JP3340867B2 - 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. More specifically, the present invention relates to a silver halide photographic material having high sensitivity, low fog and excellent storage stability.

[0002]

2. Description of the Related Art Hitherto, it has been desired to increase the sensitivity of silver halide photosensitive materials. In particular, it has been strongly desired to increase the sensitivity of spectrally sensitized silver halide photosensitive materials. Spectral sensitization technology is extremely important and indispensable for producing a photosensitive material having high sensitivity and excellent color reproducibility. The spectral sensitizer has a function of absorbing light in a long wavelength range which is not substantially absorbed by the silver halide photographic emulsion and transmitting the light absorption energy to the silver halide. Therefore, an increase in the amount of light trapped by the spectral sensitizer is advantageous for increasing photographic sensitivity. For this reason, attempts have been made to increase the amount of light trapped by increasing the amount added to the silver halide emulsion. However, if the amount of the spectral sensitizer to be added to the silver halide emulsion exceeds the optimum amount, a large desensitization is brought about. This is generally referred to as dye desensitization, and is a phenomenon in which desensitization occurs in a photosensitive region peculiar to silver halide, which has substantially no light absorption by a sensitizing dye. If the dye desensitization is large, the overall sensitivity will be low although there is a spectral sensitizing effect. In other words,
As the dye desensitization decreases, the sensitivity of the light absorption region by the sensitizing dye (that is, spectral sensitization) increases accordingly. Therefore, in spectral sensitization technology, improvement of dye desensitization is a major problem. In general, the dye desensitization is larger for a sensitizing dye having a photosensitive region at a longer wavelength. These things are TH James
s), "The Theory of the Photographic Proces
s) ", pages 265 to 268 (Macmillan Publishing Company, 1966).

[0003] As a method of increasing the sensitivity by reducing the dye sensitization, JP-A-47-28916 and JP-A-49-4673.
8, No. 54-118236, U.S. Pat.
No. 1,083. However, the techniques described above are limited in sensitizing dyes that can be used,
The effect was still unsatisfactory. At present, the most effective means for improving dye desensitization include, for example, JP-B Nos. 45-22189, JP-A-54-18726, JP-A-52-4822, JP-A-52-15126,
A method using a bisaminostilbene compound substituted with a pyrimidine derivative and a triazine derivative described in U.S. Pat. No. 2,945,762 is known. However, the sensitizing dyes for which the above compounds are effective are usually so-called M-band sensitizing dyes which exhibit a gentle sensitizing maximum such as dicarbocyanine, tricarbocyanine, rhodocyanine, merocyanine and the like, and are relatively long. It is limited to dyes having a sensitizing maximum in the wavelength region.

In US Pat. No. 3,695,888, the combination of a specific tricarbocyanine and ascorbic acid can be used to sensitize the infrared region.
No. 084 shows that the combination of a specific dye with ascorbic acid increases the minus blue sensitivity, and that British Patent No. 1,0
No. 64,193 discloses that sensitivity can be increased by using a specific dye in combination with ascorbic acid.
JP-A-09-561 describes the combined use of a desensitizing nucleus-containing cyanine dye with a supersensitizer such as ascorbic acid. However, in the above prior arts, there are few those in which the sensitizing effect of the dye is still sufficiently satisfactory,
Those having a high sensitizing effect tended to increase fog.

In addition, T. Tani et al., Journal of Physical Chemistry, (Journal of th
e Physical Chemistry) Volume 94, 1298 pages (199
It is known that a sensitizing dye having a reduction potential nobler than -1.25 V has a low relative quantum yield of spectral sensitization, as described in (0). In order to increase the relative quantum yield of spectral sensitization of such dyes, the “Theory of the Photographic Process” described above (The Theory of
the Photographic Process) 259-265 (196
Super sensitization by hole capture as described in the sixth edition) has been proposed. However, more effective supersensitizers are desired.

[0006] In order to increase the sensitivity of silver halide photographic materials, reduction sensitization has been attempted for a long time. For example, a tin compound is useful as a reduction sensitizer in US Pat. Nos. 2,487,850, a polyamine compound in US Pat. Nos. 2,512,925, and a thiourea dioxide-based compound in British Patent No. 789,823. Is disclosed. In addition, Photographic Science
and Engineering, Vol. 23, p. 113 (1979), compares properties of silver nuclei produced by various reduction sensitization methods, such as dimethylamine borane, stannous chloride, hydrazine, high pH ripening, and low pAg. An aging method is employed. Also. The method of reduction sensitization is further described in U.S. Pat. Nos. 2,518,698, 3,201,254, 3,411,917, 3,779,777,
No. 3,930,867. Not only the selection of reduction sensitizers but also the invention of reduction sensitization methods are described in JP-B-57-33572 and JP-B-58-1410.

However, the study of the present inventors has revealed that the fog is increased by adsorbing the sensitizing dye to the reduction-sensitized silver halide grains. In order to prevent the sensitizing dye from desorbing from the silver halide grains (especially at high humidity) in the photographic material, the sensitizing dye may be adsorbed at a high temperature (50 ° C. or higher). Even worse fog. Further, as a method of increasing the sensitivity, there is a method of adsorbing a sensitizing dye before chemical sensitization, and this method also deteriorates fog.

[0008]

SUMMARY OF THE INVENTION The object of the present invention is to
Another object of the present invention is to provide a silver halide photographic material having high sensitivity and low fog. The second object is to provide a silver halide photographic light-sensitive material having high storage stability.

[0009]

The object of the present invention is as follows.
This has been attained by a silver halide photographic material characterized by containing at least one hydrazone compound having a methine dye residue or an adsorptive group to silver halide through a covalent bond. A hydrazone is a condensation product of a carbonyl compound and hydrazine, and includes an aldehyde hydrazone and a ketone hydrazone. The hydrazone compound in the present invention includes both, but all of the two hydrogen atoms at the N-position are substituted. Means the compound. The compound of the present invention is preferably a compound represented by the following general formula (I) or (II). Preferred hydrazone compound having a methine dye residue through a covalent bond: general formula (I)

[0010]

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Preferred hydrazone compound having an adsorbing group through a covalent bond: General formula (II)

[0012]

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In the formula (I), MET represents a methine dye residue, Q ₁ represents a linking group comprising an atom or an atomic group containing at least one of a carbon atom, a nitrogen atom, a sulfur atom and an oxygen atom; Hyd ₁ represents a group having a hydrazone structure represented by the general formula (III), k _1a and k _3a each represent an integer of 1 to 4, and k _2a represents 0 or 1. General formula (III)

[0014]

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In the formula, R ₁ , R ₂ and R ₃ each represent an aliphatic group, an aryl group or a heterocyclic group. R ₄ represents a hydrogen atom or a group having the same meaning as R ₃ . (II) where Het
Is a group having a 5-, 6- or 7-membered heterocyclic ring which is an adsorptive group to silver halide and contains at least one nitrogen atom and may further contain a heteroatom other than a nitrogen atom. , Q ₂ represents a linking group comprising an atom or an atomic group containing at least one of a carbon atom, a nitrogen atom, a sulfur atom and an oxygen atom, and Hyd ₂ represents a group having a hydrazone structure represented by the general formula (III). K _1b and k _3b each represent an integer of 1 to 4, and k _2b represents 0 or 1. Another embodiment of the present invention relates to a photographic material having at least one silver halide emulsion layer on a support, wherein at least one of the emulsion layers contains at least one of the above-mentioned hydrazone compounds, A silver halide photographic light-sensitive material characterized in that silver halide grains in an emulsion layer are subjected to reduction sensitization. In still another embodiment of the present invention, wherein the silver halide emulsion layer contains at least one compound represented by the following general formula (XX) , (XXI) or (XXII) . It is a silver halide photographic material. Formula (XX) R ₁₀₁ -SO ₂ S-M ₁₀₁ Formula (XXI) R ₁₀₁ -SO ₂ S-R ₁₀₂ Formula (XXII) R ₁₀₁ -SO ₂ S- (E) _a -SSO ₂ -R ₁₀₃ In the formula, R ₁₀₁ , R ₁₀₂ and R ₁₀₃ represent an aliphatic group , an aromatic group or a heterocyclic group, M ₁₀₁ represents a cation, E represents a divalent linking group, and a Is 0 or 1.

Hereinafter, the present invention will be described in more detail. In the methine dye residue and the general formula (I), ME
The group represented by T is usually a cyanine structure formed by connecting a nitrogen-containing heterocycle called a basic nucleus and another nitrogen-containing heterocycle by a conjugated double bond so that they can be conjugated to each other; Or a merocyanine structure formed by connecting a carbonyl group in the acidic nucleus and a nitrogen atom in the basic nucleus with a conjugated double bond so that the heterocyclic ring and the basic nucleus can be conjugated to each other, or It represents a group having a rhodacyanine structure having these structures in combination, an oxonol structure, a hemicyanine structure, a styryl structure, a benzylidene structure, and the like.

Examples of these polymethine dyes include, for example, "The Theory of the Photographic Process" 197, edited by THJames.
Year 7, Macmillan, Chapter 8, FM Hemer, Heterocyclic Compounds-Cyanine D
yes and Related Compounds) (John Wiley and Sons, John & Sons, New York, London, 1964). , DM STAMER (DM
Sturmer), Heterocyclic Compounds-Special topics in Heterocyclic Compounds
in heterocyclic chemistry-) ", Chapter 18, Chapter 14
Verses, 482-515, John Willie and
Sands (John Wiley & Sons), New York, London, (1977). , "Rods Chemistry
Rodd's Chemistry of Ca
rbon Compounds) ”, (2nd. Ed. vol. IV, part B, 19
1977, Chapter 15, 369-422; (2nd.E
d.vol.IV, part B, 1985), Chapter 15, Chapter 26
7-296, Elsvier Science Public Company, Inc.
Company Inc.), New York, etc.

The cyanine structure preferably used as MET in the present invention is represented by the general formula (IV), the merocyanine structure is represented by the general formula (V), the rhodacyanine structure is represented by the general formula (VI), The allopolar dye structure is represented by the general formula (VII). General formula (IV)

[0019]

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General formula (V)

[0021]

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Formula (VI)

[0023]

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Formula (VII)

[0025]

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Wherein Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₁₄ , Z ₁₅ , Z
₁₆ , Z ₁₇ and Z ₁₈ represent an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. D and D _a , D
₁ and D _1a represent a group of atoms necessary to form an acyclic or cyclic acidic nucleus. R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R
₁₆ , R ₁₇ and R ₁₈ represent an alkyl group. R ₁₅ 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, L 30,} L 31, L 32, L 33, L 34, L 35,
L ₃₆ , L ₃₇ and L ₃₈ represent a methine group. M ₁₁ ,
M ₁₂ , M ₁₃ and M ₁₄ represent a charge neutralizing counter ion;
₁₁ , m ₁₂ , m ₁₃ and m ₁₄ are numbers of 0 or more and 5 or less necessary for neutralizing the charge in the molecule. n ₁₁ , n ₁₃ , n
₁₄ , n ₁₆ , n ₁₉ , n ₂₀ , n ₂₁ and n ₂₂ represent 0 or 1. n ₁₂ , n ₁₅ , n ₁₇ and n ₁₈ are each 0 to 4
Is an integer. More preferably, the compound represented by the general formula (IV) or (V
The dye structure represented by II). Particularly preferred is a dye structure represented by the general formula (VII).

The general formulas (IV), (V), (VI) and (VII) will be described below in more detail. R ₁₁ , R ₁₂ , R ₁₃ ,
R ₁₄ , R ₁₆ , R ₁₇ and R ₁₈ preferably have 1 to 18 carbon atoms, preferably 1 to 7, particularly preferably 1 to 4 carbon atoms.
Unsubstituted alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl,
Octadecyl), or C 1-18, preferably 1
Substituted alkyl groups of 1 to 7 as the substituent, for example, a carboxy group, a sulfo group, a cyano group, a halogen atom (for example, fluorine, chlorine, or bromine), a hydroxy group,
8 alkoxycarbonyl groups (for example, methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl), an alkoxy group having 1 to 8 carbon atoms (for example, methoxy, ethoxy, benzyloxy, phenethyloxy), a monocyclic ring having 6 to 10 carbon atoms An aryloxy group of the formula (e.g., phenoxy, p-tolyloxy), an acyloxy group having 1 to 3 carbon atoms (e.g., acetyloxy, propionyloxy), an acyl group having 1 to 8 carbon atoms (e.g., acetyl, propionyl, benzoyl, mesyl), A carbamoyl group having 1 to 8 carbon atoms (for example, carbamoyl, N, N
-Dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl), a sulfamoyl group having 1 to 8 carbon atoms (for example, sulfamoyl, N, N-dimethylsulfamoyl, morpholinosulfonyl, piperidinosulfonyl), aryl having 6 to 10 carbon atoms Groups (eg, phenyl,
4-chlorophenyl, 4-methylphenyl, alpha-naphthyl) substituted alkyl groups} C3-10 substituted until
Or an unsubstituted alkenyl group (for example, an allyl group) . More preferably, an unsubstituted alkyl group having 1 to 4 carbon atoms (eg, a methyl group, an ethyl group, an n-propyl group,
n-butyl group, n-pentyl group, n-hexyl group), carboxyalkyl group having 1 to 5 carbon atoms (for example, 2-carboxyethyl group, carboxymethyl group), sulfoalkyl group (for example, 2-sulfoethyl group, 3 -Sulfopropyl group, 4-sulfobutyl group, 3-sulfobutyl group) and methanesulfonylcarbamoylmethyl group. Particularly preferred is a sulfoalkyl group.

M ₁₁ m ₁₁ , M ₁₂ m ₁₂ , M ₁₃ m ₁₃ and M ₁₄
m ₁₄ is included in the formula to indicate the presence or absence of a cation or 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 ions (eg, ammonium ion, tetraalkylammonium ion, pyridinium ion) and alkali metal ions (eg, sodium ion, potassium ion) and alkaline earth metal ions (eg, calcium ion) On the other hand, the anion may specifically be either an inorganic anion or an organic anion, such as a halogen anion (for example, a fluoride ion, a chloride ion, a bromine ion, an iodine ion) and a substituted arylsulfonate ion (for example, For example, p-toluenesulfonic acid ion, p-chlorobenzenesulfonic acid ion, aryldisulfonic acid ion (for example, 1,3-benzenedisulfonic acid ion,
1,5-naphthalenedisulfonic acid ion, 2,6-naphthalenedisulfonic acid ion), alkyl sulfate ion (eg, methyl sulfate ion, ethyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion , Picrate ion, acetate ion, trifluoromethanesulfonate ion.In addition, an ionic polymer or other dye having a reverse charge to the dye may be used as a charge neutralizing counter ion,
Metal complex ions are also possible. Preferably, they are an ammonium ion, an iodine ion, and a p-toluenesulfonic acid ion. m ₁₁ , m ₁₂ , m ₁₃ and m ₁₄ are preferably 0, 1, and 2.

The nucleus formed by Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₁₄ , Z ₁₆ , Z ₁₇ and Z ₁₈ includes a thiazole nucleus and a thiazole nucleus (for example, thiazole, 4-methylthiazole, 4-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole), benzothiazole nucleus (for example, 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), naphthothiazole nucleus (for example, naphtho [2,1-d] thiazole, naphtho [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- Nitroxazole, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole), benzoxazole nucleus (for example, 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)}, oxazoline nucleus (for example,
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
-Chlorobenzoselenazole, 5-nitrobenzoselenazole,

5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, 6-nitrobenzoselenazole, 5-chloro-6-nitrobenzoselenazole,
5,6-dimethylbenzoselenazole), naphtho selenazole nucleus (for example, naphtho [2,1-d] selenazole, naphtho [1,2-d] selenazole)}, selenazoline nucleus (for example, selenazoline, 4-methyl selena) Zoline), tellurazole nucleus ｛tellurazole nucleus (eg, tellurazole, 4-methyltellurazole, 4-phenyltellurazole), benzotellurazole nucleus (eg, benzotellurazole, 5-chlorobenzotellurazole, 5-methylbenzotellurazole) , 5,6-dimethylbenzotellurazole, 6-methoxybenzotellurazole), naphthotellurazole nucleus (for example, naphtho [2,1-d] tellurazole, naphtho [1,2-d] tellurazole)}, tellurazoline nucleus ( For example, tellurazoline, 4-methyltellurazoline),

The 3,3-dialkylindolenine nucleus (for example, 3,3-dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-5-cyanoindolenine, 3,3-dimethyl-6- Nitroindolenin,
3,3-dimethyl-5-nitroindolenine, 3,3-
Dimethyl-5-methoxyindolenine, 3,3,5-trimethylindolenine, 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-chlorobenzo Imidazole, 1-arylbenzimidazole,

1-aryl-5-chlorobenzimidazole, 1-aryl-5,6-dichlorobenzimidazole, 1-aryl-5-methoxybenzimidazole, 1-aryl-5-cyanobenzimidazole),
Naphthoimidazole nucleus (for example, alkyl naphtho [1,
2-d] imidazole, 1-arylnaphtho [1,2-
d] imidazole), the alkyl group having 1 carbon atom
~ 8, such as methyl, ethyl, propyl,
Unsubstituted alkyl groups such as isopropyl and butyl, and hydroxyalkyl groups (for example, 2-hydroxyethyl, 3-
Hydroxypropyl) is 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. ｝,

A pyridine nucleus (for example, 2-pyridine, 4-pyridine
Pyridine, 5-methyl-2-pyridine, 3-methyl-4
-Pyridine), quinoline nucleus ｛quinoline nucleus (for example, 2-
Quinoline, 3-methyl-2-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] quinoxalin), oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus and pyrimidine nucleus.

The nucleus formed by Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₁₄ , Z ₁₆ , Z ₁₇ and Z ₁₈ is preferably a benzothiazole nucleus, a naphthothiazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzimidazole Nuclear,
They are a 2-quinoline nucleus and a 4-quinoline nucleus. Z ₁₇ and Z
_The nucleus formed by ₁₈ is particularly preferably a naphtho [1,2-d] thiazole nucleus.

