the following literature, edited by S. Patai, Z. Rappoport, The Chemistry of Organic Selenium and Tellurium Compounds (The Chemistry of Organi).
c Selenium and Tellurium Compounds), Volume 1 (19
1986), Volume 2 (1987) by D. Liotta,
Organoselenium chemistry
emistry), (1987), C. Paulmier, Selenium Reagents and Intermediates
In Organic Synthesis (Selenium Reagents a
nd Intermediates in Organic Synthesis), (1986
Year), and the like.

Heretofore, the compound of the general formula (I) has been converted into selenium.
Specific examples used as sensitizers or tellurium sensitizers are reported
It has not been. Therefore, the sensitizing effect of these compounds
Prediction of fog, fog and other photographic effects
Although difficult, by using the compound of the present invention,
A remarkable effect could be obtained. Used in these inventions
The amount of selenium sensitizer or tellurium sensitizer used is
Len compounds, tellurium compounds, silver halide grains, chemical ripening
Although it varies depending on the formation conditions, etc., it is generally 1 mole equivalent of silver halide.
10^-8-10^-FourMole, preferably 10^-7-10 ^-FiveMole
Use degree. As conditions for chemical sensitization in the present invention
Is not particularly limited, but has a pAg of 6 to 11, preferably
7 to 10, more preferably 7 to 9.5.
The degree is 40 to 95 ° C, preferably 50 to 85 ° C.
You.

In the present invention, it is preferable to use a noble metal sensitizer such as gold, platinum, palladium or iridium together. In particular, it is preferable to also perform gold sensitization agent include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, gold selenide, and the like, per mol of silver halide, 10 ^{- About 7} to 10 ^-2 mol can be used.

In the present invention, it is also preferable to use a sulfur sensitizer together. Specific examples thereof include known unstable sulfur compounds such as thiosulfates (for example, hypo), thioureas (for example, diphenylthiourea, triethylthiourea, allylthiourea), and rhodanines, and silver halides. About 10 ⁻⁷ to 10 ⁻² mol can be used per mol.

In the present invention, it is also possible to use a reduction sensitizer in combination. Specifically, stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives, borane compounds, silane compounds, polyamine compounds, Etc.

Further, in the present invention, it is preferable to carry out the selenium sensitizer in the presence of a silver halide solvent. Specifically, thiocyanates (for example, potassium thiocyanate) and thioether compounds (for example, US Pat. No. 3,
No. 021,215, No. 3,271,157, each specification,
JP-B-58-30571, JP-A-60-136736
Compounds described in each publication, especially 3,6-dithia-
1,8-octanediol, etc.), tetra-substituted thiourea compounds (for example, compounds described in JP-B-59-11892, US Pat. No. 4,221,863, etc., especially,
Tetramethylthiourea, etc.) and Japanese Patent Publication No. 60-113
41, Japanese Patent Publication No. 63-297.
The mercapto compounds described in JP-A No. 27, JP-A-60-1
Examples include the mesoionic compound described in Japanese Patent No. 63042, the selenoether compound described in US Pat. No. 4,782,013, the telluroether compound described in Japanese Patent Application No. 63-173474, and a sulfite. Especially,
Among these, thiocyanates, thioether compounds,
Tetrasubstituted thiourea compounds and thione compounds can be preferably used. The amount used is about 10 ^-5 to 10 ^-2 mol per mol of silver halide.

The silver halide emulsion used in the present invention is:
Silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride are preferred. The silver halide grains used in the present invention are those having a regular crystal form such as a cube and an octahedron, and irregular such as a sphere and a plate.
Or a complex form of these crystal forms. Although a mixture of particles of various crystal forms can be used, it is preferable to use a regular crystal form. The silver halide grains used in the present invention may have different phases in the inside and the surface layer, or may have a uniform phase. Also, grains whose latent image is mainly formed on the surface (eg, a negative emulsion) may be formed, and grains whose main image is mainly formed inside the grains (eg, an internal latent image type emulsion, a directly fogged emulsion which has been previously fogged) It may be.
Preferably, the particles are such that the latent image is mainly formed on the surface. The silver halide emulsion used in the present invention has a thickness of 0.5 micron or less, preferably 0.3 micron or less, a diameter of preferably 0.6 micron or more, and an average aspect ratio of 5 or more. An average grain emulsion that occupies 50% or more of the total projected area, or a statistical coefficient of variation (in the distribution represented by the diameter when the projected area is approximated to a circle, the value obtained by dividing the standard deviation S by the diameter d S / A monodisperse emulsion having d) of 20% or less is preferable. Further, two or more kinds of average grain emulsion and monodisperse emulsion may be mixed.

