JP2779747B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic 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 using noble metal sensitization such as gold, reduction sensitization, and a combination thereof are known. 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 in which development has been accelerated, and various improvements of the above-described sensitization methods have been made. .

Among the above sensitization methods, selenium sensitization method and tellurium sensitization method are described in US Pat. Nos. 1,574,944, 1,602,592, 1,623,499, and 32.
No. 97446, No. 3297447, No. 33200
No. 69, No. 3408196, No. 3408197
Nos. 3,424,653, 3,420,670, 3,591,385, 3,770,231 and 3,531
No. 289, 3655394, French Patent No. 209
No. 3038, No. 2093209, Japanese Patent Publication No. 52-34
No. 491, No. 52-34492, No. 53-295,
No. 57-22090, JP-A-59-180536,
59-185330, 59-181337, 59-187338, 59-192241, 6
No. 0-150046, No. 60-151637, No. 61
-24638, British Patent 255558, 8
Nos. 61984, 235211 and 1121496
Nos. 1295462 and 1396696; Canadian Patent No. 800958; JP-B-52-36009; 52-38408; JP-A-59-185329; 61-67845; 61-20940; 63-
No. 292126, U.S. Pat.
No. 704349, No. 4810626, and HE Spencer et al., Journal of Photographic Science (Journal of Photographic Science)
Science), Vol. 31, pp. 158-169 (1983)
Year).

[0004]

However, selenium sensitization and tellurium sensitization generally have a larger sensitizing effect than sulfur sensitization usually performed in the art, but cause large fogging and tend to be softened. In many cases, the sensitivity change during storage is large. Many of the above known patents are:
In order to improve these drawbacks, only insufficient results have been obtained, and a fundamental improvement particularly to suppress the occurrence of fogging has been eagerly desired. In particular, when gold sensitization is used in combination with sulfur sensitization, selenium sensitization, and tellurium sensitization, remarkable increases in sensitivity are obtained, but fog also increases.
Compared to gold-sulfur sensitization, gold-selenium sensitization and gold-tellurium sensitization have a particularly large increase in fog and are liable to soften easily. The development of sensitizers has been strongly desired.

An object of the present invention is to provide a high-sensitivity silver halide photographic material having less fog and excellent gradation.

[0006]

The object of the present invention is to provide at least one silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers has the following general formula (I):
A silver halide photographic light-sensitive material characterized by containing at least one compound represented by formulas (II) and (III), which has been difficult to obtain by selenium sensitization and tellurium sensitization by conventional techniques. This makes it possible to take advantage of the sensitizing effect of the present invention. General formula (I)

[0007]

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In the formula, Ch ₁ represents a selenium atom or a tellurium atom. R ₁ represents an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an ether group, a thioether group, a selenoether group, a telluroether group, R ₂ represents a hydrogen atom,
Aliphatic group, aromatic group, heterocyclic group, cation, acyl group,
Represents a carbamoyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group. General formula (II)

[0009]

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In the formula, Ch ₂ represents a selenium atom or a tellurium atom. R ₃ represents an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an ether group, a thioether group, a selenoether group, a telluroether group, R ₄ represents a hydrogen atom,
Aliphatic group, aromatic group, heterocyclic group, cation, acyl group,
Represents a carbamoyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group. General formula (III)

[0011]

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In the formula, Ch ₃ represents a selenium atom or a tellurium atom, and Ch ₄ represents an oxygen atom or a sulfur atom. Also,
R ₅ and R ₆ represents an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an ether group, a thioether group, seleno ether group, a Teruroeteru group, R ₇ is a hydrogen atom, an aliphatic group, an aromatic group , A heterocyclic group, a cation, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group.

Next, the general formula (I) will be described in detail. In the general formula (I), the aliphatic group represented by R ₁ and R ₂ preferably has 1 to 30 carbon atoms, particularly a straight-chain, branched or cyclic alkyl group having 1 to 20 carbon atoms, An alkenyl group, an alkynyl group and an aralkyl group. 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, for example, methyl group, ethyl group, isopropyl group, t-butyl group, n-octyl group,
Examples thereof include 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 and the like.

In the general formula (I), the aromatic groups represented by R ₁ and R ₂ preferably have 5 to 30 carbon atoms, particularly a monocyclic or condensed ring having 6 to 20 carbon atoms. An aryl group such as a phenyl group and a naphthyl group.

In the general formula (I), the heterocyclic group represented by R ₁ and R ₂ is a saturated or unsaturated 3- to 10-membered ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. It is a heterocyclic group. These may be monocyclic or may form a condensed ring with another aromatic ring. The heterocyclic group is preferably a 5- to 6-membered aromatic heterocyclic group, for example, a pyridyl group, an imidazolyl group,
Quinolyl, benzimidazolyl, pyrimidyl, pyrazolyl, isoquinolinyl, thiazolyl, thienyl, furyl, benzothiazolyl, and the like.

In the general formula (I), the amino group represented by R ₁ includes, for example, an unsubstituted amino group, a methylamino group, an ethylamino group, a dimethylamino group, a diethylamino group, an anilino group, an o-toluidino group, 2,4-xylidino group and the like.