D and D _a , D ₁ and D _1a represent a group of atoms necessary for forming an acidic nucleus, but can take the form of an acidic nucleus of any general merocyanine dye. The term "acid nucleus" used herein refers to, for example, "The Theory of the Photographic Process" edited by James (The T
heory of the Photographic Process) 4th edition, defined by Macmillan Publishing Company, 1977, p. 198.
In a preferred form, substituents involved in the resonance of D and D ₁ are, for example, carbonyl, thiocarbonyl, cyano, sulfonyl, sulfenyl.
D _a and D _1a represents an atomic group necessary for forming an acidic nucleus. Specifically, U.S. Patent No. 3,567,
No. 719, No. 3,575,869, No. 3,804,6
No. 34, No. 3,837,862, No. 4,002,48
No. 4,925,777, JP-A-3-16754
No. 6 and the like. When the acidic nucleus is acyclic, the terminus of the methine linkage is a group such as malononitrile, alkanesulfonylacetonitrile, cyanomethylbenzofuranyl ketone, or cyanomethylphenyl ketone. When D and D _a , and D ₁ and D _1a are cyclic, form a 5- or 6-membered heterocycle consisting of carbon, nitrogen, and chalcogen (typically oxygen, sulfur, selenium, and tellurium) atoms I do.

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-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] pyrimidine-1,3-
Dione, pyrazolo [1,5-b] quinazolone, pyrazolo [1,5-a] benzimidazole, pyrazolopyridone, 1,2,3,4-tetrahydroquinoline-2,4-
Dione, 3-oxo-2,3-dihydrobenzo [d] thiophen-1,1-dioxide, 3-dicyanomethine-2,3-dihydrobenzo [d] thiophen-1,1-
Dioxide core. More preferably, 3-alkyl rhodanine, 3-alkyl-2-thiooxazolidine-
2,4-dione, 3-alkyl-2-thiohydantoinbarbituric acid, and 2-thiobarbituric acid. D ₁
And the acid nucleus formed by D _1a is particularly preferably barbituric acid.

The substituent and R ₁₅ bonded to the nitrogen atom contained in the acidic nucleus are a hydrogen atom, a carbon atom having 1 to 1 carbon atoms.
8, preferably 1-8, more preferably 1-4 alkyl groups (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl,
Octyl group, dodecyl group, octadecyl group), carbon number 6
To 18, preferably 6 to 12 aryl groups (for example, phenyl group, 2-naphthyl group, 1-naphthyl group) and a heterocyclic group having 1 to 18 carbon atoms, preferably 6 to 12 carbon atoms (for example, 2 to 12 carbon atoms).
-Pyridyl group, 2-thiazolyl group, 2-furyl group). These substituents may be further substituted. Examples of the substituent include a carboxy group, a sulfo group, a cyano group, a nitro group, a halogen atom (for example, a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom), a hydroxy group, and an alkoxy group having 1 to 8 carbon atoms (for example, Methoxy group, ethoxy group, benzyloxy group, phenethyloxy group), aryloxy group having 6 to 15 carbon atoms (for example, phenoxy group), acyloxy group having 1 to 8 carbon atoms (for example, acetyloxy group), carbon number An alkoxycarbonyl group having 2 to 8 carbon atoms, an acyl group having 1 to 8 carbon atoms, a sulfamoyl group, a carbamoyl group, an alkanesulfonylaminocarbonyl group having 2 to 8 carbon atoms (for example, methanesulfonylaminocarbonyl group), Acylaminosulfonyl group (for example, acetylaminosulfonyl group), having 6 to 6 carbon atoms
15 aryl groups (for example, phenyl group, 4-methylphenyl group, 4-chlorophenyl group, naphthyl group) and a heterocyclic group having 4 to 15 carbon atoms (for example, pyrrolidin-2-one-
1-yl group, tetrahydrofurfuryl group, 2-morphonino group), and these substituents may be further substituted by these substituents.

More preferably, an unsubstituted alkyl group having 1 to 5 carbon atoms (for example, methyl, ethyl, n-propyl,
n-butyl, n-pentyl), a carboxyalkyl group having 2 to 5 carbon atoms (eg, carboxymethyl, 2-carboxyethyl), and a sulfoalkyl group having 2 to 5 carbon atoms (eg, 2-sulfoethyl).

The nitrogen-containing heterocyclic ring 5-membered or 6-membered formed by Z ₁₅ is minus D, in position from cyclic heterocyclic ring represented by D _a, an oxo group or a thioxo group, 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, L 30, L 31, L 32, L
_{33, L 34, L 35,} L 36, L 37 and L ₃₈ are methine group or a substituted methine group {e.g. 1 to 8 carbon atoms, preferably 1 to
4 substituted or unsubstituted alkyl groups (eg, methyl,
Ethyl, 2-carboxyethyl), a substituted or unsubstituted aryl group having 6 to 12 carbon atoms (for example, phenyl, o
-Carboxyphenyl), a heterocyclic group having 4 to 12 carbon atoms (eg, barbituric acid), a halogen atom (eg, chlorine atom, bromine atom), an alkoxy group having 1 to 6 carbon atoms (eg, methoxy, ethoxy), and carbon number 0 to 15 amino groups (for example, N, N-diphenylamino, N-methyl-N-
Phenylamino, N-methylpiperazino), having 1 to 1 carbon atoms
8 represents a group substituted with an alkylthio group (for example, methylthio, ethylthio), etc., and may form a ring with another methine group, or may form a ring with an auxochrome. _{L 11, L 12, L 16} , L 17, L
_{18, L 19, L 22,} L 23, L 29, L 30, L 31, L 32, L 37
And preferably a L ₃₈ are unsubstituted methine groups. n
₁₂ is preferably 0, 1, 2, 3, L ₁₃ , L
The ₁₄ and L ₁₅ monomethine, trimethine, and the like are formed pentamethine and heptamethine dye. While the unit of L ₁₃ and L ₁₄ are repeated if n ₁₂ is 2 or more may not be the same. Preferred examples of L ₁₃ , L ₁₄ and L ₁₅ are shown below.

[0043]

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N ₁₂ is more preferably 1. n
Preferably a ₁₅ is 0, 1, 2, 3, the L ₂₀ and L ₂₁ Zeromechin, dimethine, and the like are formed Tetoramechin and hexamethine dye. When n ₁₅ is 2 or more, the units of L ₂₀ and L ₂₁ are repeated, but need not be the same. Preferred examples of L ₂₀ and L ₂₁ are given below.

[0045]

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N ₁₇ is preferably 0, 1, 2, or 3, and L ₂₄ and L ₂₅ form zero methine, dimethine, tetramethine, hexamethine and the like. 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 L ₂₄ and L ₂₅ are the same as L ₂₀ and L _{21. As} n ₁₈ , the seeds are 0, 1, 2, and 3, and L ₂₆ , L ₂₇ and L _{28 are} monomethine, trimethine. Pentamethine, heptamethine and the like. The units of L ₂₆ and L ₂₇ are repeated when n ₁₈ is 2 or more, but need not be the same.
Preferred examples of L ₂₆ , L ₂₇ and L ₂₈ are given below.

[0047]

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In addition, L₁₃, L₁₄And L_FifteenExample shown in
Is preferred. n_{twenty one}Is preferably 0. L₃₃And
And L₃₆Is preferably an unsubstituted methine group. General formula
Represented by (IV), (V), (VI) and (VII)
Methine dye structures each have at least one meta
The locene compound is substituted. The substitution position is Z₁₁,
Z₁₂, Z₁₃, Z₁₄, Z_Fifteen, Z₁₆, Z₁₇And Z₁₈, D and
D_aAnd D₁And D_1a, R₁₁, R₁₂, R₁₃, R₁₄,
R_Fifteen, R₁₆, R₁₇And R₁₈Or L₁~ L₃₈In any case
Is also good. Preferably D₁And D_1a, R₁₁, R₁₂, R₁₃, R
₁₄, R _Fifteen, R₁₆, R₁₇And R₁₈To the group represented by
That is,

Next, the hydrazone structure represented by the general formula (III) preferably used as Hyd ₁ in the present invention will be described in more detail. R ₁ , R ₂ and R
₃ is, for example, 1-18 carbon atoms, preferably 1-8 carbon atoms.
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 having 1 to 24, preferably 1 to 18 carbon atoms. Although there is no particular limitation on the substituent, 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 having 2 to 8 carbon atoms (for example, methoxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group), an aryloxycarbonyl group having 7 to 12 carbon atoms (for example, Phenoxycarbonyl group), having 1 to 8 carbon atoms
(For example, a methoxy group, an ethoxy group, a benzyloxy group, a phenethyloxy group) having 6 to 18 carbon atoms
Aryloxy group (for example, phenoxy group, 4-methylphenoxy group, α-naphthoxy group), acyloxy group having 1 to 8 carbon atoms (for example, acetyloxy group, propionyloxy group), acyl group having 1 to 8 carbon atoms (for example, Acetyl group, propionyl group, benzoyl group, mesyl group), carbamoyl group having 1 to 8 carbon atoms (for example, carbamoyl group,
N, N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group),

A sulfamoyl group having 0 to 8 carbon atoms (for example, sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group), an aryl group having 6 to 12 carbon atoms (for example, phenyl group) , 4-chlorophenyl group, 4-methylphenyl group, α
-Naphthyl group), a heterocyclic group having 4 to 12 carbon atoms (for example,
2-pyridyl group, tetrahydrofurfuryl group, morpholino group, 2-thiopheno group), an amino group having 0 to 12 carbon atoms (for example, amino group, dimethylamino group, anilino group,
A diphenylamino group), an alkylthio group having 1 to 12 carbon atoms (eg, a methylthio group or an ethylthio group),
8 alkylsulfonyl groups (for example, methylsulfonyl group, propylsulfonyl group), alkylsulfinyl group having 1 to 8 carbon atoms (for example, methylsulfinyl group), nitro group, phosphoric acid group, acylamino group having 1 to 8 carbon atoms (for example, An acetylamino group), an ammonium group having 1 to 8 carbon atoms (eg, trimethylammonium group, tributylammonium group), a mercapto group, a hydrazino group having 0 to 8 carbon atoms (eg, trimethylhydrazino group), and a ureido having 1 to 8 carbon atoms Groups (eg, ureido group, N, N-dimethylureido group), imide group, unsaturated hydrocarbon group having 2 to 16 carbon atoms (eg, vinyl group, ethynyl group, 1-cyclohexenyl group, benzylidene group, benzylidene group) And an unsubstituted alkyl group (eg, a methyl group). V may be further substituted on these substituents.

More specifically, an alkyl group having 1 to 18 carbon atoms (for example, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 2-sulfoethyl group, 3-sulfopropyl Group, 4
-Sulfobutyl group, 3-sulfobutyl group, 2-hydroxy-3-sulfopropyl group, 2-cyanoethyl group, 2-
Chloroethyl group, 2-bromoethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, hydroxymethyl group, 2-hydroxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-ethoxycarbonylethyl group, methoxy Carbonylmethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-phenoxyethyl group, 2-acetyloxyethyl group, 2-propionyloxyethyl group, 2-acetylethyl group, 3-benzoylpropyl group, 2- Carbamoylethyl group, 2-morpholinocarbonylethyl group, sulfamoylmethyl group, 2-
(N, N-dimethylsulfamoyl) ethyl, benzyl, 2-naphthylethyl, 2- (2-pyridyl) ethyl, allyl, 3-aminopropyl, 3-dimethylaminopropyl, methylthiomethyl Group, 2-methylsulfonylethyl group, methylsulfinylmethyl group, 2
-Acetylaminoethyl group, 3-trimethylammoniumethyl group, 2-mercaptoethyl group, 2-trimethylhydrazinoethyl group, methylsulfonylcarbamoylmethyl group, (2-methoxy) ethoxymethyl group, and the like. 6 to 18, preferably 6 to 12 aryl groups (for example, phenyl group, α-naphthyl group, β-naphthyl group, for example, phenyl group and naphthyl group substituted with the aforementioned substituent V), and 4 to 18 carbon atoms , Preferably 4 to
Twelve heterocyclic groups (for example, a 2-pyridyl group, a 2-pyridyl group substituted with the aforementioned substituent V) are preferred.

Further, R ₁ and R ₂ and R ₃ and R ₄ may combine with each other to form a ring. These rings may be substituted, for example, by the substituent V described above. However, the carbon atom directly bonded to the nitrogen atom of R ₁ and R ₂ is not substituted with an oxo group, a thioxo group, or an imino group. For example, R ₁ and R ₂ represent two rings of acetyl, carboxy, benzoyl, formyl, thioacetyl, thioaldehyde, thiocarboxy, thiobenzoyl, imino, N-methylimino, and N-phenylimino. Is not a malonyl group, a succinyl group, a glutaryl group, or an adipoyl group.

More preferably, R ₁ and R ₂ are
These are the unsubstituted alkyl group and substituted alkyl group described above. Particularly preferably, an unsubstituted alkyl group having 1 to 5 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group), a substituted alkyl group having 1 to 5 carbon atoms {for example, a sulfoalkyl group (for example, 2-sulfoethyl group, 3-sulfopropyl group,
4-sulfobutyl group, 3-sulfobutyl group), carbon number 1
To 5 carboxyalkyl groups (for example, carboxymethyl group, 2-carboxyethyl group), and C1 to C5 hydroxyalkyl groups (for example, 2-hydroxyethyl group)}.

R ₃ is more preferably represented by the following general formula:
This is the case of the substituent represented by (IIIa). General formula (IIIa)

[0055]

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In the formula, L ₂ and L ₃ each represent a methine group. Ar represents an aryl group. n ₁ represents an integer of 0-4. Ar is preferably a phenyl group, having 6 to 6 carbon atoms.
18 substituted phenyl groups (the above-mentioned V is mentioned as a substituent). L ₂ and L ₃ are preferably an unsubstituted methine group. n ₁ is preferably 0 or 1
It is.

As R ₄ , a hydrogen atom or a substituent similar to R ₁ , R ₂ and R ₃ described above is used. R ₄ is preferably a hydrogen atom.

The hydrazone compound represented by the general formula (I) or (II), if it is advantageous in synthesis and storage,
No problem if isolated as a salt. In such a case, any compound may be used as long as it can form a salt with the hydrazone, but preferred salts include the following. For example, aryl sulfonates having 6 to 16 carbon atoms (e.g., p-toluene sulfonate, p-chlorobenzene sulfonate), aryl disulfonates having 6 to 16 carbon atoms (e.g., 1,3-benzenedisulfonate,
1,5-naphthalenedisulfonic acid salt, 2,6-naphthalenedisulfonic acid salt), thiocyanate, picrate,
Carboxylate (eg, oxalate, acetate, benzoate, hydrogen oxalate), halogenate (eg, hydrochloride, hydrofluoride, hydrobromide, hydroiodide) , Sulfate, perchlorate, tetrafluoroborate,
Sulfites, nitrates, phosphates, carbonates, bicarbonates. Preferred are hydrogen oxalate, oxalate and hydrochloride. Further, the general formula (III) is represented by the following general formula (III)
When b) is preferred. General formula (IIIb)

[0059]

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[0060] In the formula, R _1, R ₂ and R ₄ have the same meanings as R _1, R ₂ and R ₄ each in the general formula (III). R
₇ and R ₈ each represent a hydrogen atom, an aliphatic group, an aryl group or a heterocyclic group. V ₁ represents a hydrogen atom or a monovalent substituent. n ₃ represents an integer of 1-4. L ₂
And L ₃ are the same as L ₂ and L ₃ in the general formula (III _a) respectively. n ₂ represents 0 or 1.

Hereinafter, the formula (IIIb) will be described in detail.

R ₇ and R ₈ are a hydrogen atom or the aforementioned R
Those similar to the examples given at ₁ and R ₂ are preferred. More preferably, it is an unsubstituted alkyl group having 1 to 18 carbon atoms or a substituted alkyl group. A substituted alkyl group having 1 to 12 carbon atoms such as a sulfoalkyl group (eg, 2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, 3-
Sulfobutyl group), carboxyalkyl group (for example, carboxymethyl group, 2-carboxyethyl group), and hydroxyalkyl group (for example, 2-hydroxyethyl group)}.

[0063] V ₁ was represents a hydrogen atom or a monovalent substituent group is not particularly limited as substituent, the aforementioned R _1,
R ₂ , R ₃ and V are exemplified. Particularly preferably, an unsubstituted alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group), a substituted alkyl group having 1 to 6 carbon atoms (eg, 2-sulfobutyl group, 2-carboxyethyl group),
An alkoxy group having 1 to 4 carbon atoms (for example, a methoxy group or an ethoxy group) is exemplified.

L ₂ and L _{3 each} represent an unsubstituted methine group or a substituted methine group (for example, R ₁ , R ₂ ,
R ₃ and V are exemplified. ).
Preferably it is an unsubstituted methine group. n ₁ is preferably 0. These hydrazone compounds, at least one of _{R 1, R 2, R 3} , R 4 in formula (III), in the general formula _{(IIIa) R 1, R 2} ,
_{R 4, L 2, L 3} , at least one of Ar, and in the general formula _{(III b) R 7, R} 8, L 2, L 3, V
_In at least one of the two,-(Q ₁ ) _k2a- (M
ET) _k1a or - (Q _{2) k2b} - is bonded to the (Het) _k1b. More preferably, R ₁ , R ₂ , R ₅ , R
₆ , R ₇ and R ₈ . Particularly preferred is the case where the bond is formed at R ₇ and R ₈ .

