JPH1124195A - Silver halide emulsion and silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the silver halide emulsion enhanced in sensitivity/fog relation and improved in storage stability by chemically sensitizing the silver halide emulsion with a compound having a water-soluble group and a group adsorbable to silver halide and a site having an instable chalcogen atom in the molecule. SOLUTION: The silver halide emulsion is chemically sensitized by using the compound having the water-soluble group and the group adsorbable to silver halide and the site having the instable chalcogen atom in the molecule. An atomic group having a group adsorbable to silver halide is embodied by atomic groups having a mercapto group, a thione group, an imino group, an ethenyl group, and the like. The compound having the site of the instable chalcogen atom means the the compound forming silver chalcogenide in the presence of silver nitrate, and the chalcogen atom means sulfur, selenium, tellurium atoms.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide emulsion and a silver halide color photographic light-sensitive material (hereinafter, also simply referred to as a color photographic light-sensitive material and a light-sensitive material). The present invention relates to a silver halide emulsion having improved storage stability and a silver halide color photographic material using the same.

[0002]

2. Description of the Related Art While silver halide color photographic light-sensitive materials are said to be mature products with extremely high degree of perfection, the required performance is wide-ranging, such as high sensitivity, high image quality, and little fluctuation in performance due to storage conditions. Further, in the future, it is necessary to take into account rapid processing aptitude which has accelerated development progress and the like, and the required level has been increasing more and more in recent years.

[0003] In particular, in terms of high sensitivity, due to the recent technological advancement of digital cameras, in order to maintain the superiority of silver halide color photographic light-sensitive materials, it is necessary to keep fog low while maintaining compatibility with storability. Higher sensitivity is required.

Techniques for increasing the sensitivity of silver halide emulsions, that is, sensitization techniques, relate to a method for producing a silver halide emulsion, to chemical sensitization of a silver halide emulsion, to spectral sensitization of a silver halide emulsion, Various methods are known, such as a method based on a method for designing a silver halide color photographic light-sensitive material and a method relating to a development process of a silver halide color photographic light-sensitive material. Among them, the most preferable and essential method is silver halide. The purpose is to reduce the inefficiency in the crystal exposure process and improve the quantum efficiency. One of the means is chemical sensitization, such as sulfur sensitization, selenium sensitization, chalcogen sensitization such as tellurium sensitization, noble metal sensitization using a noble metal such as gold, and reduction sensitization using a reducing agent. These are used alone or in combination.

[0005] Above all, when gold sensitization is used in combination with sulfur sensitization, selenium or tellurium sensitization, a remarkable increase in sensitivity can be obtained, but fog also increases. In particular, gold-selenium sensitization and tellurium sensitization have a particularly large fog increase as compared with gold-sulfur sensitization, and there has been a demand for a technique for suppressing the generation of fog, as well as a sensitization technique with less fog during storage and less fluctuation in sensitivity.

In response to such demands, a technique of performing chemical sensitization with a compound having an adsorbing group to a silver halide and a chalcogen moiety to suppress the generation of fog is disclosed in Japanese Patent Application Laid-Open Nos. -8668, selenium in Japanese Patent Publication No. 5-18091, JP-A-9-15
777, 6-208186 and 6-208184
Nos. 6-31767, 6-175258, 6-43576, 4-25832, 4-109
No. 240, No. 4-147250, Japanese Patent Application No. 8-9107
No. 0 and the like. However, it is expected that the fogging / sensitivity is still insufficient, and that the inhibitory effect on silver halide is expected to be strong. However, the ultimate sensitivity is slightly inferior and further improvement has been desired.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide emulsion having an excellent fog / sensitivity relationship and improved storage stability, and a silver halide color photographic material using the same. .

[0008]

The above object of the present invention has been attained by the following constitutions.

1. A silver halide emulsion characterized by being chemically sensitized using a compound having a water-soluble group, an adsorptive group to silver halide and an unstable chalcogen atom site in a molecule.

[0010] 2. 2. The halogen according to the above 1, wherein the compound having a water-soluble group, an adsorptive group to silver halide and an unstable chalcogen atom site in the molecule is a compound represented by the following general formula (I). Silver halide emulsion.

[0011]

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In the formula, A ¹ represents an atom group containing a group adsorbable to silver halide, L ¹ represents a (12 + 2) -valent linking group, and Z ¹ represents an atom group containing an unstable chalcogen atom site. And W ¹ , W ² and W ³ represent a carboxylic acid group, a sulfonic acid group, a sulfinic acid group, a phosphoric acid group, a phosphorous acid group and a boric acid group. m1 represents 0 or 1, n1 represents an integer of 1 to 3, and 11, 12, and 13 each represent an integer of 0 to 2. However, l1, l2 and l3 do not become 0 at the same time.

3. At least one photosensitive silver halide emulsion layer is provided on a support, and at least one silver halide emulsion layer contains the silver halide emulsion described in 1 or 2 above. Silver halide color photographic material.

Hereinafter, the present invention will be described in detail.

In the present invention, the atom group having a group capable of adsorbing to silver halide is an atom group having a mercapto group (for example, mercaptooxadiazole, mercaptotetrazole, mercaptotriazole, mercaptodiazole, mercaptothiazole, mercaptothiadiazole, Each group such as mercaptooxazole, mercaptoimidazole, mercaptobenzothiazole, mercaptobenzoxazole, mercaptobenzimidazole, mercaptotetrazaindene, mercaptopyridyl, mercaptoquinolyl, 2-mercaptopyridyl, mercaptophenyl, and mercaptonaphthyl); Atomic group (for example, thiazoline-2-thione, oxazoline-2-thione, imidazoline-2-thione, benzothiazoline-2-thio) , Benzimidazoline-2-thione, thiazolidine-2-thione, etc.), an atom group forming imino silver (for example, triazole, tetrazole, benzotriazole, hydroxyazaindene, benzimidazole, indazole, etc.), an atom group having an ethenyl group (For example, 2- [N- (2-propynyl) amino] benzothiazole, N- (2-propynyl) carbazole, and the like).

In the present invention, the compound having an unstable chalcogen atom site means a compound which forms silver chalcogen in the presence of silver nitrate. The chalcogen atom means a sulfur atom, a selenium atom, and a tellurium atom. Specific examples of the atom group including an unstable sulfur site include an atom group having a thiourea group (for example, N, N'-diethylthiourea, N-
Ethyl-N '-(2-thiazolyl) thiourea, N, N-
Dimethylthiourea, N-phenylthiourea, etc.), an atom group having a thioamide group (eg, thiobenzamide, thioacetamide, etc.), an atom group having a polysulfide, phosphine sulfide group (eg, bis (pentafluorophenyl) phenylphosphine sulfide) , Diethylphosphine sulfide, dimethylphenylphosphine sulfide, etc.), an atom group having a thioxoazolidinone group (for example, ethyl rhodanine, 5-benzylidene-3-ethyl rhodanine, 1,3-diphenyl-2-
Thiohydantoin, 3-ethyl-4-oxooxazolidine-2-thione, etc.). Specific examples of the atom group including an unstable selenium site include an atom group having a selenourea group (for example, N, N-dimethylselenourea, selenourea, N-acetyl-N, N'-diethylselenourea, N- Trifluoroacetyl-N ', N'-
Dimethylselenourea, N-ethyl-N '-(2-thiazolyl) selenourea, N, N'-diphenylselenourea, etc., an atom group having a selenoamide group (for example, N-methyl-selenobenzamide, N-phenyl- Selenobenzamide, N-ethyl-selenobenzamide, etc.), an atom group having a phosphine selenide group (for example, triphenylphosphineselenide, diphenyl- (pentafluorophenyl) phosphineselenide, tris (m-chlorophenyl) phospho) Finselenide, etc.), an atom group having a selenophosphate group (eg, tris (p-tolyl) selenophosphate, etc.), and an atom group having a selenoester group (eg, p-methoxyselenobenzoic acid = O-isopropyl) Ester, selenobenzoic acid = Se- 3'-oxobutyl) ester,
p-Methoxyselenobenzoic acid = Se- (3 '
-Oxocyclohexyl) ester, etc.), an atom group having a selenide group (for example, bis (2,6-dimethoxybenzoyl) selenide, bis (n-butoxycarbonyl) selenide, bis (benzyloxycarbonyl) selenide, bis ( Each group such as (N, N-dimethylcarbamoyl) selenide), an atom group having a triselenane group (for example,
2,4,6-tris (p-methoxyphenyl) triselenane, etc.), an atom group having a selenoketone group (for example, 4
-Methoxyselenoacetophenone, 4,4-methoxyselenobenzophenone, etc.).