In the general formula (I), examples of the ether group represented by R ₁ include a methoxy group, an ethoxy group, an isopropoxy group, a butoxy group, a phenoxy group, a benzyloxy group, a 2-naphthyloxy group and a 2-naphthyloxy group. Examples of the thioether group include a methylthio group, an ethylthio group, and a phenylthio group.Examples of the selenoether group include a methylseleno group, an ethylseleno group, and a phenylseleno group.
Examples of the telluro ether group include a methyl telluro group, an ethyl telluro group, and a phenyl telluro group.

In the general formula (I), examples of the cation represented by R ₂ include alkali metal ions such as lithium ion, sodium ion, potassium ion and cesium ion, and ammonium ions such as ammonium ion and tetramethylammonium ion. And the like. Here, when R ₂ is a cation, Ch ₁ is formally assumed to have a negative charge of −1.

In formula (I), the acyl group represented by R ₂ includes, for example, formyl, acetyl, propionyl, isobutyryl, valeryl, pivaloyl, octanoyl, acryloyl, pyruvoyl,
Benzoyl group, 1-naphthoyl group, m-toluoyl group,
Examples of the carbamoyl group include an unsubstituted carbamoyl group, an N-methylcarbamoyl group, an N-ethylcarbamoyl group, an N, N-dimethylcarbamoyl group, an N, N-diethylcarbamoyl group, and a carbamoyl group.
-Phenylcarbamoyl group and the like, and as the sulfamoyl group, for example, an unsubstituted sulfamoyl group, an N-methylsulfamoyl group, an N-ethylsulfamoyl group,
Examples include N, N-dimethylsulfamoyl group, N, N-diethylsulfamoyl group, N-phenylsulfamoyl group, and examples of the sulfonyl group include mesyl, tosyl, and tauryl groups. Examples of the sulfinyl group include a methylsulfinyl group and a phenylsulfinyl group.

In formula (I), examples of the alkoxycarbonyl group represented by R ₂ include a methoxycarbonyl group, an ethoxycarbonyl group, a benzyloxycarbonyl group and an isopropoxycarbonyl group. Is, for example, a phenoxycarbonyl group, a naphthyloxycarbonyl group or the like.

In the general formula (I), R ₁ and R ₂
Each group represented by may be substituted. Examples of the substituent include the following.

A halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group (for example, a methyl group,
Ethyl group, n-propyl group, isopropyl group, t-butyl group, n-octyl group, cyclopentyl group, cyclohexyl group, etc., alkenyl group (for example, allyl group, 2-
Butenyl group, 3-pentenyl group, etc.), 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.), a 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 ( For example, phenoxy group, 2-naphthyloxy group, etc.), amino group (eg, unsubstituted amino group, dimethylamino group, ethylamino group, anilino group, etc.), acylamino group (eg, acetylamino group, benzoylamino group, etc.) Ureido group (for example, unsubstituted ureido group, N-methylureido group, N-
Phenylureido group, etc.), urethane group (eg, methoxycarbonylamino group, phenoxycarbonylamino group, etc.), sulfonylamino group (eg, methylsulfonylamino group, phenylsulfonylamino group, etc.), sulfamoyl group (eg, unsubstituted sulfamoyl group) , N, N-
Dimethylsulfamoyl group, N-phenylsulfamoyl group, etc.), carbamoyl group (eg, unsubstituted carbamoyl group, N, N-diethylcarbamoyl group, N-phenylcarbamoyl group, etc.), sulfonyl group (eg, mesyl group, A sulfinyl group (eg, a methylsulfinyl group, a phenylsulfinyl group, etc.), an alkyloxycarbonyl group (eg, a methoxycarbonyl 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.) ), A phosphoric acid amide group (eg, N, N-diethylphosphoric acid amide group, etc.), an alkylthio group (eg, methylthio group, ethylthio group, etc.), an arylthio group (eg, phenylthio group, etc.), a cyano group,
Examples include a sulfo group, a carboxy group, a hydroxy group, a mercapto group, a phosphono group, a nitro group, a sulfino group, an ammonio group (eg, a trimethylammonio group), a phosphonio group, a hydrazino group, and the like. These groups may be further substituted. When there are two or more substituents, they may be the same or different.

In the general formula (I), more preferably, R
₁ is an aliphatic group, an aromatic group, a heterocyclic group, R ₂ is an aliphatic group, a heterocyclic group, a cation, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group. There is something.

Still more preferably, in the general formula (I), R ₁ is an aliphatic group or an aromatic group, and R ₂ is a cation, an acyl group, a carbamoyl group, a sulfamoyl group or a sulfonyl group.

Most preferably, R in the general formula (I)
₁ is an aromatic group, and R ₂ is a cation, an acyl group, a carbamoyl group, a sulfamoyl group, or a sulfonyl group.

Next, the general formula (II) will be described in detail. In formula (II), R ₃ and R ₄ have the same meaning as R ₁ and R _{2 in} formula (I). Where R ₃
And each group represented by R ₄ may have a substituent. These substituents are the same as the substituents of the groups represented by R ₁ and R ₂ in formula (I).

More preferably, in the general formula (II),
R ₃ represents an aliphatic group, an aromatic group, or a heterocyclic group, and R ₄ represents an aliphatic group, a heterocyclic group, a cation, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group. It is something that is.

