JP3304160B2 - Silver halide photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide photographic material having a silver halide emulsion layer. More specifically, the present invention particularly relates to a silver halide photographic material having a silver halide emulsion layer having improved fog and sensitivity.

[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. As typical methods, sulfur sensitization, selenium sensitization, tellurium sensitization, sensitization of noble metals such as gold, reduction sensitization, and various sensitization methods using 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 progress is accelerated. Has been.

Among them, selenium sensitization is described in US Pat. Nos. 1,574,944, 1,602,592 and 1,259.
No. 623499, No. 3297446, No. 3297
No. 447, No. 3320069, No. 3408196
Nos. 3,408,197, 3,424,653, 3,420,670, 3,591,385, French Patent Nos. 2693038, 2093209, JP-B-52-34491, JP-B-52-34492, and 53.
-295, 57-22090, JP-A-59-18
Nos. 0536, 59-185330, 59-181
No. 337, No. 59-187338, No. 59-1922
No. 41, No. 60-150046, No. 60-15163
7, JP-A-61-246738, JP-A-3-4221
No. 3-148648, No. 3-11838, No. 3-116132, No. 3-237450, No. 4-1
No. 6838, No. 4-25832, No. 4-140738
No. 4-140739, EP 50609A
No. 1 and also British Patent Nos. 255,846 and 8619.
No. 84; E. FIG. Spencer et al., Journal
al of Photographic Science
e, vol. 31, pp. 158-169 (1986), which is known to have a greater sensitizing effect than the above-mentioned sulfur sensitization generally performed in the art.

[0005] Although selenium sensitization has the above-mentioned advantages such as higher arrival sensitivity compared with sulfur sensitization generally used in the art, gold sensitization is combined with higher sensitivity. However, there are drawbacks such as fogging and softening easily, and fogging during storage with time and a large decrease in sensitivity. These improvements have been strongly desired.

[0006] The chemical sensitizer is an aqueous solution having an appropriate concentration when the compound is water-soluble, and an appropriate organic compound which is miscible with water when the compound is insoluble or hardly soluble in water. It is dissolved in a solvent (for example, alcohols, glycols, ketones, esters, amides, etc., which do not adversely affect the photo specification) and added as a solution. However, when a silver halide photographic emulsion is produced by the above-described addition method, the chemical sensitizer is unevenly distributed on the silver halide grains, so that the dispersion and unevenness of the formation of the photosensitive nucleus occur, and in the course of the photosensitive process. The problem is that the inefficiency of this occurs. As a solution to these problems, for example, Japanese Patent Application Laid-Open No. 61-20940 discloses a technique in which a specific sulfur sensitizer is included in cyclodextrin to form a complex and the chemical sensitization reduces fog. It has been disclosed. However, even if this method is applied to tellurium sensitization, a sufficient effect has not been obtained. JP-A-3-91736 describes a method in which sulfur and selenium sensitizers are added individually in the form of being individually adsorbed to a substance having adsorbability.
There is no specific description about the selenium sensitizer, and there is no mention of a method of using both in combination.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic material having high sensitivity (particularly high spectral sensitivity) and low fog.

[0008]

According to the present invention, silver halide fine particles having a selenium sensitizer and a sulfur sensitizer adsorbed thereon are added to a silver halide emulsion of a host, and a silver halide solvent is used with a silver halide solvent. A silver halide photographic material having a silver halide emulsion layer chemically sensitized by dissolving silver fine particles.

The present invention preferably has the following aspects. (1) The size of the silver halide fine grains is set to be 0.
It is in the range of 01 μm to 0.3 μm. (2) The silver halide grains have a halogen composition of silver chloride,
Silver chlorobromide, silver bromide or silver iodobromide. (3) The silver halide emulsion of the host is silver iodobromide. (4) The gold sensitizer is chloroauric acid. (5) The sulfur sensitizer is a thiosulfate (particularly, hypo).

DETAILED DESCRIPTION OF THE INVENTION The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention is a silver halide fine grain (emulsion) containing a selenium sensitizer and a sulfur sensitizer.
And the selenium sensitizer and the sulfur sensitizer are adsorbed to the silver halide fine particles without causing much reaction between the sensitizer and the silver halide. The adsorbed silver halide fine particles are added to a host silver halide emulsion (a silver halide emulsion finally sensitized with selenium and sulfur to obtain a desired sensitivity) to chemically sensitize the silver halide emulsion. It is characterized by feeling. In the present invention, the silver halide fine particles having the selenium sensitizer and the sulfur sensitizer adsorbed thereon are defined as having a reaction rate of less than 30% (preferably 20%) between the selenium sensitizer and the sulfur sensitizer and the silver halide fine particles. %, More preferably 10% or less).

The size of the silver halide fine particles used in the above method is 0.01 μm to 0.3 μm.
A range of m is preferred. More preferably, 0.01
The range is from μm to 0.2 μm. The halogen composition of the silver halide fine grains may be any of silver chloride, silver bromide, silver iodide or a mixed crystal thereof. Particularly, silver chloride, silver chlorobromide, silver bromide or silver iodobromide is preferred. These silver halide fine particles dissolve during the chemical sensitization of the host silver halide emulsion.

Hereinafter, the selenium sensitizer and the sulfur sensitizer will be described. First, the selenium sensitizer will be described.
As the selenium sensitizer used in the present invention, selenium compounds (unstable selenium compounds and non-unstable selenium compounds) disclosed in conventionally known patents can be used. Examples of the unstable selenium compound used in the present invention include JP-B-43-13489 and JP-A-44-15.
748, JP-A-4-25832, 4-109
No. 240 or Japanese Patent Application Nos. 3-82929 and 3-5
Preferred are compounds described in, for example, JP-A-3693. Specific examples of unstable selenium sensitizers include, for example, isoselenocyanates (aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenoamides, and selenocarboxylic acids (for example, 2 -Selenopropionic acid, 2-selenobutyric acid), selenoesters, diacylselenides (eg, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, colloidal metal selenium And the like. The non-labile selenium compound used in the present invention is described in
Nos. 6-4553, 52-34491 and 5-52
Compounds described in JP-A-34492 are preferred. Examples of the non-labile selenium compound include selenous acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenide, diaryl diselenide, dialkyl selenide, dialkyl diselenide, and 2-alkyl selenide.
Selenazolidinedione, 2-selenooxazolidinethione and derivatives thereof are mentioned.

In the present invention, an unstable selenium compound can be preferably used rather than a non-unstable selenium compound. Among the selenium compounds, a selenium compound represented by the following formula (I) or (II) is preferable.