As a specific example of the atom group containing an unstable tellurium site, an atom group having a phosphine telluride group (for example, butyl-di-isopropylphosphine telluride,
An atom group having a tellurourea group (eg, N, N′-diethyl-N, N′-diethylenetellurourea, N, N′-dimethylene-N, N′-dimethyltellurourea) Atom group having a telluroamide group (eg, N, N-dimethyl-tellurobenzamide, N, N-tetramethylene- (p-tolyl) tellurobenzamide, etc.), and an atom group having a tellurophosphate group (eg, tris Atomic groups such as (p-tolyl) tellurophosphate, trisbutyltellurophosphate and the like, and an atomic group having a tellurophosphoric amide group (for example, hexamethyltellurophosphoric amide and the like).

Other examples of the atomic group having an unstable selenium and tellurium site include those described in JP-A-4-25832 and JP-A-4-25832.
No. 109240, No. 4-147250, No. 4-330
No. 43, No. 5-40324, No. 5-24332, No. 5-24333, No. 5-303157, No. 5-30
Nos. 6268, 5-306269 and 6-27573
Nos. 6-43576, 6-75328, 6-
No. 17528, No. 6-180478, No. 6-1752
9, 6-208184, 6-208186,
Nos. 6-317867, 7-92599, 7-9
No. 8483, No. 7-104415, No. 7-14057
No. 9, No. 7-301880 and the like.

The compound of the present invention has a water-soluble group.

Examples of the water-soluble group include a carboxylic acid group, a sulfonic acid group, a sulfinic acid group, a phosphoric acid group, a phosphorous acid group and a boric acid group.

The compound of the present invention has at least one water-soluble group, at least one adsorptive group to silver halide, and at least one unstable chalcogen atom site. The stable chalcogen atom site may be bonded directly or via a linking group. Preferred compounds of the present invention are those represented by the aforementioned general formula (I).

In the general formula (I), the (12 + 2) -valent linking group represented by L ¹ is a group comprising a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom or the like. Include an alkylene group having 1 to 20 carbon atoms (e.g., methylene, ethylene, propylene, hexylene, etc.), an arylene group (e.g., phenylene, naphthylene, etc.), -CONR _1- , -SO ₂ NR _2- , -O
-, - S -, - NR 3 -, - NR 4 CO -, - NR 5 SO 2
_{-, - NR 6 CONR 7 -} , - CO-O -, - O-CO
—, —CO— and the like, and a group in which a plurality of these groups are linked.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ each represent a hydrogen atom, an aliphatic group, an alicyclic group, an aromatic group or a heterocyclic group. As the aliphatic group represented by R _{1 to} R ₇ , a linear or branched alkyl group having 1 to 20 carbon atoms (for example, each group such as methyl, ethyl, isopropyl, 2-ethyl-hexyl), an alkenyl group ( For example, each group such as propenyl, 3-pentenyl, 2-butenyl, cyclohexenyl),
Examples include an alkynyl group (for example, each group such as propargyl and 3-pentynyl) and an aralkyl (for example, each group such as benzyl and phenethyl). The alicyclic group is an alicyclic group having 5 to 8 carbon atoms (for example, each group such as cyclopentyl and cyclohexyl), and the aromatic group is a monocyclic or condensed ring group having 6 to 10 carbon atoms. Specifically, a phenyl group or a naphthyl group is mentioned, and the heterocyclic group is a 5- to 7-membered monocyclic ring containing an oxygen atom, a sulfur atom or a nitrogen atom or a condensed ring group condensed with another ring. Yes, specifically, each group such as furyl, thienyl, benzofuryl, pyrrolyl, indolyl, thiazolyl, imidazolyl, morpholyl, piperazyl, pyrazyl and the like. Each of the groups represented by R _{1 to} R ₇ can be substituted with an arbitrary atom or group at an arbitrary position. Examples of the substituent and the substituent include a hydroxy group and a halogen atom (for example, a fluorine atom, a chlorine atom ,
Bromine atom, iodine atom), cyano group, amino group (for example,
Methylamino, anilino, diethylamino, 2-hydroxyethylamino, etc.), acyl group (eg, acetyl, benzoyl, propanoyl, etc.), carbamoyl group (eg, carbamoyl, N-methylcarbamoyl, N, N-) Groups such as tetramethylenecarbamoyl, N-methanesulfonylcarbamoyl, N-acetylcarbamoyl), alkoxy groups (eg, methoxy, ethoxy, 2-hydroxyethoxy, 2-methoxyethoxy, etc.), and alkoxycarbonyl (eg, methoxy) Carbonyl, ethoxycarbonyl, 2-methoxyethoxycarbonyl, etc.), sulfonyl group (eg, methanesulfonyl, trifluoromethanesulfonyl, benzenesulfonyl, p-toluenesulfonyl, etc.), sulfamoyl group (eg, Groups such as sulfamoyl, N, N-dimethylsulfamoyl, morpholinosulfonyl, N-ethylsulfamoyl), acylamino groups (eg, acetamido, trifluoroacetamido, benzamide, thienocarbonylamino, benzenesulfonamide, etc.) Groups) and alkoxycarbonylamino groups (for example, groups such as methoxycarbonylamino and N-methyl-ethoxycarbonylamino).

Carboxylic acid groups represented by W ¹ , W ² and W ³ ;
The sulfonic acid group, sulfinic acid group, phosphoric acid group, phosphorous acid group and boric acid group may be in a free form or form a counter salt with an alkali metal, an alkaline earth metal, ammonium or an organic amine.

Specific examples of the compound of the present invention are shown below.
The compounds of the present invention are not limited to these.

[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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The above compound of the present invention can be synthesized by utilizing a known substitution reaction. For example, a method represented by the following equation is used.

[0039] In the formulas 5, 6, 7, and 8, X is a group which leaves after the reaction, such as a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom) or a sulfonate group (for example, p-toluene Sulfonate, trifluoromethanesulfonate, m-chlorobenzenesulfonate, etc.).

[0040] Examples of the condensing agent in Formulas 1 and 2 include 1,3-
Dicyclohexylcarbodiimide, 2-chloro-1,3
-Dimethylimidazolium chloride and the like, and examples of the base in Formulas 3 to 10 include inorganic bases (e.g., sodium hydrogen carbonate, potassium hydroxide, etc.),
Organic bases (eg, triethylamine, pyridine and the like) are preferred.

In Formulas 1 to 10, W, A and Z have the same meanings as W ¹ , W ² , W ³ , A ¹ and Z ¹ in the general formula (1). Further, R in Formulas 5 and 6 represents a hydrogen atom, a halogen atom, or a monovalent substituent, and has the same meaning as R _{1 to} R ₇ described above.