Still more preferably, in the general formula (II), R ₃ is an aliphatic group or an aromatic group, and R ₄ is a cation, an acyl group, a carbamoyl group, a sulfamoyl group,
It is a sulfonyl group.

Most preferably, in the general formula (II),
R ₃ is an aromatic group, and R ₄ is a cation, an acyl group, a carbamoyl group, a sulfamoyl group, or a sulfonyl group.

Next, the general formula (III) will be described in detail. In the general formula (III), R ₅ and R ₆ have the same meaning as R ₁ in the general formula (I).
In II), R ₇ has the same meaning as R ₂ in formula (I). Here, each group represented by R ₅ , R ₆ and R ₇ may have a substituent. These substituents are the same as the substituents of the groups represented by R ₁ and R ₂ in formula (I).

In the general formula (III), more preferably, R ₅ and R ₆ are an aliphatic group, an aromatic group or a heterocyclic group, and R ₇ is an aliphatic group, a heterocyclic group, a cation, an acyl group, a carbamoyl group. Group, a sulfamoyl group, a sulfonyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group.

In the general formula (III), more preferably, R ₅ and R ₆ are an aliphatic group or an aromatic group,
R ₇ is a cation, an acyl group, a carbamoyl group, a sulfamoyl group, or a sulfonyl group.

Most preferably, in the general formula (III), R ₅ and R ₆ are aromatic groups, and R ₇ is a cation, acyl group, carbamoyl group, sulfamoyl group or sulfonyl group.

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

[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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Formulas (I), (II) and (III)
The compound represented by the following literature already known, S. Pat
ai, Z. Rappoport ed., The Chemistry of Organic Selenium and Telluriu
m Compounds), Vol. 1 (1986) pp. 359-367, ibid.
Volume 2 (1987) pp. 593-656, by D. Liotta, Organo-selenium chemistry
mistry), (1987), by KJ Irgolic, The Organic Chemistry of Tellurium
nic Chemistry of Tellurium), (1974), or even Chem. Ber., (101), 3070 (1968), Chem. Be.
r., (99), 1663 (1966), Angew. Chem., (77), 259 (196
5), Pure Appl.Chem., (52), 959 (1980), Phosphorous,
(3), 177 (1973), Zh.Obshch.khim., (48), 1073 (19
78), Dokl. Akad.Nauk SSSR, (239), 1110 (1978), J. M.
ed. Chem., (10), 115 (1967), Izv. Akad. Nauk SSSR,
Ser. Khim., 1627 (1976), Izv. Akad. Nauk SSSR, Ser.
Khim., 2635 (1977), Bull.Akad.Pol.Sci.Chem., (1
5), 153 (1967), Zh.Obshch.Khim., (38), 363 (196
8), Zh.Obshch.Khim., (48), 331 (1978), Chem. Ber.,
(101), 3070 (1968), Helv. Chim. Acta, (59), 252 (1
976), Zh.Obshch.Khim., (37), 495 (1967), J. Chem.
Soc. Dalton Trans., 527 (1977), Bull.
i., Ser. Sci. Chem., (21), 455 (1973), Acta Chem. S
cand., (4), 1241 (1950), J. Chem. Soc. Chem. Commu
n., 658 (1977), J. Chem. Soc. Chem. Commun., 693 (1
985) and the like.

Heretofore, the compound of the general formula (I) has been
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. These are used in the present invention
The amount of selenium sensitizer and tellurium sensitizer
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.
R10^-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 temperature 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 in combination. 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 preferable to use a sulfur sensitizer in combination. Specific examples include known unstable sulfur compounds such as thiosulfates (eg, hypo), thioureas (eg, diphenylthiourea, triethylthiourea, allylthiourea, etc.) and rhodanines. About 10 ^-7 to 10 ^-2 mol can be used per 1 mol.

In the present invention, a reduction sensitizer may be used in combination. Specifically, stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives, borane compounds, silane compounds, polyamine compounds, And the like.

In the present invention, selenium sensitization is preferably performed in the presence of a silver halide solvent. Specifically, thiocyanates (eg, potassium thiocyanate, etc.), thioether compounds (eg, US Pat.
No. 021215, No. 3211157, Japanese Patent Publication No. 58-3
No. 0571, JP-A-60-136736 and the like, in particular, 3,6-dithia-1,8-octanediol and the like, tetrasubstituted thiourea compounds (for example, JP-B-59-1)
No. 1892, the compounds described in U.S. Pat. No. 4,221,863, especially tetramethylthiourea), and the thione compounds described in JP-B-60-11341, JP-B-63
No. 29727, mercapto compounds described in JP-A-60
And the selenoether compound described in U.S. Pat. No. 4,781,2013, the telluroether compound described in Japanese Patent Application No. 63-173474, sulfites and the like. In particular, among these, thiocyanates, thioether compounds, tetrasubstituted thiourea compounds and thione compounds can be preferably used. The amount used is 10 ^-5 to 10 ^-2 per mol of silver halide.
About moles can be used.