[0014]

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[In the formula (I), Z ¹¹ and Z ¹² are each independently an alkyl group, an alkenyl group, an aryl group, an aralkyl group, a heterocyclic group, -NR ¹¹ (R ¹² ), -OR ¹³ or -SR ¹⁴ (R ¹¹ and R ¹² are each independently a hydrogen atom,
Represents an alkyl group, an aralkyl group, an aryl group, an acyl group or a heterocyclic group, wherein R ¹³ and R ¹⁴ independently of one another,
Represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. ). ]

[0016]

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[In the formula (II), Z ²¹ , Z ²² and Z ²³ each independently represent an aliphatic group, an aromatic group, a heterocyclic group, -O
R ²¹ , —NR ²² (R ²³ ), —SR ²⁴ , —SeR ²⁵ , a halogen atom or a hydrogen atom (R ²¹ , R ²⁴ and R
²⁵ represents an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation independently of each other, and R ²² and R ²³ each independently represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom. Express. ) Or any of Z ²¹ , Z ²² and Z ²³ as a linking group to form a dimer. ]

First, the selenium compound represented by the above formula (I) will be described in detail. Examples of the alkyl group represented by Z ¹¹ and Z ¹² include methyl, ethyl, te
Mention may be made of rt-butyl, adamantyl groups and tert-octyl. Examples of the alkenyl groups represented by Z ¹¹ and Z ¹² include vinyl and propenyl. Examples of the aralkyl groups represented by Z ¹¹ and Z ¹² include benzyl and phenethyl. Examples of the aryl group represented by Z ¹¹ and Z ¹² include phenyl, pentafluorophenyl, 4-chlorophenyl, 3-nitrophenyl,
-Octylsulfamoylphenyl and α-naphthyl. Examples of the heterocyclic group represented by Z ¹¹ and Z ¹² include pyridyl, thienyl, furyl and imidazolyl. An alkyl group represented by the above R ¹¹ , R ¹² , R ¹³ and R ¹⁴ ;
An aralkyl group, an aryl group or a heterocyclic group is a group represented by the aforementioned Z ¹¹
Has the same meaning as an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. Examples of the acyl group represented by R ¹¹ and R ¹² include acetyl, propanoyl,
Mention may be made of benzoyl, heptafluorobutanoyl, difluoroacetyl, 4-nitrobenzoyl, α-naphthoyl and 4-trifluoromethylbenzoyl.

In the above formula (I), Z ¹¹ represents an alkyl group, an aryl group or —NR ¹¹ (R ¹² ) (R ¹¹ and R
¹² represents a hydrogen atom, an alkyl group, an aryl group or an acyl group. ) Is preferable. The Z ¹² are -N
It is preferably R ¹¹ (R ¹² ) (R ¹¹ and R ¹² represent a hydrogen atom, an alkyl group, an aryl group or an acyl group). Examples of the selenium compound represented by the above formula (I) include N, N-dialkylselenourea, N, N, N ′
-Trialkyl-N'-acylselenoureas, tetraalkylselenoureas, N, N-dialkyl-arylselenoamides, N-alkyl-N-aryl-arylselenoamides are preferred.

Specific examples of the selenium compound represented by the formula (I) are shown below.

[0021]

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[0022]

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[0023]

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Next, the selenium compound represented by the above formula (II) will be described in detail. The above Z ²¹ , Z ²² and Z
Examples of the aliphatic groups represented by ²³ and R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ include linear, branched or cyclic alkyl, alkenyl, alkynyl and aralkyl groups. Can be. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-butyl, n-octyl, n-
Decyl, n-hexadecyl, cyclopentyl and cyclohexyl can be mentioned. Examples of the alkenyl group include, for example, allyl, 2-butenyl and 3-pentenyl. Examples of the alkynyl group include propargyl and 3-pentynyl. As the aralkyl group, for example,
Benzyl and phenethyl can be mentioned. The above Z ²¹ , Z ²² and Z ²³ , and R ²¹ , R ²² , R ²³ and R ²⁴
And examples of the aromatic group represented by R ²⁵ include a monocyclic or condensed-ring aryl group (eg, phenyl, pentafluorophenyl, 4-chlorophenyl, 3-sulfophenyl, α-naphthyl, 4-methylphenyl). Can be mentioned. The above Z ²¹ , Z ²² and Z ²³ , and R ²¹ , R
^The heterocyclic group represented by ²² , R ²³ , R ²⁴ and R ²⁵ is a 3- to 10-membered saturated or unsaturated heterocyclic group containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. And examples of such a heterocyclic group include pyridyl, thienyl, furyl, thiazonyl, imidazolyl and benzimidazolyl. Examples of the halogen atom represented by Z ²¹ , Z ²² and Z ²³ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. In the selenium compound represented by the formula (II), any of Z ²¹ , Z ²² and Z ²³ may be a linking group to form a dimer. As a linking group,
Methylene groups can be mentioned. The cation represented by R ²¹ , R ²⁴ and R ²⁵ represents an alkali metal atom or ammonium.

In the above formula (II), Z ²¹ , Z ²² and Z ²³ are preferably an aliphatic group, an aromatic group or —OR ²¹ (R ²¹ represents an aliphatic group or an aromatic group). As the selenium compound represented by the above formula (II), a trialkylphosphine selenide, a triarylphosphine selenide, a trialkylselenophosphate, or a triarylselenophosphate is preferable.

Specific examples of the selenium compound represented by the formula (II) are shown below.

[0027]

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[0028]

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[0029]

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The selenium compounds represented by the above formula (I) or (II) may be used alone or in combination of two or more. An unstable selenium compound and a non-unstable selenium compound can be used in combination.

Next, the sulfur sensitizer will be described. Examples of the sulfur sensitizer include thiosulfates (eg, hypo), thioureas (eg, diphenylthiourea, triethylthiourea, allylthiourea, etc.), rhodanines (eg, rhodanine, N-ethylrhodanine, 5-Penzylidene rhodanine, 5-benzylidene-N-ethyl-rhodanine), thioamides (eg, thioacetamide, N-phenylthioacetamide) and further, thiohydantoins, 4-oxo-oxazoline-2-thione , Dipolysulfides, cysteine mercapto compounds, polythionates, and known unstable sulfur compounds such as elemental sulfur.

The silver halide fine particles having the selenium sensitizer and the sulfur sensitizer adsorbed thereon used in the present invention are prepared by using the selenium sensitizer and the sulfur sensitizer described above and mixing them with water or water. It can be carried out by dissolving in the obtained organic solvent (alcohols, esters, amides, etc.), adding to a silver halide fine grain emulsion, and ripening under predetermined conditions. The amounts of the selenium sensitizer and the sulfur sensitizer vary depending on the silver halide grains of the host used, the conditions of chemical ripening, and the like. Generally, the selenium sensitizer is used in an amount of 10 ⁻ per mol of the host silver halide. ⁸ to 10 ^-2 mol, preferably 10
^{-7 to} 5 × 10 ^-3 mol, and the sulfur sensitizer is used in an amount of 10 ^-7 to 10 ^-2 mol, per mol of silver halide of the host.
Preferably, about 10 ^{-7 to} 5 × 10 ^-3 mol is used. The conditions for adsorption on the silver halide fine grains are such that the selenium sensitizer and the sulfur sensitizer react with the silver halide fine grains to form a chemical sensitization center, thereby increasing the sensitivity of the silver halide fine grains. It is possible. For this reason, as described above, it is preferable to select adsorption conditions such that the reaction rate between both the added selenium sensitizer and sulfur sensitizer and the silver halide fine particles is less than 30%. In particular,
The pAg is in the range from 6 to 11, preferably in the range from 7 to 10. The temperature is in the range 30-60 ° C, preferably
It is in the range of 35-40 ° C. The aging time in this state is in the range of 1 to 20 minutes, preferably 1 to 10 minutes.

In preparing the silver halide fine particles as described above, it is preferable to further use a noble metal sensitizer such as gold, platinum, palladium or iridium. In particular, it is preferable to use a gold sensitizer. Specific examples include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, and gold selenide. The amount of the gold sensitizer used is 10 ⁻⁷ to 1 mol per mol of silver halide.
It is about 10 ^-2 mol.