The following are synthesis examples of typical compounds.
Other compounds can be synthesized similarly.

Compound No. Synthesis of 2 2.4 g of 3-amino-5- (5-mercapto-1-tetrazolyl) benzoic acid was heated, suspended and stirred in 50 ml of a mixed solution (1: 1) of tetrahydrofuran and methanol.

1.0 g of ethyl isothiocyanate
Was added dropwise, and the mixture was heated and stirred under reflux for 30 minutes. The reaction solution was filtered, the filtrate was concentrated to dryness, and the remaining solid was recrystallized from methanol to obtain 1.6 g of pale yellow crystals. The structure was confirmed from NMR and a mass spectrum.

Compound No. Synthesis of 61 5.6 g of 3- [3-carboxy-5- (5-mercapto-1-tetrazolyl) anilinosulfonyl] phenyl-diphenylphosphine and 4 g of metal selenium were suspended in 40 ml of chloroform and heated under reflux for 24 hours. Unreacted substances were removed by filtration, and the filtrate was concentrated to dryness under reduced pressure to obtain 6.0 g of crude crystals. The crude crystals were dissolved in a mixed solvent of methanol and chloroform (1: 3), adsorbed on silica gel, and eluted and separated by flowing a mixed solvent of methanol and chloroform (1: 4). The fractions of the target component were collected and the solvent was distilled off to obtain 4.1 g of a purified product. The structure was confirmed from NMR and a mass spectrum.

The amount of the chalcogen compound of the present invention varies depending on the chalcogen compound used, silver halide grains, and chemically sensitized environment.
It is preferably 10 ^-8 to 10 ^-2 mol, more preferably 10 ^-7.
Use 〜１０10 ^-3 mol. The chemical sensitization environment in the present invention is not particularly limited, but the pAg is preferably 6 to 11, more preferably 7 to 10, and the pH is 4 to 10.
And more preferably 5 to 8, and the temperature is 40.
° C to 90 ° C, more preferably 45 ° C to 80 ° C
It is.

In the silver halide emulsion of the present invention, if the compound of the present invention has a sulfur moiety, selenium sensitization, tellurium sensitization, reduction sensitization and noble metal sensitization may be combined, or if the compound of the present invention has a selenium moiety. For example, use sulfur sensitization, tellurium sensitization, reduction sensitization and noble metal sensitization in combination, or use sulfur sensitization, selenium sensitization, reduction sensitization and noble metal sensitization in combination with a tellurium site. Is preferred.

In the sulfur sensitization, an unstable sulfur compound can be used, and specific examples thereof include 1,3-diphenylthiourea, triethylthiourea, and 1-ethyl-3- (2-thiazolyl) thiourea. Preferred are thiourea derivatives, rhodanine derivatives, dithiocarbamic acids, polysulfide organic compounds, thiosulfates, simple sulfur and the like. In addition, as the elemental sulfur, α-sulfur belonging to the orthorhombic system is preferable. Other U.S. Patent Nos. 1,574,944 and 2,410,
No. 689, No. 2,278,947, No. 2,728,6
No. 68, No. 3, 501, 313, No. 3, 656, 95
No. 5, etc., West German Application Publication (OLS) 1, 42
2,869, JP-A-56-24937, and JP-A-55-4937.
Sulfur sensitizers described in, for example, Japanese Patent No. 5016 can be used.

In the selenium sensitization, an unstable selenium compound can be used. For example, US Pat. No. 1,574,9
44, 1,602,592, 1,623,49
9, JP-A-60-150046, JP-A-4-258
No. 32, No. 4-109240 and No. 4-147250. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg,
Allyl isoselenocyanate, etc.), selenoureas (e.g., N, N-dimethylselenourea, N, N, N'-triethylselenourea, N, N, N'-trimethyl-N'-)
Heptafluoroselenourea, N, N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'-4-nitrophenylcarbonylselenourea, etc., selenoketones (for example, , Selenoacetone, selenoacetophenone, etc.), selenoamide (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid,
Methyl-3-selenobutyrate, etc.), selenophosphates (eg, tri-p-triselenophosphate, etc.), selenides (dimethyl selenide, triphenylphosphine selenide, pentafluorophenyl-).
Diphenylphosphine selenide).
Particularly preferred selenium sensitizers are selenoureas, selenamides, and selenides.

Specific examples of techniques for using these selenium sensitizers are disclosed in the following patents. U.S. Patent No. 1,574
No. 944, No. 1,602,592, No. 1,623,4
Nos. 99, 3,297,466, 3,297,44
No. 7, 3,320, 069, 3, 408, 196
No. 3,408,197, 3,442,653
No. 3,420,670, 3,591,385
No. 2,693,038 and 2,092
No. 3,209, JP-B No. 52-34491, 52-3
No. 4492, No. 53-295, No. 57-22090
And JP-A-59-180536 and 59-18533.
Nos. 0, 59-181337 and 59-187338
No. 59-192241, No. 60-150046
No., No. 60-151637, No. 61-246738
JP-A-3-4221, JP-A-3-24537 and JP-A-3-24537
-1111838, 3-116132, 3-14
No. 8648, No. 3-237450, No. 4-16838
No. 4-25832, No. 4-32831, No. 4-
No. 96059, No. 4-109240, No. 4-1407
No. 38, No. 4-140739, No. 4-147250
Nos. 4-184331, 4-190225, 4-191729, 4-195,035, British Patent Nos. 255,846, 861,984, and H.C.
E. FIG. The Journal of Pho by Spencer et al.
toographic science, Vol. 31, 15
8 to 169 (1983).

In tellurium sensitization, an unstable tellurium compound can be used. For tellurium sensitizers and sensitization methods, see US Pat. Nos. 1,623,499 and 3,32.
Nos. 0,069, 3,772,031, 3,53
Nos. 1,289 and 3,655,394, British Patent No. 2
35,211, 1,121,469, 1,29
5,462, 1,396,696 and Canadian Patent 800,958. It is disclosed in JP-A-4-20464 and the like. Specifically, phosphine tellurides (eg, butyl-diisopropylphosphine telluride, tributylphosphine telluride, etc.), telluroureas (eg, N, N-dimethylethylene tellurourea, N, N-)
Diphenylethylene tellurourea), telluramides and the like.

In noble metal sensitization, Research
Noble metal salts such as gold, platinum, palladium, and iridium described in Disclosure, Vol. 307, No. 307105, and the like can be used, and gold sensitization is particularly preferable. Useful gold sensitizers include chloroauric acid, gold thiosulfate, gold thiocyanate and the like, as well as US Pat. No. 2,597,8.
No.56, No.5,049,485, JP-B-44-157
No. 48, JP-A-1-147537, JP-A-4-70650
And organic gold compounds disclosed in US Pat.

In reduction sensitization, Research
Reducing compounds described in Disclosure, Vol. 307, No. 307105, and JP-A-7-78685 can be used. Specifically, aminoiminomethanesulfinic acid (also known as thiourea dioxide), borane compounds (eg, dimethylamine borane, etc.), hydrazine compounds (eg, hydrazine, p-tolylhydrazine, etc.),
Examples include polyamine compounds (eg, diethylenetriamine, triethylenetetramine, etc.), stannous chloride, silane compounds, reductones (eg, ascorbic acid, etc.), sodium sulfite, aldehyde compounds, hydrogen gas, and the like. Japanese Patent Application Nos. 8-277938 and 8-251
Reduction sensitization may be performed in an atmosphere having a high pH or an excess of silver ions as disclosed in JP-A-486-486 and JP-A-8-182035.