The photographic emulsion used in the present invention is described by P. Glafkides, Shimmy et Physik.
Chimie et Physique Photographiq
ue) (published by Paul Montel, 1967) by GF Duffin, Photographic Emulsion Che
mistry) (Focal Press, 1966), buoy
Making by VL Zelikman et al.
It can be prepared by the method described in Making and Coating Photographic Emulsion (Focal Press, 1964) and the like.

In order to control the grain growth during the formation of the silver halide grains, a silver halide solvent such as ammonia, rodancali, rhodammone, or a thioether compound (eg, US Pat. No. 3,27,27) is used.
No. 1,157, No. 3,574,628, No. 3,7
Nos. 04,130, 4,297,439 and 4,
276, 374, etc.), thione compounds (for example, JP-A Nos. 53-144319 and 53-82408,
55-77737, etc.), amine compounds (for example, JP-A-54-100717, etc.) and the like can be used. In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt thereof may be present together.

Gelatin is advantageously used as the binder or protective colloid that can be used in the emulsion layer and intermediate layer of the light-sensitive material of the present invention, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other macromolecules, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates, sodium alginate;
Sugar derivatives such as starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole, etc. Synthetic hydrophilic polymeric substances can be used. As the gelatin, in addition to general-purpose lime-processed gelatin, acid-processed gelatin and the Japan Society for Photographic Science (Bull. Soc. Phot. Japan) No. 1
Enzyme-treated gelatin as described in pages 6, 30 (1966) may be used, or a hydrolyzate of gelatin may be used.

In the light-sensitive material of the present invention, an inorganic or organic hardener may be contained in any hydrophilic colloid layer constituting the photographic light-sensitive layer or the back layer. Specific examples include chromium salts, aldehyde salts (formaldehyde, glyoxal, glutaraldehyde, etc.) and N-methylol compounds (dimethylol urea, etc.). Active halogen compounds (2,4-dichloro-6-hydroxy-1,3,5-triazine and its sodium salt) and active vinyl compounds (1,3, -bisvinylsulfonyl-2-propanol, 1,2-bis) (Vinylsulfonylacetamide) ethane, bis (vinylsulfonylmethyl) ether or vinyl polymer having a bitylsulfonyl group in its side chain) is preferred because it rapidly cures hydrophilic colloid such as gelatin and gives stable photographic characteristics. N
-Carbamoylpyridinium salts ((1-morpholinocarbonyl-3-pyridinio) methanesulfonate, etc.) and haloamidinium salts (1- (1-chloro-1-pyridinomethylene) pyrrolidinium-2-naphthalenesulfonate, etc.) also have a curing rate. Good early.

The silver halide photographic emulsion used in the present invention may be spectrally sensitized with a methine dye or the like. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, the pyrroline nucleus is an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, or the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and A nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, that is, an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, and a benz nucleus. Imidazole nucleus, quinoline nucleus and the like can be applied. These nuclei may have a substituent on a carbon atom. In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, a thione nucleus A 5- or 6-membered heterocyclic nucleus such as a barbituric acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and a combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. For example, a nitrogen-containing heterocyclic ring-nucleus group-substituted aminostilbenzene compound (for example, those described in US Pat. Nos. 2,933,390 and 3,635,721), aromatic organic Acid formaldehyde condensate (eg US Pat. No. 3,
No. 743,510), a cadmium salt, an azaindene compound, and the like. The combinations described in U.S. Pat. Nos. 3,615,613, 3,615,641, 3,617,295 and 3,635,721 are particularly useful.

The silver halide photographic emulsion used in the present technology contains various compounds for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. Can be made. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles,
Mercaptothiazoles, mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines Mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes such as triazaindenes;
Tetratriazaindenes (particularly 4-hydroxy-substituted (1,3,3a, 7) tetratriazaindenes), pentaazaindenes, etc .; such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. Many compounds known as antifoggants or stabilizers can be added.

The light-sensitive material of the present invention comprises a coating aid, an antistatic agent,
One or more surfactants may be contained for various purposes such as improving slipperiness, emulsifying and dispersing, preventing adhesion, and improving photographic characteristics (for example, development acceleration, hardening, and sensitization).