The silver halide emulsion used in the present invention is:
Silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride are preferred. Silver halide grains used in the present invention,
Those having a regular crystal form such as cubic or octahedral, or irregular (irregu) such as spherical or plate-like
lar) crystal form or a compound 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 μm or less, preferably 0.3 μm or less and a diameter of preferably 0.6 μm or more,
Particles with an average aspect ratio of 5 or more account for 50% of the total projected area
Either the average grain emulsion occupying the above or the statistical variation coefficient (the value S / d obtained by dividing the standard deviation S by the diameter d in the distribution represented by the diameter when the projected area is approximated by a circle) is 20.
% Or less is preferred. Further, two or more tabular grain emulsions and monodispersed emulsions may be mixed.

The photographic emulsion used in the present invention is described by P. Glafkides, Shimmy e Physique.
Photographeq (Chimie er Physique Photographeq
ue) (Paul Montell, 1967), GFDuffin, Photographic Emulsion Chemistry (Photographic EmulsionChe)
mistry) (Focal Press, 1966), Buoy
VLZelikman et al., Making
It can be prepared by a method described in, for example, Making and Coating Photographic Emulsion (Focal Press, 1964).

In forming the silver halide grains, a silver halide solvent such as ammonia, rodancali, rodanammonium, or the like may be used to control the growth of the grains.
Thioether compounds (eg, US Pat. No. 3,271,1
No. 57, No. 3,574, 628, No. 3,704,
No. 130, No. 4,297,439, No. 4,27
No. 6,374, etc.) and thione compounds (for example,
Nos. 144443, 53-82408, 55-7
7737 etc.), amine compounds (for example,
No. 100717) can be used. In the course 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 may be coexisted.

As a binder or protective colloid which can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic colloids can also be used. For example, gelatin derivatives,
Graft polymers of gelatin with other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sodium alginate;
Various sugar derivatives such as starch derivatives; mono- or copolymers such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Synthetic hydrophilic polymeric substances can be used. As gelatin, besides general-purpose lime-processed gelatin, acid-processed gelatin and the journal of the Japan Society of Science Photography (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 thereof include chromium salts, aldehyde salts (formaldehyde, glyoxal, glutaraldehyde, etc.) and N-methylol-based compounds (dimethylol urea, etc.). Active halogen compounds (such as 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 polymers having a bitylsulfonyl group in the side chain are preferred because they can quickly cure hydrophilic colloids such as gelatin and provide stable photographic properties. N-carbamoylpyridinium salts ((1-
Morpholinocarbonyl-3-pyridinio) methanesulfonate and the like and haloamidinium salts (such as 1- (1-chloro-1-pyridinomethylene) pyrrolidinium-2-naphthalenesulfate) also have fast curing rates and are excellent.

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, etc .; 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, , An indolenine nucleus, a benzindolenin nucleus, an indole nucleus, a benzoxadol nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, and the like. These nuclei may have a substituent on a carbon atom. In a merocyanine dye or a complex merocyanine dye, pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidin-
2,4-dione nucleus, thiazolidine-2,4-dione nucleus,
A 5- to 6-membered heterocyclic nucleus such as a rhodanine nucleus and a thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. 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, an aminostilbenzene compound substituted with a nitrogen-containing heterocyclic nucleus group (for example, those described in U.S. Pat. Nos. 2,933,390 and 3,635,721), formaldehyde condensation of an aromatic organic acid (Eg, US Pat. No. 3,743,743)
510), cadmium salts, azaindene compounds and the like. US Patent 3,615,6
No.13, No.3,615,641, No.3,617,29
The combinations described in JP-A Nos. 5 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, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. Can be done. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, and aminotriazole , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes such as tria Zaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes) and pentaazaindenes ; Benzenethiosulfonate, benzenesulfonic fins acid, known as antifoggants or stabilizers such as benzenesulfonic acid amide, can be added to many compounds.

The light-sensitive material of the present invention comprises a coating aid, an antistatic
One or more surfactants may be included for various purposes such as improving slipperiness, emulsifying and dispersing, preventing adhesion and improving photographic properties (eg, accelerating development, increasing contrast, sensitizing).

The light-sensitive material prepared by using the present invention may contain a water-soluble dye in a hydrophilic colloid layer as a filter dye or for the purpose of preventing irradiation or halation or other various purposes. As such dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes,
Azo dyes are preferably used, in addition to cyanine dyes,
Azomethine dyes, triarylmethane dyes and phthalocyanine dyes are also useful. 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. The multilayer natural color photographic material usually has at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support. The order of arrangement 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 layers, blue-sensitive layer, green-sensitive layer and red-sensitive layer or in order of blue-sensitive, red-sensitive and green-sensitive layers. 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.
The three-layer structure may further improve the graininess. Further, a non-photosensitive layer may be present between two or more emulsion layers having the same color sensitivity. An emulsion layer having a different color sensitivity may be inserted between emulsion layers having the same color sensitivity. A reflective layer of fine silver halide or the like may be provided below the high-sensitivity layer, particularly the high-sensitivity blue-sensitive layer, to improve the sensitivity. 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 are described in Research Disclosure (RD) No. 17643, VII-
It is described in the patents described in C to G. As the yellow coupler, for example, US Pat. No. 3,933,501
No. 4,022,620, No. 4,326,02
No. 4, No. 4,401,752, JP-B-58-107
No. 39, British Patent Nos. 1,425,020 and 1,4
No. 76,760 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.
Nos. 61,432 and 3,725,067, Research Disclosure No. 24220 (June 1984)
), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, U.S. Pat. No. 4,500,630.
No. 4,540,654 are preferred. Examples of cyan couplers include phenol-based and naphthol-based couplers.
No. 2,212, No. 4,146,396, No. 4,2
No. 28,233, No. 4,296,200, No. 2,
No. 369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826, No. 3,772,002, No. 3,758,308,
Nos. 4,334,011, 4,327,173
No. 3,329,729, EP 121,365A, U.S. Pat. No. 3,446,622.
No. 4,333,999 and 4,451,55
No. 9, No. 4,427,767, European Patent No. 161,
No. 626A is preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are described, for example, in Research Disclosure No. 17643, Section VII-G, US Pat.
No. 3,670, JP-B-57-39413, U.S. Pat. Nos. 4,004,929 and 4,138,258, and British Patent 1,146,368 are preferred.