Of these chemical sensitizations, it is preferable to combine them with gold sensitization.

Depending on the properties of the compound to be used, the above-mentioned various sensitizers can be added by dissolving them in water or an organic solvent such as methanol alone or in a mixed solvent, or adding a gelatin solution. The method disclosed in Japanese Patent Application Laid-Open No. 4-140739 also includes a method in which
That is, a method of adding in the form of an emulsified dispersion of a mixed solution with an organic solvent-soluble polymer may be used.

Next, the silver halide emulsion of the present invention will be described. The shape and the halogen composition of the silver halide grains used in the present invention are not particularly limited. However, the preferred form of the silver halide grains differs depending on the use. For example, the following tabular grains are preferred as silver halide grains used in a color negative film.

Here, a tabular (shape) particle has two parallel main planes, the equivalent circle diameter of the main plane (the diameter of a circle having the same projected area as the main plane) and the distance between the main planes. (That is, particles having an aspect ratio of 2 or more). 50% of the total projected area of all tabular grains
The above is preferably an aspect ratio of 3 or more, and more preferably an aspect ratio of 5 or more. The diameter of the tabular grains is preferably 0.3 to 10 μm, more preferably 0.5 to 5.0 μm, and still more preferably 0.5 to 2.0 μm.
m. The thickness of the particles is preferably 0.05-0.8μ
m. The measurement of the particle diameter and the particle thickness in the present invention can be obtained by the method described in U.S. Pat. No. 4,434,226.

The size distribution of tabular grains is calculated by the coefficient of variation of the circle-equivalent diameter of the principal plane (the diameter of a circle having the same projected area as the principal plane) (the standard deviation of the diameter distribution divided by the average diameter × 100 ( %)) Is preferably 30% or less,
More preferably, it is 20% or less.

The halogen composition of the tabular grains is preferably silver bromide or silver iodobromide, and the silver iodide content is preferably from 0.1 mol% to less than 15 mol%. More preferably, it is 5 mol% or more and less than 3 mol%.

The tabular grains may contain silver chloride.

The intergranular distribution of the silver iodide content of the tabular grains is calculated by calculating the coefficient of variation of the silver iodide content (the standard deviation of the silver iodide content intergranular distribution divided by the average silver iodide content). 100
(%)) Is preferably 30% or less, more preferably 20% or less.

The tabular grains may have at least two or more phases having different halogen compositions inside the grains. The silver iodide content of the largest silver iodide-containing phase in the silver halide grains excluding the outermost layer is preferably less than 15 mol%,
More preferably, it is less than 10 mol%. The volume fraction of the phase in the particles is preferably 30% or more and 90% or less.

The structure relating to the halogen composition in the grains is represented by X
It can be examined by a line diffraction method, a composition analysis method using EPMA, or the like.

The above-mentioned silver iodide content of the outermost layer of the silver halide grains means a value obtained by the following method. The silver iodide content of the outermost layer of the grains was determined by the XPS method (Xr
ayphotoelectron Spectrosc
(opy: X-ray photoelectron spectroscopy). The sample was cooled to −115 ° C. or less in an ultra-high vacuum of 1 × 10 ⁻⁸ torr or less, and Mg was used as a probe X-ray.
Kα is irradiated at an X-ray source voltage of 15 kV and an X-ray source current of 40 mA, and Ag3d5 / 2, Br3d, and I3d3 / 2 electrons are measured. The integrated intensity of the measured peak is corrected by a sensitivity factor (Sensitivity Factor),
From these intensity ratios, the silver iodide content of the outermost layer is determined.

The silver iodide content of the outermost layer of the tabular grains is preferably at least 5 mol%, more preferably at least 10 mol%.

The maximum silver iodide-containing phase in the above-mentioned grains does not include a high iodine-localized region generated by an operation described later for forming dislocation lines.

As a method for producing tabular grains, methods known in the art can be appropriately combined. For example, Japanese Patent Application Laid-Open Nos. 61-6643, 61-146305, and 6
2-157024, 62-18556, 63-
No. 92942, No. 63-163451, No. 63-22
Known methods described in JP-A Nos. 0238 and 63-31244 can be referred to. For example, a double jet method, a double jet method, a so-called controlled double jet method which maintains a constant pAg in a liquid phase in which silver halide is formed, which is a type of the double jet method, and a soluble silver halide having a different composition, respectively. A triple jet method, which is added independently, can also be used. A forward mixing method can be used, and a method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. If necessary, a silver halide solvent can be used. Silver halide solvents often used include ammonia, thioethers and thioureas. For thioethers, reference can be made to U.S. Pat. Nos. 3,271,157, 3,790,387, 3,574,628 and the like. The mixing method is not particularly limited, and a neutral method using no ammonia, an ammonia method, an acidic method, and the like can be used.However, from the viewpoint of reducing fogging of silver halide grains, it is preferably pH.
(The logarithm of the reciprocal of the hydrogen ion concentration) is 5.5 or less, more preferably 4.5 or less.

The tabular grains are preferably formed at least in part by using silver halide fine grains from the viewpoint of making the halogen composition distribution between grains more uniform and reducing the nonuniformity of photosensitive quantum efficiency. It is more preferable to grow using silver halide fine grains throughout the entire growth.

Grain formation using silver halide fine particles is as follows.
Grains may be grown using only silver halide fine grains as in the grains disclosed in JP-A-1-183417, JP-A-1-183644, JP-A-1-183645 and the like.
What is necessary is just to supply at least one of the halogen elements by silver halide fine particles. In this case, the iodide ions are preferably supplied by silver halide fine particles. As described in JP-A-5-5966, there are two or more types of silver halide fine grains used for grain growth, and at least one of them may be composed of only one type of halogen element.

Further, it is desirable to use silver halide grains having a lower solubility than the growing silver halide grains as in the case of the claims of JP-A-2-16737. It is particularly desirable to use silver halide.

It is preferable to introduce dislocations into the tabular grains.

The dislocation of tabular grains is described, for example, in J. Am. F. Ha
Milton, Photo. Sci. Eng. , 11
(1967), 57; Shiozawa, J .; Sc
i. Photo. Sci. Japan, 35 (197
2) Observation can be performed by the method described in 213, that is, a direct method using a transmission electron microscope at a low temperature. That is, silver halide grains taken out so as not to apply enough pressure from the emulsion to generate dislocations on the grains are placed on a mesh for an electron microscope to prevent damage (printout, etc.) by an electron beam. Observation is performed by a transmission method while the sample is cooled. At this time, the thicker the particle, the more difficult it is for the electron beam to pass therethrough.
The use of an electron microscope (200 kV) for a thickness of 5 μm allows more clear observation. From the grain photograph obtained by such a method, the position and number of dislocations for each grain when viewed from a direction perpendicular to the main plane can be determined.

The dislocations of the tabular grains do not necessarily have to be introduced at a specific location, but are preferably present at the fringe portions of the tabular grains.

The fringe portion of the tabular grains refers to the outer periphery of the tabular grains. Specifically, the fringe portion of the tabular grains is defined by:
It means a region outside (side side) of 50% of the length of the perpendicular.

The number of dislocations in the tabular grains is preferably 50% or more, and more preferably 80% or more, of the total projected area of silver halide grains in the emulsion. preferable.

The method for introducing the above-mentioned dislocation is not particularly limited, but a method in which an aqueous solution of an iodide ion such as potassium iodide and a water-soluble silver salt solution are added by double jet at the position where the dislocation is to be introduced, or silver iodide is added. A method of adding fine particles, a method of adding only an iodine ion solution,
The method can be carried out by a method using an iodide ion releasing agent as described in No. 1781. A method of adding an iodine ion aqueous solution and a water-soluble silver salt solution by double jet, a method of adding silver iodide fine particles, a method of using an iodide ion releasing agent are preferable, and a method of using silver iodide fine particles is more preferable. The aqueous solution of iodide ions is preferably an aqueous solution of an alkali iodide, and the aqueous solution of a water-soluble silver salt is preferably an aqueous solution of silver nitrate.