The light-sensitive material prepared according to the present invention may contain a water-soluble dye in a hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation or halation. As such dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes, azo dyes are preferably used, and in addition, cyanine dyes, azomethine dyes, triarylmethane dyes, phthalocyanine dyes, etc. are also useful. is there. The oil-soluble dye may be emulsified by an oil-in-water dispersion method and added to the hydrophilic colloid layer.

The present invention is applicable to multilayer multicolor photographic materials having at least two different spectral sensitivities on a support. Multilayer natural color color photographic materials usually have at least one red-sensitive emulsion layer, at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer on a support. The arrangement order of these layers can be arbitrarily selected as needed. The preferred layer arrangement is from the support side in the order of red-sensitive, green-sensitive and blue-sensitive, blue-sensitive layer, green-sensitive and red-sensitive layers or blue-sensitive, red-sensitive and green-sensitive. Any emulsion layer having the same color sensitivity may be composed of two or more emulsion layers having different sensitivities to improve the reaching sensitivity, or may be composed of three layers to further improve the graininess. 2 with the same color sensitivity
A non-light-sensitive layer may be present between one or more emulsion layers. An emulsion layer having a different color sensitivity may be inserted between emulsion layers having the same color sensitivity. A sensitivity layer may be improved by providing a reflective layer of fine grain silver halide under the high sensitivity layer, particularly the high sensitivity blue sensitive layer. Generally, the cyan-sensitive coupler is contained in the red-sensitive emulsion layer, the magenta-forming coupler is contained in the green-sensitive emulsion layer, and the yellow-forming coupler is contained in the blue-sensitive emulsion layer. For example, a combination of infrared-sensitive layers may be used for pseudo-color photography or semiconductor laser exposure.

Various color couplers can be used in the photographic material of the present invention, and specific examples thereof include Research Disclosure (RD) No. 17643, VII
-C to G are described in the patent specifications. Yellow couplers include, for example, US Pat.
No. 3,501, No. 4,022,620, No. 4,3
Nos. 26,024 and 4,401,752, each specification,
Japanese Patent Publication No. 58-10739, British Patent No. 1,42
Those described in each specification of No. 5,020 and No. 1,476,760 are preferable.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferable. For example, US Pat. Nos. 4,310,619 and 4,351,8
No. 97, EP 73,636, U.S. Pat.
61,432 and 3,725,067, each specification,
Research Disclosure No. 24220 (19
June 1984), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, U.S. Pat. Nos. 4,500,630, and 4,540,654 are preferred. Examples of cyan couplers include phenol-type and naphthol-type couplers, and examples thereof include US Pat.
146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162,
Nos. 2,895,826 and 3,772,002
No. 3,758,308, No. 4,334,01
No. 1, No. 4,327,173, West German Patent Publication No. 3,
329,729, European Patent 121,365A, US Patents 3,446,622 and 4,333,99.
No. 9, No. 4,451, 559, No. 4,427, 7
No. 67 and EP No. 161,626A are preferable.

Colored couplers for correcting unwanted absorption of color forming dyes are described, for example, in Research Disclosure No. 17643, Section VII-G, U.S. Pat. No. 4,16
3,670, Japanese Patent Publication No. 57-39413,
U.S. Pat. Nos. 4,004,929 and 4,138,2
No. 58 and British Patent No. 1,146,368 are preferable. Examples of the coupler in which the color forming dye has an appropriate diffusibility include, for example, U.S. Pat. No. 4,366,23.
7, British Patent 2,125,570, European Patent 9
No. 6,570, West German Patent (Publication) No. 3,234,533
Those described in each specification are preferable. Typical examples of polymerized dye-forming couplers are described in US Pat. No. 3,451,
No. 820, No. 4,080, 211, No. 4,36
7, 282 and British Patent 2,102,173.

Couplers which release a photographically useful residue upon coupling can also be preferably used in the present invention. The DIR coupler releasing the development inhibitor is the same as described above for R
D17643, Patents described in VII to F, JP-A-5
Nos. 7-151944, 57-154234, 60
-184248, U.S. Pat. No. 4,248,96
Those described in No. 2 are preferred. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include, for example, British Patents 2,097,140 and 2,131,188, JP-A-59-1576.
No. 38 and No. 59-170840 are preferable. Other couplers that can be used in the light-sensitive material of the present invention include, for example, US Pat.
Competitive couplers as described in US Pat. No. 4,427, US Pat.
No. 283,472, No. 4,338,393, No. 4,310,618, and other multiequivalent couplers described in JP-A-60-185950 and JP-A-62-242.
No. 52, etc., DIR redox compound or DIR coupler releasing coupler, European Patent No. 173,3
No. 02A, a coupler which releases a dye that recolors after release, R.I. D. No. 11449, 24241,
Examples thereof include bleaching accelerator releasing couplers described in JP-A No. 61-201247 and ligand releasing couplers described in U.S. Pat. No. 4,553,477.

The coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods. Examples of high boiling solvents used in the oil-in-water dispersion method are described in US Pat.
No. 027 specification and the like. Specific examples of the high-boiling point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-
2-ethylhexyl phthalate, decyl phthalate, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate, Esters of phosphoric acid or phosphonic acid (for example, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, J-2
-Ethylhexyl phenyl phosphate), benzoic acid esters (for example, 2-ethylhexyl benzoate,
Dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (eg, N, N-diethyldodecane amide, N, N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or ferils (eg, iso- Stearyl alcohol, 2,
4-di-tert-amylphenol), aliphatic carboxylic acid esters [eg, bis (2-ethylhexyl)
Sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate], aniline derivatives, (for example N, N-dibutyl-2-butoxy-5-tert-octylaniline), hydrocarbons (for example, Paraffin, dodecylbenzene, diisopropylnaphthalene) and the like. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used. Typical examples are ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2- Examples include ethoxyethyl acetate and dimethylformamide.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,36.
No. 3, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are a flexible support or glass such as a plastic film, paper, cloth or the like usually used for photographic light-sensitive materials,
It is applied to a rigid support such as pottery or metal. Useful as the flexible support is a film made of a semi-synthetic or synthetic polymer such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, a baryter layer or an α-olefin polymer. Examples thereof include paper coated with or laminated with (eg, polyethylene, polypropylene, ethylene / butene copolymer). The support may be colored using a dye or a pigment. It may be black for the purpose of shading. The surface of these supports is generally subjected to a subbing treatment in order to improve adhesion with a photographic emulsion layer or the like. The surface of the support may be subjected to glow discharge, corona discharge, ultraviolet irradiation, flame treatment or the like before or after the undercoat treatment.

For coating the photographic emulsion layer and other hydrophilic colloid layers, various known coating methods such as dip coating method, roller coating method, curtain coating method and extrusion coating method can be used. US Patent Nos. 2,6 as required
81,294, 2,761,791, 3,
Multiple layers may be simultaneously coated by the coating method described in each of the specifications of Nos. 526,528 and 3,508,947.

The present invention can be applied to various color and black and white light-sensitive materials. Color negative film for general or movie, color reversal film for slide or TV, color paper, color positive film,
Representative examples include color reversal paper, color diffusion transfer type photosensitive materials, and heat development type color photosensitive materials. Research Disclosure, No. 17
123 (July 1978) and the like, or by utilizing a three-color coupler mixture, or in U.S. Pat. No. 4,126,4.
The present invention can also be applied to a black-and-white light-sensitive material for X-rays or the like by utilizing the black color-forming coupler described in JP-A No. 61 and British Patent No. 2,102,136. Film for plate making such as squirrel film or scanner film,
The present invention can also be applied to direct / indirect medical or industrial X-ray films, negative black and white films for photography, black and white photographic paper, COM or ordinary microfilm, silver salt diffusion transfer type photosensitive materials and printout type photosensitive materials. .

When the photographic element of the present invention is applied to a color diffusion transfer photographic method, a peel (apartment) type or Japanese Patent Publication Nos. 46-16356 and 48-33697,
Japanese Patent Laid-Open No. 50-13040 and British Patent Nos. 1 and 3
An integrated type film unit as described in Japanese Patent No. 30,524 and a peel-free type film unit as described in JP-A-57-119345 can be used. The use of a polymeric acid layer protected by a neutralization timing layer in any of the above formats is advantageous for widening the processing temperature latitude. When used in color diffusion transfer photography, it may be used by adding it to any layer in the light-sensitive material, or may be used by being sealed in a processing solution container as a developing solution component.

Various exposing means can be used for the light-sensitive material of the present invention. Any light source that emits a broad ray corresponding to the sensitivity wavelength of the light-sensitive material can be used as an illumination light source or a writing light source. Flash light sources such as natural light (sunlight), incandescent lamps, halogen atom sealed lamps, mercury lamps, fluorescent lamps and strobes or metal burning flash bulbs are common. Gas, dye solution or semiconductor lasers, light emitting diodes, and plasma light sources that emit light in a wavelength range from ultraviolet to infrared can also be used as the recording light source. In addition, a micro-shutter array using a phosphor screen (ORT or the like) emitted from a phosphor excited by an electron beam or the like, a liquid crystal (LCD) or lanthanum-doped titanium-zirconium-zinc (PLZT) or the like is linear or planar. Exposure means combined with light sources can also be used. If necessary, the spectral distribution used for exposure can be adjusted with a color filter.