Examples of couplers in which a coloring dye has an appropriate diffusivity include, for example, US Pat. No. 4,366,237, British Patent No. 2,125,570, and European Patent No. 96,57.
No. 0 and West German Patent (Publication) No. 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are described in US Pat.
Nos. 0,211 and 4,367,282, and British Patent No. 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
Patent No. D17643, Sections VII to F
Nos. 7-151944, 57-154234, 60
Preferred are those described in U.S. Pat. No. 4,248,962. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include, for example, British Patent Nos. 2,097,140 and 2,131,1.
No. 88, JP-A Nos. 59-157638 and 59-170
No. 840 is preferred.

Other couplers usable in the light-sensitive material of the present invention include, for example, US Pat.
No. 27, etc., US Patent No. 42834.
No. 72, No. 4,338,393, No. 4,310,618, etc., multi-equivalent couplers described in JP-A-60-185950.
Redox compounds or DIR coupler releasing couplers described in JP-A-62-24252, couplers releasing dyes capable of recoloring after release described in EP 173302A, R.C. D. No. 11449, 2424
1, bleach accelerator releasing couplers described in JP-A-61-201247 and the like, 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. An example of a high boiling solvent used in the oil-in-water dispersion method is disclosed in US Pat.
No. 7, etc. Specific examples of the high-boiling organic solvent having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate). , Screw (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 (eg, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, Tricyclohexyl phosphate, tri-2-ethylhexyl phosphate,
Tridodecyl phosphate, tributoxyethyl phosphate and trichloropropyl phosphate, di-2-ethylhexylphenyl phosphate), benzoates (eg, 2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate), amides ( For example, N, N-diethyldodecaneamide, N, N-diethyllauramide,
N-tetradecylpyrrolidone), alcohols or phenols (eg, isostearyl 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 (eg, , N, N-dibutyl-2-butoxy-5-tert-octylaniline), hydrocarbons (eg, 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 include ethyl acetate, butyl acetate, ethyl propionate, and the like.
Examples include methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,3.
No. 63, West German Patent Application (OLS) No. 2,541,274
And No. 2,541,230.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are formed of a flexible support such as a plastic film, paper, cloth, etc., or a rigid support such as glass, pottery or metal, which is usually used for the photographic light-sensitive material. Applied to the body. Those useful as flexible supports include films, baryta layers or α-olefin polymers composed of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, and polycarbonate. (Eg, polyethylene, polypropylene, ethylene / butene copolymer)
And the like are coated or laminated paper. 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 undercoating treatment.

For coating the photographic emulsion layer and other hydrophilic colloid layers, various known coating methods such as dip coating, roller coating, curtain coating, and extrusion coating can be used. US Patent No. 2 if required
Nos. 681294, 2761791 and 3526
Multiple layers may be simultaneously coated by the coating method described in JP-A-528 and JP-A-3508947.

The present invention can be applied to various color and black-and-white photographic materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers, color diffusion transfer photosensitive materials and heat developable color photosensitive materials. it can. Research Disclosure, No.
17123 (July 1978), or by using a three-color coupler mixture, or as described in U.S. Pat.
The present invention can be applied to black-and-white light-sensitive materials such as those for X-rays by utilizing black color couplers described in U.S. Pat. No. 26,461 and British Patent No. 2,102,136. Plate making film such as squirrel film or scanner film, direct medical / indirect medical or industrial X-ray film, negative black and white film for photography, black and white photographic paper, CO
The present invention can be applied to microfilms for M or ordinary microfilms, 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 peeling (peel apartment) type or JP-B-46-16356, JP-B-48-33697,
JP-A-50-13040 and British Patent 1,330,
A film unit of an integral type as described in JP-A No. 524 and a peel-free type film unit as described in JP-A-57-119345 can be employed. 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 exposure 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 photosensitive material can be used as the illumination light source or the writing light source. Flash light sources such as natural light (sunlight), incandescent lamps, halogen-filled lamps, mercury lamps, fluorescent lamps, and strobe or metal-burning flash bulbs are common. A gas, dye solution or semiconductor laser that emits light in the wavelength range from ultraviolet to infrared,
Light emitting diodes and plasma light sources can also be used as recording light sources. Also, a phosphor screen (such as a CRT) emitted from a phosphor excited by an electron beam or the like, a liquid crystal (LC
Exposure means in which a linear or planar light source is combined with a micro-shutter array using D) or lanthanum-doped lead titanium zirconate (PLZT) 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 of the light-sensitive material of the present invention is preferably an alkaline aqueous solution mainly containing an aromatic primary amine-based color developing agent. 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-
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 developing solution includes a pH buffer such as an alkali metal carbonate, borate or phosphate, bromide,
It generally contains a development inhibitor or an antifoggant such as iodide, benzimidazoles, benzothiazoles or mercapto compounds. If necessary, preservatives such as hydroxylamine or sulfite, organic solvents such as triethanolamine and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dyes Forming couplers, competing couplers, nucleating agents such as sodium boron hydride, 1-phenyl-3-
Auxiliary developing agents such as pyrazolidone, viscosity-imparting agents, various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid, West German Patent Application (OLS) No. 2,622 , 95
The antioxidant described in No. 0 may be added to the color developer.