In preparing the silver halide fine particles as described above, a tellurium sensitizer may be used in combination. Examples of tellurium sensitizers include Canadian Patent No. 800958, British Patent Nos. 1295462 and 1396696, Japanese Patent Application Nos. 2-333819, 3-53693, and 3-1.
Unstable tellurium compounds described in 31598 and 4-129787 can be used. Specific tellurium sensitizers include telluroureas (eg, tetramethyltellurourea, N, N′-dimethylethylenetellurourea, N, N′-diphenylethylenetellurourea), phosphine tellurides (eg, butyl) Diisopropylphosphine telluride, tributylphosphine telluride, tributoxyphosphine telluride, ethoxy-diphenylphosphine telluride), diacyl (di)
Tellurides (eg, bis (diphenylcarbamoyl)
Ditelluride, bis (N-phenyl-N-methylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) telluride, bis (ethoxycarbonyl) telluride)), isostererocyanates, telluramides, tellurohydrazides, telluride Esters (for example,
Butylhexyl telluro ester), telluro ketones (eg, telluroacetophenone), colloidal tellurium,
(Di) tellurides, other tellurium compounds (for example, potassium telluride, sodium telluropentathionate) and the like. The amount of tellurium sensitizer used is about 10 ^-7 to 10 ^-2 mol per mol of silver halide.

In the preparation of the silver halide fine particles as described above, when a tellurium sensitizer and a gold sensitizer are used in combination, the selenium sensitizer and the sulfur sensitizer are adsorbed on the silver halide fine particles. Almost similar conditions can be selected.

The silver halide fine particles adsorbed with the selenium sensitizer and the sulfur sensitizer prepared as described above are then added to a silver halide emulsion of a host to obtain
The host silver halide emulsion is chemically sensitized. The conditions of the chemical sensitization in this case are not particularly limited, but pAg is 6
-11, preferably 7-10. The temperature is in the range of 40-95 ° C, preferably 45-85 ° C
Range. When performing chemical sensitization of the silver halide emulsion of the host using silver halide fine particles having a chemical sensitizer adsorbed thereon, the above-mentioned sulfur sensitizer, selenium sensitizer, tellurium sensitizer, A gold sensitizer or a combination thereof may be additionally added. The host silver halide emulsion will be described later.

The chemical sensitization of the silver halide emulsion of the host is carried out in the presence of a silver halide solvent. Examples of the silver halide solvent include thiocyanates (for example, potassium thiocyanate) and thioether compounds (for example, U.S. Pat. Nos. 3,021,215 and 3,271,157, JP-B-58-30571, and JP-A-60-136736). Compounds, especially 3,6-dithia-1,8-octanediol and the like; tetrasubstituted thiourea compounds (for example,
No. 9-11892, compounds described in U.S. Pat. No. 4,221,863, especially tetramethylthiourea), furthermore, thione compounds described in JP-B-60-1134, JP-B-63
No. 29727, a mercapto compound described in
-163042, a meso-ion compound described in U.S. Pat. No. 4,781,2013, a terenoether compound described in JP-A-2-118566,
Sulfites. In particular, 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.

Next, a silver halide photographic light-sensitive material of the present invention having a host silver halide emulsion chemically sensitized by the above-mentioned method as a light-sensitive emulsion layer on a support (sometimes simply referred to as a light-sensitive material). Will be described. The silver halide emulsion of the host used in the present invention is preferably silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide or silver chloride. The silver halide grains of the host used in the present invention have a regular crystal form such as cubic or octahedral, or irregular (i.e., spherical or plate-like).
(rregular) 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 of the host used in the present invention may have different phases in the inside and the surface layer or may consist of a uniform phase. Particles having two or more multi-structures having different iodine compositions between the inside of the particle and the surface layer (particularly, the iodine content inside is larger) are also preferred. Further, grains which mainly form a latent image on the surface thereof (for example, a negative emulsion) may be used, and grains which are mainly formed inside the grains (for example, an internal latent image type emulsion, a directly fogged emulsion which has been previously fogged) ). Preferably, the particles are such that the latent image is mainly formed on the surface. Further, particles containing dislocation lines are preferable.

The silver halide emulsion of the host used in the present invention has a thickness of 0.5 μm or less, preferably 0.1 μm or less.
Tabular grain emulsions having a size of 3 μm or less, preferably having a diameter of 0.6 μm or more, and having an average aspect ratio of 3 or more occupying 50% or more of the total projected area are also preferred. Further, tabular emulsions having good monodispersity described in JP-A-2-838 are particularly preferred.

The silver halide emulsion of the host used in the present invention has a statistical variation coefficient (a value obtained by dividing the standard deviation S by the diameter d in the distribution expressed by the diameter when the projected area is approximated by a circle). Monodisperse emulsions in which d) is at most 20% are particularly preferred. Further, two or more emulsions may be mixed.

The photographic emulsion used in the present invention is, for example, Chimie Physique Photography by P. Glafkids.
er Physique Photographeq
ue) (Paul Montell, 1967), by GF Duffin, Photographic Emulsion Chemistry (Photog)
raphic Emulsion Chemistr
y) (Focal Press, 1966), Making and Coating Photographic, by VL Zelikman et al.
Emulsion (Making and Coating
Photographic Emulsion (Focal Press, 1964).

In forming the silver halide grains,
As a silver halide solvent for controlling the growth of grains, for example, ammonia, rodancali, rodanammon, thioether compounds (for example, US Pat. No. 3,271)
No. 157, No. 3574628, No. 3704130
Nos. 4,297,439 and 4,276,374),
Thione compounds (for example, JP-A-53-144319, JP-A-53-82408, and JP-A-55-77737) and amine compounds (for example, JP-A-54-100717) can be used.

Cadmium salt, 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, and the like may coexist. As a binder or protective colloid that 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 and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol It is possible to use various synthetic hydrophilic polymer materials such as a single or copolymer of polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole. it can.

Examples of gelatin include general-purpose lime-processed gelatin, acid gelatin, and the journal of the Japan Society of Science Photography (Bull).
l. Soc. Photo. Japan), No. 16,3
Enzyme-treated gelatin as described on page 0 (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. For example, a chromium salt, an aldehyde salt (for example, formaldehyde, glyoxal, glutaraldehyde), and an N-methylol compound (for example, dimethylol urea) are specifically mentioned. Active halogen compounds (for example, 2,4-dichloro-6
-Hydroxy-1,3,5-triazine and its sodium salt) and active vinyl compounds (e.g., 1,3-bisvinylsulfonyl-2-propanol, 1,2-bis (vinylsulfonylacetamido) ethane, bis (vinylsulfonylmethyl) ) A vinyl polymer having an ether or bitylsulfonyl group in the side chain) is preferable because it rapidly cures a hydrophilic colloid such as gelatin and gives stable photographic properties. N-carbamoylpyridinium salts (eg, (1-morpholinocarbonyl-3-pyridinio) methanesulfonate) and haloamidinium salts (eg, 1- (1-chloro-1-pyridinomethylene) pyrrolidinium-2-naphthalenesulfonate) also cure. Excellent early.

The silver halide photographic emulsion of the host used in the present invention is preferably 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, that is, an indolenine nucleus, a benz Indolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole 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, nuclei having a ketomethylene structure such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, and a thiazolidine-2,
A 5- to 6-membered heterocyclic nucleus of a 4-dione nucleus, 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, a substituted aminostilbenzene compound having a nitrogen-containing heterocyclic nucleus group (for example, US Pat. Nos. 2,933,390 and 36)
No. 35721), formaldehyde condensates of aromatic organic acids (for example, those described in US Pat. No. 3,743,510), cadmium salts, azaindene compounds and the like. U.S. Pat. Nos. 3,615,613 and 361
The combinations described in JP-A-5641, JP-A-3617295 and JP-A-3635721 are particularly useful.