The color developing solution used in the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Aminophenol compounds are also useful as the color developing agent, but p-phenylenediamine compounds are preferably used. Typical examples thereof include 3-methyl-4-amino-N,
N-diethylaniline, 3-methyl-4-amino-N-
Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-
Examples thereof include ethyl-N-β-methoxyethylaniline and sulfates, hydrochlorides or p-toluenesulfonates thereof. These diamines are generally more stable in a salt than in a free state, and are preferably used.

The color developer contains a pH buffer such as an alkali metal carbonate, borate or phosphate, bromide,
It is common to contain a development inhibitor such as iodide, benzimidazoles, benzothiazoles or mercapto compounds, or an antifoggant. Also, if necessary,
Preservatives such as hydroxylamine or sulfite, triethanolamine, organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol,
Quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competing couplers, nucleating agents such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, amino Polycarboxylic acid, aminopolysulfonic acid, alkylphosphonic acid,
Various chelating agents represented by phosphonocarboxylic acids, antioxidants described in West German Patent Application (OLS) No. 2,622,950, and the like may be added to the color developing solution.

In the development processing of the reversal color light-sensitive material, black and white development is usually carried out and then color development is carried out. This black-and-white developer includes dihydroxybenzenes such as hydroquinone,
Known black-and-white developing agents such as 3-pyrazolidones such as phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination. The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process, or may be performed individually. In order to further speed up the processing, a processing method of performing a bleach-fixing process after the bleaching process may be used. Bleaching agents such as iron (III), cobalt (III),
Compounds of polyvalent metals such as chromium (IV), copper (II), peracids,
Quinones, nitrones and the like are used. Typical bleaching agents are ferricyanide; dichromate; organic complex salts of iron (III) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid. Aminopolycarboxylic acids such as or citric acid, tartaric acid,
Complex salts of organic acids such as malic acid; persulfates; manganates;
Nitrosophenol or the like can be used. Of these, ethylenediaminetetraacetic acid iron (III) salt, diethylenetriaminepentaacetic acid iron (III) salt and persulfate are preferable from the viewpoint of rapid treatment and environmental pollution. Further, the iron (III) complex salt of ethylenediaminetetraacetate is particularly useful in an independent bleaching solution or a single-bath bleach-fixing solution.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleach accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988. JP-A-53-32736 and JP-A-53-57831.
No. 53, No. 53-37418, No. 53-65732, No. 53-72623, No. 53-95630, No. 53-.
95631, 53-104232, 53-12
No. 4424, No. 53-141623, No. 53-284.
26, Research Disclosure No. 1
7129 (July 1978), etc., a compound having a mercapto group or a disulfide group; JP-A-50-14.
Thiazolidine derivatives as described in JP-A No. 0129; JP-B-45-8506, JP-A-52-20832
No. 53-32735, U.S. Pat. No. 3,70.
Thiourea derivatives described in 6,561; West German Patent 1,127,715, JP-A-58-1623.
Iodide described in Japanese Patent No. 5; West German Patent No. 966,410
Nos. 2,748,430 and polyethylene oxides; polyamine compounds described in JP-B-45-8836; other JP-A-49-42434.
No. 49-59644, No. 53-94927, No. 54-35727, No. 55-26506 and No. 58.
The compounds described in JP-A-163940, iodine, and bromide ions can also be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large accelerating effect, and in particular, U.S. Pat. No. 3,893,858, West German Patent No. 1,290,812, JP-A-53-9563.
The compounds described in JP-A No. 0 are preferred. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. When bleach-fixing a color photographic material for photography, these bleaching accelerators are particularly effective. Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds thioureas, and a large amount of iodides, and the use of thiosulfates is common. As a bleach-fixing solution or a preservative for the fixing solution, sulfite, bisulfite or carbonyl bisulfite adduct is preferable.

