JP2824887B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material having high sensitivity and high storage stability.

[0002]

2. Description of the Related Art Conventionally, it has been desired to increase the sensitivity and storage stability of silver halide photographic materials. Particularly in spectrally sensitized silver halide photosensitive materials, there is a strong demand for higher sensitivity and improved storage stability. Attempts have been made to add hydrazines to silver halide light-sensitive materials or developers for various purposes. In U.S. Pat. No. 2,419,975, JP-A-63-261362 and JP-B-51-15745, hydrazines are added to a developing solution. In Japanese Patent Publication Nos. 58-9410 and 58-9411, acylhydrazines are added to a light-sensitive material in order to obtain a high contrast silver halide light-sensitive material. Addition of hydrazines shows a small but sensitizing effect but increases fog. JP-A-63-95444 and JP-A-63-43145 improve the heat and light stability of a dye image by using a magenta coupler and a specific hydrazine in combination. JP-A-63-220142, 63-256951
In JP-A-63-229455, photobleaching is prevented by using an organic coloring substance and a specific hydrazine in combination. Further, various nitrogen-containing heterocyclic compounds are used for the purpose of improving photographic performance (sensitivity, storage stability, fog prevention, etc.) during the production process, storage, or photographic processing of the photosensitive material. However, there is no known example of using the hydrazines having a specific structure of the present invention in combination with a nitrogen-containing heterocyclic compound and exhibiting remarkable effects.

[0003]

SUMMARY OF THE INVENTION The object of the present invention is as follows.
Another object of the present invention is to provide a silver halide light-sensitive material having high sensitivity and low fog, especially a spectrally sensitized silver halide light-sensitive material. Second, it is to provide a silver halide photosensitive material having high storage stability.

[0004]

The object of the present invention is as follows.
General formulas (II), (III) and
And at least one compound selected from (IV) and at least one nitrogen-containing heterocyclic compound.

[0005]

Formula (II)

[0007]

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General formula (III)

[0009]

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General formula (IV)

[0011]

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In the formula, R ₅ , R ₆ , R ₇ and R ₈ represent an alkyl group, an aryl group or a heterocyclic group. Z ₁ represents an alkylene group having 4 or 6 carbon atoms. Z ₂ represents an alkylene group having 2 carbon atoms. Z ₃ represents an alkylene group having 1 or 2 carbon atoms. Z ₄ and Z ₅ represent an alkylene group having 3 carbon atoms. L ₁ and L ₂
Represents a methine group. However, R ₅ , R ₆ , R ₇ ,
Of R ₈ , Z ₁ , Z ₄ and Z ₅ , the carbon atom directly bonded to the nitrogen atom of hydrazine is not substituted with an oxo group. More preferred are compounds selected from the general formulas (II) and (III), and particularly preferred are compounds selected from the general formula (II).

Hereinafter, R ₅ , R ₆ , R ₇ and R ₈ will be described in detail. As R ₅ , R ₆ , R ₇ and R ₈ , for example, an unsubstituted alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group, octyl group, dodecyl group, octadecyl) Group, cyclopentyl group, cyclopropyl group, cyclohexyl group), substituted alkyl group. When the substituent is V, the substituent represented by V is not particularly limited. For example, a carboxy group, a sulfo group, a cyano group, a halogen atom ( For example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a hydroxy group, an alkoxycarbonyl group (for example, a methoxycarbonyl group, an ethoxycarbonyl group, a phenoxycarbonyl group, a benzyloxycarbonyl group), and an alkoxy group (for example, a methoxy group, an ethoxy group, Benzyloxy group, phenethyloxy group), carbon number 8 or less aryloxy groups (eg, phenoxy group, 4-methylphenoxy group, α-naphthoxy group), acyloxy groups (eg, acetyloxy group, propionyloxy group), acyl groups (eg, acetyl group, propionyl group, benzoyl group, mesyl) Carbamoyl group (eg, carbamoyl group, N, N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group), sulfamoyl group (eg, sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfonyl group) , Piperidinosulfonyl group), aryl group (for example, phenyl group, 4-chlorophenyl group, 4-methylphenyl group, α-naphthyl group), heterocyclic group (for example, 2-pyridyl group, tetrahydrofurfuryl group, morpholino group) , 2-thiopheno group),
Amino group (eg, amino group, dimethylamino group, anilino group, diphenylamino group), alkylthio group (eg, methylthio group, ethylthio group), alkylsulfonyl group (eg, methylsulfonyl group, propylsulfonyl group), alkylsulfinyl group ( For example, methylsulfinyl group), nitro group, phosphate group, acylamino group (eg, acetylamino group), ammonium group (eg, trimethylammonium group, tributylammonium group), mercapto group, hydracino group (eg, trimethylhydrazino group), ureido group (E.g., ureido group, N, N-dimethylureido group), imide group, unsaturated hydrocarbon group (e.g., vinyl group, ethynyl group, 1-cyclohexenyl group,
Benzylidene group, benzylidene group). The number of carbon atoms of the substituent V is preferably 18 or less. V may be further substituted on these substituents.

More specifically, alkyl groups (for example, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group , 3-sulfobutyl, 2-hydroxy-3-sulfopropyl, 2-cyanoethyl, 2-chloroethyl, 2-bromoethyl, 2-hydroxyethyl, 3
-Hydroxypropyl group, hydroxymethyl group, 2-hydroxyethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-ethoxycarbonylethyl group, methoxycarbonylmethyl group, 2-methoxyethyl group, 2-ethoxyethyl group A 2-phenoxyethyl group, a 2-acetyloxyethyl group, a 2-propionyloxyethyl group,
2-acetylethyl group, 3-benzoylpropyl group, 2
-Carbamoylethyl group, 2-morpholinocarbonylethyl group, sulfamoylmethyl group, 2- (N, N-dimethylsulfamoyl) ethyl group, benzyl group, 2-naphthylethyl group, 2- (2-pyridyl) ethyl Group, allyl group, 3-aminopropyl group, 3-ditylaminopropyl group, methylthiomethyl group, 2-methylsulfonylethyl group, methylsulfinylmethyl group, 2-acetylaminoethyl group, 3-trimethylammoniumethyl group, 2-
A mercaptoethyl group, a 2-trimethylhydrazinoethyl group, a methylsulfonylcarbamoylmethyl group, a (2-methoxy) ethoxymethyl group, and the like; and an aryl group (for example, a phenyl group, an α-naphthyl group, a β-naphthyl group, For example, a phenyl group or a naphthyl group substituted with the aforementioned substituent V), a heterocyclic group (for example, a 2-pyridyl group,
A 2-thiazolyl group and a 2-pyridyl group substituted with the aforementioned substituent V) are preferred.

R ₅ and R ₆ , and R ₇ and R ₈ may combine with each other to form a ring. However, it does not form an aromatic ring. These rings may be substituted, for example, by the substituent V described above. However, R ₅ , R
₆ , the carbon atom directly bonded to the nitrogen atom of hydrazine among R ₇ and R ₈ is not substituted with an oxo group. For example, R ₅ , R ₆ , R ₇ and R ₈ are not an acetyl group, a carboxy group, a benzoyl group, a formyl group or a malonyl group, a succinyl group, a glutaryl group or an adipoyl group when two of them form a ring. R ₅ , R
_6, thioxo group to the carbon atom directly bonded to the nitrogen atom of the hydrazine of R ₇ and R ₈ (e.g., thioacetyl, thioaldehyde group, thiocarboxy group, thiobenzoyl group) who has not been replaced preferred .

R ₅ , R ₆ , R ₇ and R ₈ are more preferably an unsubstituted alkyl group, a substituted alkyl group, or a ring wherein R ₅ and R ₆ , and R ₇ and R ₈ are bonded to each other. Is the case where an alkylene group containing no other than a carbon atom (for example, an oxygen atom, a sulfur atom, or a nitrogen atom) in the atom constituting the alkylene group (the alkylene group may be substituted (for example, the aforementioned substituent V)) is formed. . R ₅ , R ₆ , R ₇
And R ₈ is more preferably a case where the carbon atom directly bonded to the nitrogen atom of hydrazine is an unsubstituted methylene group. Particularly preferably, an unsubstituted alkyl group (for example, methyl group, ethyl group, propyl group, butyl group), a substituted alkyl group {for example, a sulfoalkyl group (for example, 2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, 3 - sulfobutyl), a carboxyalkyl group (e.g., carboxymethyl group, 2-carboxyethyl group), a hydroxyalkyl group (e.g. 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group)} and, with _{R 5} R ₆ and R ₇ and R ₈ are linked to each other by an alkylene chain to form a 5-membered ring and a 7-membered ring.

[0017]

Hereinafter, the general formula (II) will be described in detail. R _5, and R ₆ are preferably in particular, a case where a methyl group and R ₅ and R ₆ are joined together to form an unsubstituted tetramethylene group. Z ₁ represents an alkylene group having 4 or 6 carbon atoms, preferably an alkylene group having 4 carbon atoms. However, the oxo group is not substituted on the carbon atom by directly bonding to the nitrogen atom of hydrazine. This alkylene group may be unsubstituted or substituted. Examples of the substituent include the substituent V described above, and it is preferable that the carbon atom directly bonded to the nitrogen atom of hydrazine is an unsubstituted methylene group. Z ₁ is particularly preferably an unsubstituted tetramethylene group.

Hereinafter, the formula (III) will be described in detail. R ₇ and R ₈ are preferably in particular, a case where a methyl group and R ₇ and R ₈ are combined to form a trimethylene group with one another. Z ₂ represents an alkylene group having 2 carbon atoms. Z ₃ represents an alkylene group having 1 or 2 carbon atoms. These alkylene groups may be unsubstituted or substituted. Examples of the substituent include the substituent V described above. More preferably, Z ₂ is an unsubstituted ethylene group. Z ₃ is more preferably an unsubstituted methylene group or an ethylene group. L ₁ and L
₂ represents a methine group or a substituted methine group. Examples of the substituent include the aforementioned substituent V, and are preferably an unsubstituted alkyl group (for example, a methyl group or a t-butyl group). More preferably, it is an unsubstituted methine group.

The general formula (IV) will be described in detail.
Z ₄ and Z ₅ represent an alkylene group having 3 carbon atoms. However, the carbon atom directly bonded to the nitrogen atom of hydrazine is not substituted with an oxo group. These alkylene groups may be unsubstituted or substituted. Examples of the substituent include the substituent V described above, and the carbon atom directly bonded to the nitrogen atom of hydrazine is preferably an unsubstituted methylene group. Particularly preferred as Z ₄ and Z ₅ are an unsubstituted trimethylene group,
Unsubstituted alkyl group-substituted trimethylene group (for example, 2,2
-Dimethyltrimethylene group). General formula (II),
Compounds represented by (III) and (IV) are synthesized
Above, and if advantageous for storage, isolated as a salt at all
I can't do that. In such cases, hydrazines and salts
Any compound may be used as long as it can be formed.
Preferred salts include the following. For example, ants
Sulfonic acid salt (for example, p-toluenesulfonic acid salt,
p-chlorobenzenesulfonate), aryldisulfo
Phosphates (eg, 1,3-benzenedisulfonate, 1,1
5-naphthalenedisulfonic acid salt, 2,6-naphthalenedi
Sulfonate), thiocyanate, picrate, cal
Borate (eg oxalate, acetate, benzoate, citrate)
Hydrogen oxalate), halogenates (eg, hydrochloride,
Hydrofluoride, hydrobromide, hydroiodide), sulfuric acid
Acid salt, perchlorate, tetrafluoroborate, sulfurous acid
Salts, nitrates, phosphates, carbonates, bicarbonates. Preferred are hydrogen oxalate, oxalate and hydrochloride. The following formulas (II) , (III) and (I)
Typical examples of the compound represented by V) are given below, but it should not be construed that the invention is limited thereto .

[0021]

[0022]

[0023]

[0024]

[0025]

[0026]

[0027]

Compound represented by general formula (II)

[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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Compound represented by general formula (III)

[0036]

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[0037]

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[0038]

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[0039]

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Compound represented by general formula (IV)

[0041]

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[0042]

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[0043]

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The hydrazines of the present invention can be synthesized by various methods. For example, it can be synthesized by a method of alkylating hydrazine. Alkylation methods include direct alkylation using an alkyl halide and an alkyl sulfonate, reductive alkylation using a carbonyl compound and sodium cyanoborohydride, and hydrogenation after acylation. A reduction method using lithium aluminum and the like are known. For example, S.R.Sandler,
W. Karo, "Organic
Functional Group Preparations (O
rganic FunctionalGroup Pr
evolution), Volume 1, Chapter 14, 434-4
65 pages (1968), Academic Press (A
Cademic Press) .

The compound represented by the general formula (II) can be obtained, for example, from Journal of the American Chemical Society (SFNelsen) or the like.
ournal of The American Chemical Society) Volume 98 1
2, 5269 (1976), SF Nelsen, GR Weisman
man), Tetrahedron Letter
No. 26, p. 2321 (1973) and the like, and can be synthesized by referring to them. The synthesis examples of typical compounds are described below.

Synthesis Example 1 Synthesis of Compound (2-3) Synthesis Route

[0047]

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(A) 20 g (0.163 mol), (A)
16.3 g (0.163 mol) and 80 ml of acetic acid in 1
After heating under reflux for 5 hours, 50 ml of water and 100 ml of a 5% aqueous sodium hydroxide solution were added, and the mixture was extracted with 200 ml of chloroform. After drying over anhydrous sodium sulfate, the solvent is distilled off under reduced pressure. When 200 ml of ethyl acetate is added to the obtained oil and 200 ml of hexane is further added, crystals precipitate. After filtration by suction filtration, drying (c) (colorless crystals, 8.65)
g, yield 32%). 8.9 g (0.235 mol) of lithium aluminum hydride, tetrahydrofuran 10
0 ml was cooled to 0 ° C., and 7.9 g of (c) was stirred.
A solution of (0.047 mol) / 70 ml of tetrahydrofuran is gradually added dropwise. At this time, the reaction solution is kept at 5 ° C. or lower.
After stirring at room temperature for 4 hours, the reaction solution was cooled again to 0 ° C., and 9 ml of water, 9 ml of a 15% aqueous sodium hydroxide solution,
The mixture was added dropwise in the order of 7 ml, and the precipitated colorless crystals were removed by filtration with suction. The filtrate was dried over anhydrous sodium sulfate, the solvent was removed by distillation under reduced pressure, and then (2-3) was distilled off under reduced pressure (colorless liquid, 1.44 g, 85-90 ° C./25 mmHg, yield 17).
%).

Synthesis Example 2 Synthesis of compound (2-1) (2-3) 6 g (0.043 mol), ethyl acetate 100
A solution of 4.3 g (0.048 mol) of oxalic acid in 120 ml of ethyl acetate is added to the resulting solution, followed by stirring. The precipitated crystals were filtered off by suction filtration and dried (2-1) (9.3 g of colorless crystals, mp.
129-131 ° C, 94% yield).

The compound represented by the general formula (III) can be used, for example, in HRSnycler, J.
R), JGM Michels, Journal of Organic Chemistry (Journal o
f Organic Chemistry) Vol. 28, p. 1144 (1963)
Years), JE Anderson,
JMLehn, Journal of the American Chemical Society (Journal)
of The American Chemical Society) Vol. 89, No. 1,
81 (1967), Hermann Tester
Stetter), Peter Woernle (Justus Liebig Analen del Chemie)
Liebigs Annalen der Chemie) No. 724, p. 150 (1969), SF Nelsen
Et al., Tetrahedron, Vol. 42, No. 6, 1
Page 769 (1986), and can be synthesized by referring to them.

Compounds represented by the general formula (IV) include, for example, Journal of the American Chemical Society (SFNelsen) and the like.
ournal of The American Chemical Society), Vol. 96, No. 9, pp. 2916 (1974), EL Buhle, and other journals of the American Chemical Society.
Chemical Society (Journal of The American C
chemical Society), Vol. 65, p. 29 (1943)
And can be synthesized by referring to them.

The nitrogen-containing heterocyclic compound used in the present invention is preferably a compound containing a saturated or unsaturated 5- to 7-membered ring containing at least one nitrogen atom as a hetero atom, and this ring further has a substituent. And may have a condensed ring. Further, it may contain a hetero atom other than a nitrogen atom. However, Japanese Patent Publication No. 45-327
Stilbene compounds represented by the general formula (II) described in No. 41 are excluded. One preferred compound is a compound represented by the following general formula (V). General formula (V)

[0053]

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In the formula, Z ₆ is specifically an azole ring (eg, imidazole, triazole, tetrazole, thiazole, oxazole, selenazole, benzimidazole, benzotriazole, benzoxazole, benzothiazole, thiadiazole, oxadiazole, benzoselenazole , Pyrazole, naphthothiazole, naphthoimidazole, naphthoxazole, azabenzimidazole, purine), pyrimidine ring, triazine ring, pyridine ring, azaindene ring (for example, triazaindene,
Tetrazaindene, pentaazaindene) and the like. Y ₀ represents a hydrogen atom or a substituent , and examples of the substituent include those described above as R ₅ , R ₆ , R _7, and R ₈ or V. Particularly, a hydroxy group and a mercapto group are preferably used. p ₁
Represents an integer of 0 or more. These nitrogen-containing heterocyclic compounds are described in detail in the following patents. U.S. Pat. No. 3,266,897, Belgian Patent No. 671,
No. 402, JP-A-60-138548, JP-A-59-1984
68732, JP-A-59-123838, JP-B-5
8-9939, JP-A-59-137951, JP-A-57-202531, JP-A-57-164732,
JP-A-57-14836, JP-A-57-116340
No. 4,418,140, JP-A-58-9.
5728, JP-A-55-79436, OLS2,2
05,029, OLS1,962,605, JP-A-55-59463, JP-B-48-18257, JP-B-53-28084, JP-A-53-48723, JP-B-59-52414, 58-17928
No., JP-B-49-8334, U.S. Pat. No. 3,598,
No. 602, US Pat. No. 887,009, British Patent No. 9
No. 65,047, Belgian Patent No. 737809, U.S. Pat. No. 3,622,340, JP-A-60-87322.
JP-A-57- 211142, JP-A-58-158
No. 631, JP-A-59-15240, U.S. Pat.
No. 71, 255, JP-B-48-34166, JP-B-4
8-322112, JP-A-58-221839, JP-B-48-32367, JP-A-60-130731.
JP-A-60-122936, JP-A-60-117
No. 240, U.S. Pat. No. 3,228,770, JP-B-43
-13496, JP-B-43-10256, JP-B-4
7-8725, JP-B-47-30206, JP-B-4
No. 7-4417, Japanese Patent Publication No. 51-25340, British Patent No. 1,165,075, U.S. Pat. No. 3,512,982
No. 1,472,845, JP-B-39-22
No. 067, Japanese Patent Publication No. 39-22068, U.S. Pat.
No. 48,067, U.S. Pat. No. 3,759,901, U.S. Pat. No. 3,909,268, Japanese Patent Publication No. 50-40665.
No., JP-B-39-2829, U.S. Pat. No. 3,148,0
No. 66, Japanese Patent Publication No. 45-22190, U.S. Pat.
9,449, UK Patent 1,287,284, US Patent 3,900,321, US Patent 3,655,391
No. 3,910,792; British Patent 1,06
4,805, U.S. Pat. No. 3,544,336, U.S. Pat. No. 4,003,746, British Patent 1,344,525
No., British Patent No. 972,211 and Japanese Patent Publication No. 43-4136
No. 3,140,178, French Patent 2,01
5,456, U.S. Patent 3,114,637, Belgian Patent 681,359, U.S. Patent 3,220,839
No. 1,290,868, U.S. Pat.
7,578, U.S. Patent 3,420,670, U.S. Patent 2,759,908, U.S. Patent 3,622,340
No., OLS 2,501,261, DAS 1,772,
No. 424, US Pat. No. 3,157,509, French Patent 1,351,234, US Pat. No. 3,630,745.
Patent, French Patent 2,005,204, German Patent 1,44
7,796, U.S. Pat. No. 3,915,710, Japanese Patent Publication No. 49-8334, British Patent 1,021,199, British Patent 919,061, Japanese Patent Publication No. 46-17513,
U.S. Pat. No. 3,202,512, OLS 2,553,1
27, Japanese Patent Application Laid-Open No. 50-104927, French Patent 1,4
67,510; U.S. Pat. No. 3,449,126; U.S. Pat. No. 3,503,936; U.S. Pat.
8, French Patent 2,093,209, British Patent 1,2
No. 46,311; US Pat. No. 3,844,788; US Pat. No. 3,535,115; British Patent 1,161,26.
No. 4, U.S. Pat. No. 3,841,878, U.S. Pat.
15,616, JP-A-48-39039, British Patent 1,249,077, JP-B-48-34166, U.S. Pat.
No., JP-A-50-6323, British Patent 1,402,8
No. 19, OLS 2,031,314, Research Disclosure 13651, U.S. Pat. No. 3,910,79
No. 1, US Pat. No. 3,954,478, US Pat.
13,249, British Patent 1,387,654, JP-A-57-135945, JP-A-57-96331,
JP-A-57-22234, JP-A-59-26731
No. OLS 2,217,153, British Patent 1,39
4,371, British Patent 1,308,777, British Patent 1,389,089, British Patent 1,347,544
No. 1, German Patent 1,107,508, US Patent 3,38
No. 6,831, British Patent No. 1,129,623, JP-A-49-14120, JP-B-46-34675, JP-A-50-43923, U.S. Pat. No. 3,642,481
No. 1,269,268, U.S. Pat.
8,185, US Patent 3,295,981, US Patent 3,396,023, US Patent 2,895,827
No., JP-B-48-38418, JP-A-48-4733.
No. 5, JP-A-50-87028, U.S. Pat.
No. 6,652, U.S. Pat. No. 3,443,951, British Patent 1,065,669, U.S. Pat.
No. 3,310,405, US Pat. No. 3,30
0,312, British Patent 952,162, British Patent 9
52,162; British Patent 948,442;
No. 9-120628, JP-B-48-35372, JP-B-47-5315, JP-B-39-18706, JP-B-43-4941, and JP-A-59-34530. More preferred as the nitrogen-containing heterocyclic compound are compounds represented by the general formulas (VI), (VII), (VIII), (IX),
Compounds represented by (X), (XI) and (XII). General formula (VI)

[0055]

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Formula (VII)

[0057]

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Formula (VIII)

[0059]

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Formula (IX)

[0061]

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Formula (X)

[0063]

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Formula (XI)

[0065]

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Formula (XII)

[0067]

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Wherein R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R
₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ and R ₂₂ represent a hydrogen atom or a monovalent substituent. R ₂₄ represents an alkyl group, an aryl group or a heterocyclic group. X ₁ represents a hydrogen atom, an alkali metal atom, an ammonium group or a precursor. Y ₁ is an oxygen atom, a sulfur atom, ＮＨNH, ＮN-
(L ₄ ) _p3 -R ₂₈ , wherein L ₃ and L ₄ represent a divalent linking group, and R ₂₅ and R ₂₈ represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. X ₂ has the same meaning as X ₁ .
p ₂ and p ₃ is an integer of 0 or more. Z ₇ represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. R ₂₆ and R ₂₇ represent a hydrogen atom or an alkyl group. Next, general formulas (VI), (VII), (VIII), (IX),
(X), (XI) and (XII) will be described in more detail. R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ ,
R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ and R ₂₂ represent a hydrogen atom or 1
Represents a valent substituent. Examples of the monovalent substituent include the aforementioned R
Substituents and the like mentioned as preferable examples of ₁ , R ₂ , R ₃ and R ₄ can be mentioned. More preferably, a lower alkyl group (preferably a substituted or unsubstituted carbon atom having 1 carbon atom)
~ 4, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl,
Methoxyethyl group, hydroxyethyl group, hydroxymethyl group, vinyl group, allyl group), carboxy group, alkoxy group (preferably substituted or unsubstituted one having 1 to 5 carbon atoms, for example, methoxy group, ethoxy group, methoxyethoxy group) Group, hydroxyethoxy group), aralkyl group (preferably substituted or unsubstituted one having 7 to 12 carbon atoms, for example, benzyl group, phenethyl group, phenylpropyl group),
Aryl group (preferably substituted or unsubstituted C 6 -C 6)
Twelve, for example, phenyl group, 4-methylphenyl group, 4-methoxyphenyl group), heterocyclic group (for example, 2-
A pyridyl group), an alkylthio group (preferably substituted or unsubstituted one having 1 to 10 carbon atoms, for example, a methylthio group,
Ethylthio group), arylthio group (preferably substituted or unsubstituted one having 6 to 12 carbon atoms such as phenylthio group), aryloxy group (preferably substituted or unsubstituted one having 6 to 12 carbon atoms such as phenoxy group) An alkylamino group having 3 or more carbon atoms (eg, propylamino group, butylamino group), an arylamino group (eg, anilino group), a halogen atom (eg, chlorine atom,
Represents a bromine atom or a fluorine atom) or the following substituent.

[0069]

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Here, L ₅ , L ₆ and L ₇ represent a linking group represented by an alkylene group (preferably having 1 to 5 carbon atoms, for example, a methylene group, a propylene group, a 2-hydroxypropylene group). R ₂₉ and R ₃₀ may be the same or different and each represents a hydrogen atom, an alkyl group (preferably substituted or unsubstituted one having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group) , N
-Butyl group, t-butyl group, n-octyl group, methoxyethyl group, hydroxyethyl group, allyl group, propargyl group), aralkyl group (preferably substituted or unsubstituted one having 7 to 12 carbon atoms, for example, benzyl Group, phenethyl group, vinylbenzyl group), aryl group (preferably substituted or unsubstituted one having 6 to 12 carbon atoms, for example, phenyl group, 4-methylphenyl group), or heterocyclic group (for example, 2-pyridyl group) ). The alkyl group, aryl group and heterocyclic group represented by R ₂₄ may be unsubstituted or substituted. As the substituent, R ₁ , R ₂ , R ₃ and R
Substituents and the like mentioned as preferable examples of ₄ can be mentioned. More preferably, a halogen atom (eg, chlorine atom, bromine atom, fluorine atom), nitro group, cyano group, hydroxy group, alkoxy group (eg, methoxy group), aryl group (eg, phenyl group), acylamino group (eg, propionylamino Group), alkoxycarbonylamino group (eg, methoxycarbonylamino group), ureido group, amino group, heterocyclic group (eg, 2-pyridyl group), acyl group (eg, acetyl group), sulfamoyl group, sulfonamide group, thioureido group Carbamoyl group, alkylthio group (for example, methylthio group), arylthio group (for example, phenylthio group, heterocyclic thio group (for example, 2-benzothiazolylthio group), carboxylic acid group, sulfonic acid group, and salts thereof. The above ureido group, thioureido , A sulfamoyl group, a carbamoyl group, and an amino group each include an unsubstituted group, an N-alkyl-substituted group, and an N-aryl-substituted group.Examples of the aryl group include a phenyl group and a substituted phenyl group. R ₁ , R
Substituents and the like mentioned as preferable examples of ₂ , R ₃ and R ₄ can be mentioned. The alkali metal atoms represented by X ₁ and X ₂ are, for example, a sodium atom and a potassium atom, and the ammonium groups are, for example, tetramethylammonium and trimethylbenzylammonium. The precursor is a group that can become a hydrogen atom, an alkali metal or ammonium under alkaline conditions, and represents, for example, an acetyl group, a cyanoethyl group, and a methanesulfonylethyl group. Specific examples of the divalent linking group represented by L ₃ and L ₄ include the following linking groups or a combination thereof.

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R ₃₁ , R ₃₂ , R ₃₃ , R ₃₄ , R ₃₅ , R ₃₆ , R
₃₇ , R ₃₈ , R ₃₉ and R _{40 each} represent a hydrogen atom, an alkyl group (preferably substituted or unsubstituted one having 1 to 4 carbon atoms,
For example, a methyl group, an ethyl group, an n-butyl group, a methoxyethyl group, a hydroxyethyl group, an allyl group) or an aralkyl group (preferably substituted or unsubstituted 7-1)
Two, for example, benzyl, phenethyl, phenylpropyl). R ₂₅ and R ₂₈ are as defined above for R
Preferred are those similar to those shown at ₂₄ . As Z ₇ , thiazoliums {eg thiazolium, 4-
Methylthiazolium, benzothiazolium, 5-methylbenzothiazolium, 5-chlorobenzothiazolium,
5-methoxybenzothiazolium, 6-methylbenzothiazolium, 6-methoxybenzothiazolium, naphtho [1,2-d] thiazolium, naphtho [2,1-d] thiazolium, oxazoliums such as oxazolium , 4-methyloxazolium, benzoxazolium, 5-chlorobenzoxazolium, 5-phenylbenzoxazolium, 5-methylbenzoxazolium, naphtho [1,2-d] oxazolium}, imidazolium Classes such as 1-methylbenzimidazolium, 1
-Propyl-5-chlorobenzimidazolium, 1-ethyl-5,6-cyclobenzimidazolium, 1-allyl-5-trifluoromethyl-6-chloro-benzimidazolium), selenazoliums [for example, benzoselenazo Examples thereof include lium, 5-chlorobenzoselenazolium, 5-methylbenzoselenazolium, 5-methoxybenzoselenazolium, and naphtho [1,2-d] selenazolium]. Particularly preferably, thiazoliums (for example,
Benzothiazolium, 5-chlorobenzothiazolium,
5-methoxybenzothiazolium, naphtho [1,2-
d] Thiazolium). R ₂₆ and R ₂₇ are preferably a hydrogen atom, an unsubstituted alkyl group having 18 or less carbon atoms (eg, methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, octadecyl), or a substituted or alkyl group ア ル キ ル substituted Examples of the group include a vinyl group, a carboxy group, a sulfo group, a cyano group, a halogen atom (for example, fluorine, chlorine, and bromine), a hydroxy group, and an alkoxycarbonyl group having 8 or less carbon atoms (for example, methoxycarbonyl, ethoxycarbonyl, and phenoxy). Carbonyl, benzyloxycarbonyl), an alkoxy group having 8 or less carbon atoms (eg, methoxy, ethoxy, benzyloxy, phenethyloxy), a monocyclic aryloxy group having 10 or less carbon atoms (eg, phenoxy, p-tolyloxy), 3 or less acyloxy groups (eg, Acetyloxy, propionyloxy), no more than 8 acyl group (e.g. acetyl carbon, propionyl, benzoyl, mesyl), a carbamoyl group (e.g. carbamoyl, N, N
-Dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl), a sulfamoyl group (eg, sulfamoyl, N, N-dimethylsulfamoyl, morpholinosulfonyl, piperidinosulfonyl), an aryl group having 10 or less carbon atoms (eg, phenyl, 4- Chlorophenyl, 4-methylphenyl, α-naphthyl) and the like. More preferably, R ₂₆ is an unsubstituted alkyl group (eg, methyl,
Ethyl), alkenyl group (for example, allyl group),
₂₇ is a hydrogen atom and an unsubstituted lower alkyl group (for example, methyl and ethyl). M ₁ and m ₁ are included in the formula to indicate the presence or absence of a cation or an anion when necessary to neutralize the ionic charge of the compound represented by the general formula (XII). Have been. Whether a dye is a cation, an anion, or has a net ionic charge depends on its auxochrome and substituents. Typical cations are inorganic or organic ammonium and alkali metal ions, while the anion may be specifically an inorganic or organic anion, such as a halogen anion (eg, fluoride, Chlorine ion, bromide ion, iodine ion, substituted arylsulfonate ion (for example, p-toluenesulfonic acid ion, p-chlorobenzenesulfonate ion), aryldisulfonate ion (for example, 1,3-benzenedisulfonate ion, 1, 5-naphthalenedisulfonic acid ion, 2,6-naphthalenedisulfonic acid ion), alkyl sulfate ion (for example, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion,
An acetate ion and a trifluoromethanesulfonic acid ion are mentioned. Preferably, they are an ammonium ion, an iodine ion, a bromine ion, and a p-toluenesulfonic acid ion. The general formulas (VI), (VII), (VIII), (IX),
Typical examples of the compounds represented by (X), (XI), (XII) and (V) are shown below, but are not limited thereto. Specific examples of the compound represented by the general formula (VI).

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Specific examples of the compound represented by formula (VII).

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Specific examples of the compound represented by the general formula (VIII).

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A compound represented by the general formula (IX).

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[0084]

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A compound represented by the general formula (X).

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[0087]

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[0088]

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[0089]

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A compound represented by the general formula (XI).

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[0092]

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[0093]

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[0094]

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A compound represented by the general formula (XII).

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[0097]

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[0098]

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A compound represented by formula (V): (However, general formulas (VI), (VII), (VIII), (IX),
(Excluding compounds represented by (X), (XI) and (XII))

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[0101]

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[0102]

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[0103]

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[0104]

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[0105]

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[0106]

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[0107]

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[0108]

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As the spectral sensitizing dye used in the present invention, any of conventionally known dyes such as cyanine dye, merocyanine dye, rhodocyanine dye, oxonol dye, hemicyanine dye, benzylidene dye and xanthene dye can be used. it can. For example, edited by THJames, "The Theory
The Theory Process
of the Photographic Process) "(3rd edition), 198th
228 (1966), published by Macmillan. Preferably, the oxidation potential of the sensitizing dye is 0.95 (V _vs. SCE) or lower. It is known that these dyes generally have large dye desensitization. More preferred are dyes having an oxidation potential of 0.95 (V _vs. SCE) or lower and spectral sensitization of panchromatic and near-infrared regions having a spectral sensitivity maximum of 600 nm or more.

The oxidation potential was measured by phase discrimination type second high frequency alternating current polarography. The details are described below. Acetonitrile (spectral grade) dried in 4A-1 / 16 molecular sieves was used as a solvent, and normal tetrapropylammonium perchlorate (a special reagent for polarography) was used as a supporting electrolyte. The sample solution was prepared by dissolving the sensitizing dye in acetonitrile containing 0.1 M of supporting electrolyte at 10 ^-3 to 10 ^-5 mol / L, and before the measurement, a highly alkaline aqueous solution of pyrogallol and calcium chloride were passed through. Deoxygenation was performed with high-purity argon gas (99.999%) for 15 minutes or more. A rotating platinum electrode was used as a working electrode, a saturated calomel electrode (SCE) was used as a reference electrode, and platinum was used as a counter electrode. The reference electrode and the sample solution were connected with a Luggin tube filled with acetonitrile containing 0.1 M indicator electrolyte, and Vycor glass was used for the liquid junction. The measurement was performed at 25 ° C. with the tip of the lugine tube and the tip of the rotating platinum electrode separated from 5 mm to 8 mm. The measurement of the oxidation potential by the above-mentioned phase discrimination type second harmonic AC voltammetry is described in Journal
Of Imaging Science "(Journal of Imagi
ng Science), Volume 30, 27-35 (1986)
It is described in. Under these conditions, the dye (XIV-
The oxidation potential of 9) was 0.915 V (vsSCE). Sensitizing dyes satisfying the above-mentioned conditions of the oxidation potential and the maximum spectral sensitivity and represented by the following formulas (XXI), (XXII) and (XXIII) are particularly preferably used. General formula (XXI)

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General formula (XXII)

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General formula (XXIII)

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In the formula, Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₁₄ , Z ₁₅ and Z ₁₆ each represent an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. D and D 'represent the atoms required to form an acyclic or cyclic acidic nucleus.
R ₄₁ , R ₄₂ , R ₄₃ , R ₄₄ and R ₄₆ represent an alkyl group. R ₄₅ represents an alkyl group, an aryl group or a heterocyclic group. _{L 11, L 12, L 13} , L 14, L 15, L 16, L 17, L
_{18, L 19, L 20,} L 21, L 22, L 23, L 24, L 25,
L ₂₆ , L ₂₇ , L ₂₈ , L ₂₉ and L ₃₀ represent a methine group. M ₁₁ , M ₁₂ and M ₁₃ represent a charge neutralizing counter ion, and m ₁₁ , m ₁₂ and m ₁₃ are zero or more necessary to neutralize the charge in the molecule. n ₁₁ , n ₁₃ , n ₁₄ , n
₁₆ and n ₁₉ represent 0 or 1. n ₁₂ represents 1, 2 or 3. n ₁₅ represents 2 or 3. n ₁₇ and n ₁₈
Is an integer of 0 or more, and the total represents 1, 2, 3 or 4. More preferred are sensitizing dyes represented by the general formula (XXI).

The following formulas (XXI), (XXII) and (XXI)
II) will be described in more detail. R ₄₁ , R ₄₂ , R ₄₃ , R ₄₄
And R ₄₆ is preferably an unsubstituted alkyl group having 18 or less carbon atoms (eg, methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, octadecyl), or a substituted alkyl group.
A carboxy group, a sulfo group, a cyano group, a halogen atom (for example, fluorine, chlorine, or bromine), a hydroxy group, an alkoxycarbonyl group having 8 or less carbon atoms (for example, methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl); An alkoxy group having 8 or less carbon atoms (eg, methoxy, ethoxy, benzyloxy, phenethyloxy), a monocyclic aryloxy group having 10 or less carbon atoms (eg, phenoxy, p-tolyloxy), an acyloxy group having 3 or less carbon atoms (eg, Acetyloxy, propionyloxy), an acyl group having 8 or less carbon atoms (eg, acetyl, propionyl, benzoyl, mesyl), a carbamoyl group (eg, carbamoyl, N, N-
Dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl), sulfamoyl group (eg, sulfamoyl, N, N-dimethylsulfamoyl, morpholinosulfonyl, piperidinosulfonyl), aryl group having 10 or less carbon atoms (eg, phenyl, 4-chloro) Phenyl,
An alkyl group １８ having 18 or less carbon atoms, which is substituted with 4-methylphenyl or α-naphthyl). Preferably, an unsubstituted alkyl group (for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group), a carboxyalkyl group (for example, 2-carboxyethyl group, carboxymethyl group) ), A sulfoalkyl group (for example, a 2-sulfoethyl group, a 3-sulfopropyl group, a 4-sulfobutyl group, a 3-sulfobutyl group), and a methanesulfonylcarbamoylmethyl group. M ₁₁ m ₁₁ ,
M ₁₂ m ₁₂ and M ₁₃ m ₁₃ are included in the formula to indicate the presence or absence of a cation or an anion when necessary to neutralize the ionic charge of the dye. Whether a dye is a cation, an anion, or has a net ionic charge depends on its auxochrome and substituents. Typical cations are inorganic or organic ammonium and alkali metal ions, while the anion may be specifically an inorganic or organic anion, such as a halogen anion (eg, fluoride, Chloride ion, bromide ion, iodine ion, substituted arylsulfonate ion (for example, p-toluenesulfonate ion, p-chlorobenzenesulfonate ion), aryldisulfonate ion (for example, 1,3-benzenedisulfonate ion, 1,1,2) 5-naphthalenedisulfonic acid ion, 2,6-naphthalenedisulfonic acid ion), alkyl sulfate ion (for example, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetic acid Ion, trifluoromethane Preferably sulfonic acid ion and the like, ammonium ion, an iodine ion, a p- toluenesulfonic acid ion.

The nucleus formed by Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₁₄ and Z ₁₆ includes a thiazole nucleus and a thiazole nucleus (for example, thiazole, 4-methylthiazole, 4-phenylthiazole, 4,5-dimethylthiazole) , 4,5
-Diphenylthiazole), a benzothiazole nucleus (e.g., benzothiazole, 4-chlorobenzothiazole,
5-chlorobenzothiazole, 6-chlorobenzothiazole, 5-nitrobenzothiazole, 4-methylbenzothiazole, 5-methylthiobenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole,
5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 6-methylthiobenzothiazole, 5-ethoxybenzothiazole, 5- Ethoxycarbonylbenzothiazole, 5-carboxybenzothiazole, 5-phenethylbenzothiazole, 5-fluorobenzothiazole, 5-chloro-6-methylbenzothiazole, 5,6-dimethylbenzothiazole, 5,6
-Dimethylthiobenzothiazole, 5,6-dimethoxybenzothiazole, 5-hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole, a naphthothiazole nucleus (for example, naphtho [2,1-d] thiazole) , Naft [1,2
-D] thiazole, naphtho [2,3-d] thiazole,
5-methoxynaphtho [1,2-d] thiazole, 7-ethoxynaphtho [2,1-d] thiazole, 8-methoxynaphtho [2,1-d] thiazole, 5-methoxynaphtho [2,3-d] Thiazole)}, thiazoline nucleus (eg, thiazoline, 4-methylthiazoline, 4-nitrothiazoline), oxazole nucleus {oxazole nucleus (eg, oxazole, 4-methyloxazole, 4-nitrooxazole, 5-methyloxazole, 4-phenyl) Oxazole, 4,5-diphenyloxazole, 4
-Ethyloxazole), a benzoxazole nucleus (e.g., benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-
Phenylbenzoxazole, 5-methoxybenzoxazole, 5-nitrobenzoxazole, 5-trifluoromethylbenzoxazole, 5-hydroxybenzoxazole, 5-carboxybenzoxazole,
6-methylbenzoxazole, 6-chlorobenzoxazole, 6-nitrobenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 5,6-dimethylbenzoxazole, 4,6-
Dimethylbenzoxazole, 5-ethoxybenzoxazole), naphthooxazole nucleus (for example, naphtho [2,1-d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,3-d] oxazole, 5-
Nitronaphtho [2,1-d] oxazole)}, an oxazoline nucleus (eg, 4,4-dimethyloxazoline),
Selenazole nucleus ｛selenazole nucleus (for example, 4-methyl selenazole, 4-nitro selenazole, 4-phenyl selenazole), benzo selenazole nucleus (for example, benzo selenazole, 5-chlorobenzo selenazole, 5-
Nitrobenzo selenazole, 5-methoxy benzo selenazole, 5-hydroxy benzo selenazole, 6-nitro benzo selenazole, 5-chloro-6-nitro benzo selenazole, 5,6-dimethyl benzo selenazole), naphtho selenazole Nuclei (for example, naphtho [2, 1
-D] selenazole, naphtho [1,2-d] selenazole)}, selenazoline nucleus (for example, selenazoline, 4-
Methyl selenazoline), a tellurazole nucleus and a tellurazole nucleus (for example, tellurazole, 4-methyltellurazole,
4-phenyltellurazole), benzotellurazole nucleus (for example, benzotellurazole, 5-chlorobenzotellurazole, 5-methylbenzotellurazole, 5,6-dimethylbenzotellurazole, 6-methoxybenzotellurazole), naphtho Tellurazole nucleus (for example, naphtho [2,1-d] tellurazole, naphtho [1,2-d] tellurazole)}, tellurazoline nucleus (for example, tellurazoline, 4-methyltellurazoline), 3,3-dialkylindolenine nucleus (For example, 3,3-dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-5-cyanoindolenine, 3,3-dimethyl-6-nitroindolenine, 3,3-dimethyl-5 Nitroindolenin, 3,3-dimethyl-5-methoxyindolenine, 3,3,5-trimethyl Indolenine, 3,3-dimethyl-5-chloroindolenine), imidazole nucleus ｛imidazole nucleus (for example, 1-alkylimidazole, 1-alkyl-4-phenylimidazole, 1-arylimidazole), benzimidazole nucleus (for example, 1-alkylbenzimidazole, 1-alkyl-
5-chlorobenzimidazole, 1-alkyl-5,6
-Dichlorobenzimidazole, 1-alkyl-5-methoxybenzimidazole, 1-alkyl-5-cyanobenzimidazole, 1-alkyl-5-fluorobenzimidazole, 1-alkyl-5-trifluoromethylbenzimidazole, 1-alkyl -6-chloro-5
-Cyanobenzimidazole, 1-alkyl-6-chloro-5-trifluoromethylbenzimidazole, 1-
Allyl-5,6-dichlorobenzimidazole, 1-allyl-5-chlorobenzimidazole, 1-arylbenzimidazole, 1-aryl-5-chlorobenzimidazole, 1-aryl-5,6-dichlorobenzimidazole, 1- Aryl-5-methoxybenzimidazole, 1-aryl-5-cyanobenzimidazole), naphthoimidazole nucleus (for example, alkylnaphtho [1,2-d] imidazole, 1-arylnaphtho [1,2-d] imidazole), The aforementioned alkyl groups have 1 to 8 carbon atoms, for example, methyl, ethyl,
Unsubstituted alkyl groups such as propyl, isopropyl and butyl, and hydroxyalkyl groups (eg, 2-hydroxyethyl, 3-hydroxypropyl) are preferred. Particularly preferred are a methyl group and an ethyl group. The aforementioned aryl groups represent phenyl, halogen (eg, chloro) substituted phenyl, alkyl (eg, methyl) substituted phenyl, alkoxy (eg, methoxy) substituted phenyl. ｝, Pyridine nucleus (for example, 2-pyridine, 4-pyridine, 5-methyl-2-pyridine, 3-methyl-4-pyridine), quinoline nucleus ｛quinoline nucleus (for example, 2-quinoline, 3-methyl-2-pyridine) Quinoline, 5-ethyl-2-quinoline, 6-
Methyl-2-quinoline, 6-nitro-2-quinoline, 8
-Fluoro-2-quinoline, 6-methoxy-2-quinoline, 6-hydroxy-2-quinoline, 8-chloro-2-
Quinoline, 4-quinoline, 6-ethoxy-4-quinoline, 6-nitro-4-quinoline, 8-chloro-4-quinoline, 8-fluoro-4-quinoline, 8-methyl-4-
Quinoline, 8-methoxy-4-quinoline, 6-methyl-
4-quinoline, 6-methoxy-4-quinoline, 6-chloro-4-quinoline), isoquinoline nucleus (for example, 6-nitro-1-isoquinoline, 3,4-dihydro-1-isoquinoline, 6-nitro-3- Isoquinoline)}, imidazo [4,5-b] quinoxaline nucleus (for example, 1,3-diethylimidazo [4,5-b] quinoxaline, 6-chloro-1,3-diallylimidazo [4,5-b] quinoxaline ), An oxadiazole nucleus, a thiadiazole nucleus, a tetrazole nucleus, and a pyrimidine nucleus. However, in the general formula, when n ₁₂ is 1, neither Z ₁₁ nor Z ₁₂ is an oxazole nucleus or an imidazole nucleus. The nucleus formed by Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₁₄ and Z ₁₆ is preferably a benzothiazole nucleus, a naphthothiazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzimidazole nucleus, a 2-quinoline nucleus,
It is a quinoline nucleus.

D and D 'represent a group of atoms necessary for forming an acidic nucleus, and can take the form of an acidic nucleus of any general merocyanine dye. The acidic nucleus here means
For example, James, edited by The Theory of the Photographic Process
Photographic Process) 4th edition, Macmillan publisher,
1977, p. 198. In a preferred form, substituents involved in the resonance of D are, for example, carbonyl, cyano, sulfonyl, sulfenyl. D 'represents a group of remaining atoms necessary for forming an acidic nucleus. Specifically, US Pat. No. 3,567,7
No. 19, No. 3,575,869, No. 3,804,63
No. 4, No. 3,837,862, No. 4,002,480
No. 4,925,777, JP-A-3-167546
No. are described in the number.

When the acidic nucleus is acyclic, the terminus of the methine linkage is a group such as malononitrile, alkanesulfonylacetonitrile, cyanomethylbenzofuranyl ketone, or cyanomethylphenyl ketone. D and D '
When is cyclic, it forms a 5- or 6-membered heterocycle consisting of carbon, nitrogen, and chalcogen (typically oxygen, sulfur, selenium, and tellurium) atoms.

The following nuclei are preferred. 2-pyrazolin-5-one, pyrazolidine-3,5-dione, imidazolin-5-one, hydantoin, 2 or 4-thiohydantoin, 2-iminooxazolidin-4-one, 2-oxazoline-5-one, 2- Thiooxazolidin-2,4-dione, isoxazolin-5-one,
2-thiazolin-4-one, thiazolidine-4-one,
Thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, isorhodanine, indan-
1,3-dione, thiophen-3-one, thiophen-
3-one-1,1-dioxide, indoline-2-one, indoline-3-one, indazolin-3-one,
2-oxoindazolinium, 3-oxoindazolinium, 5,7-dioxo-6,7-dihydrothiazolo [3,2-a] pyrimidine, cyclohexane-1,3-
Dione, 3,4-dihydroisoquinolin-4-one,
1,3-dioxane-4,4-dione, barbituric acid, 2-thiobarbituric acid, chroman-2,4-dione, indazolin-2-one, or pyrido [1,2-
a] Core of pyrimidine-1,3-dione. More preferably, 3-alkyl rhodanine, 3-alkyl-2-thiooxazolidine-2,4-dione, 3-alkyl-2-
It is a thiohydantoin.

The substituent bonded to the nitrogen atom contained in the above nucleus and R ₁₅ are a hydrogen atom, an alkyl group having 1 to 18, preferably 1 to 7, and particularly preferably 1 to 4 carbon atoms (eg, methyl , Ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), substituted alkyl groups (eg, aralkyl groups (eg, benzyl, 2-phenylethyl), hydroxyalkyl groups (eg, 2-hydroxyethyl, 3- Hydroxypropyl), carboxyalkyl group (eg, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, carboxymethyl), alkoxyalkyl group (eg, 2-methoxyethyl, 2- (2-methoxyethoxy) ethyl) , A sulfoalkyl group (for example, 2-
Sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2- [3-sulfopropoxy]
Ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl), a sulfatoalkyl group (eg, 3-sulfatopropyl, 4-sulfatobutyl), a heterocyclic-substituted alkyl group (eg, 2- (pyrrolidine) -2-one-1-yl) ethyl, tetrahydrofurfuryl, 2-morpholinoethyl), 2-acetoxyethyl, carbomethoxymethyl, 2-methanesulfonylaminoethyl｝, allyl group, aryl group (for example, phenyl,
2-naphthyl), a substituted aryl group (eg, 4-carboxyphenyl, 4-sulfophenyl, 3-chlorophenyl, 3-methylphenyl), and a heterocyclic group (eg, 2-pyridyl, 2-thiazolyl) are preferred. More preferably, an unsubstituted alkyl group (for example, methyl, ethyl, n-
Propyl, n-butyl, n-pentyl, n-hexyl), carboxyalkyl groups (for example, carboxymethyl, 2-carboxyethyl, and sulfoalkyl groups (for example, 2-sulfoethyl)).

The 5- or 6-membered nitrogen-containing heterocyclic ring formed by Z ₁₅ is a cyclic heterocyclic ring represented by D or D 'in which an oxo group or a thiooxo group is removed at an appropriate position. It is. More preferably, the thiooxo group of the rhodanine nucleus is removed.

L ₁₁ , L ₁₂ , L ₁₃ , L ₁₄ , L ₁₅ , L ₁₆ , L
_{17, L 18, L 19,} L 20, L 21, L 22, L 23, L 24,
L ₂₅ , L ₂₆ , L ₂₇ , L ₂₈ , L ₂₉ and L _{30 each} represent a methine group or a substituted methine group such as a substituted or unsubstituted alkyl group (eg, methyl, ethyl, 2-carboxyethyl), a substituted or unsubstituted group; Aryl group (eg, phenyl, o-carboxyphenyl), heterocyclic group (eg, barbituric acid), halogen atom (eg, chlorine atom, bromine atom), alkoxy group (eg, methoxy, ethoxy), amino group (eg, N, N-diphenylamino, N
-Methyl-N-phenylamino, N-methylpiperazino), those substituted with an alkylthio group (eg, methylthio, ethylthio), etc., and may form a ring with another methine group, or Rings can also be formed with chromophores. _{L 11, L 12, L 16} , L 17, L
₁₈ , L ₁₉ , L ₂₂ , L ₂₃ , L ₂₉ and L ₃₀ are preferably unsubstituted methine groups. The L _13, L ₁₄ and L ₁₅ trimethine, to form a pentamethine and heptamethine dye. While the unit of L ₁₃ and L ₁₄ are repeated if n ₁₂ is 2, 3 need not be identical. L ₁₃ below, L ₁₄
And preferred examples of the methine chain formed by L _15.

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[0126] The L ₂₀ and L ₂₁ form a tetramethylene and hexamethine dye. While the unit of L ₂₀ and L ₂₁ are repeated need not be the same. L ₂₀ and L
Preferred examples of the methine chain formed by ₂₁ are given.

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[0128] dimethine by L ₂₄ and L _25, Tetoramechin, and the like are formed hexamethine. The units of L ₂₄ and L ₂₅ are repeated when n ₁₇ is 2 or more, but need not be the same. Preferred examples of the methine chain formed by L ₂₄ and L ₂₅ will be described.

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A preferred example when n ₁₇ is 2 or more is (Chemical Formula 7)
0). L ₂₆ , L ₂₇ and L ₂₈ form monomethine, trimethine, pentamethine and the like. L ₂₆
And the unit of L ₂₇ is repeated when n ₁₈ is 2 or more, but need not be the same. Preferred examples of the methine chain formed by L ₂₆ , L ₂₇ and L ₂₈ will be given.

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In addition, the example shown in (Formula 69) is preferable. Among the compounds represented by the general formula (XXI), the compound represented by the following general formula (XXIV) is more preferably used. General formula (XXIV)

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In the formula, Z ₁₇ and Z ₁₈ represent a sulfur atom or a selenium atom. R ₄₇ and R ₄₈ represent an alkyl group. _{R 49, V 11, V 12} , V 13, V 14, V 15, V 16, V 17
And V ₁₈ represent a hydrogen atom or a monovalent substituent. M
₁₄ represents a charge neutralizing counter ion, and m ₁₄ is a number of 0 or more necessary to neutralize the charge in the molecule. General formula (XI
V) will be described in further detail. R ₄₇ and R ₄₈ are preferably the same as R ₄₁ , R ₄₂ , R ₄₃ , R ₄₄ and R ₄₆ . _{R 49, V 11, V 12} , V 13, V 14, V 15, V
₁₆ no particular restriction on the substituent represented by, V ₁₇ and V _18, but include the substituents shown in the above V. The _{V 11, V 12, V 13} , V 14, V 15, V 16, V 17 and V ₁₈
Two bonded to adjacent carbon atoms may form a condensed ring with each other.

For example, the condensed ring includes a benzene ring and a heterocyclic ring (for example, pyrrole, thiophene, furan, pyridine, imidazole, triazole, thiazole). R ₁₉ is preferably a methyl group, an ethyl group, a propyl group, or a cyclopropyl group. More preferably, it is an ethyl group. _{V 11, V 12, V 14} , V 15, V 16
And V ₁₈ is preferably a hydrogen atom. V ₁₃ and V ₁₇ are preferably a chloro group, a methyl group, a methoxy group, a phenyl group and a carboxy group. Also, V
_It is also preferable that ₁₃ and V ₁₄ and V ₁₇ and V ₁₈ be bonded to each other to form a benzene ring. M ₁₄ m ₁₄ is M ₁₁ m _11, M ₁₂
m ₁₂ and M ₁₃ are synonymous with m ₁₃ . Hereinafter, typical examples of the sensitizing dye used in the present invention will be described, but the present invention is not limited thereto. The sensitizing dyes of the superordinate concept are exemplified in order, and the sensitizing dyes of the lower concept which are more preferable at this time are excluded. (1) sensitizing dye used in the present invention

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[0137]

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(2) Sensitizing dye having an oxidation potential of 0.95 (V _vs. SCE) or lower

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(3) Sensitizing dye having an oxidation potential of 0.95 (V _vs. SCE) or lower and a spectral sensitivity maximum of 600 nm or more

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[0150]

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(4) The conditions of the above (3) regarding the oxidation potential and the spectral sensitivity maximum are satisfied, and the general formulas (XXI), (XXII) and
Sensitizing dye represented by formula (XXIII) (4-1) Sensitizing dye represented by formula (XXI)

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(4-2) Sensitizing dye represented by formula (XXII)

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(4-3) Sensitizing dye represented by formula (XXIII)

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(5) A sensitizing dye represented by the general formula (XXIV) which satisfies the condition (3) described above regarding the oxidation potential and the spectral sensitivity maximum.

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The sensitizing dye used in the present invention is FM
Hemmer, FM Hemer, Heterocyclic Compounds-Cyanine Dyes
and Related Compounds (John Willie and Sons, John & Sons-New York, London, 1
964). , DMSturme
r), "Heterocyclic Compounds-Special topics in heterocyclic chemistry"
terocyclic chemistry- ", Chapter 18, Section 14, pp. 482-515, John Wiley & Sons, New York, London,
(1977). , "Rods Chemistry of
Carbon Compounds (Rodd's Chemistry of Carbon C
ompounds) ", (2nd.Ed.vol.IV, part B, published in 1977), Chapter 15, pp. 369-422; (2nd.Ed.vol.I.
V, part B, 1985), Chapter 15, Chapters 267-29
Page 6, Elsvier Science Publishing Company, Inc.
Inc.), New York, and the like.

In order to incorporate the compounds represented by formulas ( II ) to (XII) of the present invention and the sensitizing dye used in the present invention into the silver halide emulsion of the present invention, they are dispersed directly in the emulsion. Or water, methanol, ethanol, propanol, acetone, methylcellosolve, 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol , 3-methoxy-1-butanol, 1-methoxy-2-propanol, N, N-dimethylformamide or the like, alone or in a mixed solvent. U.S. Pat.
No. 9,987, etc., the dye or the compounds ( II ) to (XII) of the present invention are dissolved in a volatile organic solvent, and the solution is dispersed in water or a hydrophilic colloid,
A method of adding this dispersion to an emulsion, JP-B-46-2
No. 4,185, and the like, a method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving it and adding this dispersion to an emulsion, JP-B-44-23389, JP-B-44 No. 27,555, JP-B-57-22,091
And a method of dissolving a dye in an acid and adding the solution to an emulsion, or adding an acid or a base in the form of an aqueous solution in the presence of an acid and adding it to an emulsion, U.S. Pat.
No. 135, U.S. Pat. No. 4,006,026, etc., a method of adding an aqueous solution or a colloidal dispersion in the presence of a surfactant to an emulsion, as described in JP-A-53-102733. No., JP-A-58-105,14
No. 1, as described in Japanese Patent Application Laid-Open No. Sho 5 (1994), in which a dye is directly dispersed in a hydrophilic colloid and the resulting dispersion is added to an emulsion.
As described in JP-A No. 1-74,624, a method in which a dye is dissolved using a compound that causes redox, and the solution is added to an emulsion can also be used. Also, ultrasonic waves can be used for dissolution.

The timing of adding the sensitizing dye used in the present invention or the compounds (II) to (XII) of the present invention to the silver halide emulsion of the present invention corresponds to the emulsion preparation which has been recognized to be useful. During any process. For example, US Pat. No. 2,735,766, US Pat.
No. 8,960, U.S. Pat. No. 4,183,756, U.S. Pat. No. 4,225,666, JP-A-58-184142.
As disclosed in the specification of JP-A-60-196,749, etc.
And before the desalting, during the desalting step and / or after the desalting and before the start of chemical ripening, see JP-A-58-113,92.
As disclosed in the specification of No. 0, etc., at any time before chemical ripening or during the process, at any time before the emulsion is coated at the time after chemical ripening and before coating, it can be added in the process. good. Further, as disclosed in specifications such as U.S. Pat. No. 4,225,666 and JP-A-58-7,629, the same compound may be used alone or in combination with a compound having a different structure. During the formation step and during the chemical ripening step or after the completion of the chemical ripening, or may be divided and added before or during the completion of the chemical ripening or during the step, and may be added separately, The compound may be added by changing the kind of combination.

The amount of the sensitizing dye used in the present invention varies depending on the shape and size of silver halide grains.
Preferably, 4 × 10 ⁻⁸ to 1 mol per mol of silver halide.
It can be used at 8 × 10 ⁻² mol. The addition time of the compounds represented by formulas (II) to (XII) of the present invention is preferably 1 × 10 ^{−6 to} 5 × 10 ⁻¹ per mol of silver halide, regardless of before or after the sensitizing dye. Mol, more preferably 1 × 10 ⁻⁵ to 2 × 10 ⁻² mol, particularly preferably 1 × 10 ^{−4 to} 1.6 × 10 ^2- mol, in the silver halide emulsion. The ratio (molar ratio) of the sensitizing dye to the compounds represented by the general formulas ( II ) to (IV) and the compounds represented by the general formulas ( II ) to (IV) and the general formulas (V) to (XII) The ratio of the compound to be used may be any value, but the sensitizing dye / ( I
I )-(IV) or ( II )-(IV) / (V)-
The range of (XII) = 1000/1 to 1/1000 is advantageously used, and the range of 100/1 to 1/100 is particularly preferably used. The silver halide used in the present invention is
Any of silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver chloroiodobromide, and silver iodobromide may be used. Further, the silver halide emulsion used in the present invention may contain these silver halide grains singly or in combination. Silver halide grains, even if the inside and the surface have different phases,
It may have a multiphase structure having a bonding structure, a localized phase on the particle surface, or a uniform phase of the whole particle. They may be mixed. The silver halide grains used in the present invention may be monodisperse or polydisperse, and may have a regular (such as cubic, octahedral, or tetradecahedral) crystal, or may have an irregular ( It may have an irregular crystal form, or may have a complex form of these crystal forms. Further, an AgX having an aspect ratio (ratio of circle equivalent diameter of silver halide grains / grain thickness) of 3 or more is used.
A tabular emulsion in which grains account for 50% or more of the total projected area of the grains may be used. The aspect ratio is more preferably 5 or more and 8 or more. Further, an emulsion comprising a mixture of these various crystal forms may be used. These various emulsions may be either a surface latent image type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside a grain.

The photographic emulsions used in the present invention are described in "Graftkides, Chemistry and Physics" (P. Glafkides, Chemie et P.).
hysique Photographique, Paul Montel, 1967.), "Emulsion Chemistry" by Daffin (GFDaffin, Photographic Emu
lsion Chemistry, Focal Press, 1966.), Zerikman et al., "Production and Coating of Photographic Emulsions" (VLZelikman et al., Mak
ing and Coating Photographic Emulsion, Focal Pres
s, 1964.), FHClaes et al., The Journal of Photo.
graphic Science, (21) 39-50, 1973. and FHClaes et
al., The Journal of Photographic Science, (21) 85-
Nos. 92, 1973., JP-B-55-42737, U.S. Pat. No. 4,400,463, U.S. Pat.
1,523, JP-A-62-218959, 63
213,836, 63-218,938, and Japanese Patent Application No. 62-291,487. That is, acid method, neutral method,
Any method such as the ammonium method may be used, and the method of reacting the soluble silver salt with the soluble halogen salt may be any one of a one-sided mixing method, a simultaneous mixing method, and a combination thereof. A method of forming grains in the presence of excess silver (so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and nearly uniform grain size can be obtained.

Further, an emulsion prepared by a so-called conversion method including a step of converting into silver halide already formed before the step of forming silver halide grains is completed, or an emulsion prepared after the step of forming silver halide grains is completed. Emulsions subjected to the same halogen conversion can also be used.

In the production of the silver halide grains of the present invention, a silver halide solvent may be used. Examples of frequently used silver halide solvents include, for example, thioether compounds (for example, U.S. Pat. Nos. 3,271,157 and 3,57
4,628, 3,704,130, 4,27
No. 6,347, etc.), thione compounds and thiourea compounds (for example, JP-A Nos. 53-144,319 and 53-8).
2,408, 55-77,737), amine compounds (for example, JP-A-54-100,717) and the like, and these can be used. Ammonia can also be used in a range that does not cause adverse effects. In the production of the silver halide grains of the present invention, in order to accelerate the grain growth, the addition rate, amount and concentration of the added silver salt solution (for example, aqueous silver nitrate solution) and the halide solution (for example, aqueous sodium chloride solution) are changed. Is preferably used. Regarding these methods, for example, British Patent 1,335,925, US Pat.
Nos. 72,900, 3,650,757, 4,24
2,445, JP-A-55-142,329, and 55
-158,124, 55-113,927, 5
Nos. 8-113, 928, 58-111, 934 and 58-111, 936 can be referred to.

In the course of silver halide grain formation or physical ripening, cadmium salt, zinc salt, lead salt, potassium salt, rhenium salt, ruthenium salt, iridium salt or complex salt thereof, rhodium salt or complex salt thereof, iron salt or The complex salt may coexist. Particularly, a rhenium salt, an iridium salt, a rhodium salt, or an iron salt is more preferable. Any of these addition amounts can be added as needed. For example, iridium salts (eg, Na ₃ IrCl ₆ , Na ₂ Ir
Cl ₆ , Na ₃ Ir (CN) _6, etc. are contained in an amount of 1 × 10 ⁻⁸ or more and 1 × 10 ⁻⁵ or less per mol of silver, and rhodium salts (eg, RhCl ₃ , K ₃ Rh (CN) ₆ )) is 1 × 10 per mole of silver
^-8 above, an amount in the range of 1 × 10 ^-8 or less.

The silver halide emulsion of the present invention may be left unchemically sensitized, but can be chemically sensitized if necessary. As the chemical sensitization method, a so-called gold sensitization method using a gold compound (for example, US Pat. Nos. 2,448,060 and 3,320,069) or a sensitization method using a metal such as iridium, platinum, rhodium, and palladium (For example, U.S. Pat. Nos. 2,448,060 and 2,566,245,
No. 2,566,263) or a sulfur sensitization method using a sulfur-containing compound (for example, US Pat. No. 2,222,264).
), A selenium sensitization method using a selenium compound, or a reduction sensitization method using tin salts, thiourea dioxide, polyamide or the like (for example, US Pat. Nos. 2,487,850 and 2,51).
8,698, 2,521,925), or a combination of two or more of these. The silver halide emulsion of the present invention is more preferably gold sensitized or sulfur sensitized, or a combination thereof. Preferred amounts of the gold sensitizer and the sulfur sensitizer to be added are 1 × 10 ⁻⁷ to 1 mol per silver.
1 × 10 ⁻² mol, more preferably 5 × 10 ⁻⁶ to 1
× 10 ^-3 . When gold sensitization and sulfur sensitization are used in combination, the preferred ratio of the gold sensitizer to the sulfur sensitizer is 1: 3 to
The ratio is 3: 1, more preferably 1: 2 to 2: 1.
The temperature at which the chemical sensitization of the present invention is performed is from 30 ° C to 90 ° C.
Any temperature between ° C can be selected. Further, the pH at the time of performing the chemical sensitization is 4.5 to 9.0, preferably 5.0.
To 7.0. The time of chemical sensitization varies depending on the temperature, the type and amount of the chemical sensitizer, the pH, and the like, and thus cannot be unconditionally determined. However, it can be arbitrarily selected from a few minutes to several hours. It takes place for 200 minutes.

The sensitizing dye used in the present invention enhances its adsorption to silver halide and formation of J-aggregates, and obtains water-soluble iodide salts such as potassium iodide or bromide in order to obtain higher spectral sensitivity. A water-soluble bromide salt such as potassium or a water-soluble thiocyanate such as potassium thiocyanate is often used in combination, but is also preferably used in the present invention, and is preferably used in the present invention. Is silver chloride or silver chlorobromide having a high silver chloride content, and the effect is remarkable. In order to achieve ultra-rapid processing with a development time of 30 seconds or less, a high silver chloride emulsion having a silver chloride content of 50 mol% or more is preferred. For this purpose, as is well known, iodide ions have a strong development inhibiting property and include the above-mentioned water-soluble iodide salts.
It is preferable that the content be suppressed to not more than mol%. For the production of a silver halide light-sensitive material suitable for ultra-rapid processing, a high silver chloride emulsion having a silver chloride content of 80 mol% or more is more preferable. In such an emulsion, a water-soluble bromide salt is used as described above. And / or a combination use of a water-soluble thiocyanate enhances the formation of J-aggregates and obtains higher spectral sensitivity, but is preferably in the range of 0.03 to 3 mol% per mol of silver, especially A range of 0.08 to 1 mol% is preferred.

In the case of high silver chloride grains having a silver chloride content of 80 mol% or more, high sensitivity is obtained when spectral sensitization is performed in the infrared region, and the stability thereof, particularly, the stability of the latent image is excellent. High silver chloride grains having a localized phase among grains disclosed in JP-A-2-248,945 and the like having the following characteristics are more preferable. The localized phase preferably has a silver bromide content of more than 15 mol%, more preferably 20 to 60 mol%, and more preferably 30 to 50 mol%, as disclosed in the above patent. Most preferably, the balance is silver chloride. The localized phase may be inside the silver halide grains, on the surface or subsurface, or the interior may be divided into the surface or subsurface. Further, the localized phase may have a layered structure surrounding the silver halide grains or a discontinuous and independent structure inside or on the surface. A preferred embodiment of the arrangement of the localized phase having a silver bromide content higher than the surroundings, wherein a localized phase having a silver bromide content of at least 15 mol% or more locally epitaxially grows on the surface of the silver halide grains. Things. The silver bromide content of the localized phase can be determined by an X-ray diffraction method (for example, described in “Chemical Society of Japan, New Experimental Chemistry Course 6, Structural Analysis”, Maruzen) or an XPS method (for example, surface analysis, IMA). , The application of Auger electron / photoelectron spectroscopy "described in Kodansha). The localized phase is preferably composed of silver of 0.1 to 20% of the total silver constituting the silver halide grains, and more preferably of 0.5 to 7% of silver. preferable.

The interface between the localized phase having a high silver bromide content and the other phase may have a clear phase boundary, or may have a short transition region in which the halogen composition changes gradually. May be. Various methods can be used to form such a localized phase having a high silver bromide content. For example, a localized phase can be formed by reacting a soluble silver salt and a soluble halogen salt by a one-side mixing method or a simultaneous mixing method. Further, a localized phase can be formed by using a so-called conversion method including a process of converting already formed silver halide into silver halide having a smaller solubility product. Alternatively, a localized phase can be formed by recrystallizing the surface of silver chloride particles by adding silver bromide fine particles.
The silver halide emulsion prepared according to the present invention can be used for both color photographic materials and black-and-white photographic materials. The composition, crystal phase, size, etc. of the silver halide of the silver halide emulsion of the present invention may be any known one. Preferred examples are described in JP-A-2-269334, page 17, upper right column, line 17 to page 20, upper right column, line 7. As color photographic light-sensitive materials, especially color paper,
Examples of the color photographing film, the color reversal film, and the black-and-white photographic light-sensitive material include an X-ray film, a general photographing film, and a film for a printing photosensitive material. There are no particular restrictions on the additives of the photographic light-sensitive material to which the emulsion of the present invention is applied. For example, Research Disclosure, Vol. 176, Item 1
7643 (RD17643) and 187 volumes Item 1
8716 (RD18716) can be referred to. The places where the various additives are described in RD17643 and RD18716 are listed below (Table 1).

[0188]

[Table 1]

The dye will be described in more detail. Colloidal silver and dyes are used in the light-sensitive material of the present invention to prevent irradiation and halation, in particular, to separate the spectral sensitivity distribution of each light-sensitive layer and to ensure safety against safelight. Such dyes include, for example, U.S. Patent Nos. 506,385, 1,177,429,
131,884, 1,338,799, 1,3
No. 85,371, No. 1,467,214, No. 1,43
Nos. 8,102 and 1,553,516, JP-A-48-48
Nos. 85, 130, 49-114, 420, 52-
Nos. 117, 123, 55-161, 233, 59
-111,640, JP-B-39-22,069, JP-B-43-13,168, JP-B-62-273527, U.S. Pat. Nos. 3,247,127 and 3,469,985.
Oxonol dyes having a pyrazolone nucleus, a barbitur nucleus or a barbituric acid nucleus described in U.S. Pat. Nos. 4,078,933 and 3,078,933;
379,533, British Patent 1,278,621,
Other oxonol dyes described in JP-A Nos. 1-134447 and 1-183652, British Patent No. 57
Nos. 5,691, 680,631, 599,623
Nos. 786,907, 907,125, 1,
No. 045,609, U.S. Pat. No. 4,255,326,
Azo dyes described in JP-A-59-211,043, JP-A-50-100,116, JP-A-54-118,
No. 247, British Patent Nos. 2,014,598 and 75
Azomethine dyes described in U.S. Patent Nos. 0,031 and 0, and the like, anthraquinone dyes described in U.S. Patent No. 2,865,752, and U.S. Patent Nos. 2,538,009 and 2,688,
Nos. 541 and 2,538,008, and British Patent No. 58
4,609, 1,210,252, JP-A-50-
Nos. 40,625, 51-3,623, 51-1
Nos. 0,927 and 54-118,247, Tokubo Sho48
Arylidene dyes described in JP-A-3-3,286 and JP-A-59-37,303; JP-B-28-3,082;
Styryl dyes described in JP-A Nos. 4-16,594 and 59-28,898, and in British Patent Nos. 446,538 and 1,335,422 and JP-A-59-228,250. Triarylmethane dyes described in British Patent Nos. 1,075,653, 1,153,341, 1,284,730, 1,475,228, 1,542,807 and the like. Merocyanine dyes described, U.S. Pat. Nos. 2,843,486 and 3,294,
539 and JP-A-1-291247.

In order to prevent the diffusion of these dyes, the following methods are mentioned. For example, a dye may be ballasted to make it diffusion resistant. Further, for example, a method in which a hydrophilic polymer having a charge opposite to that of a dissociated anionic dye is coexisted in a layer as a mordant, and the dye is localized in a specific layer by interaction with dye molecules is disclosed in U.S. Pat. 564
Nos. 4,124,386 and 3,625,694. Further, a method of dyeing a specific layer using a dye solid which is insoluble in water is disclosed in JP-A-56-1263.
No. 9, No. 55-155350, No. 55-155351
No. 63-27838, No. 63-197943,
It is disclosed in European Patent No. 15,601 and the like.

A method for dyeing a specific layer using metal salt fine particles having a dye adsorbed thereon is disclosed in US Pat. No. 2,719,08.
8, 2,496,841 and 2,496,843
And JP-A-60-45237. Among the additives, antifoggants and stabilizers include azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles and benzotriazoles. , Aminotriazoles, etc .; mercapto compounds {eg, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles,
Mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines, mercaptotriazines, etc .; thioketo compounds such as oxazolinethione; azaindenes {eg triazaindenes, tetraazaindenes (especially 4 -Hydroxy-substituted (1,3,3a, 7) tetraazaindenes, pentaazaindenes and the like; benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide and the like can be preferably used.

The color coupler is preferably a non-diffusible one having a hydrophobic group called a ballast group in the molecule, or a polymerized one. The coupler may be either 4-equivalent or 2-equivalent to silver ion.
Further, a colored coupler having a color correcting effect or a coupler which releases a development inhibitor during development (a so-called DIR coupler) may be included. Further, the product of the coupling reaction may be colorless and may contain a colorless DIR coupling compound that releases a development inhibitor. Preferred examples are described in JP-A-62-215272, page 91, upper right column, line 4 to page 121, upper left column, line 6, JP-A-2-33144.
Page 14 upper right column line 14 to page 18 upper left column last line and page 30 upper right column line 6 to page 35 lower right column line 11; EP 4, page 15 to line 27, page 5 line 30 to Page 28, last line, page 45, 29
Lines 31 to 31, page 47, lines 23 to 63, line 50.

For example, magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, pyrazolotetrazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers and the like, and yellow couplers are acylacetamide couplers. (For example, benzoylacetoanilides, pivaloylacetoanilides), and the like, and examples of cyan couplers include naphthol couplers and phenol couplers. U.S. Pat. Nos. 3772002 and 2772 for cyan couplers
No. 162, No. 3758308, No. 4126396
Nos. 4334011, 4327173, 34
No. 46622, No. 4333999, No. 4451559
Phenol couplers having an ethyl group at the meta-position of the phenol nucleus described in
Diacylamino-substituted phenol couplers, phenol couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, and couplers substituted with a sulfonamide or amide at the 5-position of naphthol have excellent image robustness. And preferred. The couplers and the like can be used in combination of two or more in the same layer in order to satisfy the characteristics required for the light-sensitive material.
Of course, it can be added to more than one layer.

Hydroquinones, 6
-Hydroxychromans, 5-hydroxycoumarins,
Spirochroman, p-alkoxyphenols, hindered phenols, mainly bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines and the phenolic hydroxyl groups of these compounds were silylated and alkylated. Ether or ester derivatives are typical examples.
Further, a metal complex represented by a (bissalicylaldoximato) nickel complex and a (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

In the photographic processing of the photosensitive material using the present invention,
Any of the known methods can be used, and a known processing solution can be used. The processing temperature is usually selected between 18 ° C and 50 ° C, but may be lower than 18 ° C or higher than 50 ° C. Depending on the purpose, any of a developing process for forming a silver image (black-and-white photographic process) and a color photographic process including a developing process for forming a dye image can be applied.

Known black and white developers include known dihydroxybenzenes (eg, hydroquinone), 3-pyrazolidones (eg, 1-phenyl-3-pyrazolidone), and aminophenols (eg, N-methyl-p-aminophenol). Developing agents can be used alone or in combination. The color developer generally comprises an alkaline aqueous solution containing a color developing agent. Color developing agents include known primary aromatic amine developers such as phenylenediamines (eg, 4-amino-N, N-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline, 4-amino-N -Ethyl-N-β-hydroxyethylaniline,
3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfamidoethylaniline,
-Amino-3-methyl-N-ethyl-N-β-methoxyethylaniline). In addition, L. F. A. Meson, "Photographic Processing Chemistry", Focal Press (1966)
226-229, U.S. Patent 2,193,015
No. 2,592,364, JP-A-48-64933.
Those described in the numbers may be used.

The developing solution may further include a pH buffer such as a sulfite, a carbonate, a borate and a phosphate of an alkali metal; a development inhibitor such as a bromide, an iodide and an organic antifoggant; Agents and the like.
If necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, polyethylene glycol, quaternary ammonium salts, development inhibitors such as amines, dye-forming couplers, competitive couplers, Fogging agents such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity improvers, U.S. Pat. No. 4,083,723
No. 2, the polycarboxylic acid chelating agent disclosed in West Germany (O
LS) No. 2,622,950.

When color photographic processing is performed, the photographic light-sensitive material after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed individually. As the bleaching agent, for example, iron (III), cobalt (III)
And compounds of polyvalent metals such as chromium (VI) and copper (II), peracids, quinones, nitroso compounds and the like. For example, organic complex salts of ferricyanide, dichromate, iron (III) or cobalt (III), for example, aminopolycarboxylic acids such as ethylenediamine tetracomplex, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid, or Complex salts of organic acids such as citric acid, tartaric acid, and malic acid; persulfates, permanganates, and nitrosophenols can be used. Of these, potassium ferricyanide, sodium ethylenediaminetetracomplex iron (III) and ammonium ethylenediaminetetracomplex iron (III) are particularly useful. The ethylenediamine tetracomplex iron (III) complex is useful both in an independent bleaching solution and in a single bath bleach-fixing solution.
Bleach or bleach-fix solutions are disclosed in U.S. Pat.
No. 0, No. 3, 241, 966, Japanese Patent Publication No. 45-8506
No., bleaching accelerators described in JP-B No. 45-8836,
In addition to the thiol compounds described in JP-A-53-65732, various additives can be added. After the bleaching or the bleaching / fixing treatment, a washing treatment or a stabilizing bath treatment may be used.

As the support used in the present invention, a transparent film such as a cellulose nitrate film or a polyethylene terephthalate, which is usually used for a photographic light-sensitive material, or a reflective support can be used. The term "reflective support" used in the present invention refers to a material which enhances reflectivity and sharpens a dye image formed in a silver halide emulsion layer. In order to increase the reflectance in the visible light wavelength region, coated with a hydrophobic resin containing dispersed light-reflecting substances such as titanium oxide, zinc oxide, calcium carbonate, calcium sulfate, and hydrophobic resins containing dispersed light-reflecting substances Used as a support. For example, baryta paper, polyethylene-coated paper, polypropylene-based synthetic paper, a transparent support having a reflective layer, or a reflective material used in combination, such as a glass plate, polyethylene terephthalate, a polyester film such as cellulose triacetate or cellulose nitrate, There are a polyamide film, a polycarbonate film, a polystyrene film, a vinyl chloride resin and the like, and these supports can be appropriately selected depending on the purpose of use.

Exposure for obtaining a photographic image may be performed by a usual method. That is, natural light (sunlight), tungsten electric lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, laser, LED,
Any of various known light sources such as a CRT can be used. The exposure time is usually 1/1000 second to 1 second, which is usually used in a camera, or is shorter than 1/1000 second, for example, 1/10 ⁴ to 1/1 / using a xenon flash lamp.
Exposures of 10 ⁶ seconds can be used, and exposures longer than 1 second can be used. If necessary, the spectral composition of light used for exposure can be adjusted by a color filter. Laser light can also be used for exposure. Further, exposure may be performed by light emitted from a phosphor excited by an electron beam, X-ray, γ-ray, α-ray, or the like.

[0201]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. Example 1 1000 ml of water, 25 g of deionized bone gelatin, 15 ml of 50% NH ₄ NO ₃ aqueous solution and 2 in a reaction vessel
Add 7.5 ml of 5% aqueous NH ₄ solution and keep at 50 ° C.
After stirring well, 750 ml of a 1N aqueous solution of silver nitrate and a 1N aqueous solution of potassium bromide were added in 50 minutes, and the silver potential during the reaction was kept at +60 mV with respect to the saturated calomel electrode. The obtained silver bromide particles are cubic and have a side length of 0.76 ± 0.06 μm.
Met. The temperature of the emulsion was lowered, a copolymer of isobutene and monosodium maleate was added as a flocculant, and the mixture was sedimented, washed and desalted. Next, 95 g of deionized bone gelatin and 430 ml of water were added, and p
H6.5 and pAg 8.3 were adjusted. Subsequently, sodium thiosulfate, potassium chloroaurate and potassium thiocyanate were added so as to obtain the optimum sensitivity, and the mixture was aged at 60 ° C. for 45 minutes. 1 kg of this emulsion contained 0.74 mol of silver bromide. 50 g of each of these emulsions was weighed, and at 40 ° C., spectral sensitizing dyes represented by general formulas (II) to (IV) as shown in Tables 2-1 to -4. A hydrazine compound and / or a nitrogen-containing heterocyclic compound represented by the general formula (V) were added. Next, 15 g of a 10% gel of deionized gelatin and 55 ml of water were added per 50 g of the emulsion, and coated on a cellulose triacetate film base as follows. The amount of the coating solution was 2.
5 g / ^{m 2,} set so that the amount of gelatin 3.8 g / ^{m 2,} so that the amount of gelatin 1.0 g / ^{m 2} in the upper layer, sodium dodecylbenzenesulfonate 0.22g
/ L, sodium p-sulfostyrene homopolymer 0.50 g / l, 1,3-bis (vinylsulfonyl) -2-propanol 3.9 g / l, and an aqueous solution mainly containing gelatin 50 g / l were simultaneously coated.

Each of the prepared coated samples was divided into two parts, and one of the samples was stored at 75% relative humidity and 50 ° C. for 4 days.
The other sample was stored in the freezer at −30 ° C. during that time. Two blue filters V40 (a band-pass filter that transmits light of 370 nm to 440 nm) manufactured by Toshiba Glass Co., Ltd. or Fuji Photo Film Co., Ltd.
Exposure was performed for 1 second with tungsten (2856K) through a continuous wedge using an orange filter SC54 (transmitting light having a wavelength longer than 520 nm) manufactured by Co., Ltd. The exposed sample is D
After diluting the -72 developing solution to 1/3, developing with a developing solution adjusted to pH 10.4 was stopped, fixed, washed with water and dried. Next, the density was measured using a densitometer manufactured by Fuji Photo Film Co., Ltd., and the blue filter sensitivity (SB), the orange filter sensitivity (S0), and the fogging were determined. The reference point of the optical density at which the sensitivity was determined was “coverage + 0.2”. The sensitivity was represented by the reciprocal of the exposure required to give the density, and is shown in the table as a relative value. That is, with respect to the blue filter sensitivity, the relative sensitivity was defined as 100, where the sensitivity of the sample stored in the freezer at −30 ° C. of the sample 1-1 to which the spectral sensitizing dye and the compound according to the present invention were not added was 100. For the orange filter sensitivity, the general formulas (II) to (I) were used for each sample group to which the same spectral sensitizing dye was added.
V) , and the relative sensitivity was set to 100 for each of the samples which were not added with the compound represented by the general formula (V) and which were stored in a freezer at −30 ° C.

[0203]

[Table 2]

[0204]

[Table 3]

[0205]

[Table 4]

[0206]

[Table 5]

[0207]

[Table 6]

From the results shown in Table 2, it can be understood that the present invention is excellent. That is, the general formula (II):
Even when only the compounds represented by (III) and (IV) are added, a considerable sensitizing effect is exhibited, but a decrease in sensitivity and an increase in fogging under high temperature and high humidity are often observed. On the other hand, when only the compound represented by the general formula (V) is added, not only the sensitizing effect is hardly exerted, but also many compounds show a decrease in sensitivity.
When these are used in combination as in the present invention, not only the fog is suppressed to a low level, and further higher sensitivity is obtained, but also deterioration of the performance is extremely small even when stored under high temperature and high humidity.

Example 2 The silver halide emulsion used in Example 2 was prepared as follows. (1 solution) Water 1000 cc NaCl 4.65 g gelatin 22 g Citric acid 0.80 g (2 _{liquid) KBr 25.3g NaC1 32.3g K 2 IrC1} 6 (0.005%) 11.2cc Na 3 RhCl 6 · 2H ₂₀ ( ^10-5 mol / l) 18.9 cc Add water 348 cc (3 liquid) AgNO ₃ 120.6 g Add water 348 cc (4 liquid) KBr 30.0 g NaC1 48.7 g Add water 552 cc (5 liquids) 176.3 g of AgNO ₃ Add water and heat 552 cc (1 liquid) to 50 ° C, spend 262 cc each of (2 liquids) and (3 liquids) for 12 minutes and simultaneously add at a constant flow rate did. Thereafter, (liquid 4) and (liquid 5) were added simultaneously over 20 minutes. Next, the temperature was lowered, a copolymer of isobutene and monosodium maleate was added as a flocculant, and the mixture was washed by settling and desalting. Water and deionized bone gelatin were added and the pH was adjusted to 6.1 and the pAg to 7.5. Sodium thiosulfate, chloroauric acid and potassium thiocyanate were added to this emulsion, and the emulsion was ripened at 60 ° C. and subjected to chemical sensitization to obtain an optimum sensitivity. The silver chlorobromide emulsion thus prepared has an average side length of 0.2 in the grain size.
8 μm, coefficient of variation (standard deviation divided by average side length: s
/ D) A monodispersed cube of 0.08, 30 mol% of silver bromide. These emulsions were divided, and 280 g of a 10% gel of deionized gelatin per kg of the emulsion and 1.04 liter of water were added to each emulsion. As shown in Table 3, spectral sensitizing dyes represented by the general formula (II), The hydrazine compounds represented by (III) and (IV) and / or the nitrogen-containing heterocyclic compound represented by the general formula (V) were added at 40 ° C. Subsequently, 7 g of 1,2-bis (vinylsulfonylacetylamino) ethane was added per kg of the emulsion, and the mixture was coated on a polyethylene terephthalate film base in the same manner as in Example 1 so that the silver amount was 1.2 g / m ² . .

Each of the coated samples was divided into two portions. One sample was stored naturally at room temperature for 10 months, and the other sample was stored in a freezer at -30 ° C. during that time. The development process was performed in exactly the same manner as in Example 1 except that the development processing was performed at 38 ° C. for 20 seconds using a developing solution LD-835 manufactured by Fuji Photo Film Co., Ltd. on an automatic developing machine FD-800RA manufactured by Fuji Photo Film Co., Ltd. The samples were exposed, developed, and measured for density to determine relative sensitivity and fogging, and the results are shown in Table 3. Note that the reference point of the optical density for which the sensitivity was determined was “coverage + 0.5”.

[0211]

[Table 7]

[0212]

[Table 8]

Similar to the results of Example 1, the combination of the present invention not only provides less fog and higher sensitivity, but also
Even if left for a long period of time, there is little change in sensitivity and almost no increase in fogging is recognized.

Example 3 The silver halide emulsion used in Example 3 was prepared as follows. To 1000 ml of a 3% aqueous solution of lime-processed gelatin, 3.3 g of sodium chloride was added, and 3.2 ml of a 1% aqueous solution of N, N'-dimethylimidazolidin-2-thione was added. To this aqueous solution, an aqueous solution containing 0.2 mol of silver nitrate and an aqueous solution containing 15 μg of rhodium trichloride and 0.2 mol of sodium chloride were added and mixed at 56 ° C. with vigorous stirring. Subsequently, an aqueous solution containing 0.780 mol of silver nitrate and an aqueous solution containing 0.780 mol of sodium chloride and 4.2 mg of potassium ferrocyanide were stirred at 56 ° C. while vigorously stirring.
And mixed. Five minutes after the addition of the aqueous silver nitrate solution and the aqueous sodium chloride solution was completed, an aqueous solution further containing 0.020 mol of silver nitrate, 0.015 mol of potassium bromide, 0.005 mol of sodium chloride and hexachloroiridium (IV)
An aqueous solution containing 0.8 mg of potassium acid was added and mixed at 40 ° C. with vigorous stirring. Thereafter, a polymer flocculant was added and the mixture was sedimented, and desalted and washed with water. Next, 90.0 g of lime-processed gelatin was added per mole of silver, and the pAg was adjusted to 7.5 and the pH was adjusted to 6.5 with sodium chloride and sodium hydroxide. Subsequently, this emulsion was divided, and after adding 8 × 10 ⁻⁵ mol of a red-sensitive sensitizing dye (XI-14) per mol of silver, the emulsion was ripened with triethylthiourea at 55 ° C. to obtain an optimum sensitivity. And sensitized with sulfur. This silver chlorobromide emulsion was used as emulsion A. The silver chlorobromide grains of the emulsion thus prepared have an average grain size of 0.52 μm.
(Coefficient of variation 0.08) was cubic. The grain size was represented by the diameter of a circle equivalent to the projected area of the grain, and the coefficient of variation used was a value obtained by dividing the standard deviation of the grain size by the average grain size.

Next, the halogen composition of the emulsion grains was determined by measuring the X-ray diffraction from the silver halide crystals. A monochromatic CuK (α) ray is used as a source (20
The diffraction angle from the 0) plane was measured in detail. Diffraction lines from crystals having a uniform halogen composition give a single peak, whereas diffraction lines from crystals having localized phases with different compositions give a plurality of peaks corresponding to those compositions. By calculating the lattice constant from the diffraction angle of the measured peak,
The halogen composition of the silver halide constituting the crystal can be determined. The measurement results of the silver chlorobromide emulsion prepared as described above show that, in addition to the main peak of silver chloride of 100%, silver chloride has a center at 70 mol% (30 mol% of silver bromide) and 60 mol% of silver chloride. A broad diffraction pattern with a tail extending to around (silver bromide 40 mol%) could be observed.

After adding a 14% gel of gelatin deionized at 40 ° C. and water to the silver chlorobromide emulsion prepared as described above, as shown in Table 4, the compound represented by the general formula (II):
The hydrazine compounds represented by (III) and (IV) and / or the nitrogen-containing heterocyclic compound represented by the general formula (V) were added, and the mixture was aged and applied. As a support, a polyethylene terephthalate film support was used. The amount of the coating solution was set so that the amount of silver was 1.6 g / m ² and the amount of gelatin was 3.0 g / m ^2, and the upper layer was coated with sodium dodecylbenzenesulfonate 0 so that the amount of gelatin was 1.0 g / m ^2. .
1 g, sodium p-sulfostyrene homopolymer
An aqueous solution mainly containing 22 g / liter, 3.1 g / liter of sodium salt of 2-hydroxy-4,6-dichloro-1,3,5-triazine and 50 g / liter of gelatin was simultaneously applied.

The coated sample was exposed, developed, and measured for density in the same manner as in Example 1.
In order to determine the red filter sensitivity (SR), a red filter SC64 (transmitting light having a wavelength longer than 620 nm) manufactured by Fuji Photo Film Co., Ltd. was used instead of the orange filter SC54. Developing was performed at 20 ° C. for 2 minutes using a developing solution having the composition. The sensitivity and fogging thus obtained are shown in Table 4. The sensitivity of the blue filter (SB) is shown as a relative value with respect to that of Sample 3-1 as 100, and the sensitivity of the red filter (SR) is shown in Sample 3. -2 is shown as a relative value with that of 100. Note that the reference point of the optical density for which the sensitivity was determined was “coverage + 0.5”.

[Composition of developer] Methol 2.5 g L-ascorbic acid 10.0 g Sodium chloride 0.6 g Nabox 35.0 g Water was added to 1.0 liter (pH 9.8)

[0219]

[Table 9]

As in Example 1, in the case of silver chloride emulsions, the combination of the present invention, as in the case of other silver halide emulsions, reduces fogging and greatly increases sensitivity.

Example 4 On an undercoated cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare Sample 4-1 as a multilayer color photosensitive material.

[Layer Structure] The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver. <First layer (antihalation layer)> Black colloidal silver silver 0.18 gelatin 1.40 <Second layer (intermediate layer)> 2,5-di-t-pentadecylhydroquinone 0.18 EX-1 0.07 EX-3 0.02 EX-12 0.002 U-1 0.06 U-2 0.08 U-3 0.10 HBS-1 0.10 HBS-2 0.02 Gelatin 1.04 <Third layer (first red-sensitive emulsion layer)> Emulsion A silver 0.25 Emulsion B silver 0.25 sensitizing dye (XI-1 ) 6.9 × 10 ^-5 sensitizing dye (XIV-15) 1.8 × 10 ^-5 sensitizing dye (XIV-7) 3.1 × 10 ^-5 EX-2 0.34 EX-10 0.02 U-1 0.07 U-2 0.05 U- 3 0.07 HBS-1 0.06 gelatin 0.87 <Fourth layer (second red-sensitive emulsion layer)> Emulsion G Silver 1.00 Sensitizing dye (XI-1) 5.1 × 10 ^-5 Sensitizing dye (XIV-15) 1.4 × 10 ^{− 5} Sensitizing dye (XIV-7) 2.3 × 10 ^-5 EX-2 0.40 EX-3 0.05 EX-10 0.0015 U-1 0.07 U-2 0.05 U-3 0.07 Gelatin 1.30 <No. Five layers (third red-sensitive emulsion layer)> Emulsion D silver 1.60 Sensitizing dye (XI-1) 5.4 × 10 ^-5 sensitizing dye (XIV-15) 1.4 × 10 ^-5 sensitizing dye (XIV-7) 2.4 × 10 ^-5 EX-2 0.097 EX-3 0.01 EX-4 0.08 HBS-1 0.22 HBS-2 0.10 Gelatin 1.63 <Sixth layer (intermediate layer)> EX-5 0.04 HBS-1 0.02 Gelatin 0.80 <Seventh layer ( First green-sensitive emulsion layer)> Emulsion A silver 0.15 emulsion B silver 0.15 sensitizing dye (B-6) 3.0 × 10 ^-5 sensitizing dye (B-9) 1.0 × 10 ^-4 sensitizing dye (A-12) 3.8 × 10 ^-4 EX-1 0.021 EX-6 0.26 EX-7 0.03 EX-8 0.025 HBS-1 0.10 HBS-3 0.01 Gelatin 0.63 <Eighth layer (second green-sensitive emulsion layer)> Emulsion C silver 0.45 sensitized Dye (B-6) 2.1 × 10 ^-5 sensitizing dye (B-9) 7.0 × 10 ^-5 sensitizing dye (A-12) 2.6 × 10 ^-4 EX-6 0.094 EX-7 0.026 EX-8 0.018 HBS -1 0.16 HBS-3 0.008 Gelatin 0.50 <ninth layer (third green-sensitive emulsion layer)> Emulsion E silver 1.20 sensitizing dye (B-6) 3.5 × 10 ^-5 sensitizing dye (B-9) 8.0 × 10 ^-5 sensitizing dye (A -12) 3.0 × 10 ^-4 EX-1 0.025 EX-11 0.10 EX-13 0.015 HBS-1 0.25 HBS-2 0.10 Gelatin 1.54 <10th layer (yellow filter layer)> Yellow colloidal silver silver 0.05 EX-5 0.08 HBS -1 0.03 Gelatin 0.95 <Tenth layer (first blue-sensitive emulsion layer)> Emulsion A Silver 0.08 Emulsion B Silver 0.07 Emulsion F Silver 0.07 Sensitizing dye (A-2) 3.5 × 10 ^-4 EX-8 0.042 EX- 9 0.72 HBS-1 0.28 Gelatin 1.10 <Twelfth layer (second blue-sensitive emulsion layer)> Emulsion G Silver 0.45 Sensitizing dye (A-2) 2.1 × 10 ^-4 EX-9 0.15 EX-10 0.007 HBS-1 0.05 gelatin 0.78 <13th layer (third blue-sensitive emulsion layer)> Emulsion H silver 0.77 sensitizing dye (A-2) 2.2 × 10 ^-4 EX-9 0 .20 HBS-1 0.07 gelatin 0.69 <14th layer (first protective layer)> Emulsion I silver 0.20 U-4 0.11 U-5 0.17 HBS-1 0.05 gelatin 1.00 <15th layer (second protective layer)> H-1 0.40 BP-1 (diameter 1.7 μm) 0.05 BP-2 (diameter 1.7 μm) 0.10 BP-3 0.10 S-1 0.20 Gelatin 1.20

Further, all layers have storability, processability, pressure resistance,
In order to improve the antifungal / antibacterial properties, antistatic and coating properties,
W-1, W-2, W-3, BP-4, BP-5, 5-nitro-1H-indazole, 5-methyl-1H-benzotriazole, 2-mercapto-benzothiazole, 6
-(2-ethylhexanoylamino) -2-mercaptobenzimidazole, α-lipoic acid, 2-hydroxyamino-4,6-bis (hexylamino) -1,3,5-triazole, 2-hydroxyamino-4 1,6-bis (ethylamino) -1,3,5-triazole, sodium p-toluenesulfinate, iron salt, lead salt, gold salt, platinum salt, iridium salt and rhodium salt, the first red-sensitive emulsion Layers, silver halide emulsion layers other than the second red-sensitive emulsion layer and the third red-sensitive emulsion layer, Compounds 6-1 and 10-17,
It also contains 10-18, 10-24 and 11-6.

[0224]

[Table 10]

[0225]

Embedded image

[0226]

Embedded image

[0227]

Embedded image

[0228]

Embedded image

[0229]

Embedded image

[0230]

Embedded image

[0231]

Embedded image

[0232]

Embedded image

[0233]

Embedded image

Next, a hydrazine compound 2-24 represented by the general formula ( II ) was added to the first red-sensitive emulsion layer to prepare a silver halide 1
5.0 × 10 ^-2 mol per mol, 3.0 × 10 ^-2 mol per mol of silver halide in the second red-sensitive emulsion layer, and 3.0 × 10 ^-2 mol per mol of silver halide in the third red-sensitive emulsion layer. ×
A sample 4-2 was prepared in exactly the same manner as the sample 4-1 except that ^10-2 mol was contained, and the nitrogen-containing heterocyclic compounds 6-1 and 10-17 represented by the general formula (V) were respectively The first red-sensitive emulsion layer, the second red-sensitive emulsion layer, and the third red-sensitive emulsion layer each contained 5.0 × 10 ^-4 per mol of silver halide.
Mol and 5.0 × ^{10 -3} except that is the molar content samples 4-
Sample 4-3 was prepared in exactly the same manner as in Example 1, and the nitrogen-containing heterocyclic compounds 6-1 and 10-17 were further added to the first red-sensitive emulsion layer, the second red-sensitive emulsion layer, and the third red-sensitive emulsion, respectively. Sample 4-2 except that the three layers contained 5.0 × 10 ⁻⁴ mol and 5.0 × 10 ⁻³ mol per mol of silver halide.
A sample 4-4 was prepared in exactly the same manner as in the above. Each of these samples was assigned a blue filter (395 nm to 485 nm).
Exposure for 1/100 second through a continuous wedge using a band-pass filter that transmits light up to 100 nm or a red filter (a filter that transmits light longer than 600 nm), and development processing with the following processing solutions and processing steps Then, the concentration was measured. The reference point of the optical density at which the sensitivity was determined is the point of "coverage +0.2". The sensitivity was defined as the reciprocal of the exposure required to give the density, and the sensitivity of each sample 4-1 was defined as 100. The results expressed as relative values are shown in Table 6 as relative sensitivities. In the table, “increase in fog” is indicated by an increase or decrease in fog density from sample 4-1.

Processing method Step Processing time Processing temperature Replenishment amount Tank capacity Color development 2 minutes 45 seconds 38 ° C 33 ml 20 liter Bleaching 6 minutes 30 seconds 38 ° C 25 ml 40 liter Washing water 2 minutes 10 seconds 24 ° C 1200 ml 20 liter Constant 4 minutes 20 seconds 38 ° C 25 ml 30 liters Rinse with water (1) 1 minute 05 seconds 24 ° C 10 liters from (2) to (1) Countercurrent piping type Rinse with water (2) 1 minute 00 seconds 24 ° C 1200ml 10 liters Constant 1 minute 05 seconds 38 ° C 25 ml 10 liter Drying 4 minutes 20 seconds 55 ° C Replenishment amount is 35 mm width 1 m length Next, the composition of the processing solution is described. (Color developing solution) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-Hydroxyethylidene-1,1-3.0 3.2 Diphosphonic acid Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.7 Potassium iodide 1.5 mg -Hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N-β-hydroxy 4.5 5.5 ethylamino] -2-methylaniline sulfate 1.0 liter 1.0 liter with addition of water pH 10.05 10.10 (bleach solution) Mother liquor (g) Replenisher (g) Sodium ferric ethylenediaminetetraacetate 100.0 120.0 Trisodium ethylenediaminetetraacetate Disodium ethylenediaminetetraacetate 10.0 11.0 Ammonium bromide 140.0 160.0 Ammonium nitrate 30.0 35.0 Ammonia water (27%) 6.5ml 4.0ml Add water and 1.0L 1.0 liter pH 6.0 5.7 (fixer) Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetic acid sodium salt 0.5 0.7 Sodium acid 7.0 8.0 Sodium bisulfite 5.0 5.5 Ammonium thiosulfate aqueous solution (70%) 170.0 ml 200.0 ml Add water 1.0 liter 1.0 liter pH 6.7 6.6 (stabilizer) Mother liquor (g) Replenisher (g) Formalin (37%) 2.0 ml 3.0ml Polyoxyethylene-p-monononylphenyl 0.3 0.45 Ether (average degree of polymerization 10) Ethylenediaminetetraacetic acid disodium salt 0.05 0.08 Add water 1.0 liter 1.0 liter pH 5.0-8.0 5.8-8.0

[0236]

[Table 11]

In the color light-sensitive material having a multi-layer structure, the combination of the present invention, as in the above-mentioned embodiments, did not increase the fog, and high sensitivity was obtained.

[0238]

As described in Examples 1, 2, 3, and 4, the combined use of the hydrazine compound of the present invention and a nitrogen-containing heterocyclic compound gives a silver halide light-sensitive material, particularly a spectrally sensitized silver halide photographic light-sensitive material, with high sensitivity. It can be seen that the fogging does not increase and the storage stability is good. The combined use of the hydrazine compound and the nitrogen-containing heterocyclic compound of the present invention is extremely useful for improving the sensitivity and storage stability of a silver halide photographic light-sensitive material.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) G03C 1/34 G03C 1/08 G03C 1/12 G03C 1/06 501

Claims (2)

(57) [Claims] 1. A compound represented by the following general formulas (II), (III) and
A silver halide photographic material comprising at least one compound selected from (IV) and at least one nitrogen-containing heterocyclic compound. Embedded image Wherein R ₅ , R ₆ , R ₇ and R ₈ are an alkyl group,
A heterocyclic group or a heterocyclic group. Z ₁ has up to 4 carbon atoms
Or 6 alkylene groups . Z ₂ has ₂ carbon atoms
Represents an alkylene group . Z ₃ has 1 or 2 carbon atoms
Represents an alkylene group . Z ₄ and Z _{5 each} have 3 carbon atoms
Represents an alkylene group . L ₁ and L ₂ represent a methine group
Express . However, R ₅ , R ₆ , R ₇ , R ₈ , Z ₁ , Z ₄
And among the Z _5, bonded directly to the nitrogen atom of the hydrazine
No oxo group is substituted on the carbon atom . 2. The compound of the general formula (II), (I)
The halogenation according to claim 1, wherein the halogenation contains at least one of the compounds selected from II) and (IV ) , at least one of the nitrogen-containing heterocyclic compounds, and at least one of the spectral sensitizing dyes. Silver photographic photosensitive material.