In the development process of the reversal color photosensitive material, color development is usually performed after black and white development. The black-and-white developer includes dihydroxybenzenes such as hydroquinone,
Known black-and-white developers 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 subjected to bleaching. The bleaching process may be performed simultaneously with 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. Examples of bleaching agents include iron (III), cobalt (III),
Compounds of polyvalent metals such as chromium (IV) and copper (II), peracids, quinones, nitrones and the like are used. Ferricyanide; dichromate; iron (II) as a typical bleach
Organic complex salts of I) or cobalt (III), for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid or citric acid, tartaric acid, malic acid, etc. Complex salts of organic acids; persulfates; manganates; nitrosophenols and the like can be used. Of these, iron (III) ethylenediaminetetraacetate,
Diethylenetriaminepentaacetate iron (III) salt and persulfate are preferred from the viewpoint of rapid processing and environmental pollution. Further, the ethylene (III) complex salt of ethylenediaminetetraacetate is particularly useful in an independent bleaching solution or a single-bath bleach-fixing solution.

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
Specific examples of useful bleach accelerators are described in the following specification: U.S. Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988, JP No. 53-32736, No. 53-57831, No. 37
No. 418, No. 53-65732, No. 53-72623
Nos. 53-95630, 53-95631, 53-104232, 53-124424, and 5
Nos. 3-141623 and 53-28426, Research Disclosure No. 17129 (July 1978
Compounds having a mercapto group or a disulfide group described in JP-A-50-14129; a thiazolidine derivative as described in JP-A-50-140129;
JP-A-52-20832 and JP-A-53-32735.
Thiourea derivatives described in U.S. Patent No. 3,706,561; West German Patent No. 1,127,715;
Iodides described in JP-A-16235; West German Patent No. 966,4
Polyethylene oxides described in JP-A Nos. 10 and 2,748,430; Polyamine compounds described in JP-B-45-8836;
-59644, 53-94927, 54-35
Nos. 727, 55-26506 and 58-163
Compounds described in No. 940 and iodine and bromide ions can also be used. Among them, compounds having a mercapto group or a disulfide group are preferred in view of a large accelerating effect, and in particular, U.S. Pat. No. 3,893,858 and West German Patent 1,29.
0,812 and JP-A-53-95630 are preferred. Further, the compounds described in U.S. 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 thiosulfate, thiocyanate, thioether-based compound thioureas, and a large amount of iodide, and thiosulfate is generally used. As a preservative for the bleach-fixing solution or the fixing solution, a sulfite, a bisulfite or a carbonyl bisulfite adduct is preferable.

After the bleach-fixing process or the fixing process, a washing process and a stabilizing process are usually performed. 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 typified by magnesium salts and 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.

In the water washing step, two or more tanks are counter-currently washed.
It is common to save water. Further, instead of the water washing step, a multi-stage countercurrent stabilizing step as described in JP-A-57-8543 may be carried out. In the case of this step, 2 to 9 countercurrent baths 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, various buffers (for example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, etc.) for adjusting the membrane pH (for example, pH 3 to 9) Aldehydes such as monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc.) and formalin can be mentioned as typical examples. In addition, if necessary, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericides (benzoisothiazolinone, irithiazolone, 4- Thiazoline benzimidazole, halogenated phenol, sulfanilamide, benzotriazole, etc.), surfactants, optical brighteners, hardeners, etc., may be used. These may be used in combination.

It is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, ammonium thiosulfate and the like as a membrane pH adjuster after the treatment. In the color light-sensitive material for photographing, the step (washing-stabilization) usually performed after fixing 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 time of the present invention varies depending on the type of photosensitive material and the treatment conditions, but is usually 20 seconds to 10 minutes, preferably 20 seconds to 5 minutes.