The silver halide emulsion used in the present invention is preferably spectrally sensitized with a methine dye or another sensitizing dye. The sensitizing dyes may be used alone or in combination of two or more. A dye which has no spectral sensitizing effect by itself together with the sensitizing dye or a compound which does not substantially absorb visible light and which enhances the sensitizing effect of the sensitizing dye is contained in the emulsion. You may. Examples of sensitizing dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, hemioxonol dyes, oxonol, polymethine dyes including merostyril and streptocyanin, and the like. I can do it.

The silver halide emulsion used in the present invention is
Various antifoggants and stabilizers can be contained for the purpose of preventing fogging during the production process, storage or processing of the photographic material and stabilizing photographic performance. Specifically, tetrazaindenes, azoles, benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, promobenzimidazoles, mercaptothiazoles, mercaptobenzimidazoles, aminotriazoles , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles, mercaptopyrimidines, mercaptotriazines, thioketo compounds, benzenethiosulfinic acid, benzenesulfinic acid, benzenesulfonamide, hydroquinone derivatives, aminophenol derivatives, gallic acid Derivatives and ascorbic acid derivatives.

In the present invention, chemical sensitization may be carried out in the presence of a silver halide solvent. As the silver halide solvent used in the present invention, US Pat. No. 3,271,157
No. 3,574,628, JP-A-54-1019.
Thioethers described in JP-A-54-158917 and JP-A-53-82408 and JP-A-55-158917.
Nos. 77737 and 55-2982, thiourea derivatives described in JP-A-53-144319, and halogenated compounds having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom described in JP-A-53-144319. Silver solvent, JP-A-5
Imidazoles described in JP 4-100717 A;
Sulfites, thiocyanates and the like.

Known photographic additives which can be used in the present invention include RD17643, page 25, VIII-A to page 27, XIII
Item, RD18716, pages 650 to 651, RD3081
19, 1003, VIII-A to 1012, XXI-E, and specific examples of various couplers are described in RD17643, 2
Page 5, VII-CG, RD308119, page 1001, VII
-C to G.

In the present invention, the aforementioned RD 17643,
Page 28, section XVII, RD 18716, pages 647-8, and RD
The support described in section 308119, page 1009, XVII can be used.

The light-sensitive materials include the aforementioned RD308119,1
An auxiliary layer such as a filter layer or an intermediate layer described in section VII-K on page 002 can be provided.

The photosensitive material is the same as that of RD308119, VII
Various layer configurations such as a normal layer, a reverse layer, and a unit configuration described in the section -K can be adopted.

[0084]

EXAMPLES The present invention will be specifically described below with reference to examples, but the embodiments of the present invention are not limited to these examples.

Example 1 [Preparation of Seed Emulsion] A seed emulsion having two parallel twin planes was prepared by the following method.

(E-5 solution) Deionized alkali-treated gelatin (average molecular weight: 15,000) 244.0 g Potassium bromide 156.6 g HO (CH ₂ CH ₂ O) m (CH (CH ₃ ) CH ₂ O) _19.8 0.48 mL of a 10% methanol solution of (CH ₂ CH ₂ O) nH (m + n = 9.77) is added to make up 34.0 L with water.

(F-5 solution) Silver nitrate 1200 g Water was added to make 3716 mL.

(G-5 solution) 31.6 g of deionized alkali-treated gelatin (average molecular weight: 15,000) 906.0 g of potassium bromide Water was added to make 4.0 L.

(H-5 solution) Ammonia water (28%) 299 mL (I-5 solution) Water 8.0 L (J-5 solution) Ossein gelatin 400.0 g Add water to make 4832 mL.

(K-5 solution) 69.2 g of potassium bromide Water was added to make 386 mL.

(L-5 solution) A 56% by weight aqueous solution of acetic acid (1000 mL) was prepared using a stirring device described in JP-A-62-160128.
Solution K-5 was added to solution E-5 which was vigorously stirred at 0 ° C., and then solution F-5 and solution G-5 were mixed by double jet method.
Per minute to produce silver halide nuclei.

Thereafter, the J-5 solution was added, the temperature was raised to 68 ° C. over 41 minutes, and the H-5 solution was further added, followed by aging for 7 minutes. Thereafter, the I-5 solution was further added, and one minute later, the pH was adjusted to 4.7 using the L-5 solution, and immediately desalting was performed by a conventional method. When this seed emulsion was observed with an electron microscope, the average grain size having two twin planes parallel to each other (the grain size here is a grain size equivalent to a projected area circle).
This was a monodisperse spherical emulsion having a particle size distribution of 0.31 μm and a particle size distribution of 16%.

[Preparation of Emulsion Em-1] Emulsion Em-1 was prepared using the following solution.

(H-6 solution) Ossein gelatin 223.6 g HO (CH ₂ CH ₂ O) m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) nH (m + n = 9.77) 10% methanol solution of 3.6 mL seed emulsion 0.774 mol equivalent in terms of Ag amount Add water to make 5904 mL.

(I-6 solution) 3.5N silver nitrate aqueous solution 6490 mL (J-6 solution) 3.5N potassium bromide aqueous solution 7500 mL (K-6 solution) 3.0% by weight of gelatin and silver iodide fine particles (average grain size) Fine particle emulsion composed of required amount (L-6 solution) 1.75N aqueous potassium bromide solution required amount (M-6 solution) 56% by weight acetic acid aqueous solution required amount (N-6 solution) 3.5N bromide Aqueous potassium solution 500 mL Add the H-6 solution into the reaction vessel and, with vigorous stirring,
Solution I-6, Solution J-6 and Solution K-6 were added by a double jet method according to Table 1, and a seed emulsion was grown to prepare a core / shell type silver halide emulsion.

Here, the addition rate of the liquid I-6, liquid J-6, and liquid K-6 is varied in a function with respect to the addition time in consideration of the critical growth rate. The generation of small particles and the deterioration of the particle size distribution due to Ostwald ripening between growing particles were prevented.

In the crystal growth, first, the first addition was performed while controlling the solution temperature in the reaction vessel to 75 ° C. and the pAg to 8.8, and then the solution temperature in the reaction vessel was reduced to 60 ° C. in 15 minutes. Solution -6 was added for 4 minutes, and K-6 solution was added in an amount corresponding to 2% of the total silver used, followed by a second addition. Second
The addition was performed by setting the solution temperature in the reaction vessel to 60 ° C. and the pAg to 9.
8. The pH was controlled at 5.8. For control of pAg and pH, L-6 solution as needed,
M-6 solution was added.

After the particles are formed, desalting is carried out according to the method described in JP-A-5-72658, and then gelatin is added and dispersed, and pAg 8.06, pH 5.0 at 40 ° C.
8 were obtained.

When the silver halide grains in this emulsion were observed with an electron microscope, the average grain size (as described above) was 1.30.
Hexagonal tabular monodisperse silver halide grains having a mean particle size distribution of 17% and a mean aspect ratio of 8.0 or more were found to have a particle size distribution of 17% in μm and 50% or more of the total projected area. The tabular silver halide grains had dislocation lines at the fringe portions.

[0100]

[Table 1]

This emulsion Em-1 was subdivided and emulsions A to I were prepared by the following method.