Q ₁ and Q ₂ represent a linking group comprising an atom or an atomic group containing at least one of a carbon atom, a nitrogen atom, a sulfur atom and an oxygen atom. The linking groups Q ₁ and Q ₂ can have a valence as required. That is, Q
₁ is (K _1a +1) valence, and Q ₂ is (K _1b +1) valence. For example, when K _1a is 1, Q ₁ is a divalent linking group. Preferably, the alkylene group has 1 to 18 carbon atoms, more preferably 1 to 6 (e.g., methylene group, ethylene group, propylene group, butylene group, pentylene group), and 6 to 1 carbon atoms.
8, more preferably 6 to 12 arylene groups (eg, phenylene group, naphthylene group), 1 to 18 carbon atoms,
More preferably, an alkenylene group having 1 to 6 (for example, an ethenylene group or a propenylene group), -N having 1 to 12 carbon atoms
(R ¹ )-(R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group.),
A heterocyclic divalent group having 4 to 18 carbon atoms, preferably 4 to 12 carbon atoms (for example, 6-chloro-1,3,5-triazine-2,4
-Diyl group, pyrimidine-2,4-diyl group, quinoxaline-2,3-diyl group) and 1 to 20 carbon atoms formed by combining one or more linking groups of
Represents a divalent linking group. Particularly preferably, 1Q, 2Q,
5Q.

[0066]

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K _1a is preferably 1 or 2, and k _3a is preferably 1 or 2. More preferably,
k _1a is 1, k _2a is 1, and k _3a is 1.

The group adsorbed on silver halide may be any group adsorbed on silver halide, but a group having the following characteristics in terms of chemical structure is preferred. Preferably,
And 5, 6 or 7 represented by A having a quaternary nitrogen atom
Membered nitrogen-containing heterocyclic ring A 5, 6 or 7-membered heterocyclic ring represented by B having a thioxo group A nitrogen-containing heterocyclic ring having three or more 5, 6 or 7-membered nitrogen atoms represented by C However, Za is not substituted with _a thioether group (—SR _b ). R _b represents an aliphatic group, an aryl group or a heterocyclic group. 5, 6 or 7-membered nitrogen-containing heterocycle represented by D and E

[0069]

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[0070]

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In the formula, Za represents an atom group necessary for forming a 5-, 6- or 7-membered nitrogen-containing heterocyclic ring. L _a and L
_b represents a methine group. n _a represents 0, 1, 2, or 3. Ra represents an aliphatic group.

The group represented by Het represented by the general formula (II) is an adsorptive group to silver halide, has the above-mentioned characteristics, has at least one nitrogen atom, and has at least one nitrogen atom. 5 which may contain other hetero atoms (eg, oxygen atom, sulfur atom, selenium atom, tellurium atom)
A group having a 6-membered, 6-membered or 7-membered heterocyclic ring. Preferably an azole ring (eg imidazole, triazole,
Tetrazole, oxazole, selenazole, benzimidazole, benzotriazole, indazole, benzoxazole, benzothiazole, thiadiazole,
Oxadiazole, benzoselenazole, pyrazole,
Naphthothiazole, naphthoimidazole, naphthoxazole, azabenzimidazole, purine), pyrimidine ring, triazine ring, azaindene ring (eg, triazaindene, tetrazaindene, pentaazaindene)
And the like. Further preferred Het are those represented by the general formulas (XI), (XII), (XIII), (XIV) and (XV)
Is a group having a compound structure represented by General formula (XI)

[0073]

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Formula (XII)

[0075]

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Formula (XIII)

[0077]

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Formula (XIV)

[0079]

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Formula (XV)

[0081]

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[0082] In the formula, Q _a is = N- or = C (R ₃₃₎ - represents, when Q _a is = N- of, Q _b is = C (R ₃₃₎ - represents, Q _a is = C (R ₃₃₎ - when, Q _b is = represents the N-. Q _c is = N- or = C (R ₃₆₎ - represents, Q
When _c is = N- of, Q _d is = C (R ₃₆₎ - represents, Q
_c is = C (R ₃₆₎ - when, Q _d is = represents the N-. R
₃₁ , R ₃₂ , R ₃₃ , R ₃₄ , R ₃₅ and R ₃₆ represent a hydrogen atom or a monovalent substituent. R ₄₄ represents an aliphatic group, an aryl group or a heterocyclic group. X ₂₁ represents a hydrogen atom, an alkali metal atom, an ammonium group or a precursor.
Y ₂₁ is an oxygen atom, a sulfur atom, ＮＨNH, ＮN- (L ₄₄ ) _p3
—R ₄₈ , L ₄₃ and L ₄₄ represent a divalent linking group,
₄₅ and R ₄₈ represent a hydrogen atom, an aliphatic group, an aryl group or a heterocyclic group. X ₂₂ has the same meaning as X ₂₁ . p ₂ or p
₃ is an integer of 0-3. Z ₂₇ represents an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. R ₄₆ represents an aliphatic group. R ₄₇ represents a hydrogen atom or an aliphatic group. However, in general formula (XI) ~ (XV), at least one respective _{- (Q 2) k2b - (} H yd2) is substituted. However, X ₂₁ and X ₂₂ in formulas (XIII) and (XIV) are not substituted. Of the general formulas (XI) to (XV), preferably the general formula
(XI) and (XIII), more preferably the general formula (XII
I). Next, the general formulas (XI), (XII), (XIII), (XIV)
And (XV) will be described in more detail. An aliphatic group in the present specification may be linear, branched or cyclic, or may contain a saturated or unsaturated bond,
It refers to an aliphatic hydrocarbon group which may be unsubstituted or substituted, and includes a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group and the like. R ₃₁ , R ₃₂ ,
R ₃₃ , R ₃₄ , R ₃₅ and R ₃₆ represent a hydrogen atom or a monovalent substituent. Examples of the monovalent substituent include R ₁ and R
Substituents and the like mentioned as preferable examples of ₂ and V can be mentioned. More preferably, a lower aliphatic group (preferably substituted or unsubstituted one having 1 to 4 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, 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, such as benzyl group, phenethyl group, phenylpropyl group), aryl group (preferably substituted or unsubstituted carbon number) 6 to 12 phenyl groups, 4-methylphenyl groups, 4-methoxyphenyl groups), heterocyclic groups (for example, -Pyridyl group), alkylthio group (preferably substituted or unsubstituted one having 1 to 10 carbon atoms such as methylthio group, ethylthio group), arylthio group (preferably substituted or unsubstituted one having 6 to 12 carbon atoms, e.g., A phenylthio group), an aryloxy group (preferably substituted or unsubstituted one having 6 to 12 carbon atoms, for example, a phenoxy group), a carbon atom of 3
The above alkylamino group (for example, propylamino group,
Butylamino group), arylamino group (for example, anilino group), halogen atom (for example, chlorine atom, bromine atom,
A fluorine atom) or the following substituent.

[0083]

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Here, L ₄₅ , L ₄₆ and L ₄₇ 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 ₄₉ and R ₅₀ may be the same or different, and each represents a hydrogen atom, an aliphatic group (preferably substituted or unsubstituted one having 1 to 10 carbon atoms, for example, methyl group, ethyl group, n-propyl group, 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) Represents

The aliphatic group, aryl group and heterocyclic group represented by R ₄₄ may be unsubstituted or substituted. Examples of the substituent include the substituents described above as preferred examples of R ₁ , R ₂ and V. More preferably, a halogen atom (e.g., a chlorine atom, a bromine atom, a fluorine atom), a nitro group, a cyano group, a hydroxy group, a carbon number of 1 to 1
4 alkoxy groups (for example, methoxy group), having 6 to 1 carbon atoms
2 aryl groups (for example, phenyl group), C 1-4 acylamino group (for example, propionylamino group), C 2-6 alkoxycarbonylamino group (for example, methoxycarbonylamino group), C 1-8 Ureido group, amino group having 0 to 8 carbon atoms, heterocyclic group having 4 to 12 carbon atoms (for example, 2-pyridyl group), acyl group having 1 to 4 carbon atoms (for example, acetyl group), and sulfamoyl having 0 to 8 carbon atoms A sulfonamide group having 0 to 8 carbon atoms, a thioureido group having 1 to 8 carbon atoms, a carbamoyl group having 1 to 8 carbon atoms, an alkylthio group having 1 to 5 carbon atoms (eg, a methylthio group), an arylthio group having 6 to 12 carbon atoms Groups (eg phenylthio groups,
A heterocyclic thio group (for example, a 2-benzothiazolylthio group),
Examples thereof include carboxylic acid groups, sulfonic acid groups, and salts thereof.

The above ureido group, thioureido group, sulfamoyl group, carbamoyl group and amino group each include unsubstituted, N-alkyl-substituted and N-aryl-substituted ones. Examples of the aryl group include a phenyl group and a substituted phenyl group. Examples of the substituent include the substituents described as preferable examples of R ₁ , R ₂ and V described above. The alkali metal atoms represented by X ₂₁ and X ₂₂ 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 ₄₃ and L ₄₄ include the following linking groups or a combination thereof.

[0087]

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R ₅₁ , R ₅₂ , R ₅₃ , R ₅₄ , R ₅₅ , R ₅₆ , R
₅₇ , R ₅₈ , R ₅₉ and R _{60 each} represent a hydrogen atom, an aliphatic group (preferably substituted or unsubstituted one having 1 to 4 carbon atoms, for example, methyl group, ethyl group, n-butyl group, methoxyethyl Group, hydroxyethyl group, allyl group) or aralkyl group (preferably substituted or unsubstituted C 7 -C 12)
Benzyl group, phenethyl group, phenylpropyl group).

R ₄₅ and R ₄₈ are preferably the same as those described above for R ₄₄ . Preferably as Z ₂₇ ,
Thiazoliums such as 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 {eg oxazolium, 4-
Methyl oxazolium, benzoxazolium, 5-chlorobenzoxazolium, 5-phenylbenzoxazolium, 5-methylbenzoxazolium, naphtho [1,2-d] oxazolium, imidazoliums, for example 1-methylbenzimidazolium, 1-propyl-5-chlorobenzimidazolium, 1-ethyl-
5,6-cyclobenzimidazolium, 1-allyl-
5-trifluoromethyl-6-chloro-benzimidazolium), selenazoliums {e.g., benzoselenazolium, 5-chlorobenzoselenazolium, 5-methylbenzoselenazolium, 5-methoxybenzoselenazolium, naphtho [ 1,2-d] selenazolium} and the like. Particularly preferably, thiazoliums (for example, benzothiazolium, 5-chlorobenzoxazolium, 5
-Methoxybenzothiazolium, naphtho [1,2-d]
Thiazolium).

R ₄₆ and R ₄₇ are preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 18 carbon atoms (eg, methyl, ethyl, propyl, butyl, pentyl, octyl,
Decyl, dodecyl, octadecyl) or a substituted alkyl group as a substituent, for example, a vinyl group, a carboxy group,
Sulfo group, cyano group, halogen atom (for example, fluorine, chlorine, bromine), hydroxy group, alkoxycarbonyl group having 2 to 8 carbon atoms (for example, methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl), carbon number 1 to 8 alkoxy groups (for example, methoxy, ethoxy, benzyloxy, phenethyloxy), C1 to C10 monocyclic aryloxy groups (for example, phenoxy, p-tolyloxy), and C1 to C1
3 acyloxy groups (eg, acetyloxy, propionyloxy), 1-8 carbon acyl groups (eg, acetyl, propionyl, benzoyl, mesyl), 1 carbon atoms
8 carbamoyl groups (e.g., carpamoyl, N, N-dimethylcarpamoyl, morpholinocarpamoyl, piperidinocarpamoyl), and sulfamoyl groups having 0 to 8 carbon atoms (e.g., sulfamoyl, N, N-dimethylsulfamoyl, morpholinosulfonyl) , Piperidinosulfonyl), an aryl group having 10 or less carbon atoms (eg, phenyl,
4-chlorophenyl, 4-methylphenyl, α-naphthyl), a substituted or unsubstituted alkenyl group (eg, an allyl group)}. However, R ₄₆ is not a hydrogen atom. More preferably, R ₄₆ is an unsubstituted alkyl group (eg, methyl, ethyl) or alkenyl group (eg, allyl group), and R ₄₇ is a hydrogen atom and an unsubstituted lower alkyl group (eg, methyl, ethyl).

When M ₂₁ m ₂₁ is necessary to neutralize the ionic charge of the hydrazone compound represented by the general formula (II), it is necessary to represent the presence or absence of a cation or an anion in the formula. Included in 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, a fluoride ion, Chlorine ion, bromine ion, iodine ion, substituted arylsulfonate ion (for example, p-toluenesulfonate ion, p-chlorobenzenesulfonate ion), aryldisulfonate ion (for example, 1,3-benzenesulfonate 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, trifluoromethanes Acid ion. Preferably, they are an ammonium ion, an iodine ion, a bromine ion, and a p-toluenesulfonic acid ion.

The hydrazone compound of the present invention has the general formula (XI)
Has at least one adsorbing group to silver halide represented by (XV). The substitution position is R ₃₁ ,
_R32 , _R33 , _R34 , _R35 , _R36 , _R44 , _R45 , _R46 , R
₄₇ , Y ₂₁ , L ₄₃ and Z ₂₇ . Particularly preferred is the case of R ₄₄ of the general formula (XIII).

Hyd ₂ has the same meaning as Hyd ₁ . k _1b
And k _3b is preferably 1 or 2, and K _3b is preferably 1 or 2. More preferably k
_1b is 1, k _2b is 1 and k _3b is 1. Q ₂ has the same meaning as Q ₁ and is preferably the same.

A particularly preferred compound of the present invention is a compound of the general formula (XV
It is represented by I). General formula (XVI)

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In the formula, Q _x has the same meaning as Q ₂ . R ₇₁ and R ₇₅ each represent a monovalent substituent. R ₇₃ and R ₇₄ each represent a hydrogen atom or a monovalent substituent. R ₇₂ , R ₇₆ and R ₇₇ each represent an aliphatic group. n ₁ and n ₄ are each an integer from 0 to 4, n ₂ is 0 or 1, n ₃ is an integer of 1-6.

Q _x is preferably the same as Q ₂ , more preferably a ureido group, an ester group or an amide group. R ₇₁ and R ₇₅ are preferably the same as V ₁ .
R ₇₃ and R ₇₄ are preferably the same as R _41, and particularly preferably a hydrogen atom. R ₇₂ , R ₇₆ and R ₇₇ represent R
_{The same as} the aliphatic group for ₁ and R ₂ are preferable, and an unsubstituted alkyl group having 1 to 4 carbon atoms (eg, methyl and ethyl) is particularly preferable. n ₂ is preferably 1. n ₃ is preferably 2 to 4. When n _1, n ₂ Contact <br/> preliminary n ₄ is 2 or _{more, R 71, C (R 73} ) (R 74) and R ₇₅ theories returned but need not be the same.

Next, typical examples of the compound of the present invention will be given, but it should not be construed that the invention is limited thereto.

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The MET of the general formula (I) used in the present invention
The structure is described by FM Hamer, "Heterocyclic Compounds-Heterocyclic Compounds-Cyanine Soybeans and Related Compounds.
nds-Cyanine Dyes and Related Compounds (John Willie and Sons, John & Sons, New York, London, 1964). , DMSturmer, "Heterocyclic Compounds-Special Topics in Heterocyclic Compounds-
Special topics in heterocyclic 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 Compounds) ”, (2nd.Ed.vol.I
V, part B, 1977), Chapter 15, Chapters 369-42
2nd page; (2nd. Ed. Vol. IV, part B, 1985), 1st.
Chapter 5, pages 267-296, Elsvier Science Public Company, Inc.
e Publishing Company Inc.), New York, and the like.

The hydrazone structure represented by the general formula (III) can be easily produced by a known method. That is, hydrazines, aldehydes, or ketones can be obtained by adding a small amount of an acid (for example, acetic acid or hydrochloric acid) as a condensing agent, if necessary, and condensing it. The specific method is described in JP-B-60-34099 and JP-B-60-34100.

The Het of the general formula (II) used in the present invention
The structure is described in U.S. Pat. No. 3,266,897, Belgian Patent No. 671,402, and JP-A-60-138548.
JP-A-59-68732, JP-A-59-1238
No. 38, JP-B-58-9939, and JP-A-59-137.
No. 951, JP-A-57-202531, JP-A-57-20253
164,734, JP-A-57-14836, JP-A-5-14836
No. 7-116340, U.S. Pat. No. 4,418,140
JP-A-58-95728, JP-A-55-7943.
No. 6, OLS 2, 205, 029, OLS 1, 96
2,605, JP-A-55-59463, JP-B-48
No.-18257, JP-B-53-28084, JP-A-5-1982
3-48723, JP-B-59-52414, JP-A-58-217929, JP-B-49-8334, U.S. Pat. No. 3,598,602, U.S. Pat.
9, UK Patent No. 965,047, Belgian Patent No. 7
No. 37809, U.S. Pat. No. 3,622,340, JP-A-60-87322, JP-A-57-211142,
JP-A-58-158631, JP-A-59-15240
No. 3,671,255, Japanese Patent Publication No. 48-34.
No. 166, JP-B-48-322112, and JP-A-58-1982.
No. 221839, JP-B-48-32367, JP-A-6-82
No. 0-130731, JP-A-60-122936, JP-A-60-117240, U.S. Pat. No. 3,228,77.
0, JP-B-43-13496, JP-B-43-102
No. 56, JP-B-47-8725, JP-B-47-302
06, JP-B-47-4417, JP-B-51-253
No. 40, British Patent 1,165,075, U.S. Pat.
No. 512,982, U.S. Pat. No. 1,472,845, JP-B-39-22067, JP-B-39-22068,
U.S. Pat. No. 3,148,067, U.S. Pat.
No. 901; U.S. Pat. No. 3,909,268;
No. 40665, Japanese Patent Publication No. 39-2829, U.S. Pat. No. 3,148,066, Japanese Patent Publication No. 45-22190, U.S. Pat. No. 1,399,449, British Patent 1,287,2
No. 84, U.S. Pat. No. 3,900,321, U.S. Pat.
655,391; U.S. Pat. No. 3,910,792; British Patent 1,064,805; U.S. Pat.
No. 36, US Pat. No. 4,003,746, British Patent 1,
No. 344,525, British Patent No. 972,211, Japanese Patent Publication No. 43-4136, U.S. Pat. No. 3,140,178, French Patent No. 2,015,456, U.S. Pat. No. 3,114,6
37, Belgian Patent 681,359, U.S. Pat.
220,839; British Patent 1,290,868; US Patent 3,137,578; US Patent 3,420,6.
No. 70, U.S. Pat. No. 2,759,908, U.S. Pat.
622,340, OLS2,501,261, DA
S1,772,424, U.S. Pat. No. 3,157,509
No. 1, French Patent 1,351,234, US Patent 3,63
0,745, French Patent 2,005,204, German Patent 1,447,796, US Patent 3,915,710
No. JP-B-49-8334, British Patent 1,021,1
No. 99, UK Patent 919,061, Japanese Patent Publication No. 46-17
No. 513, U.S. Pat. No. 3,202,512, OLS2.
553,127, JP-A-50-104927, French Patent 1,467,510, U.S. Pat.
No. 6, US Pat. No. 3,503,936, US Pat.
No. 76,638, French patent 2,093,209, British patent 1,246,311, U.S. Pat.
No. 8, US Pat. No. 3,535,115, British Patent 1,1
No. 61,264, U.S. Pat. No. 3,841,878, U.S. Pat. No. 3,615,616, JP-A-48-39039.
No., UK Patent 1,249,077, JP-B-48-34
No. 166, US Pat. No. 3,671,255, British Patent 1
No. 459160, JP-A-50-6323, British Patent 1,402,819, OLS 2,031,314,
Research Disclosure 13651, U.S. Pat. No. 3,910,791, U.S. Pat. No. 3,954,478
No. 3,813,249; British Patent 1,38
7,654, JP-A-57-135945, JP-A-5-135
7-96331, JP-A-57-22234, JP-A-59-26731, OLS 2,217,153, British Patent 1,394,371, British Patent 1,308,7
77, British Patent 1,389,089, British Patent 1,
No. 347,544, German Patent 1,107,508, U.S. Pat. No. 3,386,831, British Patent 1,129,6
No. 23, JP-A-49-14120, JP-B-46-34
675, JP-A-50-43923, U.S. Pat.
42,481; British Patent 1,269,268; U.S. Patent 3,128,185; U.S. Patent 3,295,98.
No. 1, US Pat. No. 3,396,023, US Pat.
No. 95,827, JP-B-48-38418, JP-A-Showa 4
8-47335, JP-A-50-87028, U.S. Pat. No. 3,236,652, U.S. Pat. No. 3,443,951
No., UK Patent 1,065,669, US Patent 3,31
2,552, U.S. Patent 3,310,405, U.S. Patent 3,300,312, British Patent 952,162,
UK Patent 952,162, UK Patent 948,442
No., JP-A-49-120628, JP-B-48-353
No. 72, JP-B-47-5315, JP-B-39-187
06, JP-B-43-4941, JP-A-59-345
No. 30, etc., and can be synthesized with reference to these.

Further, (MET) and ( Q ₁ ) _k2a − ( Hy
For the bond formation reaction including the amide bond formation reaction and the ester bond formation reaction between ( d ₁ ) and (Het) and the (Q ₂ ) _K 2b- ( Hyd ₂ ) moiety, a method known in organic chemistry may be used. it can. That method of synthesizing MET or Het and Hyd _{1, 2} method in which linking, M ET or Het synthetic materials and MET or Het intermediates from ligate the Hyd _{1, 2} of, Hyd conversely
Any method such as a method of synthesizing Hyd _1,2 after linking the synthesis raw materials and intermediates of ₁ , ₂ to the MET or Het portion may be used, and the method may be appropriately selected and synthesized. For the synthesis reaction for these linkages, for example,
New Laboratory Chemistry Course 14, Synthesis and Reaction of Organic Compounds, IV
Maki, Maruzen, Tokyo (1977), Yoshiro Ogata, Organic Reaction Theory, Maruzen, Tokyo (1962) LFFieser and M. Fiese
r, Advanced Organic Chemistry, Maruzen, Tokyo (1962)
Year)) can be referred to in many organic synthesis reactions.

The hydrazone compound represented by the general formula (I) or (II), if advantageous in synthesis and storage,
No problem if isolated as a salt. In such a case, any compound may be used as long as it can form a salt with the hydrazone, but preferred salts include the following. For example, aryl sulfonates having 6 to 16 carbon atoms (e.g., p-toluene sulfonate, p-chlorobenzene sulfonate), aryl disulfonates having 6 to 16 carbon atoms (e.g., 1,3-benzenedisulfonate,
1,5-naphthalenedisulfonic acid salt, 2,6-naphthalenedisulfonic acid salt), thiocyanate, picrate,
Carboxylate (eg, oxalate, acetate, benzoate, hydrogen oxalate), halogenate (eg, hydrochloride, hydrofluoride, hydrobromide, hydroiodide) , Sulfate, perchlorate, tetrafluoroborate,
Sulfites, nitrates, phosphates, carbonates, bicarbonates. Preferred are hydrogen oxalate, oxalate and hydrochloride. Specifically, the results are shown in Synthesis Examples 1 to 3.

The compounds represented by formulas (I) and (II) of the present invention may be used alone, but it is more preferable to use them together with another spectral sensitizing dye. As these dyes, cyanine dyes have a structure represented by the general formula (IV),
(Q ₁ ) _k2a- (Hyd ₁ ) unsubstituted dye {, merocyanine dye} having a structure represented by general formula (V),
(Q ₁ ) _k2a- (Hyd ₁ ) unsubstituted dye {, rhodacyanine dye} having a structure represented by general formula (VI),
_{1) k2a} - (Hyd ₁₎ dye which is not substituted}, having the structure shown in allopolar dye {general formula (VII), (Q _1)
k2a - dye (Hyd ₁₎ is not substituted}, is preferably used. In addition, a hemicyanine dye, an oxonol dye, a hemioxonol dye, a styryl dye, and the like are used.

Most preferably, the (Q ₁ ) _k2a- (Hd ₁ ) -substituted allopolar dye represented by the general formula (VII) has the structure shown by the general formula (IV) and (Q ₁ ) _k2a- (H
In this case, a thiacarbocyanine dye not substituted with yd ₁ ) is used in combination. In the present invention, it is preferable to use a spectral sensitizing dye. For example, any dyes such as conventionally known cyanine dyes, merocyanine dyes, rhodacyanine dyes, oxonol dyes, hemicyanine dyes, benzylidene dyes, xanthene dyes, and styryl dyes can be used. For example, TH James, "The Theort of the Photograph Process"
ic Procrss) "(3rd edition) pp. 198-228 (196
6 years) and dyes described in Macmillan. More preferably, general formulas (XI) and (XI) described in JP-A-5-216152 are preferred.
The dyes represented by I), (XIII) and (XIV), and the dyes described as specific examples are particularly preferred.

The hydrazone compound of the present invention (general formula (I)
Or (II)) and the sensitizing dye used in the present invention may be contained in the silver halide emulsion of the present invention by dispersing them directly in the emulsion or by adding 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,
It may be added to the emulsion by dissolving it in a solvent such as N, N-dimethylformamide alone or in a mixed solvent. Further, as described in US Pat. No. 3,469,987, a dye or the like is dissolved in a volatile organic solvent, the solution is dispersed in water or a hydrophilic colloid, and this dispersion is added to an emulsion. As described in JP-B-46-24,185, a method of dispersing a water-insoluble dye or the like in a water-soluble solvent without dissolving it, and adding this dispersion to an emulsion. No. 23,389, JP-B-44-27,555
No., JP-B-57-22091, etc., the dye is dissolved in an acid and the solution is added to the emulsion, or the solution is added to the emulsion as an aqueous solution in the presence of an acid or a base. As described in U.S. Pat. No. 3,822,135 and U.S. Pat. No. 4,006,026, a method of adding an aqueous solution or a colloidal dispersion in the presence of a surfactant to an emulsion, JP-A-53-1022.7
No. 33, JP-A-58-105,141, a method of directly dispersing a dye or the like in a hydrophilic colloid and adding the dispersion to an emulsion;
As described in No. 24, a method of dissolving a dye using a compound to be redox and adding the solution to an emulsion can also be used. Also, ultrasonic waves can be used for dissolution.

The sensitizing dye used in the present invention or the hydrazone compound of the present invention is added to the silver halide emulsion of the present invention at any time during the preparation of the emulsion which has been recognized to be useful. You may. For example, US Pat. No. 2,735,766, US Pat. No. 3,628,960
No. 4,183,756, U.S. Pat.
No. 5,666, JP-A-58-184142, JP-A-60-196,749 and the like. Timing, during the desalting step and / or after desalting and before the start of chemical ripening, as disclosed in the specification of JP-A-58-113,920, etc., immediately before or during the process of chemical ripening. At any time before the application of the emulsion after the chemical ripening and before the coating. U.S. Pat. No. 4,225,666;
As disclosed in the specification of US Pat. No. 7,629 or the like, the same compound may be used alone or in combination with a compound having a different structure, for example, during the particle formation step and during the chemical ripening step or after the completion of the chemical ripening. The compound may be added separately before or after chemical ripening or during the process and after completion, or may be added by changing the kind of compound to be added and the combination of compounds.

As the amount of the sensitizing dye used in the present invention,
Depends on the shape and size of the silver halide grains,
Preferably, 4 × 10 4 mol per mol of silver halide^-8~ 8
× 10 ^-2It can be used in moles. The hydrazo of the present invention
The timing of the addition of the sensitizing compound is before or after the sensitizing dye.
And preferably 1 × 10 5 per mole of silver halide.^-9~
5 × 10^-1Mol, more preferably 1 × 10^-8~ 2 × 1
0^-2It is contained in the silver halide emulsion in a molar ratio. Sensitization
Ratio of dye and hydrazone compound of the present invention (molar ratio)
Can be any value, but the sensitizing dye / hydrazone compound
Object = 1000/1 to 1/1000 range is advantageously used, especially 10
A range from 0/1 to 1/10 is advantageously used.

In addition to the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. For example, aminostil compounds substituted with a nitrogen-containing heterocyclic group (for example, US Pat. Nos. 2,933,390 and 3,933)
635,721), formaldehyde condensates of aromatic organic acids (for example, US Pat. No. 3,743,51).
0), cadmium salts, azaindene compounds and the like. US Patent 3,615,613
Nos. 3,615,641 and 3,617,295
No. 3,635,721 are particularly useful.

The process for producing a silver halide emulsion is roughly divided into processes such as grain formation, desalting and chemical sensitization. Particle formation is divided into nucleation, ripening and growth. These steps are not performed uniformly, but the order of the steps is reversed or the steps are repeatedly performed. Performing the reduction sensitization during the production process of the silver halide emulsion basically means that it can be performed in any process. Reduction sensitization may be performed during nucleation or physical ripening, which is the initial stage of grain formation, during growth, or may be performed prior to chemical sensitization other than reduction sensitization or after this chemical sensitization. . When performing chemical sensitization in combination with gold sensitization, reduction sensitization is preferably performed prior to chemical sensitization so as not to cause undesirable fog. Most preferred is a method of reduction sensitization during growth of silver halide grains. Here, growing is also referred to as a method of performing reduction sensitization while silver halide grains are growing by physical ripening or addition of a water-soluble silver salt and a water-soluble alkali halide. The method also includes a method of further growing after subjecting to reduction sensitization in a heated state.

The reduction sensitization of the present invention is a method in which a known reducing agent is added to a silver halide emulsion, or a pAg called silver ripening.
Either a method of growing or ripening in a low pAg atmosphere of 1 to 7 or a method of growing or ripening in a high pH atmosphere of pH 8 to 11 called high pH ripening can be selected. Further, two or more methods can be used in combination.

The method of adding a reduction sensitizer is a preferable method because the level of reduction sensitization can be finely adjusted.

As reduction sensitizers, stannous salts, amine and polyamic acids, hydrazine derivatives, formamidinesulfinic acid, silane compounds, borane compounds and the like are known. In the present invention, these known compounds can be selected and used, or two or more compounds can be used in combination. Stannous chloride, thiourea dioxide, and dimethylamine borane are preferred compounds as reduction sensitizers. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but 10 ^-7 to 10 ^-3 per mol of silver halide.
A molar range is appropriate.

Ascorbic acid and its derivatives can also be used as the reduction sensitizer of the present invention.

Ascorbic acid and its derivatives (hereinafter referred to as
It is called "ascorbic acid compound". The following can be mentioned as specific examples of ()). (A-1) L-ascorbic acid (A-2) Sodium L-ascorbate (A-3) Potassium L-ascorbate (A-4) DL-ascorbic acid (A-5) D-sodium ascorbate (A -6) L-ascorbic acid-6-acetate (A-7) L-ascorbic acid-6-palmitate (A-8) L-ascorbic acid-6-benzoate (A-9) L-ascorbic acid-5,6 -Diacetate (A-10) L-ascorbic acid-5,6-O-isopropylidene The ascorbic acid compound used in the present invention is used in a larger amount as compared with the amount in which a reduction sensitizer is conventionally preferably used. It is desirable. For example, JP-B-57-33572
No. "The amount of reducing agent is usually 0.75 × g per silver ion.
Does not exceed 10 ^-2 meq (8 × 10 ^-4 mol / AgX mol). An amount of 0.1 to 10 mg per kg of silver nitrate (10 ^-7 to 10 ^-5 mol / AgX mol ascorbic acid) is often effective. (The converted value is based on the inventors). U.S. Pat. No. 2,487,850 states that "the addition amount of a tin compound as a reduction sensitizer is 1
describes a x × 10 ^-7 ~44 × 10 ^-6 mol ". JP-A-57-179835 discloses that the amount of thiourea dioxide added is about 0.01 mg to about 2 mg per mole of silver halide.
It is stated that from about 0.01 mg to about 3 mg of stannous chloride is suitable. Ascorbic acid compound used in the present invention the particle size of the emulsion, the halogen composition, the temperature of emulsion preparation, pH, depends preferably amount by factors such as pAg, per mole of silver halide 5 × 10 ^-5 ~
It is desirable to select from the range of 1 × 10 ^-1 mol. More preferably, it is preferably selected from the range of 5 × 10 ⁻⁴ mol to 1 × 10 ⁻² mol. It is particularly preferable to select from a range of 1 × 10 ⁻³ mol to 1 × 10 ⁻² mol.

The reduction sensitizer is dissolved in water or a solvent such as alcohols, glycols, ketones, esters and amides, and can be added during grain formation, before or after chemical sensitization. The compound may be added at any stage of the emulsion production process, but a particularly preferable method is to add the compound during grain growth. It may be added to the reaction vessel in advance, but it is more preferable to add it at an appropriate time during particle formation. Alternatively, a reduction sensitizer may be added in advance to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide, and particles may be formed using these aqueous solutions. It is also a preferable method to add the solution of the reduction sensitizer in several portions as the grains are formed, or to add the solution continuously for a long time.

It is preferable to use an oxidizing agent for silver during the production process of the emulsion of the present invention. The oxidizing agent for silver refers to a compound having an action of converting metallic silver into silver ions. In particular, a compound that converts extremely fine silver grains by-produced in the course of silver halide grain formation and chemical sensitization into silver ions is effective. The silver ions generated here may form a silver salt which is hardly soluble in water such as silver halide, silver sulfide or silver selenide, or may form a silver salt which is easily soluble in water such as silver nitrate. Is also good. The oxidizing agent for silver may be inorganic or organic. Examples of the inorganic oxidizing agent include ozone, hydrogen peroxide and adducts thereof (eg, NaBO ₂ .H ₂ O ₂ .3H ₂ O, 2NaCO
_{3 · 3H 2 O 2, Na} 4 P 2 O 7 · 2H 2 O 2, 2Na 2 SO 4
.H ₂ O ₂ .2H ₂ O), peroxyacid salt (for example, K ₂ S)
₂ O ₈ , K ₂ C ₂ O ₆ , K ₂ P ₂ O ₈ ), peroxy complex compounds (for example, K ₂ [Ti (O ₂ ) C ₂ O ₄ ] .3H ₂ O, 4K ₂ S
O ₄ .Ti (O ₂ ) OH.SO ₄ .SO ₄ .2H ₂ O, Na ₃
[VO (O ₂ ) (C ₂ H ₄ ) ₂ .6H ₂ O), permanganate (eg, KMnO ₄ ), colomate (eg, K ₂ Cr ₂₎
Oxygen salts such as O ₇ ), halogen elements such as iodine and bromine,
Perhalates (eg, potassium periodate), high valent metal salts (eg, potassium hexacyanoferrate) and thiosulfonates. Examples of the organic oxidizing agent include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (for example, N-bromosuccinimide, chloramine T, chloramine B). Etc.) are given as examples.

Preferred oxidizing agents of the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, inorganic oxides of thiosiphonates and organic oxidants of quinones. It is a preferred embodiment to use the above-described reduction sensitization and an oxidizing agent for silver in combination. A method of performing reduction sensitization after using an oxidizing agent,
The method can be selected from the reverse method or a method in which both coexist at the same time. These methods can be selectively used in both the grain formation step and the chemical sensitization step. The silver halide photographic material of the present invention preferably contains at least one compound selected from the compounds represented by the following formulas (XX), (XXI) or (XXII). Formula (XX) R ₁₀₁ SO ₂ S-M ₁₀₁ Formula (XXI) R ₁₀₁ SO ₂ S-R ₁₀₂ Formula (XXII) R ₁₀₁ SO ₂ S- (E) _a -SSO ₂ -R ₁₀₃ R _101, R _102, R ₁₀₃ represents an aliphatic group, an aromatic group or <br/> other represents a heterocyclic group, M ₁₀₁ represents a cation, E is 2
A represents 0 or 1;

The compounds of the general formulas (XX), (XXI) and (XXII) will be described in more detail. R ₁₀₁ , R ₁₀₂ and R
_{When 103} is an aliphatic group, it preferably has 1 to 22 carbon atoms.
An alkenyl group having 2 to 22 carbon atoms, or an alkynyl group, which may have a substituent. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, isopropyl, and t-butyl.

Examples of the alkenyl group include allyl and butenyl.

Examples of the alkynyl group include, for example, propargyl and butynyl.

The aromatic group represented by R ₁₀₁ , R ₁₀₂ and R ₁₀₃ preferably has 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. These may be substituted.

The heterocyclic group represented by R ₁₀₁ , R ₁₀₂ and R ₁₀₃ is a 3- to 15-membered ring having at least one element selected from nitrogen, oxygen, sulfur, selenium and tellurium. In, for example, a pyrrolidine ring, a piperidine ring, a pyridine ring,
Tetrahydrofuran, thiophene, oxazole, thiazole, imidazole, benzothiazole, benzoxazole, benzimidazole, selenazole, benzoselenazole, tellurazole, triazole, benzotriazole, tetrazole, oxazi An azole ring and a thiadiazole ring are exemplified.

Examples of the substituent for R ₁₀₁ , R ₁₀₂ and R ₁₀₃ include an alkyl group (eg, methyl, ethyl, hexyl) and an alkoxy group (eg, methoxy, ethoxy,
Octyloxy), aryl groups (phenyl, naphthyl,
Tolyl), hydroxy group, halogen atom (eg, fluorine, chlorine, bromine, iodine), aryloxy group (eg, phenoxy), alkylthio group (eg, methylthio, butylthio), arylthio group (eg, phenylthio), acyl group (eg, acetyl, propionyl, Butyryl, valeryl), a sulfonyl group (eg, methylsulfonyl, phenylsulfonyl), an acylamino group (eg, acetylamino, benzamino), a sulfonylamino acid (eg, methanesulfonylamino, benzenesulfonylamino),
Examples include acyloxy groups (eg, acetoxy, benzoxy), carboxyl groups, cyano groups, sulfo groups, amino groups, and the like.

E is preferably a divalent aliphatic group or a divalent aromatic group. Examples of the divalent aliphatic group of E include-(CH ₂ ) _n- (n = 1 to 12) and -CH ₂ -CH
= CH-CH ₂ -,

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Xylylene groups and the like. Examples of the divalent aromatic group of E include phenylene and naphthylene. These substituents may be further substituted with substituents such as V ₁ ~V ₄ described so far.

M ₁₀₁ is preferably a metal ion or an organic cation. Examples of the metal ion include a lithium ion, a sodium ion, and a potassium ion. Examples of the organic cation include an ammonium ion (for example, ammonium, tetramethylammonium, tetrabutylammonium), a phosphonium ion (tetraphenylphosphonium), and a guanidine group.

Specific examples of the compound represented by the general formula (XX), (XXI) or (XXII) will be given below, but it should not be construed that the invention is limited thereto.

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The compound of the formula (XX) is disclosed in JP-A-54-1.
019 and British Patent 972,211. The compound represented by formula (XX), (XXI) or (XXII) is preferably added in an amount of 10 ^-7 to 10 ^-1 mol per mol of silver halide. Further, the addition amount is preferably from 10 ^-6 to 10 ^-2 , particularly preferably from 10 ^-5 to 10 ^-3 mol.

The compound represented by the general formula (XX), (XXI) or (XXII) can be added during the production process by a method usually used for adding an additive to a photographic emulsion. For example, a water-soluble compound is an aqueous solution having an appropriate concentration, and a compound insoluble or hardly soluble in water is a suitable organic solvent miscible with water, for example, alcohols, glycols, ketones, esters, amides and the like. At home,
It can be dissolved in a solvent that does not adversely affect photographic properties and added as a solution.

The compound represented by the general formula (XX), (XXI) or (XXII) is used during the grain formation of the silver halide emulsion.
It may be added at any stage during production before or after chemical sensitization. Preferred is a method in which a compound is added before or during reduction sensitization.
Particularly preferred is a method of adding during grain growth.

Although it is possible to add it to the reaction vessel in advance, it is preferable to add it at an appropriate time during the formation of particles. In addition, an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide is added to the compound of the general formula (XX), (XXI) or (XXII) in advance.
May be added, and particles may be formed using these aqueous solutions. The general formula (XX),
It is also preferable to add the solution of the compound (XXI) or (XXII) in several portions or to add it continuously for a long time.

Among the compounds represented by formula (XX), (XXI) or (XXII), the most preferred compound for the present invention is a compound represented by formula (XX).

The emulsion of the present invention preferably has an aspect ratio of 3 or more, more preferably an average aspect ratio of 3 or more.
Less than tabular silver halide grains. Here, the tabular grains are a general term for grains having one twin plane or two or more parallel twin planes. The twin plane is (111) in this case.
This means the (111) plane when ions at all lattice points on both sides of the plane are in a mirror image relationship. These tabular grains have a triangular, hexagonal or rounded circular shape when the grains are viewed from above. Have circular outer surfaces parallel to each other.

The aspect ratio of the tabular grains in the present invention refers to a value obtained by dividing the particle diameter by the thickness of each tabular grain having a grain diameter of 0.1 μm or more. The thickness of the particles is measured by evaporating a metal from the oblique direction of the particles together with a reference latex, measuring the length of the shadow on an electron micrograph, and calculating with reference to the shadow length of the latex. Easy.

The particle diameter in the present invention is the diameter of a circle having an area equal to the projected area of the parallel outer surface of the particle.

The projected area of a particle can be obtained by measuring the area on an electron micrograph and correcting the photographing magnification.

The diameter of the tabular grains is 0.15 to 5.
It is preferably 0 μm. The thickness of the tabular grains is preferably 0.05 to 1.0 μm.

The average aspect ratio is determined as an arithmetic mean of the aspect ratio of each of at least 100 silver halide grains. It can also be determined as the ratio of the average diameter to the average thickness of the particles.

The emulsion of the present invention contains tabular silver halide grains having an aspect ratio of 3 or more, preferably tabular silver halide grains having an average aspect ratio of 3 or more and less than 8, and preferably has a total projected area of 60 or more. % Or more is accounted for by such tabular silver halide grains.

The proportion occupied by tabular grains is preferably at least 60%, particularly preferably at least 80% of the total projected area.

Further, when monodisperse tabular grains are used, more preferable results may be obtained. The structure and production method of monodisperse tabular grains are described, for example, in JP-A-63-1516.
According to the description of No. 18, etc., the shape is briefly described as follows: 70% or more of the total projected area of the silver halide grains is the length of the side having the maximum length with respect to the length of the side having the minimum length. Is occupied by tabular silver halide having a hexagonal shape having an aspect ratio of 2 or less and having two parallel surfaces as outer surfaces, and further, a grain size distribution of the hexagonal tabular silver halide grains. (A value obtained by dividing the variation (standard deviation) of the particle size expressed by the circle-converted diameter of the projected area thereof by the average particle size) of 20% or less.

Further, the emulsion of the present invention preferably has dislocation lines. Dislocations in tabular grains are described, for example, in J. Am. F. Ha
Milton, Photo. Sci. Eng. , 11,5
7, (1967); Shiozawa, J .; So
c. Photo. Sci. Japan, 35, 213,
(1972) can be observed by a direct method using a transmission electron microscope at a low temperature. That is, the silver halide grains taken out from the emulsion so as not to apply enough pressure to generate dislocations on the grains are placed on a mesh for observation with an electron microscope, and the sample is placed so as to prevent damage (printout, etc.) by electron beams. Observation is performed by a transmission method in a cooled state. At this time, the thicker the particles, the more difficult it is for an electron beam to pass through. Therefore, a clearer image can be observed by using a high-pressure electron microscope (200 kV or more for particles having a thickness of 0.25 μm). . From the photograph of the particles obtained by such a method, the position and number of dislocations for each particle when viewed from the direction perpendicular to the main plane can be obtained.

The average number of dislocation lines is 10 or more per particle. More preferably, the average is 20 or more per particle. When dislocation lines exist in a dense manner, or when dislocation lines are observed to cross each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, approximately 10
It is possible to count as many as 20 or 30, and it is clearly distinguishable from the case where there are only a few. The average number of dislocation lines per grain is 100
The number of dislocation lines is counted for particles or more, and the number is determined as a number average.

The dislocation lines can be introduced, for example, near the outer periphery of the tabular grains. In this case, the dislocation is almost perpendicular to the outer periphery, and a dislocation line is generated from the position of x% of the distance from the center of the tabular grain to the side (outer periphery) to the outer periphery. The value of x is preferably 10 or more and 100 or more.
Less than 30, more preferably 30 or more and less than 99,
Most preferably, it is 50 or more and less than 98. At this time, the shape formed by connecting the positions at which the dislocations start is similar to the grain shape, but may not be a perfect similar shape and may be distorted. This type of dislocation is not found in the central region of the grain. The direction of the dislocation lines is approximately (211) crystallographically, but is often meandering, and may intersect each other.

The tabular grains may have dislocation lines almost uniformly over the entire area on the outer periphery, or may have dislocation lines at local positions on the outer periphery. That is, in the case of hexagonal tabular silver halide grains as an example, dislocation lines may be limited only near six vertices, or dislocation lines may be limited only near one of the vertices. . Conversely, it is also possible that the dislocation lines are limited only to the sides excluding the vicinity of the six vertices.

Further, dislocation lines may be formed over a region including the center of the two parallel main planes of the tabular grains.
When dislocation lines are formed over the entire area of the main plane, the direction of the dislocation lines may be crystallographically approximately (211) when viewed from a direction perpendicular to the main plane. In some cases, the dislocation lines are formed randomly, and the length of each dislocation line is also random. is there. Dislocation lines are sometimes straight or meandering. They also often intersect with each other.

As described above, the position of the dislocation may be limited to the outer periphery, the main plane, or a local position.
These may be combined and formed. That is, it may exist on the outer periphery and on the main plane at the same time.

The introduction of dislocation lines on the outer periphery of tabular grains can be achieved by providing a specific high silver iodide layer inside the grains. Here, the case where the high silver iodide layer is provided discontinuously in the high silver iodide layer is included. Specifically, it is obtained by preparing a base grain, providing a high silver iodide layer, and covering the outside with a layer having a lower silver iodide content than the high silver iodide layer. The silver iodide content of the tabular grains of the base is lower than that of the high silver iodide layer, preferably 0 to 20 mol%, more preferably 0 to 15 mol%.
Mol%.

The high silver iodide layer in the grain refers to a silver halide solid solution containing silver iodide. The silver halide in this case is preferably silver iodide, silver iodobromide, or silver chloroiodobromide, but is preferably silver iodide or silver iodobromide (silver iodide content: 10 to 40 mol%). More preferred. In order to selectively allow the high silver iodide layer inside the grain (hereinafter referred to as the internal silver high iodide layer) to be present either on the side or on the corner of the base grain, the conditions for forming the base grain and the internal It can be controlled by the conditions for forming the high silver iodide layer. Conditions for forming the base silver grains include pAg (the logarithm of the reciprocal of silver ion concentration) and the presence, type, amount, and temperature of the silver halide solvent. By controlling the pAg at the time of growth of the base grains to 8.5 or less, more preferably 8 or less, the internal high silver iodide layer can be selectively present near the apex of the base grains. On the other hand, when the pAg at the time of growing the base grains is 8.5 or more, more preferably 9 or more, the internal high silver iodide layer can be present on the sides of the base grains. These pAg
Varies depending on the temperature and the presence / absence, type and amount of the silver halide solvent. As a silver halide solvent, for example, when thiocyanate is used, this pAg
Are shifted in the direction of higher values. Particularly important as the pAg during growth is the pAg at the end of growth of the base particle.
It is. On the other hand, even when the pAg during the growth does not satisfy the above value, it is possible to control the selected position of the internal silver iodide-rich layer by adjusting the pAg after the growth of the base grains and ripening. is there. At this time, ammonia, amine compounds, and thiocyanate salts are effective as silver halide solvents. The so-called conversion method can be used to form the internal silver iodide-rich layer. In this method, during the grain formation, there is a method of adding a halogen ion having a lower solubility of a salt for forming a silver ion than a halogen ion forming a grain or a vicinity of the surface of the grain at that time. In the present invention, it is preferable that the amount of halogen ions having low solubility added to the surface area of the particles at that time is not less than a certain value (related to the halogen composition). For example, during the particle formation, AgB at that time
It is preferable to add a certain amount or more of KI to the surface area of the r particles. Specifically, 8.2 × 10 ⁻⁵ mol / m ²
It is preferable to add the above iodide salts.

A more preferred method of forming an internal silver iodide-rich layer is a method in which an aqueous silver salt solution is added simultaneously with the addition of an aqueous halide salt solution containing an iodide salt.

For example, AgNO is added simultaneously with the addition of the KI aqueous solution.
₃ Add the aqueous solution by double jet. At this time, the addition start time and the addition end time of the KI aqueous solution and the AgNO ₃ aqueous solution may be shifted before and after each other. The addition molar ratio of the AgNO ₃ aqueous solution to the KI aqueous solution is preferably 0.1 or more, more preferably 0.5 or more. More preferably, it is 1 or more. The total added molar amount of the AgNO ₃ aqueous solution may be in the silver excess region with respect to the halogen ions and the added iodine ions in the system. It is preferable that the pAg at the time of adding the aqueous halide solution containing these iodide ions and the aqueous silver salt solution by double jetting decreases with the time of double jet addition. PAg before starting addition
Is preferably 6.5 or more and 13 or less. More preferably, it is 7.0 or more and 11 or less. The pAg at the end of the addition is most preferably 6.5 or more and 10.0 or less.

In carrying out the above method, it is preferable that the solubility of the mixed silver halide is as low as possible. Therefore, the temperature of the mixed system when forming a high silver iodide layer is preferably 30 ° C. or more and 70 ° C. or less, more preferably 30 ° C. or more and 5 ° C. or less.
0 ° C. or less.

Most preferably, the formation of the internal silver iodide-rich layer is fine silver iodide (fine silver iodide; the same applies hereinafter).
Alternatively, fine grain silver iodobromide, fine grain silver chloroiodide, or fine grain silver chloroiodobromide can be added. In particular, it is preferable to add fine silver iodide. These fine particles usually have a particle size of 0.01 μm or more and 0.1 μm, but fine particles having a particle size of 0.01 μm or less or 0.1 μm or more can also be used. The method for preparing these fine silver halide grains is described in Japanese Patent Application No. 63-785.
No. 1, No. 63-195778, No. 63-7852,
References to JP-A-63-7853, JP-A-63-194861, and JP-A-63-194862 can be referred to. An internal high silver iodide layer can be provided by adding and ripening these fine grain silver halides.
When the fine particles are dissolved by ripening, the above-mentioned silver halide solvent can be used. It is not necessary that all of the added fine particles dissolve and disappear immediately, and it is sufficient that the fine particles are dissolved and disappear when the final particles are completed.

The outer layer covering the inner high silver iodide layer is lower than the silver iodide content of the high silver iodide layer, and preferably has a silver iodide content of 0 to 30 mol%, more preferably 0 to 20 mol%. Mol%
Most preferably, it is 0 to 10 mol%. The position of this internal silver iodide-rich layer is measured from the center of the hexagon or the like on which the grains are projected, and is 5 mol% to 100 mol% with respect to the total silver content of the grains.
It is preferably present in a range of less than 20 mol%, more preferably less than 95 mol%, and particularly preferably more than 50 mol%.
It is preferable that the content is within a range of less than 0 mol%. The amount of silver halide forming these internal high silver iodide layers is not more than 50 mol%, more preferably not more than 20 mol% of the total silver content of the grains. These high silver iodide layers are the prescription values for the production of silver halide emulsions, not the values obtained by measuring the halogen composition of the final grains by various analytical methods. The internal silver iodide-rich layer often disappears in the final grain due to a recrystallization process or the like, and the above all relates to the production method.

Therefore, in the final grain, dislocation lines can be easily observed by the above-mentioned method, but the internal silver iodide layer introduced for introducing dislocation lines cannot be confirmed as a clear layer in many cases. For example, in some cases, the entire peripheral region of tabular grains is observed as a high silver iodide layer. X-ray diffraction, EP
MA (also known as XMA) method (a method of detecting silver halide composition by scanning silver halide grains with an electron beam), ESCA (also known as XPS) method (irradiating X-rays and exiting from the grain surface) The method can be confirmed by a combination of a method of dispersing incoming photoelectrons.

The temperature and pAg at the time of forming the outer layer covering the inner silver iodide-rich layer are arbitrary, but the preferred temperature is 30.
The temperature is not less than 80 ° C and not less than 80 ° C. Most preferably, it is 35 ° C or more and 70 ° C or less. Preferred pAg is 6.5 or more and 11.5
It is as follows. In some cases, it is preferable to use the above-mentioned silver halide solvent, and the most preferable silver halide solvent is a thiocyanate salt.

In order to introduce dislocation lines into the main surface of tabular grains, after preparing base grains, silver halochloride is deposited on the main surface, and the halochloride is converted to high silver bromide or silver iodide after conversion. A layer may be formed, and a shell may be further provided outside the layer. Examples of the silver halochloride include silver chloride or silver chlorobromide or silver chloroiodobromide having a silver chloride content of 10 mol% or more, preferably 60 mol% or more. These halo-silver chloride base grains can be deposited on the main plane by separately or simultaneously adding an aqueous solution of silver nitrate and an aqueous solution of a suitable alkali metal salt (eg, potassium chloride), or an emulsion comprising these silver salts. Can be deposited by aging with the addition of The deposition of these silver halochlorides is possible in the region of any pAg, but is most preferably between 5.0 and 9.5. In this method, tabular grains are grown mainly in the thickness direction. The amount of the silver halochloride layer is 1 mol% or more and 80 mol% or less in terms of silver mol% based on the base grains. More preferably, it is 2 mol% or more and 60 mol% or less. By converting this silver halochloride layer with an aqueous halide solution capable of forming a silver salt having lower solubility than silver halochloride, dislocation lines can be introduced on the main plane of the tabular grains. After conversion of this silver halochloride layer with, for example, an aqueous KI solution, the shell can be grown to obtain the final grains. The halogen conversion of these silver halochloride layers does not mean that all of them are replaced by silver salts having lower solubility than silver halochloride, but is preferably 5% or more, more preferably 10% or more, and most preferably 20% or more. Replace with poorly soluble silver salts. By controlling the halogen structure of the base grain on which the silver halochloride layer is provided, it is possible to introduce dislocation lines at local sites on the main plane. For example, when a base grain having an internal silver iodide-rich structure displaced in the lateral direction of the base tabular grain is used, dislocation lines can be introduced only into the main plane of the peripheral part excluding the center part of the main plane. In addition, when a base grain having an outer silver iodide-rich structure is used while being displaced in the lateral direction of the base tabular grains, dislocation lines can be introduced only into the central part of the main plane excluding the peripheral part. Furthermore, it is also possible to deposit silver halochloride only in a region having a limited area by using a local controlling substance such as iodide for the epitaxial growth of silver halochloride, and to introduce dislocation lines only in that region. The temperature at the time of silver halochloride deposition is 30 ° C. or more and 70 ° C.
° C or less is preferable, and more preferably 30 ° C or more and 50 ° C
It is as follows. It is possible to perform conversion after the deposition of the silver halochloride and then grow the shell, but it is also possible to perform the halogen conversion while growing the shell after the deposition of the silver halochloride.

The position of the internal silver halochloride layer formed substantially parallel to the main plane may be present on both sides from the center of the grain thickness in a range of 5 mol% or more and less than 100 mol% with respect to the total silver content of the grains. Preferably, it is more preferably in the range of 20 mol% or more and less than 95 mol%, particularly preferably in the range of 50 mol% or more and less than 90 mol%.

The silver iodide content of the shell is preferably from 0 to 3
0 mol%, more preferably 0 to 20 mol%. Although the temperature and pAg at the time of shell formation are arbitrary, the preferable temperature is 30 ° C. or more and 80 ° C. or less. Most preferably 35 ° C
Not less than 70 ° C. Preferred pAg is 6.5 or more and 1
1.5 or less. In some cases, it is preferable to use the above-mentioned silver halide solvent, and the most preferable silver halide solvent is a thiocyanate salt. In the final grain, the halogen-converted internal halo-silver chloride layer may not be confirmed by the above-described halogen composition analysis method depending on conditions such as the degree of the halogen conversion. However, dislocation lines can be clearly observed.

The method for introducing dislocation lines at any position on the main plane of the tabular grains and the method for introducing dislocation lines at any positions on the outer periphery of the tabular grains are appropriately combined and used. It is also possible to introduce dislocation lines.

As the silver halide emulsion that can be used in combination with the present invention, any of silver bromide, silver iodobromide, silver iodochlorobromide and silver chlorobromide may be used. Preferred silver halide is silver iodobromide containing 30 mol% or less of silver iodide, or silver iodochlorobromide.

The tabular grains of the present invention are described in "Theory and Practice of Photography" by Cleeve (Cleve, Photography).
Theory and Practice (193
0)), 131; Gaft, Photographic Science and Engineering (Gutoff, Ph.
autographic Science and En
14, 248-257 (1970); U.S. Patent Nos. 4,434,226, 4,414,310, 4,433,048, 4,439,520 and UK Patent No. 2,112,1
It can be easily prepared by the method described in No. 57 or the like.

The silver halide emulsion is usually chemically sensitized. For chemical sensitization, for example, H.I. H. Frieser, di Grundrager
Die Grundlagen, Del Photography Shen Protesse Mitt Jilberhalogeniden
der Photographischen Proz
esse mit Silverhalogenide
n) (Academiche Ferragus Gesellschakt 1)
968) pp. 675-734 can be used.

That is, compounds containing sulfur which can react with active gelatin or silver (for example, thiosulfates, thioureas,
Sulfur sensitization method using mercapto compounds, rhodanines); reduction sensitization method using reducing substances (eg, stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); noble metal compounds (eg, Noble metal sensitization using selenium compounds (selenoureas, selenoketones, selenides, etc.) using noble metal, gold complex salts, and complex salts of Group VIII metals such as Pt, Ir, and Pd. Etc. can be used alone or in combination.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. . Azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (especially nitro- or halogen-substituted);
Heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; carboxyl group and sulfone group, etc. The above heterocyclic mercapto compounds having a water-soluble group; thioketo compounds such as oxazolinethione; azaindenes such as tetraazaindenes (especially 4-hydroxy-substituted (1,3,3
a, 7) Tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acid; and many other compounds known as antifoggants or stabilizers can be added. .

The timing of adding these antifoggants or stabilizers is usually performed after chemical sensitization, but can be more preferably selected during chemical ripening or before chemical ripening. That is, in the course of silver halide emulsion grain formation, even during the addition of the silver salt solution or during the period from the addition to the start of chemical ripening, during chemical ripening (during the chemical ripening time, preferably within 50% from the start, More preferably, the time may be up to 20%).

The addition amount of the above compound used in the present invention cannot be univocally determined by the addition method or the amount of silver halide, but is preferably 10 ⁻⁷ mol to 10 ⁻² mol per mol of silver halide. , More preferably 10
^-5 to 10 ^-2 mol.

As a preservative (bound or protective colloid) of the photographic emulsion of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide,
Various kinds of synthetic hydrophilic high molecular substances such as a single or copolymer such as polyvinylimidazole and polyvinylpyrazole can be used.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin, and Bull. Soc. Sci. Pho
t. Japan. No. Enzyme-treated gelatin as described in pages 16 and 30 (1966) may be used, and a hydrolyzate or enzymatic degradation product of gelatin can also be used.
As the gelatin derivative, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinylsulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds are added to gelatin. What is obtained by reacting is used.

As the dispersion medium used in the present invention, specifically, RESEARCH
DISCLOSURE) Vol. 17643
(December 1978), section IX.

The silver halide photographic light-sensitive material of the present invention includes general-purpose, cinema color photographic materials such as color negative films, reversal films, cinema color negative films, color positive films, cinema positive films, black-and-white negative films, and microfilms. , X-ray films and the like. Preferred are general-purpose color and black-and-white photographic photosensitive materials.

When the present invention is applied to a color light-sensitive material, it is sufficient that at least one light-sensitive layer is provided on a support. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. It is. The photosensitive layer is blue light,
A unit light-sensitive layer having color sensitivity to either green light or red light. In a multilayer silver halide color photographic light-sensitive material, the arrangement of the unit light-sensitive layers is generally arranged in order from the support side to red color sensitivity. Layer, green color sensitive layer, and blue color sensitivity. However, even if the above installation order is reversed according to the purpose,
Also, the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. A non-light-sensitive layer may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer.
These may contain a coupler, a DIR compound, a color mixing inhibitor and the like described below. The plurality of silver halide emulsion layers constituting each unit photosensitive layer are DE 1,121,470 or GB
As described in US Pat. No. 923,045, it is preferred that two layers of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer are arranged so that the sensitivity gradually decreases toward the support. Also, Japanese Patent Application Laid-Open No. 57-112751
As described in JP-A Nos. 62-200350, 62-206541 and 62-206543, a low-speed emulsion layer may be provided on the side farther from the support and a high-speed emulsion layer may be provided on the side closer to the support. As specific examples, from the farthest side from the support, a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH) / a high-sensitivity green-sensitive layer (GH) / a low-sensitivity green-sensitive layer (GL) / High-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL) or BH / BL /
They can be installed in the order of GL / GH / RH / RL or BH / BL / GH / GL / RL / RH. As described in JP-B-55-34932, the layers can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Further, as described in JP-A-56-25738 and JP-A-62-63936, a blue-sensitive layer / GL / RL is selected from the side farthest from the support.
It can also be arranged in the order of / GH / RH. In addition, Tokiko 49-1
As described in 5495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is the silver halide emulsion having a lower sensitivity than the middle layer. An example is an arrangement of three layers in which the layers are arranged and the sensitivities are sequentially reduced toward the support. Even when such three layers having different sensitivities are used, as described in JP-A-59-202464, the medium-sensitive emulsion layer / high The layers may be arranged in the order of a light-sensitive emulsion layer / a light-sensitive emulsion layer. In addition, high-speed emulsion layer / low-speed emulsion layer /
Medium-speed emulsion layer or low-speed emulsion layer / medium-speed emulsion layer /
They may be arranged in the order of the high sensitivity emulsion layer. Also, 4
The arrangement may be changed as described above even in the case of more than layers. To improve color reproducibility, US 4,663,271, US 4,705,744,
No. 4,707,436, JP-A-62-160448 and JP-A-63-89850, a donor layer (CL) having a multilayer effect having a spectral sensitivity distribution different from that of a main photosensitive layer such as BL, GL, RL is used as a main photosensitive layer. It is preferable to arrange them adjacent or close to each other.

The preferred silver halide used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 30 mol% or less of silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. Silver halide grains in photographic emulsions include those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystal forms such as spheres and plates, twin planes, etc. Or a composite form thereof. Even if the grain size of silver halide is about 0.2 μm or less, the projected area diameter is about
Large-sized grains up to 10 μm may be used, and polydisperse emulsions or monodisperse emulsions may be used. Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (hereinafter abbreviated as RD) No. 17643 (December 1978), 22-23.
Page, “I. Emulsion preparation and type
s) ”and No. 18716 (November 1979), p.648, N
o.307105 (November 1989), pp.863-865, and Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P.Gl.
afkides, Chemie et Phisique Photographique, Paul M
ontel, 1967), Duffin, Photographic Emulsion Chemistry, Focal Press (GF Duffin, Photographic Emulsion C)
hemistry, Focal Press, 1966), "Manufacture and coating of photographic emulsions" by Zerikman et al., published by Focal Press (VLZel)
ikman, et al., Making and Coating Photographic Emu
lsion, Focal Press, 1964).

US 3,574,628, US 3,655,394 and GB 1,4
The monodisperse emulsion described in 13,748 is also preferred. Tabular grains having an aspect ratio of about 3 or more can also be used in the present invention. Tabular grains are described in Photographic Science and Engineering (Gutof)
f, Photographic Science and Engineering), Volume 14
248-257 (1970); US 4,434,226; 4,414,310;
It can be easily prepared by the methods described in 4,433,048, 4,439,520 and GB 2,112,157. The crystal structure may be uniform, the inside and outside may have different halogen compositions, or may have a layered structure. Silver halides having different compositions may be bonded by epitaxial bonding, or may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide. Also, a mixture of particles of various crystal forms may be used. The above emulsion is a surface latent image type in which a latent image is mainly formed on the surface,
Either an internal latent image type formed inside the grains or a type having a latent image on both the surface and the inside may be used, but a negative emulsion is required. Of the internal latent image type,
The emulsion may be a core / shell type internal latent image type emulsion described in 3-264740, and its preparation method is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion usually used is one subjected to physical ripening, chemical ripening and spectral sensitization. The additives used in such a process are RD No. 17643, RD No. 1
8716 and No. 307105, and the relevant portions are summarized in the table below. In the light-sensitive material of the present invention, two or more types of emulsions having at least one characteristic different from each other in the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the photosensitive silver halide emulsion are mixed in the same layer. Can be used. U.S. Pat.No.4,082,553.
It is preferred to apply the silver halide grains or the colloidal silver having the inside of the grains described in 214852 to the light-sensitive silver halide emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer. The term "silver halide particles having a fogged interior or surface" refers to silver halide grains that can be uniformly (non-imagewise) developed regardless of unexposed portions and exposed portions of the photosensitive material. Its preparation is described in US Pat. No. 4,626,498, JP-A-59-214852. The silver halide forming the internal nucleus of the core / shell type silver halide grain having the inside of the grain fogged may have a different halogen composition. Any of silver chloride, silver chlorobromide, silver bromoiodide and silver chloroiodobromide can be used as the silver halide having the inside or the surface of the grain fogged. The average grain size of these fogged silver halide grains is 0.01 to 0.75 μm
And particularly preferably 0.05 to 0.6 μm. The grains may be regular grains or polydisperse emulsions, but may be monodisperse (at least the weight or number of grains of silver halide grains).
95% have a particle size within ± 40% of the average particle size)
It is preferable that

In the present invention, it is preferable to use non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide as needed. Preferably, it contains 0.5 to 10 mol% of silver iodide. Fine grain silver halide has an average grain size (average value of projected area equivalent circle diameter)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. Fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. The surface of the silver halide grains does not need to be optically sensitized, and no spectral sensitization is required. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be contained in the layer containing fine silver halide grains. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

The photographic additives that can be used in the present invention are also described in RD, and the relevant portions are shown in the following table. Type of additive RD17643 RD18716 RD307105 Chemical sensitizer page 23 page 648 right column page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, pages 23-24, page 648, right column 866-868 Super sensitizer, page 649, right column 4. Brightener 24, page 647, right column, page 868 5 Light absorbers, pages 25 to 26, page 649, right column, page 873 Filters-page 650, left column Dyes, ultraviolet absorbers 6. Binders, page 26, page 651, left column, pages 873 to 874 Column 876 Lubricant 8. Coating aid, pages 26-27 650 right column 875-876 Surfactant 9. Static 27 page 650 right column 876-877 Inhibitor 10. Matting agent 878-879

Various dye-forming couplers can be used in the light-sensitive material of the present invention, and the following couplers are particularly preferable. Yellow coupler: a coupler represented by formulas (I) and (II) of EP 502,424A; a coupler represented by formulas (1) and (2) of EP 513,496A (especially Y-28 on page 18); A coupler represented by the general formula (I) according to claim 1 of US Pat. No. 5,066,576; a coupler represented by the general formula (I) in column 45 to line 55 of US Pat. No. 5,066,576; A coupler represented by I); a coupler described in claim 1 on page 40 of EP 498,381A1 (particularly D-35 on page 18);
Couplers represented by (Y) (especially Y-1 (page 17), Y-54 (41
P.)); US Pat. No. 4,476,219, column 7, lines 36-58, formulas (II)-(I
V) (especially II-17, 19 (column 17), II
-24 (column 19)). Magenta coupler; JP-A-3-39737 (L-57 (page 11, lower right), L-
68 (lower right of page 12), L-77 (lower right of page 13); [A-4] -6 of EP 456,257
3 (p. 134), [A-4] -73, -75 (p. 139); M-4, -6 in EP 486,965
(P. 26), M-7 (p. 27); M-4 of paragraph 0024 of Japanese Patent Application No. 4-234120.
5; M-1 in paragraph 0036 of Japanese Patent Application No. 4-36917; M-22 in paragraph 0237 of Japanese Patent Application Laid-Open No. 4-362631. Cyan coupler: CX-1,3,4,5,11,12,1 of JP-A-4-204843
4,15 (pages 14 to 16); JP-A-4-43345, C-7,10 (page 35), 3
4,35 (p. 37), (I-1), (I-17) (pp. 42-43);
3. The coupler represented by the general formula (Ia) or (Ib) according to claim 1. Polymer coupler: P-1, P-5 (p. 11) of JP-A-2-44345.

Examples of couplers in which the coloring dye has an appropriate diffusibility include US Pat. No. 4,366,237, GB 2,125,570, EP 96,873B,
Those described in DE 3,234,533 are preferred. Couplers for correcting unnecessary absorption of color-forming dyes are yellow colored cyan couplers represented by the formulas (CI), (CII), (CIII) and (CIV) described on page 5 of EP 456,257A1 (especially on page 84). YC-86), the EP
Yellow colored magenta coupler ExM-7 (202
), EX-1 (page 249), EX-7 (page 251), US 4,833,069
Magenta colored cyan coupler CC-9 (column
8), CC-13 (column 10), (2) of US 4,837,136 (column 8),
Preference is given to colorless masking couplers of formula (A) of claim 1 of WO 92/11575 (especially the exemplary compounds on pages 36 to 45). Examples of compounds (including couplers) that release a photographically useful compound residue by reacting with an oxidized developing agent include the following. Development inhibitor releasing compound: EP 37
Compounds represented by the formulas (I), (II), (III) and (IV) described on page 11 of 8,236A1 (especially T-101 (page 30), T-104 (page 31), T-113 ( 36
T-131 (p. 45), T-144 (p. 51), T-158 (p. 58)), EP436, 93
Compounds of formula (I) described on page 7 of 8A2 (particularly D-4
9 (p. 51)), the compound represented by the formula (1) in Japanese Patent Application No. 4-134523 (particularly, paragraph (0027) (23)), and the compounds represented by the formulas (I) and (II) described on pages 5 to 6 of EP 440,195A2 ), Compounds of the formula (III) (especially I- (1) on page 29); bleaching accelerator releasing compounds: EP 310,125 A2
Compounds represented by formulas (I) and (I ') on page 61 (especially (60) on page 61,
(61)) and a compound represented by formula (I) of claim 1 of Japanese Patent Application No. 4-325564 (particularly, paragraph (0022) (7)); a ligand releasing compound: LIG-X described in claim 1 of US Pat. No. 4,555,478. Compounds represented (especially compounds on lines 21-41 of column 12); Leuco dye releasing compounds: compounds 1-6 of columns 3-8 of US 4,749,641; Fluorescent dye releasing compounds: COUP-DYE of claim 1 of US 4,774,181. Compounds represented (particularly columns 7 to 10
Compounds of formulas (1) to (11); Development accelerator or fogging agent release compounds: compounds represented by formulas (1), (2) and (3) in column 3 of US Pat. No. 4,656,123 (especially (I-22) in column 25) and EP 450,6
ExZK-2, p. 75, lines 36-38 of 37A2; a compound which releases a group which becomes a dye only when it is cleaved: a compound represented by formula (I) in claim 1 of US Pat. No. 4,857,447 (especially, Y- 1 to
Y-19).