In the silver halide color light-sensitive material of the present invention, a color developing agent may be incorporated for the purpose of simplifying and speeding up the processing. In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, indoaniline compounds described in U.S. Pat. Nos. 3,342,597, Schiff base-type compounds described in 3,342,599, Research Disclosure No. 14850 and No. 15159, aldol compounds described in No. 13924, and the like. In addition to the metal salt complexes described in U.S. Pat. No. 3,719,492, urethane compounds described in JP-A-53-135628, JP-A-56-6235 and JP-A-56-235.
No. 16133, No. 56-59232, No. 56-678
No. 42, No. 56-87334, No. 56-83735
Nos. 56-83736, 56-89735, 56-81837, 56-54430, 56-
No. 106241, No. 56-107236, No. 57-9
Examples of the precursor include various salt-type precursors described in Nos. 7531 and 57-83565. The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3-pyrazolidones for the purpose of accelerating color development. Typical compounds are described in JP-A-56-64339, JP-A-57-144547 and JP-A-5-14447.
Nos. 7-111147, 58-50532, 58-
No. 50536, No. 58-50533, No. 58-505
Nos. 34, 58-50535 and 58-1154
No. 38, etc.

Various processing solutions in the present invention may be used at a temperature of 10 ° C. to 50 ° C.
Used at ° C. A temperature of 33 ° C. to 38 ° C. is standard, but higher temperatures can accelerate the processing and shorten the processing time, and lower temperatures can achieve higher image quality and improved processing solution stability. it can. Further, in order to save silver in the photosensitive material, a process using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed. A heater, a temperature sensor, a liquid level sensor, a circulating pump, a filter, a floating pig, a squeegee, and the like may be provided in the various treatment baths as needed. 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.

[0083]

【Example】

Example 1 0.05 g of potassium bromide and gelatin 30 kept at 75 ° C.
g, and stirred with 1 liter of an aqueous solution maintained at pH 2 with nitric acid, simultaneously adding 75 ml of an aqueous silver nitrate solution (1 M) and an aqueous solution of potassium bromide (1 M) while maintaining the silver potential at 0 mV with respect to the saturated calomel electrode. Minutes. Thereafter, 675 ml of an aqueous silver nitrate solution (1M) and an aqueous solution of potassium bromide (1M) were further added over 36 minutes while keeping the silver potential at -30 mV. After completion of particle formation, the mixture was desalted and washed with a usual flocculation method, and then gelatin and water were added to adjust the pH to 6.4 and the pAg to 8.6. The obtained silver bromide emulsion is a monodispersed octahedral emulsion having a grain diameter of 0.25 μm and a variation coefficient of the grain diameter of 11%. After this emulsion was divided into small portions, the temperature was raised to 60 ° C., and a sensitizer was added as shown in Table 1 and chemically ripened for 60 minutes.

Thereafter, 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 a light 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 is represented by the relative value of the reciprocal of the exposure required to obtain an optical density of fog value + 0.2.

[0085]

[Table 1]

As is clear from the table, although the sensitizing performance is often slightly inferior to that of the well-known selenium sensitizer (comparative compound (A)), the compound of the present invention has a sufficient sensitizing activity. It was found to have.

(Color development processing method) Step Processing time Processing temperature Color development 2 minutes 45 seconds 38 ° C. Bleaching 3 minutes 00 seconds 38 ° C. Rinse 30 seconds 24 ° C. Fix 3 minutes 00 seconds 38 ° C. Rinse water (1) 30 Second 24 ° C. Rinse with water (2) 30 seconds 24 ° C. Stable 30 seconds 38 ° C. Dry 4 minutes 20 seconds 55 ° C.

Next, the composition of the processing solution will be described. (Color developing solution) (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 and 1.0 liter pH 10.05

(Bleaching Solution) (Unit g) Sodium ferric ethylenediaminetetraacetate trihydrate 100.0 Disodium ethylenediaminetetraacetate 10.0 3-Mercapto-1,2,4-triazole 0.08 Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonia water (27%) 6.5 ml Add water 1.0 liter pH 6.0

(Fixing solution) (Unit: g) Disodium ethylenediaminetetraacetate 0.5 Ammonium sulfite 20.0 Ammonium thiosulfate aqueous solution (700 g / L) 290.0 mL Water was added to add 1.0 L pH 6.7

(Stabilizing solution) (Unit g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether 0.2 (Average degree of polymerization 10) Disodium ethylenediaminetetraacetate 0.05 1, 2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 1.0 liter with addition of water pH 8.5

Example 2 According to Example 6 of JP-A-2-838, the average particle diameter was 1.05 μm, the particle thickness was 0.19 μm, the aspect ratio was 5.8, and the variation coefficient of the particle diameter was 10. A 5% monodispersed silver bromide emulsion was prepared. After the particles were formed, the temperature was lowered 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 the pAg to 8.3. After subdividing this emulsion, sensitizers shown in Table 2 were added, and chloroauric acid (2.4 × 10 ⁻⁵ mol / mol Ag) and potassium thiocyanate (4 × 10 ⁻⁴ mol / mol Ag) were further added. And aged at 55 ° C. for 60 minutes.