After the bleach-fixing treatment or the fixing treatment, washing treatment and stabilizing treatment are usually carried out. In the washing step and the stabilizing step, various known compounds may be added for the purpose of preventing precipitation and saving water. For example, in order to prevent precipitation, water hardeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic aminopolyphosphonic acid, and organic phosphoric acid, fungicides for preventing the generation of various bacteria, algae and fungi, and antibacterial agents are used. Agents, metal salts such as magnesium salts, aluminum salts, and bismuth salts, surfactants for preventing drying load and unevenness, and various hardeners can be added as necessary. Or West Photographic Science and Engineering magazine (L.
E. West, Phot. Sci. Eng.), Volume 6, 344-359
The compounds described on page (1965) and the like may be added. In particular, the addition of a chelating agent or an anti-binder is effective.

Countercurrent washing of two or more tanks in the water washing step,
It is common to save water. Further, instead of the water washing step, a multistage countercurrent stabilization treatment step as described in JP-A-57-8543 may be carried out. 2 in case of this process
-9 baths of countercurrent bath are required. Various compounds other than the above-mentioned additives are added to the stabilizing bath for the purpose of stabilizing an image. For example, adjust membrane pH (eg pH 3-9)
Buffers for various purposes (for example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc. Representative examples thereof include aldehydes (used in combination) and formalin. In addition, if necessary, a chelating agent (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericidal agent (benzisothiazolinone, irithiazolone, 4- Thiazoline benzimidar, halogenated phenol, sulfanilamide, benzotriazole, etc.), surfactants, optical brighteners, hardeners, and various other additives may be used, and the same or different target compounds may be used. You may use together more than one kind.

Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as a film pH adjuster after the treatment. Further, in the color photographic material for photographing, the (washing-stabilizing) step after fixing which is usually carried out can be replaced with the above-mentioned stabilizing step and washing step (water saving processing). At this time, when the amount of the magenta coupler is 2 equivalents, formalin in the stabilizing bath may be removed. The washing and stabilizing treatment times of the present invention differ depending on the type of the photosensitive material and the treatment conditions, but are usually 2
It is 0 seconds to 10 minutes, preferably 20 seconds to 5 minutes.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, indaniline compounds described in U.S. Pat. No. 3,342,597, Schiff base type compounds described in No. 3,342,599, Research Disclosure 14850 and No. 15159, and No. 13924 described. Aldol compounds of US Pat. No. 3,719,492, metal salt complexes described in U.S. Pat. No. 3,719,492, and urethane compounds described in JP-A-53-135628, and JP-A-56-623.
No. 5, No. 56-16133, No. 56-59232,
56-67842, 56-83734, 56
No. 83735, No. 56-83736, No. 56-89.
735, 56-81837, 56-54430.
No. 56-106241 and No. 56-107236.
No. 57-97531 and No. 57-83565, various salt-type precursors can be mentioned. The silver halide color light-sensitive material of the present invention comprises
If necessary, various types of 1
-Phenyl-3-pyrazolidones may be incorporated. Typical compounds are disclosed in JP-A-56-64339 and JP-A-57-64339.
144547, 57-211147, 58-5.
No. 0532, No. 58-50536, No. 58-5053
3, No. 58-50534, No. 58-50535, and No. 58-11543.

Various processing solutions used in the present invention are 10 ° C. to 50 ° C.
Used at ° C. A temperature of 33 ° C. to 38 ° C. is standard, but it is possible to increase the temperature to accelerate the processing to shorten the processing time, and to lower the temperature to improve the image quality and the stability of the processing liquid. it can. Further, in order to save silver in the light-sensitive material, the processing using cobalt intensification or hydrogen peroxide intensification described in each of West German Patent No. 2,226,770 and US Pat. No. 3,674,499 is performed. Good. If necessary, a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating pig, a squeegee, etc. may be provided in each processing bath. In the case of continuous processing, a certain finish can be obtained by using a replenisher for each processing liquid to prevent fluctuations in the liquid composition. The replenishment amount can be reduced to half or less than the standard replenishment amount for cost reduction and the like. When the light-sensitive material of the present invention is a color paper, it can be subjected to a bleach-fixing process, if necessary, even if it is a color photographic material for photography.

[0056]

EXAMPLES Example 1 0.05 g of potassium bromide and gelatin 30 kept at 75 ° C.
g, and 75 ml of an aqueous solution of silver nitrate (1M) and 75 ml of an aqueous potassium bromide solution (1M) were simultaneously stirred while stirring in 1 liter of an aqueous solution kept at pH 2 with nitric acid, while maintaining the silver potential at 0 mV against a saturated calomel electrode. Added in 4 minutes. Thereafter, 675 ml of an aqueous solution of silver nitrate (1M) and an aqueous solution of potassium bromide (1M) were further added, and the silver potential was -30 mV.
Was added for 36 minutes. After the formation of particles, desalting and washing with water were carried out by a usual flocculation method, and gelatin and water were added to adjust pH to 6.2 and pAg to 8.4. The obtained silver bromide emulsion has a grain diameter of 0.25 μm.
m is a monodisperse octahedron emulsion having a variation coefficient of grain diameter of 11%. The emulsion was subdivided and then heated to 60 ° C.
A sensitizer was added as shown in (4) and the mixture was aged for 60 minutes.