After the temperature of each subdivided emulsion was raised to 58 ° C., SD-1 was 4 × 10 ⁻⁴ mol / mol Ag, SD-2 was 8 × 10 ⁻⁵ mol / mol Ag, and SD-3 was 5 × 10 mol / mol Ag. 10 ^-5 mol / mol Ag was added, and after 20 minutes, a sulfur sensitizer shown in Table 2 was added.
3.2 × 10 ⁻⁶ mol / mol Ag of chloroauric acid, 3.5 × 10 ⁻⁴ mol / mol Ag of potassium thiocyanate, 2.5 × 10 ⁻⁶ mol / mol Ag of triphenylphosphine selenide, and 1 Aging was performed so that the / 100 second sensitivity was optimal. At the end of ripening, a stabilizer ST-1 and an antifoggant AF-1 were added, the temperature was lowered, and the mixture was cooled and solidified to prepare respective emulsions.

Ethyl acetate and magenta coupler M-1 dissolved in tricresyl phosphate (OIL-1) were added to each of the obtained emulsions, and emulsified and dispersed in an aqueous solution containing a dispersing aid (SU-1) and gelatin. Dispersion, spreading agent (SU-
2) and a hardener (H-1, H-2) were added to prepare a coating solution, each of which was applied to a subbed cellulose triacetate support by a conventional method, dried, and dried. 109 were produced.

A method for preparing a single emulsion layer coated sample will be described below.

<Coating Formula> In succession from the support side First layer: green-sensitive silver halide emulsion layer Emulsion Coating amount of silver 1.5 g / m ² Magenta coupler (M-1) 0.33 g / m ² Tricresyl phosphate (OIL-1) 0.50 g / m ² gelatin 3.5 g / m ² Second layer: surface protective layer PM-1 0.15 g / m ² PM-2 0.04 g / m ² Gelatin 0.65 g / m ²

[0106]

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[0107]

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The sample obtained as described above was
Using a K light source, wedge exposure was performed through a Toshiba glass filter Y-48, and development was performed according to the following processing steps.

The sensitivity of each sample was such that the green density was fog +0.
The sample N
o. The relative values are shown with the value of 101 as 100.

Further, in order to evaluate fog generated during storage, the sample was subjected to a temperature of 23 ° C. and a relative humidity of 65% for 2 hours.
After humidifying for 4 hours, it was sealed in a resin can and aged at 55 ° C. for 5 days. After each of the samples was processed together with the samples that had been refrigerated and stored, the difference between the minimum density values of the obtained characteristic curves was evaluated as the fog increase during storage.

Further, regarding the granularity of the magenta color image, RMS
It was evaluated in terms of granularity. RMS granularity is green density fog +
A portion of 0.3 was scanned with a microdensitometer having an opening scanning area of 1800 μm ² (slit width 10 μm, slit length 180 μm), and the density measurement sampling number was 100.
A value 1000 times the standard deviation of the fluctuation of the density value of 0 or more was obtained, and the relative value when the sample 101 was set to 100 was shown in Table 2. The smaller the value, the better the graininess. Table 2 shows the results.

(Processing step) Processing step Processing time Processing temperature Replenishment amount * Color development 2 minutes and 30 seconds 38 ± 0.3 ° C. 780 cc Bleaching 45 seconds 38 ± 2.0 ° C. 150 cc Fixing 1 minute and 30 seconds 38 ± 2. 0 ° C. 830 cc Stability 60 seconds 38 ± 5.0 ° C. 830 cc Drying 1 minute 55 ± 5.0 ° C. * The replenishing amount is a value per 1 m ² of the photosensitive material.

The following color developing solutions, bleaching solutions, fixing solutions, stabilizing solutions and replenishers were used.

Color developer water 800 cc Potassium carbonate 30 g Sodium bicarbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-amino- 3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Add water to make 1 liter, and add potassium hydroxide or 20
The pH is adjusted to 10.06 with% sulfuric acid.

Color developing replenisher water 800 cc Potassium carbonate 35 g Sodium bicarbonate 3 g Potassium sulfite 5 g Sodium bromide 0.4 g Hydroxylamine sulfate 3.1 g 4-Amino-methyl-N-ethyl-N- (β-hydroxylethyl) Aniline sulfate 6.3 g Potassium hydroxide 2 g Diethylenetriaminepentaacetic acid 3.0 g Add water to make 1 liter, and add potassium hydroxide or 20
Adjust to pH 10.18 with%.

Bleaching solution water 700 cc Ammonium iron (III) 1,3-diaminopropanetetraacetate 125 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 40 g Ammonium bromide 150 g Glacial acetic acid 40 g Add water to make 1 liter, and use ammonia water or glacial acetic acid. And adjust to pH 4.4.

Bleach replenisher water 700 cc 1,3-diaminopropanetetraacetate iron (III) ammonium 175 g ethylenediaminetetraacetic acid 2 g sodium nitrate 50 g ammonium bromide 200 g glacial acetic acid 56 g After adjusting the pH to 4.4 using aqueous ammonia or glacial acetic acid Add water to make 1 liter.

Fixing solution water 800 cc Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.2 using aqueous ammonia or glacial acetic acid, add water to make 1 liter.

Fixing replenisher water 800 cc Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g Adjust the pH to 6.5 using aqueous ammonia or glacial acetic acid, and add water to make 1 liter.

Stabilizing solution and stabilizing replenishing solution Water 900 cc Paraoctylphenyl polyoxyethylene ether (n = 10) 2.0 g Dimethylol urea 0.5 g Hexamethylenetetramine 0.2 g 1,2-Benzoisothiazolin-3-one 0.1 g Siloxane (UCC L-77) 0.1 g Ammonia water 0.5 cc Add water to make 1 liter, then add ammonia water or 5
Adjust to pH 8.5 with 0% sulfuric acid.

[0121]

[Table 2]

[0122]

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As is clear from Table 2, the sample using the compound of the present invention has a lower fog / sensitivity relationship than the sample using Comparative Compounds-1 and 2 having no water-soluble group and no adsorptive group in the molecule. It was excellent, and the fog during storage was smaller and improved as compared with the sample using the comparative compound. The sample using Comparative Compound-3 which has an adsorptive group in the molecule but has no water-soluble group has low fog, but at the same time has low sensitivity, whereas the compound of the present invention can achieve low fog and high sensitivity. Was.

In the present invention, the granularity is also excellent.

Example 2 Emulsion J-1 was prepared by subdividing Emulsion Em-1 in the following manner.

After raising the temperature of each subdivided emulsion to 55 ° C., SD-1 was 4 × 10 ⁻⁴ mol / mol Ag, SD-2 was 8 × 10 ⁻⁵ mol / mol Ag, and SD-3 was 5 × 10 mol / mol Ag. After addition of 10 ^-5 mol / mol Ag, and 20 minutes later, sodium thiosulfate pentahydrate 5 × 10 ^-6 mol / mol Ag, selenium sensitizer shown in Table 3, 3.5 × 10 ^-6 mol of chloroauric acid / Mol Ag and 3.5 × 10 ⁻⁴ mol / mol Ag of potassium thiocyanate were added and the mixture was aged so that the sensitivity was optimal for 1/100 second. At the end of ripening, a stabilizer ST-1 and an antifoggant AF-1 were added, the temperature was lowered, and the mixture was cooled and solidified to prepare respective emulsions. Sample 201 was added to the obtained emulsion in the same manner as in Example-1.
To 210 were prepared, processed and evaluated. Table 3 shows the results.

[0127]

[Table 3]

[0128]

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As is clear from Table 3, even in the case of the sample of the present invention in which the chalcogen site was changed to selenium, the sample using the compound of the present invention having a water-soluble group and an adsorptive group in the molecule was not fogged. The sensitivity was excellent, the fog during storage was smaller and improved than the sample using the comparative compound, and the granularity was also excellent.