As the additives other than the coupler, the following are preferable. Dispersion medium for oil-soluble organic compound: JP-A-62-2
15272 P-3,5,16,19,25,30,42,49,54,55,66,81,85,86,
93 (pp. 140-144); Latex for impregnation of oil-soluble organic compound: latex described in US Pat. (Especially I-, (1), (2), (6), (12)
(Columns 4-5), US Pat. No. 4,923,787, column 5, lines 5-10 (especially compound 1 (column 3); stain inhibitor: EP
Formulas (I) to (III) on page 4, lines 30 to 33 of 298321A, especially I-47, 72,
III-1, 27 (pages 24 to 48); Anti-fading agent: A-6 of EP 298321A,
7,20,21,23,24,25,26,30,37,40,42,48,63,90,92,94,164
(Pp. 69-118), II-5-II of columns 25-38 of US 5,122,444
I-23, especially III-10, I-1 to III- on pages 8 to 12 of EP 471347A
4, especially II-2, US 5,139,931 columns 32 to 40, A-1 to 48,
In particular, A-39, 42; a material that reduces the amount of a color-enhancing agent or color-mixing inhibitor used:
Especially I-46; Formalin Scavenger: 24 of EP 477932A
SCV-1 to 28 on page 29, especially SCV-8; hardener: JP-A 1-21
4845, page 17, H-1,4,6,8,14, US 4,618,573, columns 13-
Compounds (H-1 to 54) represented by the formulas (VII) to (XII) of 23, compounds represented by the formula (6) at the lower right of page 8 of JP-A-2-214852 (H
-1 to 76), especially compounds described in claim 1 of H-14, US Pat. No. 3,325,287; development inhibitor precursors: disclosed in JP-A-62-168139.
P-24, 37, 39 (pages 6 to 7); compounds described in claim 1 of US Pat. No. 5,019,492, especially 28, 29 of column 7;
US 4,923,790, columns 3-15, I-1 to III-43, especially II-
1,9,10,18, III-25; stabilizer, antifoggant: US 4,923,
793 columns 6 to 16 I-1 to (14), especially I-1,60, (2), (13),
Compounds 1-65, especially 3 in columns 25-32 of US 4,952,483
6: Chemical sensitizer: triphenylphosphine selenide, compound 50 of JP-A-5-40324; dye: 15-1 of JP-A-3-156450
A-1 to b-20 on page 8, especially a-1,12,18,27,35,36, b-5,27 to 2
V-1 to 23 on page 9, especially FI on page 33 to 55 of V-1, EP 445627A
-1 to F-II-43, especially FI-11, F-II-8, 17 to 2 of EP 457153A
III-1 to 36 on page 8, especially III-1,3, 8 to 26 in WO 88/04794
A microcrystalline dispersion of Dye-1 to 124, compounds 1 to 22 on pages 6 to 11 of EP 319999A, in particular, compounds D-1 to 87 ( (Pages 3 to 28), US 4,2
Compounds 1 to 22 represented by the formula (I)
10), compounds (1) to (4) of the formula (I) of US Pat.
(31) (Columns 2 to 9); UV absorber: Formula of JP-A-46-3335
Compounds (18b) to (18r), 101 to 427 (6 to
9), and the compounds (3) to (6) represented by the formula (I) in EP 520938A.
6) (Pages 10 to 44) and compound HBT-1 represented by formula (III)
~ 10 (page 14), a compound represented by formula (1) in EP 521823A
(1) to (31) (columns 2 to 9).

The present invention can be applied to various color light-sensitive materials such as color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. In addition, Tokuhei 2-32615, actual fairness
It is suitable for the film unit with lens described in 3-39784. Suitable supports that can be used in the present invention are
For example, the RD. No. 17643, page 28, No. 18716
From the right column on page 647 to the left column on page 648, and 879 of No. 307105
Page. In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
μm or less is more preferable, and 16 μm or less is particularly preferable.
Further, the film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. T _1/2 is 30 minutes at 30 ° C with a color developing solution for 15 minutes.
Assuming that 90% of the maximum swelling film thickness reached after the seconds treatment is the saturated film thickness, it is defined as the time until the film thickness reaches 1/2. The film thickness means a film thickness measured under humidity control at 25 ° C. and a relative humidity of 55% (2 days), and T _1/2 is A green (A.
Green) et al. Photographic Science and
Engineering (Photogr.Sci.Eng.), Volume 19, 2,124
It can be measured by using a serometer (swelling meter) of the type described on pages 129 to 129. T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating.
The swelling ratio is preferably from 150 to 400%. The swelling ratio is
From the maximum swollen film thickness under the conditions described above, it can be calculated by the formula: (maximum swollen film thickness−film thickness) / film thickness. In the light-sensitive material of the present invention, a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm is preferably provided on the side opposite to the side having the emulsion layer. The back layer preferably contains the above-described light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surfactant. The swelling ratio of the back layer is preferably from 150 to 500%.

The light-sensitive material of the present invention can be prepared according to the RD. No. 17
No. 18716, pages 28-29, No. 18716, 651 left column to right column, and No. 307105, pages 880-881. The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution mainly containing an aromatic primary amine color developing agent. As the color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used.Typical examples and preferred examples thereof include compounds described in EP 556700A, page 28, lines 43 to 52. Is mentioned. These compounds can be used in combination of two or more depending on the purpose. Color developing solutions include alkali metal carbonates, pH buffers such as borates or phosphates, chlorides, bromides, iodides, benzimidazoles,
It generally contains a development inhibitor such as benzothiazoles or a mercapto compound or an antifoggant. Also, if necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazide, triethanolamine, various preservatives such as catecholsulfonic acid, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting Various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanedia Tetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, Ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof are added.

When the reversal process is performed, color development is usually performed after black and white development. Known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol are used alone in the black-and-white developer. Alternatively, they can be used in combination. The pH of these color developing solutions and black-and-white developing solutions is generally 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of the light-sensitive material. You can also. When the replenishment amount is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. The processing effect due to the contact between the photographic processing solution and the air in the processing tank is determined by the aperture ratio (= [the contact area
m ² ] ÷ [volume of treatment liquid cm ³ ]). This aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method for reducing the aperture ratio, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033, and JP-A-63-216050. The described slit developing method can be mentioned. The aperture ratio is preferably reduced not only in both the color development and black-and-white development steps but also in the subsequent steps, for example, in all of the steps such as bleaching, bleach-fixing, fixing, washing, stabilization, and the like. The amount of replenishment can also be reduced by using means for suppressing the accumulation of bromide ions in the developer. The time of the color development processing is usually set between 2 and 5 minutes, but by using a high temperature, a high pH, and using a high concentration of the color developing agent,
Further, the processing time can be reduced.

The photographic emulsion layer after color development is usually subjected to bleaching. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process) or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further, processing in two continuous bleach-fixing baths, fixing before bleach-fixing, or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. Examples of the bleaching agent include compounds of a polyvalent metal such as iron (III), peracids, quinones, and nitro compounds. Representative bleaching agents include organic complex salts of iron (III) such as amino diamines such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycol ether diaminetetraacetic acid. Polycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid and the like can be used. Of these, iron (III) complex salts of aminopolycarboxylic acid such as iron (III) complex salt of ethylenediaminetetraacetate and 1,3-diaminopropanetetraacetate are preferred from the viewpoint of rapid treatment and prevention of environmental pollution. . Further, the iron (III) complex salt of aminopolycarboxylic acid is particularly useful in a bleaching solution and a bleach-fixing solution. The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but the processing can be carried out at a lower pH to speed up the processing.

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
Specific examples of useful bleaching accelerators are described in the following specification: US Pat. No. 3,893,858, DE 1,290,812, JP 2,059,988, JP-A-53-32736, JP-A 53-57831, JP-A 53-37418, JP-A 53-72623. ,
53-95630, 53-95631, 53-104232, 53-12442
4, the compounds having a mercapto group or a disulfide group described in RD No. 17129 (July, 1978); thiazolidine derivatives described in JP-A-50-140129; , JP 52-20832, JP 53-32735,
Thiourea derivatives according to US 3,706,561; DE 1,127,715;
Iodide salts described in JP-A-58-16,235; DE 966,410;
Polyoxyethylene compounds described in 2,748,430; Polyamine compounds described in JP-B-45-8836;
0,943, 49-59,644, 53-94,927, 54-35,727,
Compounds described in JP-A-55-26,506 and JP-A-58-163,940; bromide ions can be used. Among them, compounds having a mercapto group or a disulfide group are preferred in view of a large accelerating effect, and particularly, US 3,893,858, DE 1,290,812, and JP-A-53-95,63.
The compounds described in 0 are preferred. Further, compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography. The bleaching solution and the bleach-fixing solution preferably contain an organic acid in addition to the above compounds for the purpose of preventing bleaching stain. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5, specifically acetic acid, propionic acid, hydroxyacetic acid and the like. Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts. Yes, especially ammonium thiosulfate can be used most widely. Also,
Thiosulfates and thiocyanates, thioether compounds,
Combinations of thioureas are also preferred. As a preservative of the fixing solution or the bleach-fixing solution, a sulfite, a bisulfite, a carbonyl bisulfite adduct or a sulfinic acid compound described in EP 294769A is preferable. Furthermore, aminopolycarboxylic acids or organic phosphonic acids are preferably added to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution. In the present invention, the fixing solution or the bleach-fixing solution contains a compound having a pKa of 6.0 to 9.0 for adjusting pH, preferably imidazoles such as imidazole, 1-methylimidazole, 1-ethylimidazole and 2-methylimidazole. It is preferable to add 0.1 to 10 mol per liter.

[0216] The total time of the desilvering step is preferably as short as possible without causing desilvering failure. Preferred time is 1 minute to 3
Minutes, more preferably 1 to 2 minutes. The processing temperature is from 25 ° C to 50 ° C, preferably from 35 ° C to 45 ° C. In a preferable temperature range, the desilvering speed is improved, and generation of stain after processing is effectively prevented. In the desilvering step, it is preferable that the stirring is strengthened as much as possible.
As a specific method of strengthening the stirring, a method of impinging a jet of a processing solution on the emulsion surface of the photosensitive material described in JP-A-62-183460, or a stirring effect using the rotating means of JP-A-62-183461 can be used. A method of increasing the stirring effect by moving the photosensitive material while bringing the emulsion surface into contact with the wiper blade provided in the solution, and making the emulsion surface turbulent, and a method of increasing the circulation flow rate of the entire processing solution. There is a method of increasing. Such a stirring improving means is effective for any of a bleaching solution, a bleach-fixing solution and a fixing solution. It is considered that improving the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and as a result, increases the desilvering speed. Further, the above-described means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator. The automatic developing machine used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257,
It is preferable to have the photosensitive material conveying means described in 60-191258 and 60-191259. As described in the above-mentioned JP-A-60-191257, such a transport means can significantly reduce the carry-in of the processing liquid from the pre-bath to the post-bath, and have a high effect of preventing the performance of the processing liquid from deteriorating. This is particularly effective in reducing the processing time and the replenishing amount of the processing solution.

The photographic material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, the material used such as a coupler), the intended use, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set widely. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal of t
he Society of MotionPicture and Television Enginee
rs Volume 64, pages 248 to 253 (May, 1955). According to the multi-stage countercurrent method described in this document, the amount of washing water can be significantly reduced, but bacteria increase due to the increase in the residence time of water in the tank, and the generated suspended matter adheres to the photosensitive material. Problem arises. As a solution to this, a method of reducing calcium ions and magnesium ions described in JP-A-62-288,838 is extremely effective. Also, isothiazolone compounds and thiabendazoles described in JP-A-57-8542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, written by Hiroshi Horiguchi, "The Chemistry of Bactericidal and Antifungal Agents"
(1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Society of Antimicrobial and Antifungal Activities, "Encyclopedia of Antimicrobial and Antifungal Agents" (1986) The bactericides described can also be used. The pH of the washing water in the processing of the light-sensitive material of the present invention is from 4 to 9, preferably from 5 to 8.
The washing temperature and washing time can also be set according to the characteristics and application of the photosensitive material. In general, a range of 20 seconds to 10 minutes at 15 to 45 ° C, preferably 30 seconds to 5 minutes at 25 to 40 ° C is selected. . Furthermore,
The light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned water washing. In such a stabilization treatment, known methods described in JP-A-57-8543, JP-A-58-14834, and JP-A-60-220345 can be applied. Further, following the water washing process, a stabilization process may be further performed. As an example, a stabilizing bath containing a dye stabilizer and a surfactant used as a final bath of a color light-sensitive material for photography may be mentioned. Can be. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine and aldehyde sulfite adducts. Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution accompanying the washing and / or replenishment of the stabilizing solution can be reused in other steps such as a desilvering step. In the processing using an automatic developing machine or the like, when each of the above processing solutions is concentrated by evaporation,
It is preferable to correct the concentration by adding water. The light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing. In order to incorporate the color developing agent, it is preferable to use a precursor of a color developing agent. For example, US 3,34
Indaniline compounds described in 2,597, 3,342,599,
Research Disclosure No.14,850 and No.15,1
Schiff base compound according to 59, aldol compound according to 13,924, metal salt complex according to US 3,719,492, JP
-135628. The light-sensitive material of the present invention may optionally contain various 1-phenyl-3-pyrazolidones for the purpose of accelerating color development. Typical compounds are described in JP-A-56-64339,
57-144547 and 58-115438. The processing solution used for processing the light-sensitive material of the present invention is used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard. it can.

There are no particular restrictions on the various additives, development methods, and the like used when the present invention is applied to black-and-white photographic materials.
Nos. 9 and 2-58041 can be preferably used.

[0220] 1. Silver halide emulsion and method for producing the same
From page 6, lower right column, line 6 to page 10, upper right column, line 12, line 2-68539. 2. Chemical sensitization method: page 10, top right column, line 13 to bottom left column, 16
Line, selenium sensitization method described in JP-A-5-11389. 3. Antifoggant / stabilizer: JP-A-2-68539, No. 10
Line 17 in the lower left column of the page to line 7 in the upper left column of the page 11, and line 2 in the lower left column of the page 3 to the lower left column of the page 4. 4. Spectral sensitizing dye: page 4, lower right column, line 4 to page 8, lower right column, and JP-A-2-58041, page 12, lower left column, line 8 to lower right column, line 19. 5. Surfactant / antistatic agent: Japanese Patent Laid-Open No. 2-68539 No. 1
Line 1 on page 1, upper left column to line 9 on page 12, upper left column and JP-A-2-5
8041, page 2, lower left column, line 14 to page 5, line 12. 6. Matting agent, plasticizer, slip agent: page 12, upper left column, line 10 to upper right column, line 10 and JP-A-2-58041, page 5, lower left column, line 13 to page 10, lower left column, line 3 Eye. 7. Hydrophilic colloid: JP-A-2-68539, page 12, upper right column, line 11 to lower left column, line 16; 8. Hardener: page 12, lower left column, line 17 to page 13, upper right column 6,
Line. 9. Developing method: same as page 15, upper left column, line 14 to lower left column 13,
Line.

The silver halide light-sensitive material of the present invention is disclosed in US Pat. No. 4,500,626 and JP-A-60-1334.
No. 49, 59-218443, 61-23805
No. 6, EP 210,660 A2 and the like.

The following is a synthesis example of the hydrazone compound of the present invention. Synthesis Example 1 Synthesis of (I-32) It was synthesized according to Scheme 1. Scheme 1

[0223]

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(1) 1.6 g (0.0032 mol), (2) 1.
3 g (0.0049 mol), 1.32 g (0.0064 mol) of DCC (dicyclohexylcarbodiimide) and 16 ml of pyridine were stirred at room temperature for 24 hours. 100 ml of ethyl acetate was added to the reaction solution, and the precipitated crystals were separated by suction filtration to obtain (3)
2.27 g was obtained (96% yield). Next, (3) 2.2 g
(4) 1.87 g (0.0045 mol), dimethylacetamide (25 ml) and triethylamine (1.5 ml, 0.04 mol)
105 mol) and stirred at an external temperature of 70 ° C. for 1 hour. Ethyl acetate (200 ml) was added to the reaction solution, and the precipitated crystals were separated by suction filtration. This crystal was subjected to silica gel column chromatography (developing solvent methanol / chloroform = 1 /
After purification in 9), recrystallization from methanol (I-
32) 70.28 g (yield = 10%, melting point = 13)
8-142 ° C., λ _max = 598 nm, ε = 1.87 × 10 ⁵
(methanol)). Synthesis Example 2 Synthesis of (I-4) and (I-2) Synthesis was performed according to Scheme 2. Scheme 2

[0225]

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A) Synthesis of (I-4) (5) 2.9 g (0.006 mol), (6) 5.5 g (0.009 mol), p-toluenesulfonic acid monohydrate 0.34 g,
11.2 g of DCC (dicyclohexylcarbodiimide)
(0.054 mol) was heated to reflux for 30 minutes. After evaporating the reaction solution under reduced pressure, the residue was purified by silica gel-column chromatography (developing solvent: methanol / chloroform = 1/4), recrystallized from isopropanol, and purified by (I-
4) 1.14 g was obtained (yield = 26%, melting point = 161-161).
163 ° C., λ _max = 492 nm (ε = 4.53 × 10 ⁴ ),
316 nm (ε = 3.23 × 10 ⁴ )). b) Synthesis of (I-2) (I-2) was obtained in the same manner as in the above a) except that (6) was changed to (8) (yield = 10%, melting point = 111).
１１６116 ° C., λ _max = 492 nm (ε = 5.14 × 1
0 ⁴ ), 314 nm (ε = 3.31 × 10 ⁴ )). Synthesis Example 3 Synthesis of (III-10) The compound was synthesized according to Scheme 3. Scheme 3

[0227]

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(7) 3 g (0.0096 mol), (2) 1.73
g (0.021 mol), 2.8 g of 2-methylimidazole (0.0105 mol)
Mol) and 30 ml of acetonitrile were heated under reflux for 1 hour. To the reaction mixture, 3 ml of triethylamine, 100 ml of chloroform and 100 ml of H ₂ O were added, and the chloroform layer was extracted with a separating funnel, dried over Na ₂ SO ₄ , and the solvent was distilled off. 20 ml of methanol, H ₂
10 ml of O and 0.8 g of concentrated hydrochloric acid were added, and the mixture was cooled to -20 ° C. The obtained crystals were separated by suction filtration to give (III-
10) 1.68 g was obtained (yield 36%, melting point = 101-101).
106 ° C).

Hereinafter, the present invention will be described in more detail by way of examples, but it is needless to say that the present invention is not limited to these examples.