The host or fine grain silver halide photographic emulsion used in the present invention is used for various purposes, for example, to prevent fog during the production process, storage or photographic processing of the photographic material, or to stabilize the photographic performance. Can be contained. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, and aminotriazole , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-
Mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrithione; azaindenes; for example, triazaindenes, tetraazaindenes (especially 4-
Hydroxy-6-methyl (1,3,3a, 7) tetraazaindene), pentaazaindenes; known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid and benzenesulfonamide Many compounds can be added.

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 of the present invention may contain a water-soluble dye in the 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, and azo dyes are preferably used.In addition, 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 photographic light-sensitive material of the present invention can be constituted as a multilayer multicolor photographic material 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 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 sensitivity, green sensitivity and blue sensitivity, blue sensitivity, green sensitivity and red sensitivity or blue sensitivity, red sensitivity and green sensitivity. In addition, 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 a three-layer constitution may be used to 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 grain silver halide or the like may be provided below the high-sensitivity layer, particularly the high-sensitivity blue-sensitive layer, to improve the sensitivity.

It is common that the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler. You can also. 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
-Described in the patents described in CG.

As the yellow coupler, for example, US Pat. Nos. 3,933,501 and 4,022,620
No. 4,326,024 and 4,401,75
No. 2, Japanese Patent Publication No. 58-10739, British Patent No. 1,42
Nos. 5,020 and 1,476,760 are preferred.

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.
No. 61,432, No. 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. 4,500,603
No. 4,540,654 are preferred.

Examples of cyan couplers include phenol-based and naphthol-based couplers. For example, US Pat. Nos. 4,052,212, 4,146,396, 4,228,233, and 4 , 296, 200,
Nos. 2,369,929 and 2,801,171
No. 2,772,162, No. 2,895,82
No. 6, No. 3,772,002, No. 3,758,3
08, 4,334,011, 4,327,
No. 173, West German Patent Publication No. 3,329,729, European Patent No. 121,365A, U.S. Pat. No. 3,446,6.
No. 22, No. 4,333,999, No. 4,451,
No. 559, No. 4,427,767, European Patent No. 16
Those described in 1,626A are preferred.

A colored coupler for correcting unnecessary absorption of a coloring dye is described in, for example, Research Disclosure No. 17643, section VII-G, U.S. 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 diffusibility 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 disclosed in US Pat. Nos. 3,451,820 and 4,082.
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
D17643, Patents described in Section VII-F,
Nos. 7-151944, 57-154234, 6
No. 0-184248 and U.S. Pat. No. 4,248,962 are preferred.

Examples of couplers which release a nucleating agent or a development accelerator imagewise during development include, for example, British Patent No.
Nos. 097,140 and 2,131,188, and JP-A-59-157638 and JP-A-59-170840 are preferred.

Other couplers usable in the light-sensitive material of the present invention include, for example, US Pat.
No. 0,427, competing couplers, U.S. Pat.
No. 83,472, No. 4,338,393, No. 4,
No. 310,618, a multi-equivalent coupler disclosed in
DIR redox compounds or DIR coupler releasing couplers described in JP-A-185950 and JP-A-62-24252; D. No. 114
49, 24241, bleaching accelerator releasing couplers described in JP-A-61-201247, U.S. Pat.
No. 477, and the like.

The coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like.

Specific examples of high-boiling organic solvents 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, bis (2,4-di-t-aminophenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate), phosphoric acid or Esters of phosphonic acid (for example, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridecyl phosphate, tributoxyethyl phosphate and trichloropropyl phosphate DOO, di-2-ethylhexyl phenyl phosphate), benzoic acid esters (e.g., 2-
Ethylhexyl benzoate, dodecyl benzoate,
2-ethylhexyl-p-hydroxybenzoate),
Amides (for example, N, N-diethyldodecaneamide,
N, N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (eg, isostearyl alcohol, 2,4-di-tert)
-Amylphenol), aliphatic carboxylic acid esters (for example, bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate),
Examples include aniline derivatives (for example, N, N-dibutyl-2-butoxy-5-tert-octylaniline) and hydrocarbons (for example, paraffin, dodecylbenzene, diisopropylnaphthalene). The auxiliary solvent has a boiling point of 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C.
Organic solvents having a temperature of not more than ℃ can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-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. 4,199,3.
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, metal, etc., which are usually used for the photographic light-sensitive material. Applied to the body. Useful as a flexible support are films made of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc., baryta layer or α-olefin polymer. (For example, polyethene, polypropylene, and 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 undercoating treatment.

For coating the photographic emulsion layer and other hydrophilic colloid layers, various known coating methods such as a dip coating method, a roller coating method, a curtain coating method, and an extrusion coating method can be used. U.S. Pat.
No. 681,294, No. 2,761,791, No. 3,526,528 and No. 3,508,947, the multilayer may be applied simultaneously.

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 type photosensitive materials and heat development type color photosensitive materials. . Research Disclosure No. 171
23 (July 1978), or by utilizing a three-color coupler mixture or as described in U.S. Pat.
The present invention can be applied to black-and-white photographic materials such as those for X-rays by utilizing the black color couplers described in U.S. Pat. No. 461 and British Patent No. 2,102,136. Stencil film such as squirrel film or scanner film,
The present invention is also applied to X-ray film for direct medical treatment, indirect medical treatment, or industrial use, negative black-and-white film for photography, black-and-white photographic paper, COM or ordinary microfilm, silver salt diffusion transfer type photosensitive material and printout type photosensitive material. it can.

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-524, and a peel-free type film unit as described in JP-A-57-119345 can be employed.

The use of a polymer acid layer protected by a neutralization timing layer in any of the above formats is advantageous for widening the allowable range of processing temperatures. When used in color diffusion transfer photography, it may be used by adding to any layer in the light-sensitive material, or
It may be used as a developer component by being enclosed in a processing solution container.

Various exposure means can be used in the light-sensitive material of the present invention. Any light source that emits radiation 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.

Gas, dye solution or semiconductor lasers, light emitting diodes, and plasma light sources that emit light in the wavelength range from ultraviolet to infrared can also be used as the recording light source. Also, a phosphor screen (such as a CRT) emitted from a phosphor excited by an electron beam or the like, a liquid crystal (LCD) or lanthanum-doped lead zirconate titanate (PLZ)
Exposure means in which a linear or planar light source is combined with a micro shutter array using T) or the like can also be used. If necessary, the spectral distribution used for exposure can be adjusted with a color filter.

The light-emitting developer 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 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 development inhibitors or antifoggants such as iodides, benzimidazoles, benzothiazoles or mercapto compounds. Also, if necessary,
Preservatives such as hydroxyamine or sulfite, organic solvents such as triethanolamine, 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, viscosity-imparting agents, amino Polycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid,
Various chelating agents represented by phosphonocarboxylic acid and antioxidants described in West German Patent Application (OLS) No. 2,622,950 may be added to the color developer.