Example 3 Emulsion Em-1 was subdivided, and Emulsions T to W were prepared by the following method.

After raising the temperature of each subdivided emulsion to 52 ° C., SD-1 was 4 × 10 ⁻⁴ mol / mol Ag, SD-2 was 8 × 10 ⁻⁵ mol / mol Ag, and SD-3 was 5 × 10 mol / mol Ag. After addition of 10 ^-5 mol / mol Ag, and 20 minutes later, sodium thiosulfate pentahydrate 8.5 × 10 ^-6 mol / mol Ag, tellurium sensitizer shown in Table 4, chloroauric acid 4 × 10 ^-6 mol / Mol Ag, 3.5 × 10 ^-4 mol / mol Ag of potassium thiocyanate and 1
Aging was performed so that the / 100 second sensitivity was optimal. At the end of ripening, a stabilizer ST-1 and an antifoggant AF-1 were added, the temperature was lowered, and the mixture was cooled and solidified to prepare respective emulsions.
The obtained emulsion was prepared in the same manner as in Example 1 for Samples 301 to 30.
4 were prepared, processed and evaluated. Table 4 shows the results.

[0132]

[Table 4]

[0133]

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As is clear from Table 4, even in the case of the sample of the present invention in which the chalcogen moiety was changed to tellurium, the sample using the compound of the present invention having a water-soluble group and an adsorptive group in the molecule was not fog / fog. The sensitivity was excellent, the fog during storage was smaller and improved than the sample using the comparative compound, and the granularity was also excellent.

Example 4 Compounds 2 and 45 of the present invention and Comparative Compounds 3 and 6 were dissolved in methanol, respectively.
As a result, crystals of all the comparative compounds were precipitated on the third day. Further, when an emulsified dispersion was prepared by the method described in JP-A-4-140739, the compound of the present invention was excellent in dispersion stability, but the comparative compound showed a large deterioration in performance over time. It can be said that the compound of the present invention has high stability in the production process in addition to the effects of the present invention.

Example 5 A multilayer color photographic light-sensitive material sample 401 was prepared by sequentially forming layers having the following compositions from the support side on a triacetyl cellulose film support provided with an undercoat layer.

The amount of addition is expressed in grams per m ² .
However, silver halide and colloidal silver were converted to the amount of silver, and sensitizing dyes (indicated by SD) were shown in moles per mole of silver.

First Layer (Antihalation Layer) Black Colloidal Silver 0.16 UV-1 0.3 CM-1 0.123 CC-1 0.044 OIL-1 0.167 Gelatin 1.33 Second Layer (Intermediate) Layer) AS-1 0.160 OIL-1 0.20 Gelatin 0.69 Third layer (low-sensitivity red-sensitive layer) Silver iodobromide a 0.20 Silver iodobromide b 0.29 SD-12 37 × 10 ^-5 SD-2 1.2 × 10 ^-4 SD-3 2.4 × 10 ^-4 SD-4 2.4 × 10 ^-6 C-1 0.32 CC-1 0.038 OIL- 2 0.28 AS-2 0.002 Gelatin 0.73 Fourth layer (medium-speed red-sensitive layer) Silver iodobromide c 0.10 Silver iodobromide d 0.86 SD-1 4.5 × 10 ^-5 SD-2 2.3 × 10 ^-4 SD-3 4.5 × 10 ^-4 C-2 0.52 CC-1 0.06 DI-1 0.04 7 OIL-2 0.46 AS-2 0.004 Gelatin 1.30 Fifth layer (high-sensitivity red-sensitive layer) Silver iodobromide c 0.13 Silver iodobromide d 1.18 SD-1 0 × 10 ^-5 SD-2 1.5 × 10 ^-4 SD-3 3.0 × 10 ^-4 C-2 0.047 C-3 0.09 CC-1 0.036 DI-1 0.024 OIL -0.27 AS-2 0.006 gelatin 1.28 6th layer (intermediate layer) OIL-1 0.29 AS-1 0.23 gelatin 1.00 7th layer (low sensitivity green color sensitive layer) Silver iodobromide a 0.19 Silver iodobromide b 0.062 SD-4 3.6 × 10 ^-4 SD-5 3.6 × 10 ^-4 M-1 0.18 CM-1 0.033 OIL- 1 0.22 AS-2 0.002 AS-3 0.05 Gelatin 0.61 Eighth layer (intermediate layer) OIL-1 0.26 AS-1 0.0 54 gelatin 0.80 ninth layer (medium speed green-sensitive layer) silver iodobromide e 0.54 silver iodobromide f 0.54 SD-6 3.7 × 10 ^-4 SD-7 7.4 × ^10-5 SD-8 5.0 x ^10-5 M-1 0.17 M-2 0.33 CM-1 0.024 CM-2 0.029 DI-2 0.024 DI-3 0.005 OIL -1 0.73 AS-3 0.035 AS-2 0.003 Gelatin 1.80 10th layer (high-sensitivity green color-sensitive layer) Silver iodobromide f 1.19 SD-6 4.0 × 10 ^{− 4} SD-7 8.0 × 10 ^-5 SD-8 5.0 × 10 ^-5 M-1 0.065 CM-2 0.026 CM-1 0.022 DI-3 0.003 DI-2 003 OIL-1 0.19 OIL-2 0.43 AS-3 0.017 AS-2 0.014 Gelatin 1.23 11th layer (yellow filter Yellow layer colloidal silver 0.05 OIL-1 0.18 AS-1 0.16 gelatin 1.00 twelfth layer (low-sensitivity blue-sensitive layer) silver iodobromide b 0.22 silver iodobromide a 0.08 Silver iodobromide h 0.09 Emulsion j was added in an amount of 7 mol% based on the weight of Ag. SD-9 6.5 × 10 ^-4 SD-10 2.5 × 10 ^-4 YA 0.77 DI-4 0.017 OIL-1 0.31 AS-2 0.002 Gelatin 1.29 13th layer (high-sensitivity blue-sensitive layer) Silver iodobromide h 0.41 Silver iodobromide i 0.61 SD-9 4.4 × 10 ^-4 SD-10 1.5 × 10 ^-4 YA 0.23 OIL-1 0.10 AS-2 004 Gelatin 1.20 14th layer (first protective layer) Silver iodobromide j 0.30 UV-1 0.055 UV-2 0.110 OIL-20. 30 gelatin 1.32 15th layer (second protective layer) PM-1 0.15 PM-2 0.04 WAX-1 0.02 D-1 0.001 gelatin 0.55 Characteristics of the above silver iodobromide It is shown below (the average particle size is one side length of a cube having the same volume).

Emulsion No. Average particle size (μm) Average AgI amount (mol%) Diameter / thickness ratio Silver iodobromide a 0.30 2.0 1.0 b 0.40 8.0 1.4 c 0.60 7.0 3.0. 1 d 0.74 7.0 5.0 e 0.60 7.0 4.1 f 0.65 8.7 6.5 g 0.40 2.0 4.0 h 0.65 8.0 1. 4 i 1.00 8.0 2.0 j 0.05 2.0 1.0 k 0.10 2.0 1.0 l 0.15 2.0 1.0 Typical silver halide grains Examples of the production of silver iodobromide d and f are shown below. Also, silver iodobromide j,
k and l (hereinafter also referred to as emulsions j, k and l) are described in JP-A Nos. 1-183417, 1-183644 and 1-1.
It made with reference to the description about 183645 and 2-166442.

A silver halide emulsion was first prepared and prepared as Seed Emulsion-1.