Thereafter, the sensitizing dye anhydro-5,5'-
Dichloro-9-ethyl-3,3'-di (3-sulfopropyl) oxacarbocyanine hydroxide sodium salt and potassium iodide are added, followed by gelatin, 4-hydroxy-6-methyl-1,3,3. 3a, 7-
Add tetrazaindene, sodium poly-styrenesulfonate, sodium dodecylbenzenesulfonate,
On a triacetyl cellulose film support having an undercoat layer, gelatin, polymethyl methacrylate particles,
Co-extrusion was applied with a protective layer containing 2,4-dichloro-6-hydroxy-s-triazine sodium salt. These samples were exposed to sensitometric exposure (1/1).
00) was applied through an optical wedge and a yellow filter, developed with a MAA-1 developer having the following formulation at 20 ° C. for 10 minutes, stopped, fixed, washed with water and dried by a conventional method, and the density was measured. The relative sensitivity is represented by the relative value of the reciprocal of the exposure required to obtain an optical density of fog value + 0.2.
The value of 0 was set to 100.

[0094]

[Table 2]

MAA-1 developer Metol 2.5 g Ascorbic acid 10 g Nabox 35 g Potassium bromide 1 g To 1 liter of water As can be seen from the table, the compound of the present invention is a well-known selenium sensitizer. Although the sensitivity was slightly lower than that of the agent (comparative compound (A)), preferable results were obtained in which the sensitivity was higher than that of the sulfur sensitizer and the gradation was harder.

Example 3 An aqueous solution of silver nitrate and an aqueous solution of potassium bromide were added simultaneously while stirring and maintaining an aqueous solution of gelatin 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 completion of the addition, the mixture was desalted and washed with a usual flocculation method, and gelatin and water were added to adjust the pH to 6.3 and the 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,
Temperature to 6 ° C,

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 × 10 ⁻⁵ mol / mol AgX) and an increase as shown in Table 3 were added. A sensitizer was added, chloroauric acid (1.6 × 10 ⁻⁵ mol / mol Ag) and potassium thiocyanate (1 × 10 ⁻³ mol / mol Ag) were added, and the mixture was aged for 30 minutes.

Thereafter, 1- (3-sulfophenyl) -5
-Mercaptotetrazole monosodium salt and the same additives as in Example 1 were added, coated in the same manner, and subjected to the same treatment (except for 1/10000 second exposure) to obtain the results shown in Table 3. The spectral relative sensitivity was set to 100 for sample 30.

[0100]

[Table 3]

As is clear from the table, when the compound of the present invention was used alone or in combination with the comparative compound (A), a light-sensitive material having almost the same sensitivity particularly under high-illuminance short-time exposure and having high contrast was obtained. .

[0102]

When the compound of the present invention is used for selenium sensitization, the compound exhibits a favorable effect that the sensitivity is higher than that of conventional sulfur sensitization and that the gradation is harder than that of conventional selenium sensitization. all right.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-4-109240 (JP, A) JP-A-4-113349 (JP, A) JP-A-4-3303043 (JP, A) JP-A-3- 91735 (JP, A) JP-A-53-5817 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03C 1/09

Claims (4)

(57) [Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers has the following general formula (I), (II) or (III): A silver halide photographic light-sensitive material comprising at least one compound represented by the formula: General formula (I) In the formula, Ch ₁ represents a selenium atom or a tellurium atom.
R ₁ is an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an ether group, a thioether group, a selenoether group,
R ₂ represents a hydrogen atom, an aliphatic group,
Represents an aromatic group, a heterocyclic group, a cation, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group. Formula (II) In the formula, Ch ₂ represents a selenium atom or a tellurium atom.
R ₃ represents an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an ether group, a thioether group, a selenoether group,
R ₄ represents a hydrogen atom, an aliphatic group,
Represents an aromatic group, a heterocyclic group, a cation, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group. General formula (III) In the formula, Ch ₃ represents a selenium atom, a tellurium atom,
Ch ₄ represents an oxygen atom or a sulfur atom. Also, R ₅ and R
₆ represents an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an ether group, a thioether group, a selenoether group, or a telluroether group, and R ₇ represents a hydrogen atom, an aliphatic group, an aromatic group,
Represents a heterocyclic group, a cation, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group. 2. A silver halide photographic material comprising a silver halide emulsion chemically sensitized with at least one compound represented by the following general formula (I). General formula (I) In the formula, Ch ₁ represents a selenium atom or a tellurium atom.
R ₁ is an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an ether group, a thioether group, a selenoether group,
R ₂ represents a hydrogen atom, an aliphatic group,
Represents an aromatic group, a heterocyclic group, a cation, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group. 3. A silver halide photographic material comprising a silver halide emulsion chemically sensitized with at least one compound represented by the following formula (II). General formula (II) In the formula, Ch ₂ represents a selenium atom or a tellurium atom.
R ₃ represents an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an ether group, a thioether group, a selenoether group,
R ₄ represents a hydrogen atom, an aliphatic group,
Represents an aromatic group, a heterocyclic group, a cation, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group. 4. A silver halide photographic light-sensitive material comprising a silver halide emulsion chemically sensitized with at least one compound represented by the following general formula (III). General formula (III) In the formula, Ch ₃ represents a selenium atom, a tellurium atom,
Ch ₄ represents an oxygen atom or a sulfur atom. Also, R ₅ and R
₆ represents an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an ether group, a thioether group, a selenoether group, a telluroether group, and R ₇ represents a hydrogen atom, an aliphatic group, an aromatic group,
Represents a heterocyclic group, a cation, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group.