In the developing 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 N-methyl-p-aminophenols 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 bleach-fixing after bleaching may be used. Examples of the bleaching agent include compounds of polyvalent metals such as iron (III), cobalt (III), chromium (IV), and copper (II), peracids, quinones, and nitrone compounds. Representative bleaches include ferricyanide; dichromate; organic complexes of iron (III) or cobalt (III), such as ethylenediaminetetraacetic acid, diethyleneaminepentaacetic acid, nitrilotriacetic acid,
Use of aminopolycarboxylic acids such as 1,3-diamino-2-propanoltetraacetic acid or complex salts of organic acids such as citric acid, tartaric acid and malic acid; manganate; persulfate; manganate; Can be. Of these, iron (III) ethylenediaminetetraacetate,
Diethylenetriaminepentaacetate iron (III) salt and persulfate are preferred from the viewpoint of rapid processing 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.

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. Patent 3,893,858, West German Patent 1,290,812
No. 2,059,988, JP-A-53-32736, JP-A-53-57831
Nos. 37418, 53-65732, 53-72623, 53-9
No. 5630, No. 53-95631, No. 53-104232, No. 53-124424
No. 53-141623, 53-28426, Research Disclosure No. 17129 (July 1978), etc., having a mercapto group or a disulfide group;
Thiazolidine derivatives as described in JP-A-50-140129; JP-B-45-8506; JP-A-52-20832;
Thiourea derivatives described in U.S. Pat. No. 3,706,561;
Iodides described in West German Patent No. 1,127,715, JP-A-58-16235; Polyethylene oxides described in West German Patents 966,410 and 2,748,430; Polyamine compounds described in JP-B-45-8836; No.49-42434, 49-596
The compounds described in Nos. 44, 53-94927, 54-35727, 55-26506 and 58-163940 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 1,290,8
No. 12, JP-A-53-95630 are preferred. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferred.
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 iodide, and thiosulfates are 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 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 (LE West, Phot. Sci. Eng.), No. 6,
Vol., Pages 344 to 359 (1965) and the like. Particularly, the addition of a chelating agent or an anti-binder is effective.

In the water washing step, two or more tanks are subjected to countercurrent water washing.
It is common to save water. Further, instead of the water washing step, a multi-stage countercurrent stabilization 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 and polycarboxylic acid) and formalin can be mentioned as typical examples. In addition, if necessary, chelating agents (eg, inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, organic phosphonic acid, aminophosphonic acid, phosphonocarboxylic acid), bactericides (eg, benzoisothiazolinone, isothiazolone, 4- Various additives such as thiazoline benzimidazole, halogenated phenol, sulfanilamide, benzotriazole), surfactants, optical brighteners, hardeners, etc. may be used, and two or more kinds of the same or different target compounds may be used. You may use together.

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 photographic 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 stabilization processing time of the present invention varies depending on the type of the light-sensitive material and the processing conditions, but is usually 20 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 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.
No. 342,599, Schiff base compounds described in Research Disclosure Nos. 14850 and 15159, aldol compounds described in No. 13924, metal salt complexes described in U.S. Pat. And JP-A-56-6235, JP-A-56-16133
Nos. 56-59232, 56-67842, 56-83734, 56
-83735, 56-83736, 56-89735, 56-81837
Nos. 56-54430, 56-106241, 56-107236,
The precursors of various salt types described in JP-A-57-97531 and JP-A-57-83565 can be exemplified.

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 described in JP-A-56-64339, JP-A-57-144547,
57-211147, 58-50532, 58-50536, 58-5
0533, 58-50534, 58-50535 and 58-11543
It is described in No. 8.

The various processing solutions used in the present invention are at 10 ° C. to 50 ° C.
Used at ° C. A temperature of 33 ° C to 38 ° C is standard, but higher temperatures promote processing and reduce processing time, and conversely lower temperatures to achieve improved image quality and improved processing solution stability. Can be. Also, to save silver on photosensitive materials, West German Patent No. 2,226,770 or U.S. Patent
The treatment using cobalt intensification or hydrogen peroxide intensification described in 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, if necessary.

In the continuous processing, a certain finish can be obtained by using a replenisher of each processing liquid to prevent the fluctuation of the liquid composition. The replenishment amount can be reduced to half or less of 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 bleach-fixed very generally, and when it is a color photographic material for photography, if necessary.

[0093]

EXAMPLES The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to only these examples.

Reference Example 1 (Preparation of silver halide fine grain emulsion adsorbed with chalcogen sensitizer) AgCl _0.75 Br _0.25 fine grain emulsion (particle diameter 0.12 μm)
m, pH 6.5, pAg 7.6, gelatin 8%)
Was added with a chemical sensitizer shown in Table 1 below,
For 10 minutes to prepare silver halide fine grain emulsions Em-101 to Em-107 having a chemical sensitizer adsorbed thereon. In addition, in the adsorption operation to the silver halide fine particles, the reaction rate between the added chemical sensitizer and the silver halide fine particles was 10% or less. I-1, 6, 12, and II
The selenium sensitizer represented by -1, 21 is given by the following formula.

[0095]

Table 1 微粒子 Fine grain emulsion Chalcogen sensitizer (added Amount: mol / mol Ag) Ｅ Em-101 sodium thiosulfate ( S) (3.2 × 10 ^-3 ) ──────────────────────────────────── Em-102 I-1 (Se) (1.6 × 10 ⁻³ ) + sodium thiosulfate (S) (1.6 × 10 ⁻³ ) ───────────────── Em-103 I-6 (Se) (1.3 × 10 ⁻³ ) + sodium thiosulfate (S) (1.6 × 10 ⁻³ ) ) ──────────────────────────────────── Em-104 I-12 (S ) (2.0 × 10 ^-3) + sodium thiosulphate ^{(S) (1.6 × 10 -3} ) ──────────────────────── {Em-105 II-1 (Se) (1.7 × 10 ⁻³ ) + sodium thiosulfate (S) (1.6 × 10 ⁻³ )} ──────────────────────────────── Em-106 II-21 (Se) (1.2 × 10 ^-3 ) + Sodium thiosulfate (S) (1.6 × 10 ^-3 ) ────────────────────────────────── {Em-107 I-1 (Se) (3.2 × 10 ⁻³ )} ──────

[0096]

Embedded image

[0097]

Embedded image

(Preparation of Host Silver Halide Emulsion Em-A) A silver nitrate aqueous solution (18 g of AgNO ₃₎ was stirred in 1 liter of an aqueous solution of pH 5.0 containing 0.35 g of potassium bromide and 40 g of gelatin kept at 75 ° C. ) And an aqueous potassium bromide solution (KBr 12.7 g) were added simultaneously over 20 minutes. Next, an aqueous silver nitrate solution (156 g of AgNO ₃ )
Mixed aqueous solution of potassium, potassium iodide and potassium bromide (6.1 g
+196 g / liter) were added simultaneously over 20 minutes by a flow rate accelerating method at which the final rate of the addition flow rate was 5.4 times the final rate.
Kept at V. After completion of particle formation, desalting and washing with normal flocculation method, gelatin and water were added, and pH was adjusted.
Was adjusted to 6.3 and pAg to 8.3. The obtained silver bromide emulsion (Em-A) was a monodispersed octahedral emulsion having a silver iodide content of about 2 mol%, a grain diameter of 0.49 μm, and a coefficient of variation of the grain diameter of 9.5%. Was.

(Preparation of Chemically Sensitized Silver Halide Emulsion of the Host) Emulsion Em-A prepared above was divided into small portions and heated to 60 ° C. Next, the mole A of the emulsion Em-A
per g, as shown in Table 2, the corresponding Em-101-1
07 (fine grain emulsion to which the above chemical sensitizer was adsorbed) was added and ripened for 60 minutes to prepare a chemically sensitized emulsion.