Preparation of Seed Emulsion-1 A seed crystal emulsion was prepared as follows.

JP-B-58-58288, 58-58
No. 289, a silver nitrate aqueous solution (1.161 mol) was added to the following solution A1 adjusted to 35 ° C.
And a mixed aqueous solution of potassium bromide and potassium iodide (potassium iodide 2 mol%) while maintaining the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) at 0 mV. For 2 minutes to form nuclei. Subsequently, the temperature of the solution was raised to 60 ° C. over a period of 60 minutes, the pH was adjusted to 5.0 with an aqueous solution of sodium carbonate, and then an aqueous solution of silver nitrate (5.902 mol), potassium bromide and iodide were added. A mixed aqueous solution of potassium (2 mol% of potassium iodide) was added over 42 minutes by a double jet method while keeping the silver potential at 9 mV. After the addition was completed, the temperature was lowered to 40 ° C., and desalting and washing were immediately performed using a normal flocculation method.

The obtained seed crystal emulsion had an average sphere-equivalent diameter of 0.24 μm, an average aspect ratio of 4.8, and a maximum side length ratio of 90% or more of the total projected area of the silver halide grains (maximum ratio of each grain). The emulsion was composed of hexagonal tabular grains having a ratio of a side length to a minimum side length of 1.0 to 2.0. This emulsion is referred to as seed emulsion-1.

[Solution A1] Ossein gelatin 24.2 g Potassium bromide 10.8 g HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) (10% ethanol solution) 6.78 ml 10% nitric acid 114 ml H ₂ O 9657 ml Preparation of silver iodide fine grain emulsion SMC-1 6.0% by weight gelatin aqueous solution containing 0.06 mol of potassium iodide While stirring 5 liters vigorously, 7.06
An aqueous silver nitrate solution and an aqueous 7.06 mol potassium iodide solution, 2 liters each, were added over 10 minutes. During this time, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the particles are prepared, the pH is adjusted using an aqueous sodium carbonate solution.
Was adjusted to 5.0. The average particle size of the obtained silver iodide fine particles was 0.05 μm. This emulsion is designated as SMC-1.

Preparation of silver iodobromide d Seed emulsion-1 equivalent to 0.178 mol and HO (CH ₂ CH ₂
O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n
H (m + n = 9.77) in 10% ethanol solution 0.5
4.5% by weight of an aqueous inert gelatin solution 70
0 ml at 75 ° C., pAg 8.4, pH 5.0.
Then, particles were formed by the simultaneous mixing method with vigorous stirring according to the following procedure.

1) An aqueous solution of 3.093 mol of silver nitrate, 0.287 mol of SMC-1 and an aqueous solution of potassium bromide were added while maintaining the pAg at 8.4 and the pH at 5.0.

2) Subsequently, the solution was cooled to 60 ° C.
g was adjusted to 9.8. Thereafter, 0.071 mol of SM
C-1 was added and aging was performed for 2 minutes (introduction of dislocation lines).

3) An aqueous solution of 0.959 mol of silver nitrate, 0.03 mol of SMC-1 and an aqueous solution of potassium bromide were added while maintaining the pAg at 9.8 and the pH at 5.0.

Each solution was added at an optimum rate throughout the particle formation so as to prevent formation of new nuclei and Ostwald ripening between particles. After completion of the addition, the resultant was subjected to a water washing treatment at 40 ° C. using a normal flocculation method, and then gelatin was added and redispersed to adjust the pAg to 8.1 and the pH to 5.8.

The obtained emulsion had a particle size (cubic 1 of the same volume).
Tabular grains having a halogen composition having a side length of 0.74 μm, an average aspect ratio of 5.0, and a silver iodide content of 2 / 8.5 / X / 3 mol% (X is a dislocation line introduction position) from the inside of the grains. Emulsion. When this emulsion was observed with an electron microscope, five or more dislocation lines were observed both in the fringe portion and in the inside of the grain in 60% or more of the total projected area of the grain in the emulsion. The surface silver iodide content was 6.7 mol%.

Preparation of silver iodobromide f In the preparation of silver iodobromide d, pAg was adjusted to 8. in step 1).
8 and the amount of silver nitrate to be added was 2.077 mol SMC-1.
And the amount of silver nitrate added in step 3) was 0.91 mol and the amount of SMC-1 was 0.079 mol in the same manner as for silver iodobromide d. Silver fide f was prepared.

The obtained emulsion had a particle size (cubic 1 of the same volume).
Edge length) 0.65 μm, average aspect ratio 6.5, silver iodide content 2 / 9.5 / X / 8.0 mol% from the inside of the grain
The emulsion was composed of tabular grains having a halogen composition of (X is a dislocation line introduction position). When this emulsion was observed with an electron microscope, five or more dislocation lines were observed both in the fringe portion and in the inside of the grain in 60% or more of the total projected area of the grain in the emulsion. The surface silver iodide content was 11.9 mol%.

After the above-mentioned sensitizing dyes were added to each of the above emulsions and ripened, triphosphine selenide, sodium thiosulfate, chloroauric acid and potassium thiocyanate were added, and the fog and sensitivity were optimized according to the conventional method. Chemical sensitization was applied to obtain.

Further, silver iodobromide a, b, c, e, g, h,
i was also prepared according to the above silver iodobromide d and f and subjected to spectral sensitization and chemical sensitization.

In addition to the above composition, a coating aid SU-
1, SU-2, SU-3, dispersing aid SU-4, viscosity modifier V-1, stabilizers ST-1, ST-2, antifoggant A
F-1, two types of polyvinylpyrrolidone (AF-2) having a weight average molecular weight of 10,000 and a weight average molecular weight of 1,100,000, inhibitors AF-3, AF-4 and AF-
5. Hardeners H-1, H-2 and preservative Ase-1 were added.

The structure of the compound used above is shown below.

[0157]

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[0158]

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[0159]

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[0160]

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[0161]

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[0162]

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[0163]

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[0164]

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[0165]

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Thus, a light-sensitive material sample 401 was obtained.

Emulsions B and D obtained in Example 1 were used for the above-mentioned sample Nos. When the same processing and evaluation as in Example 1 were carried out using the 10th layer in the photosensitive material construction of No. 401, the emulsion D of the present invention was obtained.
Showed good results.

[0168]

The silver halide emulsion according to the present invention and the silver halide color photographic light-sensitive material using the same are fogged /
It has excellent sensitivity, has improved storage stability, and has excellent effects.

Claims (3)

[Claims] 1. A silver halide emulsion which is chemically sensitized using a compound having a water-soluble group, an adsorptive group to silver halide and an unstable chalcogen atom site in a molecule. 2. The compound having a water-soluble group, an adsorptive group to silver halide, and an unstable chalcogen atom site in the molecule is a compound represented by the following general formula (I). Item 7. The silver halide emulsion according to Item 1. Embedded image (In the formula, A ¹ represents an atom group containing a group that can be adsorbed to silver halide, L ¹ represents a (12 + 2) -valent linking group, Z ¹ represents an atom group containing an unstable chalcogen atom site, W ¹ ,
W ² and W ³ represents a carboxylic acid group, a sulfonic acid group, sulfinic acid group, a phosphoric acid group, phosphorous acid group and boric acid. m1
Represents 0 or 1; n1 represents an integer of 1 to 3;
l2 and l3 each represent an integer of 0 to 2. Where l1,
l2 and l3 do not become 0 at the same time. ) 3. A support having at least one photosensitive silver halide emulsion layer on a support, wherein at least one silver halide emulsion layer contains the silver halide emulsion according to claim 1 or 2. A silver halide color photographic light-sensitive material, characterized in that: