JPH117098A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide photographic sensitive material restrained from deterioration of sensitivity and increase of fog even in the case of storage under high temperature and high humidity by incorporating a specified compound in a silver halide emulsion. SOLUTION: At least one of the silver halide emulsion layers formed on a support contains at least one of the compounds represented by the formula in which Z is a nonmetallic atomic group necessary to form a 5- or 6-membered N-containing hetero ring; each of R1 and R2 is an H atom or an alkyl or alkenyl or aryl or heterocyclic group, but at least one of them is an alkyl or alkenyl or aryl or heterocyclic group; D is a nonmetallic atomic group necessary to form a methine dye; M1 is an H atom or a univalent cation; M2 is a counter ion necessary to neutralize a charge; (m) is 0 or 1; (n) is 0, 1, 2, or 3; p1 is 0 or 1; and p2 is an integer of >=0 necessary to neutralize the intramolecular charge.

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, and more particularly, to a silver halide photographic material (hereinafter referred to as both a photographic material and a photographic material) which is spectrally sensitized by a novel photosensitive dye and has improved photographic characteristics. ).

[0002]

2. Description of the Related Art When a certain kind of dye is added to a light-sensitive silver halide emulsion (hereinafter referred to as a silver halide emulsion or simply an emulsion), the photosensitive area of the silver halide emulsion is enlarged and optically sensitized. Is known to be.

A large number of compounds have been known as dyes used for this purpose. For example, James, "Theory of the Photographic Process,"
Edition, Macmillan Publishing Company, 1977, 194-234
Page, Francis M. Harmer, "The Cyanine Soybean and Relaunched Compound" (196
4, John Welly and Sons, N.M. Y. ),
Dem Sturmer, "The Chemistry of Heterocyclic Compounds, Vol. 30," p. 441 et seq. (1977, John Welly and Sons,
N. Y. Various dyes such as styryl dyes, hemicyanine dyes, cyanine dyes, merocyanine dyes, xanthene dyes, and the like described in, for example, are known. By selecting and combining the substituents, a dye having an arbitrary absorption maximum wavelength in the near ultraviolet to near infrared region is derived.

These photosensitive sensitizing dyes must not only extend the photosensitive wavelength range of a silver halide emulsion but also satisfy the following conditions.

[0005] 1) Spectral sensitivity is appropriate, 2) Spectral sensitization efficiency is high, 3) Between other additives such as a stabilizer, an antifoggant, a coating aid, a high boiling point solvent and the like. 4) No adverse effects such as fogging and gamma change on the characteristic curve. 5) When silver halide photographic materials containing photosensitive dyes are stored over time (especially at high temperatures).・ When stored under high humidity), the photographic performance such as increase in fog and decrease in sensitivity is not changed. 6) The added photosensitive dye is not diffused to layers in different wavelength ranges to cause color turbidity. ) After the development and fixing, the photosensitive dye is not removed after washing with water and does not cause color contamination.

However, the photosensitive dyes disclosed hitherto have not yet reached a level satisfying all of these conditions.

In particular, various sensitization methods have been adopted as the sensitivity of silver halide photographic materials has been increased, and as a result, fogging has been caused by photosensitive dyes, and this improvement has been particularly required. As a countermeasure for these, Japanese Patent Laid-Open No.
And Japanese Patent Application Laid-Open No. 8-328189, but they have not been satisfactory yet.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material which has little fog and excellent storage stability without deteriorating photographic sensitivity, and particularly, can be stored for a long time under high temperature and high humidity. Another object of the present invention is to provide a silver halide photographic light-sensitive material in which a decrease in sensitivity and an increase in fog are suppressed.

[0009]

The above objects of the present invention have been attained by the following constitutions.

(1) In a silver halide photographic material having at least one silver halide emulsion layer on a support, the silver halide emulsion layer contains at least one compound represented by the following general formula (1). A silver halide photographic light-sensitive material characterized by containing:

[0011]

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[In the formula, Z represents a non-metallic atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. R ₁ and R ₂ each represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. Here, at least one of R ₁ and R ₂ is an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. D represents a group of nonmetallic atoms necessary for forming a methine dye. M ₁ represents a hydrogen atom or a monovalent cation. M ₂ represents a counter ion necessary for neutralizing the charge. m represents 0 or 1. n represents an integer from 0 to 3. p ₁ represents 0 or 1. p ₂ is an integer of 0 or more necessary for neutralizing the molecular charge. (2) The compound described in the above item 1, wherein the compound represented by the general formula (1) is a compound selected from the following general formulas (2), (3) and (4). Silver halide photographic material.