(Preparation of Silver Halide Emulsion of Host Above Chemically Sensitized by Conventional Method) Emulsion Em-A prepared above was divided into small portions and heated to 60 ° C. Then, the same chemical sensitizer as the chemical sensitizer adsorbed on the fine grain emulsion is dissolved in water or a methanol solution so as to have the same addition amount, and the emulsion Em-A is chemically sensitized using the same, A comparative emulsion was prepared.

(Preparation of photographic light-sensitive material (sample)) Anhydro-5-chloro-5'-phenyl-9-ethyl-3,3'-di (3-sulfopropyl) benzoxa was added to each emulsion obtained above. Carbocyanine hydroxide sodium salt (sensitizing dye), phenoxyethanol, gelatin,
4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, potassium poly-styrenesulfonate, and sodium dodecylbenzenesulfonate are added to prepare a coating solution for forming a photosensitive layer, and the undercoat layer is formed. Gelatin, polymethyl methacrylate particles, and 2,4-dichloro-
Co-extrusion was applied together with a coating liquid for forming a protective layer containing 6-hydroxy-s-triazine sodium salt to prepare Samples 1 to 14 corresponding to each.

The samples obtained above were evaluated for photographic properties (fog, relative spectral sensitivity) as follows. (1) To the sample obtained above, exposure for sensitometry (1/100 second) was given through an optical wedge using an SC-50 filter (manufactured by Fuji Photo Film Co., Ltd.). Then, it developed with Kodak prescription D-19 developer at 20 degreeC for 10 minutes. Stop, fix, wash, dry, and
The concentration was measured to obtain the results shown in Table 2. The relative spectral sensitivity is represented by a relative value of a reciprocal of an exposure amount necessary to obtain an optical density of (fog value + maximum density) / 2.

[0103]

Table 2 ──────────────────────────────────── Sample Fine particles used for emulsion preparation or Sensitizer Relative spectral number (addition amount: mol / mol Ag) Fog sensitivity ───────────────────────────────── １ 1 (comparison) Sodium thiosulfate (S) 0.08 100 2 (comparison) Em-101 (S: 1.6 × 10 ^-5 ) 0.07 120 ───────────── ３3 (comparison) I-1 (Se) + sodium thiosulfate (S) 0.16 146 4 (reference) Em- 102 (Se: 8.0 × 10 ^-6 /S:8.0×10 ^-6 ) 0.10 198 ──────────────────────────── ──────── 5 (comparison) I-6 (Se) + sodium thiosulfate (S) 0.15 144 6 (Reference) Em-103 (Se: 6.5 × 10 ^-6 /S:8.0×10 ^-6 ) 0.10 190 ─────────────────────── ７7 (comparison) I-12 (Se) + sodium thiosulfate (S) 0.15 151 8 (reference) Em-104 (Se: 1.0 × 10 ^-5 / S: 8.0 × 10 ^-6 ) 0.09 200────────────────────────────────────9 ( Comparison) II-1 (Se) + sodium thiosulfate (S) 0.13 167 10 (reference) Em-105 (Se: 8.5 × 10 ⁻⁵ /S:8.0×10 ⁻⁶ ) ───────────────────────────────── 11 (comparison) II-21 (Se) + sodium thiosulfate (S) 0.13 171 12 (Reference) Em-106 (Se: 6.0 × 10 ⁻⁶ /S:8.0×10 ⁻⁶ ) 0.09 232 ────────────────── ────── ─────────── 13 (Comparative) I-1 (Se) 0.38 140 14 ( Comparative) Em-107 (Se: 1.6 × 10 -5) 0.32 175 ───── ───────────────────────────────

As is evident from the results shown in Table 2 above, a photograph using a silver halide emulsion sensitized using silver halide fine particles having a selenium sensitizer and a sulfur sensitizer adsorbed thereon. The photosensitive materials (Samples 4, 6, 8, 10 and 12) show high spectral sensitivity. These photographic materials are
Fog is less than that of a photographic material using a silver halide emulsion obtained by using a method of directly adding a sensitizer to a silver halide emulsion to be sensitized. on the other hand,
A comparative photographic light-sensitive material (sample 2) using a silver halide emulsion sensitized using silver halide fine particles having a sulfur sensitizer adsorbed thereon has increased sensitivity and reduced fog. The effect was small. When the selenium sensitizer alone was used, even when a silver halide emulsion sensitized by using silver halide fine particles to which the selenium sensitizer was adsorbed was used (sample 14), the feet had high sensitivity. However, since it is soft, the midpoint sensitivity is not so high and fog is large.

[Example 1] (Preparation of silver halide fine grain emulsion with adsorbed chalcogen sensitizer) The same fine grain emulsion as used in Reference Example 1 was added to a chemical sensitizer (Table 3) shown in Table 3 below. Further, chloroauric acid was further added to the chemical sensitizer used in Reference Example 1 above, and the mixture was stirred at 40 ° C. for 10 minutes, and silver halide fine grain emulsions Em-201 to Em having the chemical sensitizer adsorbed thereon. -206 was made. In addition,
In the adsorption operation to the silver halide fine particles, the reaction rate between the added chemical sensitizer and the silver halide fine particles was 10% or less.

[0106]

[Table 3] Table 3 微粒子 Fine particle chalcogen sensitizer Chloroauric acid (Au) Emulsion (addition amount: mol / mol Ag) (addition amount: mol / mol Ag) ──────── Em-201 Sodium thiosulfate (S) (3.2 × 10 ^-3 ) 4.8 × 10 ^-3 ─────────────────── ─────────────────Em-202 I-1 (Se) (1.6 × 10 ⁻³ ) 4.8 × 10 ⁻³ + sodium thiosulfate (S) ( 1.6 × 10 ^-3 ) ──────────────────────────────────── Em-203 I-6 (Se ) (1.3 × 10 ⁻³ ) 4.8 × 10 ⁻³ + sodium thiosulfate (S) (1.6 × 10 ⁻³ ) ─── ────────────── Em-204 I-12 (Se) (2.0 × 10 ⁻³ ) 4.8 × 10 ⁻³ + sodium thiosulfate (S) (1.6 × 10 ⁻³ ) ^-3 ) ──────────────────────────────────── Em-205 II-1 (Se) (1 0.7 × 10 ^-3 ) 4.8 × 10 ^-3 + sodium thiosulfate (S) (1.6 × 10 ^-3 ) Em-206 II-21 (Se) (1.2 × 10 ⁻³ ) 4.8 × 10 ⁻³ + sodium thiosulfate (S) (1.6 × 10 ⁻³ ) ^-3 ) ────────────────────────────────────

(Preparation of Chemically Sensitized Silver Halide Emulsion of the Host) Emulsion Em-A used in Reference Example 1 was subdivided into 56 ° C.
The temperature rose. Next, per mol Ag of the emulsion Em-A, Table 3
As shown in (1), the corresponding Em-201 to 206 (fine grain emulsion having the chemical sensitizer adsorbed thereon) were added thereto, and potassium thiocyanate (1.0 × 10 ⁻³ mol / mol Ag) was further added. After ripening for minutes, various emulsions were prepared.

(Preparation of Silver Halide Emulsion of Host Above Chemically Sensitized by Conventional Method) Emulsion Em-A used in Reference Example 1 was subdivided into 60 ° C.
The temperature rose. Then, the same chemical sensitizer as the chemical sensitizer adsorbed on the fine grain emulsion is dissolved in water or a methanol solution so as to have the same addition amount.
mA was chemically sensitized to prepare a comparative emulsion.