Then, a magenta coupler; 3- {3-
[2- (2,4-di-tert-amylphenoxy) butyrylamino] benzoylamino} -1- (2,4,6
-Trichlorophenyl) pyrazolone-5-one, tricresyl phosphate, 4-hydroxy-6-methyl-
Addition of 1,3,3a, 7-tetrazaindene, sodium poly-styrenesulfonate, sodium dodecylbenzenesulfonate, 1,2-bis (vinylsulfonylacetylamino) ethane to protect gelatin containing polymethyl methacrylate particles Along with the layers, they were coated on a triacetyl cellulose film support by a coextrusion method. These samples were exposed under an optical wedge (10 seconds) and subjected to the following color development processing. The density of the treated sample was measured with a green filter. The obtained photographic performance is shown in Table 1. The relative sensitivity was represented by the relative value of the reciprocal of the exposure amount required to obtain an optical density of fog value + 0.2, and Sample 3 was set to 100.

[0058]

[Table 1]

As is clear from Table 1, the sensitivity was equal to or higher than that of the well-known selenium sensitizer (comparative compound C), and the fog was extremely low. Further, the compounds having a structure somewhat similar to the compound of the present invention (Comparative Compounds A and B) had higher fog and were extremely inferior in sensitivity to those of the present invention.

[0060]

Next, the composition of the treatment liquid will be described. (Color developer) (Unit g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1. 5 mg hydroxylamine sulfate 2.4 4- (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 4.5 water was added to 1.0 liter pH 10.05

(Bleaching Solution) (Unit: g) Ethylenediaminetetraacetic acid sodium ferric trihydrate 100.0 Ethylenediaminetetraacetic acid disodium salt 10.0 3-Mercapto-1,2,4-triazole 0.08 Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonia water (27%) 6.5 ml Water was added to 1.0 liter pH 6.0

(Fixing Solution) (Unit: g) Ethylenediaminetetraacetic acid disodium salt 0.5 Ammonium sulfite 20.0 Ammonium thiosulfate aqueous solution (700 g / liter) 290.0 ml Water was added to 1.0 liter pH 6.7

(Stabilizing Solution) (Unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization: 10) 0.2 Ethylenediaminetetraacetic acid disodium salt 0.05 1, 2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5

Example 2 In accordance with Example 6 described in JP-A-2-838,
Average particle diameter 1.05 μm, particle thickness 0.19 μm
m, aspect ratio 5.8, variation coefficient of particle diameter 1
A 0.5% monodisperse silver bromide emulsion was prepared. After particle formation,
The mixture was cooled to 35 ° C, desalted by a conventional flocculation method, washed with water, and gelatin and water were added to adjust the pH to 6.2 and p.
Ag was adjusted to 8.3. After subdividing this emulsion,
The sensitizer shown in Table 2 was added, and chloroauric acid (2.4 x 1
0 ^-5 mol / mol Ag) and potassium thiocyanate (4 × 1
0 ⁻⁴ mol / mol Ag) was added, and the mixture was aged at 55 ° C. for 60 minutes.

After this, the sensitizing dye anhydro-5,5'-
Dichloro-9-ethyl-3,3'-di (3-sulfopropyl) oxacarbocyanine hydroxide sodium salt and potassium iodide were added, followed by gelatin and 4-hydroxy-6-methyl-1,3. 3a, 7-
Add tetrazaindene, sodium poly-styrenesulfonate, sodium dodecylbenzenesulfonate,
On a triacetyl cellulose film support having an undercoat layer, gelatin, polymethylmethacrylate particles,
It was applied by coextrusion with a protective layer containing 2,4-dichloro-6-hydroxy-s-triazine sodium salt.

These samples were exposed to sensitometry (1/100 sec) through an optical wedge and a yellow filter and then developed with a MAA-1 developer having the following formulation at 20 ° C. for 10 minutes. The concentration was measured by stopping, fixing, washing with water and drying by the method. Relative sensitivity is fog value +0.2
The value of Sample 20 was set to 100, which is represented by the relative value of the reciprocal of the exposure amount required to obtain the optical density of.