Example 1 1000 ml of water, 25 g of deionized bone gelatin, 15 ml of a 50% NH ₄ NO ₃ aqueous solution and 25% NH
₃ Add 7.5 ml of aqueous solution, keep at 50 ° C, dry well,
750 ml of a 1N-AgNO ₃ aqueous solution and 5
Added at 0 minutes. The silver potential during the reaction was kept at +50 mV with respect to the saturated calomel electrode. The resulting silver bromide particles are cubic,
Monodisperse particles each having an average side length in the range of 0.75 to 0.8 μm. A copolymer of isobutene and monosodium maleate was added to the above emulsion, and the emulsion was precipitated and washed, and the emulsion was desalted, and 95 g of deionized bone gelatin was added.
And 430 ml of water, pH = 6.5 at 50 ° C., and p
After adjusting to Ag = 8.3, sodium thiosulfate was added to obtain the optimum sensitivity, and aging was performed at 55 ° C. for 50 minutes. 0.74 mol of silver bromide was contained in 1 kg of this emulsion. Further, as shown in Table 2, a sensitizing dye was added to 45 g of this emulsion, followed by the addition of the compound represented by formula (I) or (III), followed by mixing and stirring at 40 ° C. Further, 15 g of a 10% gel of deionized gelatin and 55 ml of water were added, and coated on a polyethylene terephthalate film base as follows. The amount of the coating solution was 2.5 g of silver /
m ^2, the amount of gelatin 3.8 g / m ² and set so that, sodium 0.22 g / liter dodecylbenzenesulfonate such as a gelatin amount 1.0 g / m ² in the upper layer, p- sulfo sodium styrene homopolymer 0.50 g / liter, 2,4-dichloro-6-hydroxy-1,3,5
-An aqueous solution mainly containing 3.1 g / l of sodium triazine and 50 g / l of gelatin was simultaneously applied. Each of these samples has a blue filter (395 nm).
Through a continuous wedge using a bandpass filter that transmits light from .ANG. To 440 nm and a yellow filter (a filter that transmits light longer than 560 nm) for 1 second. After the exposure, development was performed at 20 ° C. for 10 minutes using a developer having the following composition. The density of the developed film was measured using a densitometer manufactured by Fuji Photo Film Co., Ltd., and the yellow filter sensitivity (S
Y), blue filter sensitivity (SB) and fog were determined. The reference point of the optical density for which the sensitivity was determined is [fog + 0.
2]. Note that the sensitivity of the sample to which neither the sensitizing dye nor the hydrazone compound was added was 100%.
The SY was expressed as a relative value when the sensitizing dye was used as a reference, and SY was expressed as a relative value between samples to which the same sensitizing dye was added, with the sensitivity of a sample to which no hydrazone compound was added as 100. [Composition of Developer] Methol 2.5 g α-Ascorbic acid 10.0 g Potassium bromide 1.0 g Nabox 35.0 g Water added to 1.0 liter (pH 9.8) Relative values obtained Are shown in Table 1. (Comparative compound)

[0231]

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[0232]

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[0233]

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[0234]

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[0235]

[Table 1]

[0236]

[Table 2]

As is clear from the results shown in Table 1, the use of the hydrazone compound of the present invention improves dye desensitization (S _B ) and remarkably increases spectral sensitivity (Sy). . Also, fog is reduced. The improvement effect is remarkably large as compared with a conventionally known comparative compound.

Example 2 (1) Preparation of Emulsion An aqueous solution prepared by dissolving 6 g of potassium bromide and 30 g of inert gelatin having an average molecular weight of 15,000 in 3.7 l of distilled water was thoroughly mixed with 14% by a double jet method. Of potassium bromide and a 20% aqueous solution of silver nitrate were added at a constant flow rate over 1 minute at 55 ° C. and pBr 1.0 (2.4% of the total silver was consumed in this addition).

An aqueous gelatin solution (17%, 300 cc) was added, and the mixture was stirred at 55 ° C., and then a 20% aqueous silver nitrate solution was added at a constant flow rate until the pBr reached 1.4 (this addition made the total silver amount to 5.25). 0% was consumed). In addition, 20%
Potassium iodobromide solution (KBr _1-x I _x : x = 0.0
4) and a 33% aqueous silver nitrate solution were added by a double jet method over 43 minutes (this addition resulted in a total silver content of 5%).
0% was consumed). Here, after adding an aqueous solution containing 8.3 g of potassium iodide, 0.001% by weight of K ₃ I was added.
14.5 ml of an aqueous rCl ₆ solution were added and a 20% potassium bromide solution and a 33% aqueous silver nitrate solution were added by the double-bett method over a period of 39 minutes (this addition consumed 42.6% of the total silver). The amount of silver nitrate used in this emulsion was 425 g. Next, after desalting by a usual flocculation method, pAg was adjusted to 8.2 and pH 5.8 at 40 ° C. A tabular silver iodobromide emulsion having an average aspect ratio of 6.5, a coefficient of variation of 18%, and a sphere equivalent diameter of 0.8 μm (Em-
1) was prepared. Observation with a 200 kV transmission electron microscope at the temperature of liquid N ₂ revealed that an average of 50 or more dislocation lines per grain existed near the outer periphery of the tabular grains. In contrast, p
Emulsion E was prepared in exactly the same manner as Emulsion Em-1, except that after Br reached 1.4, thiourea dioxide was added to the reaction pot at a concentration of 1.2 × 10 ^-5 mol per mol of silver.
m-2 was produced. Emulsion Em-3 was prepared in exactly the same manner as Emulsion Em-2, except that the thiourea dioxide was changed to 2.5 × 10 ⁻³ mol / mol Ag of L-ascorbic acid.

When grains are formed in the same manner as in the emulsion Em-2, the emulsion Em-2 is added except that the compound XX-2 is added in an amount of 1.2 × 10 ^-4 mol per mol of silver 10 minutes after the formation of the final shell. Emulsion Em-4 was prepared in exactly the same manner.

Emulsions Em-1 to 4 thus prepared
Sensitizing dye A shown in Table 3 at 5 × 10 ⁻⁴ mol / mol Ag,
After adding sensitizing dye B at 2 × 10 ^-4 mol / mol Ag and sensitizing dye C at 2 × 10 ^-4 mol / mol Ag, sodium thiosulfate, chloroauric acid, N, N-dimethylselenourea and thiocyanate were added. Emulsions 101 to 104 were prepared by optimally sensitizing gold-selenium-sulfur using potassium acid.

[0242]

[Table 3]

To the emulsions Em-1 to Em-4, the compound (I-6) of the present invention was added in an amount of 0.5 × 10 ⁻⁴ mol / mol Ag, and the sensitizing dye C was added in an amount of 5.5 × 10 ⁻⁴ mol / mol. Emulsion 10 was prepared in the same manner as emulsions 101 to 104 except that the emulsion was reduced to Ag.
5-108 were produced. Also. Emulsion E _m-1 to 4, except that the compound of the invention (III -10) was added 0.9X10 ^-4 mol / mol Ag was prepared in the same manner as Emulsion 101-104 emulsion 109-112. The emulsion layer and the protective layer were coated on the triacetyl cellulose support provided with the undercoat layer in the coating amounts shown in Table 4 to obtain emulsions 101 to 11
Using No. 2 , samples 1001 to 1012 were produced.

[0244]

[Table 4]

Each of these samples was exposed to sensitometry for 1/100 second through a continuous wedge at a color temperature of 4800 ° K, and subjected to the following color development processing.

The developing process used here was carried out under the following conditions.
C. was performed.

[0247] * Stabilization was based on the countercurrent method from (3) to (1).

The composition of the processing liquid is shown below. (Color developing solution) Ethylene diantetraacetic acid 3.0 g 4,5-dihydroxybenzene-1,3-disulfonic acid 2-sodium salt 0.3 g potassium carbonate 30.0 g sodium chloride 5.0 g disodium-N, N-bis (sulfonateethyl ) Hydroxylamine 6.0 g 4- [N-ethyl-N- (β-hydroxylethyl) amino] -2-methylaniline sulfate 5.0 g Water was added thereto, and 1.0 liter pH (with potassium hydroxide and sulfuric acid) Preparation) 10.00

(Bleaching solution) Ferric ammonium 1,3-diaminopropanetetraacetate monohydrate 140 g 1,3-Diaminopropanetetraacetic acid 3 g Ammonium bromide 80 g Ammonium nitrate 15 g Hydroxyacetic acid 25 g Acetic acid (98%) 40 g Water was added. 1.0 liter pH (prepared with ammonia water and acetic acid) 4.3

(Fixing solution) Ethylenediaminetetraacetic acid disodium salt 15 g Ammonium sulfite 19 g Imidazole 15 g Ammonium thiosulfate (70 WT%) 280 ml Water was added to 1.0 L pH (prepared with ammonia water and acetic acid) 7.4

(Stabilizing solution) Sodium p-toluenesulfinate 0.03 g Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.2 g Disodium ethylenediamontetraacetate 0.05 g 1,2,2 4-triazole 1.3 g 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 g Water was added and 1.0 liter pH (prepared with aqueous ammonia and acetic acid) 8.5 Treatment A sample of the agent was measured for concentration with a green filter.

The obtained sensitivity and fog were evaluated.
The sensitivity was represented by the relative value of the reciprocal of the exposure amount required for increasing the optical density by 0.2 from the fog. Further, the unexposed film was stored for 3 days at a relative humidity of 30% and 60 ° C., then exposed and developed in the same manner, and then evaluated for sensitivity and fog. Table 5 shows the results thus obtained.

[0253]

[Table 5]

As can be seen from Table 5, Sample 10 of the present invention
Samples Nos. 05 to 1012 have higher feeling and less fogging and higher storage stability than the comparative sample. These effects are remarkably recognized in the sample subjected to reduction sensitization. The effect is particularly remarkable in the samples 1008 and 1012 using thiosulfonic acid.

Example 3 On an undercoated cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare a sample 101 as a multilayer color photosensitive material. (Composition of photosensitive layer) The number corresponding to each component indicates the coating amount expressed in g / m ² , and for silver halide, it indicates the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol units per mol of silver halide in the same layer. (Sample 101) First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.09 Gelatin 1.30 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 Solid Disperse Dye ExF-2 0.030 Solid Disperse Dye ExF-3 0.040 HBS-1 0.15 HBS -2 0.02 Second layer (intermediate layer) ExC-2 0.04 Polyethyl acrylate latex 0.20 Gelatin 1.04

Third layer (low-sensitivity red-sensitive emulsion layer) Emulsion A silver 0.25 Emulsion B silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-6 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium Speed Red Sensitive Emulsion Layer) Emulsion D Silver 0.70 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.015 ExC-6 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Emulsion D Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.10 ExC-3 0.045 ExC-6 0.020 ExC-7 0.010 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.050 Gelatin 1.10

Sixth layer (intermediate layer) Cpd-1 0.090 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.15 Gelatin 1.10

Seventh layer (low-sensitivity green-sensitive emulsion layer) Emulsion A silver 0.15 Emulsion B silver 0.15 Emulsion C silver 0.10 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium Speed Green Sensitive Emulsion Layer) Emulsion 101
112 Silver 1.20 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExC-8 0.010 ExM-2 0.10 ExM-3 0.025 ExY-1 0.018 ExY-4 0.010 ExY- 5 0.040 HBS-1 0.13 HBS-3 4.0 × 10 ^-3 gelatin 0.88

Ninth layer (high-sensitivity green-sensitive emulsion layer) Emulsion D Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.020 ExM-4 0.025 ExM-5 0.040 Cpd-3 0.040 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1.00

Tenth layer (yellow filter layer) Yellow colloidal silver silver 0.015 Cpd-1 0.16 solid disperse dye ExF-5 0.060 solid disperse dye ExF-6 0.060 oil-soluble dye ExF-7 0.010 HBS-1 0.60 gelatin 0.70

Eleventh layer (low-sensitivity blue-sensitive emulsion layer) Emulsion A silver 0.08 Emulsion B silver 0.07 Emulsion F silver 0.07 ExS-7 8.6 × 10 ^-4 ExC-8 7.0 × 10 ^-3 ExY-1 0.050 ExY-2 0.73 ExY-4 0.020 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.32 Gelatin 1.20

Twelfth layer (high-sensitivity blue-sensitive emulsion layer) Emulsion G Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 ExY-4 0.010 Cpd-2 0.10 Cpd-3 1.0 × 10 ^-3 HBS-1 0.070 Gelatin 0.70

Thirteenth layer (first protective layer) UV-1 0.19 UV-2 0.075 UV-3 0.065 HBS-1 5.0 × 10 ^-2 HBS-4 5.0 × 10 ^-2 Gelatin 1.2

Fourteenth layer (second protective layer) Emulsion I silver 0.10 H-1 0.40 B-1 (1.7 μm in diameter) 5.0 × 10 ^-2 B-2 (1.7 μm in diameter) 0.15 B-3 0.05 S-1 0.20 Gelatin 0.70

In order to improve the storability, processability, pressure resistance, fungicide / antibacterial properties, antistatic properties and coating properties of each layer, W-1 to W-3, B-4 to B- 6, F
-1 to F-17, and iron salts, lead salts, gold salts, platinum salts,
Contains palladium, iridium and rhodium salts.

Preparation of Dispersion of Organic Solid Disperse Dye
ExF-2 was dispersed by the following method. That is, 21.7 ml of water, 3 ml of a 5% aqueous solution of sodium p-octylphenoxyethoxyethoxyethanesulfonate and 0.5 g of a 5% aqueous solution of p-octylphenoxypolyoxyethylene ether (polymerization degree: 10) were mixed with a 700 ml pot mill. And 5.0 g of dye ExF-2 and 500 ml of zirconium oxide beads (diameter: 1 mm) were added thereto, and the contents were dispersed for 2 hours. For this dispersion, a BO type vibration ball mill manufactured by Chuo Koki was used. After the dispersion, the contents were taken out, added to 8 g of a 12.5% gelatin aqueous solution, and the beads were removed by filtration to obtain a dye dispersion of gelatin. The average particle size of the fine dye particles was 0.44 μm.

In the same manner, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameter of the fine dye particles was 0.24 μm, 0.45 μm, and 0.52 μm, respectively.
ExF-5 is a microprecipitation described in Example 1 of EP-A-549,489A.
Dispersed by a dispersion method. The average particle size was 0.06 μm.

The contents of the emulsions used are shown in Table 6, and the structural formulas of the compounds are shown in Chemical formulas 62 to 78.

[0272]

[Table 6]

[0273]

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[0274]

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[0275]

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[0276]

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[0277]

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[0278]

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[0279]

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[0280]

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[0281]

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[0282]

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[0283]

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[0284]

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[0285]

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[0286]

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[0287]

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[0288]

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[0289]

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Emulsion 101 prepared in Example 2 for the eleventh layer
Samples 3001 to 3012 were prepared using Nos. To 112 and exposed and processed in the same manner as in Example 2. However, the color development time of the processing was changed to 3 minutes and 15 seconds.

The samples using the emulsions 105 to 112 of the present invention had high sensitivity and low fog, as shown in Example 2.

The same sample was stored at 50 ° C. and a relative humidity of 80% for 2 months, subjected to the same exposure and processing, and the change in fog density was measured. Table 7 shows the obtained results.

[0293]

[Table 7]

It was revealed that samples 3005 to 3012 using the emulsions 105 to 112 of the present invention not only have high sensitivity and little fog, but also have very little change in fog density under high temperature and high humidity .

[0295]

As described in Examples 1 to 3, the compounds of the present invention shown in Synthesis Examples 1 to 3 increase the sensitivity of silver halide photographic light-sensitive materials, reduce fogging, and maintain storage stability. It turns out that it is excellent. These effects are particularly remarkable in the reduction sensitized emulsion.

──────────────────────────────────────────────────続 き Continued on the front page (58) Fields surveyed (Int. Cl. ⁷ , DB name) G03C 1/08 G03C 1/12 G03C 1/34 G03C 7/00 510 G03C 7/28

Claims (4)

(57) [Claims] 1. A silver halide photographic material comprising at least one hydrazone compound having a methine dye residue or a group adsorbed to silver halide by a covalent bond. 2. The silver halide photographic material according to claim 1, wherein the hydrazone compound according to claim 1 is represented by the general formula (I) or (II). General formula (I) General formula (II) In the formula, MET represents a methine dye residue. Het is an adsorptive group to silver halide according to claim 1, wherein at least one
Represents a group having a 5-, 6-, or 7-membered heterocyclic ring which contains nitrogen atoms and may further contain a hetero atom other than a nitrogen atom. Q ₁ and Q ₂ are each a carbon atom, a nitrogen atom,
It represents a linking group consisting of an atom or an atomic group containing at least one of a sulfur atom and an oxygen atom. k _1a , k _3a , k _3b ,
And k _1b each represents an integer of 1 to 4, and k _2a and k _2b each represent 0 or 1. Hyd ₁ and Hyd ₂ have the general formula (II
It represents a group having a hydrazone structure represented by I). Embedded image In the formula, R ₁ , R ₂ and R ₃ each represent an aliphatic group, an aryl group or a heterocyclic group. R ₄ represents a hydrogen atom or a group having the same meaning as R ₃ . 3. A photographic material having at least one silver halide emulsion layer on a support, wherein at least one of the emulsion layers contains at least one hydrazone compound according to claim 1 or 2. A silver halide photographic material, wherein the silver halide grains in the emulsion layer are subjected to reduction sensitization. 4. A silver halide emulsion layer represented by the following general formula (X)
4. The silver halide photographic material according to claim 1, which contains at least one compound selected from the group consisting of ( X) , (XXI) and (XXII) . Formula (XX) R ₁₀₁ SO ₂ S-M ₁₀₁ Formula (XXI) R ₁₀₁ -SO ₂ S-R ₁₀₂ Formula (XXII) R ₁₀₁ -SO ₂ S- (E) _a -SSO ₂ -R ₁₀₃ Formula _{among, R 101, R 102, R} 103 represents an aliphatic group, an aromatic group or a heterocyclic group, M ₁₀₁ represents a cation, E is a divalent linking group, a is is 0 or 1 .