(Preparation of Photographic Material (Sample)) Samples 31 to 42 corresponding to the respective emulsions were prepared in the same manner as in Reference Example 1 except that each of the emulsions obtained above was used. Then, exposure and development were performed in the same manner as in Reference Example 1, and the density was measured to evaluate the photographic properties (fog, relative spectral sensitivity). The relative spectral sensitivity was set to 100 for the value of Sample 31. Table 4 shows the results.

[0110]

Table 4 試 料 Sample Fine particles used for emulsion preparation or Sensitizer Relative spectral number (addition amount: mol / mol Ag) Fog sensitivity ───────────────────────────────── ─── 31 (comparison) Sodium thiosulfate (S) + chloroauric acid (Au) 0.10 100 32 (comparison) Em-201 (S: 1.6 × 10 ^{-5 /} Au: 2.4 × 10 ^-5 ) 08 120 ──────────────────────────────────── 33 (comparative) I-1 (Se) + thio sodium sulfate (S) 0.27 202 + chloroauric acid (Au) 34 (invention) Em-202 0.19 301 (Se : 8.0 × 10 -6 /S:8.0 × 10 -6 /Au:2.4 × 10 ^-5 ) ──────────────────────────────────── 35 (comparison) I- 6 (Se) + sodium thiosulfate (S) 0.25 188 + chloroauric acid (Au) 36 (invention) Em-203 0.14 261 (Se: 6.5 × 10 ^-6 /S:8.0×10 ^-6 /Au:2.4 × 10 ^-5 ) ──────────────────────────────────── 37 (comparison) I -12 (Se) + sodium thiosulphate (S) 0.22 174 + chloroauric acid (Au) 38 (invention) Em-204 0.12 243 (Se : 1.0 × 10 -5 /S:8.0 × 10 - ⁶ /Au:2.4 × 10 ^-5 ) ──────────────────────────────────── 39 (comparison) II-1 (Se) + sodium thiosulfate (S) 0.18 191 + chloroauric acid (Au) 40 (invention) Em-205 0.12 310 (Se: 8.5 x 10 ^{-6 /} S: 8.0 x 10 ^-6 / Au: 2.4 × 10 ^-5 ) ──────────────────────────────────── 41 (comparison) II) 21 (Se) + sodium thiosulfate (S) 0.17 202 + chloroauric acid (Au) 42 (invention) Em-206 0.12 318 (Se : 6.0 × 10 -6 /S:8.0 × 10 -6 / Au: 2.4 × 10 -5) ── ──────────────────────────────────

As is clear from the results shown in Table 4 above, silver halide sensitized by using silver halide fine particles further adsorbing a gold sensitizer to a selenium sensitizer and a sulfur sensitizer. The photographic light-sensitive materials according to the present invention using emulsions (samples 34, 36, 38, 40 and 42) show higher spectral sensitivity.

Example 2 AgBr _0.995 I _0.005 fine grain emulsion (particle size 0.08 μm)
m, pH 6.5, pAg 8.0, gelatin 8%)
Was added with a chemical sensitizer shown in Table 5 below,
And the emulsion Em- on which the chemical sensitizer has been adsorbed.
301-Em-306 were made. In addition, in the adsorption operation to the silver halide fine particles, the reaction rate between the added chemical sensitizer and the silver halide fine particles was 10% or less.

[0113]

[Table 5] Table 5 ──────────────────────────────────── Fine particle chalcogen sensitizer Chloroauric acid Emulsion (addition amount: mol / mol Ag) (addition amount: mol / mol Ag) {Em-301 Sodium thiosulfate (S) (9.0 × 10 ⁻⁴ ) 2.0 × 10 ⁻³ } ────────────────Em-302 I-1 (Se) (5.0 × 10 ⁻⁴ ) 2.0 × 10 ⁻³ + sodium thiosulfate (S) (4 0.5 × 10 ^-4 ) ──────────────────────────────────── Em-303 I-6 ( ^{Se) (6.0 × 10 -4)} 2.0 × 10 -3 + sodium thiosulphate ^{(S) (4.5 × 10 -4} ) ────── ───────────────────────────── Em-304 I-12 ( Se) (1.0 × 10 -4) 2.0 × 10 ^-3 + sodium thiosulfate (S) (4.5 × 10 ^-4 ) {Em-305 II-1 (Se) (9.0 × 10 ⁻⁴ ) 2.0 × 10 ⁻³ + sodium thiosulfate (S) (4.5 × 10 ⁻⁴ )} ───────────────────────────────── Em-306 II-21 (Se) (6.0 × 10 ^-4 ) 2.0 × 10 ⁻³ + sodium thiosulfate (S) (4.5 × 10 ⁻⁴ ) {Em-307 II-1 (Se) (5.0 × 10 ⁻⁴ ) 2.0 × 10 ⁻³ } ─── ─────────────────

(Preparation of Host Silver Halide Emulsion Em-B) 10 g of potassium bromide, 0.4 g of potassium iodide, and 15 g of inert gelatin having an average molecular weight of 15,000 were distilled water.
While thoroughly stirring the aqueous solution dissolved in 7 liters, a 14% aqueous solution of potassium bromide and a 20% aqueous solution of silver nitrate were added thereto at a constant flow rate for 15 seconds at 55 ° C. and pBr 1.0 by the double jet method ( This addition consumed 5.5% of the total silver.) Gelatin aqueous solution (1
After stirring at 55 ° C., a 20% aqueous silver nitrate solution was added at a constant flow rate until pBr reached 1.4 (this addition consumed 5.0% of the total silver). . Furthermore, a 20% potassium iodobromide solution (KB
_{r 1-X I X:.} X = 0.04) and was added over 43 minutes with a 33% aqueous solution of silver nitrate double jet (consumed 25% of the total silver amount in this added) Here,
After adding an aqueous solution containing 4.5 g of potassium iodide,
14.5m of 0.001 / wt% K ₃ IrCl ₆ aqueous solution
and a mixed aqueous solution of 18% potassium bromide and 3% potassium iodide and a 33% aqueous silver nitrate solution were added by a double jet method over 39 minutes (this addition consumed 64.5% of the total silver amount). did). The amount of silver nitrate used in this emulsion was 425 g. Next, desalting was carried out by a usual flocculation method. After desalting, gelatin and water were added to adjust the pAg to 8.2 and the pH to 5.8 at 40 ° C. Thus, tabular grains having an aspect ratio of 5 or more have a total projected area of 5
Tabular grains having an aspect ratio of 2 or more occupy 90% of the total projected area;
0), a tabular silver iodobromide emulsion (Em-B) having a coefficient of variation of 18% and an equivalent sphere diameter of 0.6 μm was prepared. According to observation with a 200 kV transmission electron microscope at liquid N ₂ temperature, 1
Grains having more than 50 dislocation lines per grain accounted for 60%.

(Preparation of Chemically Sensitized Silver Halide Emulsion of the Host) Emulsion Em-B prepared above was divided into small portions and heated to 56 ° C. Next, the mole A of the emulsion Em-B
Per g, as shown in Table 6, the corresponding Em-301-3
07 (fine grain emulsion having the chemical sensitizer adsorbed thereon), potassium thiocyanate (1 × 10 ⁻³ mol / mol Ag) was further added, and the mixture was aged for 45 minutes to prepare various emulsions according to the present invention. did.