[0068]

[Table 2]

(MAA-1 Developer) Methol 2.5 g Ascorbic acid 10 g Nabox 35 g Potassium bromide 1 g Water added to 1 liter As is apparent from Table 2, the compound of the present invention is conventionally well-known. As compared with the known selenium sensitizer (Comparative Compound C), preferable results were obtained, which showed a sensitivity equal to or higher than that of the known selenium sensitizer and markedly low fog.

Example 3 An aqueous solution of silver nitrate and an aqueous solution of potassium bromide were added at the same time while stirring the aqueous gelatin solution containing potassium bromide at 40 ° C. Next, the temperature was raised to 75 ° C., aging was performed by adding ammonia, neutralized with acetic acid, and furthermore, an aqueous solution of silver nitrate, potassium iodide, potassium bromide, and K ₃ IrCl ₆ (3 × 10
^-6 mol / mol Ag) was added at the same time, then an aqueous potassium iodide solution was added, followed by shelling with an aqueous silver nitrate solution and an aqueous potassium bromide solution.

After the completion of the addition, the salt was desalted by an ordinary flocculation method and washed with water, and gelatin and water were added to adjust pH to 6.3 and pAg to 8.6. The resulting tabular silver bromide emulsion had an average grain diameter of 1.32 μm, a grain thickness of 0.21 μm, an average diameter / thickness ratio of 6.3, and a silver iodide content of 6 mol%. . After subdividing this emulsion,
The temperature was raised to 6 ° C, and the sensitizing dye anhydro-5-chloro-5 '
-Phenyl-9-ethyl-3,3'-di (3-sulfopropyl) oxacarbocyanine hydroxide sodium salt was added, and sodium thiosulfate (1.2 x 10 ^-5
Mol / mol Ag) and the sensitizer shown in Table 3, and further added chloroauric acid (1.6 × 10 ⁻⁵ mol / mol Ag) and potassium thiocyanate (1 × 10 ⁻³ mol / mol Ag). And aged for 30 minutes. Thereafter, 1- (3-sulfophenyl) -5-mercaptotetrazole monosodium salt and the same additives as in Example 1 were added and coated in the same manner, and the same treatment was carried out (however, exposure for 1/1000000 seconds). Three
Was obtained.

[0072]

[Table 3]

As is clear from Table 3, the compounds of the present invention were excellent in low fog and showed sensitivity equal to or higher than that of the conventional compounds.

[0074]

When the compound of the present invention is sensitized with selenium, it has higher sensitivity than the conventional sulfur sensitization, and has a sensitivity equal to or higher than that of the conventional selenium sensitization and low fog. It has been found that there is a positive effect.

Claims (3)

[Claims] 1. The method according to claim 1, wherein the at least one layer is halogenated on a support.
In a silver halide photographic material having a silver emulsion layer,
At least one of the silver halide emulsion layers has the following general formula
It must contain at least one compound represented by (I).
A silver halide photographic light-sensitive material characterized by
(I) R₁-Ch-M-NR_TwoR_Three (Where R₁, R_Two, R_ThreeIs an aliphatic hydrocarbon group, aromatic
Hydrocarbon group, heterocyclic group, acyl group, oxycarbonyl
Group, carbamoyl group, sulfonyl group, sulfamoyl
Group, a sulfinyl group, and R_Two, R_ThreeIs a hydrogen atom
And R _TwoAnd R_ThreeBind to each other and contain
May form a heterocyclic ring, Ch represents Se, Te,
M represents a methylene chain). 2. A silver halide photographic light-sensitive material comprising a silver halide emulsion chemically sensitized with at least one compound represented by the general formula (I). 3. A silver halide photographic material having at least one silver halide emulsion layer on a support,
At least one of the silver halide emulsion layers has the following general formula
A silver halide photographic light-sensitive material according to claim 1, which contains at least one compound represented by formula (II), R ₁ -Ch-M-NR ₂ R ₃ (formula Wherein R ₁ represents an acyl group, an oxycarbonyl group, a carbamoyl group, a sulfonyl group or a sulfamoyl group, and R 1
₂ and R ₃ represent a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, an acyl group, an oxycarbonyl group, a carbamoyl group, a sulfonyl group, a sulfamoyl group and a sulfinyl group, and R ₂ and R ₃ May combine with each other to form a nitrogen-containing heterocycle, Ch represents Se, Te, and M represents a methylene chain).