(Preparation of Silver Halide Emulsion of Host Above Chemically Sensitized by Conventional Method) Emulsion Em-B prepared above was divided into small portions and heated to 56 ° C. Then, the same chemical sensitizer as the chemical sensitizer adsorbed on the fine grain emulsion is dissolved in water or a methanol solution so as to have the same addition amount, and the emulsion Em-B is chemically sensitized using the same, and A comparative emulsion was prepared.

(Preparation of Photographic Material (Sample)) Each of the emulsions obtained above was further added to a sensitizing dye represented by the following formula (ExS
-1, ExS-2 and ExS-3) were added in a molar ratio of 60: 3: 37, and the following components were further added to prepare a coating solution for forming a photosensitive layer.

[0118]

Embedded image

[0119]

Embedded image

Magenta coupler; 3- {3- [2- (2,4-di-tert-amylphenoxy) butyrylamino] benzoylamino} -1- (2,
4,6-trichlorophenyl) pyrazolone-5-one oil; tricresyl phosphate stabilizer; 4-hydroxy-6-methyl-1,3,3a,
7-tetrazaindene antifoggant; 1- (m-sulfophenyl) -5-mercaptotetrazole monosodium salt Coating aid; sodium dodecylbenzenesulfonate hardener; 1,2-bis (vinylsulfonylacetylamino) ethane Preservative: phenoxyethanol Triacetylcellulose film having an undercoat layer (support) with the above coating solution and a separately prepared coating solution for forming a gelatin protective layer containing polymethyl methacrylate fine particles
Coated on top by coextrusion method, photographic light-sensitive material (sample) 5
1 to 64 were prepared.

The samples obtained above were evaluated for photographic properties (fog, relative spectral sensitivity) as follows. (1) The sample obtained above was exposed to red light for sensitometry (1/100 second) and subjected to the following color development processing.

(Processing Method) 処理 Processing Step Processing Time Processing Temperature Coloring Developing 2 minutes 15 seconds 38 ° C Bleaching 6 minutes 30 seconds 38 ° C Washing 2 minutes 10 seconds 24 ° C Fixing 4 minutes 20 seconds 38 ° C Washing (1) 1 minute 5 seconds 24 ° C Washing (2) 1 minute 0 seconds 24 ° C Stable 1 Min 5 sec 38 ℃ drying 4min 20sec 55 ℃ ────────────────────────────────────

Next, the composition of the processing solution is shown. ──────────────────────────────────── (Color developing solution) Unit g Diethylenetriaminepentaacetic acid 1.0 1 -Hydroxyethylidene-1,1 3.0 diphosphonic acid 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-4.5 hydroxyethylamino) -2-methylaniline sulfate Add water and add 1 liter pH 10.05０．０５ ─────────────

──────────────────────────────────── (Bleaching solution) Unit g Ethylenediaminetetraacetic acid second Iron 100.0 Sodium trihydrate Ethylenediaminetetraacetic acid di 10.0 Sodium salt 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 Ethylenediaminetetraacetic acid 5.5 Sodium salt Sodium sulfite 7.0 Sodium bisulfite 5.0 Ammonium thiosulfate aqueous solution (70%) 170 ml Add water 1.0 liter pH 6.7─────────────── ─────────────────────

──────────────────────────────────── (Stabilizing solution) Unit g Formalin (37%) 2.0 ml Polyoxyethylene-p-monononyl phenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid di-0.05 sodium salt Water was added to add 1.0 liter, pH 5.0-8.0. ────────────────────────────────

The density of the treated sample was measured with a green filter. Table 6 shows the obtained photographic performance results. The relative spectral sensitivity is represented by a relative value of a reciprocal of an exposure amount necessary to obtain an optical density of (fog value + maximum density) / 2, and the value of sample 51 is set to 100.

[0128]

Table 6 ──────────────────────────────────── Sample Fine particles used for emulsion preparation or Sensitizer Relative spectral number (addition amount: mol / mol Ag) Fog sensitivity ───────────────────────────────── ─── 51 (comparison) sodium thiosulfate (S) + chloroauric acid (Au) 0.13 100 52 (comparison) Em-301 (S: 9.0 × 10 ^{−6 /} Au: 2.0 × 10 ⁻⁵ ) 11 111 ──────────────────────────────────── 53 (comparative) I-1 (Se) + thio Sodium sulfate (S) 0.26 129 + chloroauric acid (Au) 54 (invention) Em-302 0.21 186 (Se: 5.0 × 10 ^{-6 /S:4.5×10 -6} /Au:2.0×10 ^-5) ──────────────────────────────────── 55 (Comparative) -6 (Se) + sodium thiosulphate (S) 0.24 131 + chloroauric acid (Au) 56 (invention) Em-303 0.18 189 (Se : 6.0 × 10 -6 / S: 4.5 × 10 - ⁶ / Au: 2.0 × 10 ^-5 ) ──────────────────────────────────── 57 (comparison) I-12 (Se) + sodium thiosulfate (S) 0.23 139 + chloroauric acid (Au) 58 (invention) Em-304 0.19 197 (Se: 1.0 x 10 ^-5 / S: 4.5 x 10 ^-6 / Au: 2.0 × 10 ^-5 ) ──────────────────────────────────── 59 (Compare ) II-1 (Se) + sodium thiosulfate (S) 0.21 137 + chloroauric acid (Au) 60 (invention) Em-305 0.16 187 (Se: 9.0 × 10 ⁻⁶ / S: 4.5 ×) 10 ^-6 / Au: 2.0 × 10 ^-5 ) ──────────────────────────────────── 61 ( Comparison) II-21 (Se) + thio Sodium sulfate (S) 0.21 136 + Chloroauric acid (Au) 62 (invention) Em-306 0.16 190 (Se: 6.0 × 10 ^{-6 /S:4.5×10 -6} /Au:2.0×10 ^-5 ) ──────────────────────────────────── 63 (comparison) I-1 (Se) + Chloroauric acid (Au) 0.82 63 64 (comparison) Em-307 (Se: 9.0 × 10 ^-6 /Au:2.0×10 ^-5 ) 0.68 94 ──────────── ────────────────────────

As is clear from the results shown in Table 6 above, the selenium sensitizer is extremely easy to fog (Comparative Sample 6
2, 63), when a sulfur sensitizer is used in combination with a selenium sensitizer and a silver halide emulsion chemically sensitized using silver halide fine particles to which a gold sensitizer is adsorbed (the present invention) Samples 54, 56, 58, 60, and 62) show low fog and high spectral sensitivity. The photographic light-sensitive material according to the present invention obtained as described above is obtained by using a conventional silver halide obtained by a method of directly adding a sensitizer to a silver halide emulsion to be sensitized. Compared to photographic light-sensitive materials using emulsions, fog is reduced and spectral sensitivity is high.

[0130]

The photographic light-sensitive material according to the present invention has high sensitivity and good photographic performance with relatively little fog.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-3-91736 (JP, A) JP-A-3-4221 (JP, A) JP-A-3-194538 (JP, A) JP-A-5-194538 2231 (JP, A) JP-A-6-175260 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03C 1/09, 1/035, 1/07

Claims (2)

(57) [Claims] 1. A chemical reaction comprising adding silver halide fine particles adsorbed by a selenium sensitizer and a sulfur sensitizer to a silver halide emulsion of a host and dissolving the silver halide fine particles using a silver halide solvent. A silver halide photographic material having a sensitized silver halide emulsion layer. 2. The silver halide photographic material according to claim 1, wherein a gold sensitizer is further adsorbed on said silver halide fine particles.