[0013]

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[Wherein Z ₁₁ and Z ₁₂ have the same meaning as Z.
L ₁₁ , L ₁₂ and L ₁₃ each represent a methine group. R ₁₁ , R
₁₂ has the same meaning as R ₁ and R ₂ , respectively. R ₁₃ represents an alkyl group or an aryl group. M ₁₁ and M ₁₂ are respectively M ₁ ,
It has the same meaning as M _2. m ₁₁ and m ₁₃ each represent 0 or 1. m ₁₂ represents an integer from 0 to 4. When m ₁₂ is 2 to 4, m ₁₂ L ₁₁ and L ₁₂ may be the same or different. p ₁₁ represents 0 or 1. p ₁₂ represents an integer of 0 or more necessary for neutralizing the molecular charge. n ₁₁ is from 0 to 3
Represents an integer up to. ]

[0015]

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[Wherein, Z ₂₁ has the same meaning as Z. Z ₂₂ , Z
₂₃ represents an atomic group necessary for forming an acidic nucleus. L ₂₁ and L ₂₂ each represent a methine group. R ₂₁ , R ₂₂
Has the same meaning as R ₁ and R ₂ , respectively. M ₂₁ has the same meaning as M ₁ , and R ₂₄ has the same meaning as R ₁₃ . R ₂₃ represents an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. Z ₂₄ ,
Z ₂₅ represents an oxygen atom or a sulfur atom, respectively. n ₂₁ is 0
Represents an integer from to 3. m ₂₁ represents 0 or 1. m ₂₂ represents an integer of 0 to 2. m ₂₃ represents an integer from 0 to 2. When m ₂₂ and m ₂₃ are 2, two L ₂₁ , L ₂₂ and

[0017]

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May be the same or different. p ₂₁
Represents an integer of 0 or more necessary to neutralize the charge of the molecule. ]

[0019]

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Wherein Z ₃₁ and Z ₃₃ have the same meanings as Z. Z ₃₂ has the same meaning as Z ₂₂ . L _{31 to} L ₃₅ each represent a methine group. R ₃₁ and R ₃₂ have the same meanings as R ₁ and R ₂ , respectively. M ₃₁ and M ₃₂ have the same meanings as M ₁ and M ₂ , respectively. R ₃₃ has the same meaning as R ₂₃ , and R ₃₄ has the same meaning as R ₁₃ . Z ₃₄ represents an oxygen atom or a sulfur atom. m ₃₁ and m ₃₄ each represent 0 or 1. n ₃₁ represents an integer from 0 to 3, and m ₃₂ and m ₃₃ each represent an integer from 0 to 2. When m ₃₂ and m ₃₃ are 2, the two L ₃₁ , L ₃₂ and L ₃₄ , L ₃₅ may be the same or different. p ₃₁ represents 0 or 1. p ₃₂ represents an integer of 0 or more necessary for neutralizing the molecular charge. Hereinafter, the compound of the present invention will be described in detail. Z, Z ₁₁ , Z
_12, Z _21, Z ₃₁ and indole ring Examples of 5-membered or 6-membered nitrogen-containing heterocyclic ring formed by Z _33, pyrrole ring, pyridine ring, quinoline ring, an isoquinoline ring, an oxazole ring, benzoxazole ring, naphtho Oxazole ring, imidazole ring, benzimidazole ring, naphthymidazole ring, pyrazole ring, indazole ring, naphthopyrazole ring, thiazole ring, benzothiazole ring, naphthothiazole ring, selenazole ring, benzoselenazole ring,
Examples include a naphthoselenazole ring, a tellurazole ring, a benzotellurazole ring, and a naphthotellurazole ring. Preferably, a ring condensed with a benzene ring or the like is preferable, and examples thereof include a quinoline ring, an isoquinoline ring, a benzoxazole ring, a naphthoxazole ring, a benzimidazole ring, a naphthoimidazole ring, a benzothiazole ring, and a naphthothiazole ring.

These rings may have a substituent.
Preferred examples of the substituent include an alkyl group which may be substituted (for example, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, an ethoxyethyl group, a trifluoromethyl group, a benzyl group, an o-chlorobenzyl group, Phenethyl group), alkenyl group (eg, ethenyl group, allyl group, butenyl group, etc.), alkynyl group (eg, ethynyl group, propynyl group, butynyl group, etc.), and optionally substituted aryl group (eg, phenyl group, A tolyl group, a chlorophenyl group, a biphenyl group, etc.), an optionally substituted heterocyclic group (for example, a pyrrolyl group, a thienyl group, an imidazolyl group, a furanyl group, a pyridinyl group, a thiadiazolyl group, a 5-methyl-benzothiazolyl group, etc.), halogen Atoms (for example, fluorine, chlorine, bromine, etc.),
Cyano group, hydroxyl group, nitro group, sulfo group, carboxyl group, mercapto group, optionally substituted alkoxy group (for example, methoxy group, ethoxy group, 2-hydroxyethoxy group, 2-ethoxyethoxy group, poly (ethyleneoxy) An aryloxy group which may be substituted,
(Eg, phenoxy group), carbonyl group (eg, acetyl group, propionyl group, octanoyl group, lauroyl group, stearoyl group, acetoacetyl group, benzoyl group, thienylcarbonyl group, etc.), oxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.) Group, phenoxycarbonyl group, methoxycarbonyloxy group, ethoxycarbonyloxy group, acetoacetyloxy group, phenoxycarbonyloxy group, etc.), amide group (eg, acetamido group, propionamido group, octanoylamino group, benzoylamino group) , A sulfonyl group (for example, a methanesulfonyl group, an ethanesulfonyl group, a tosyl group, etc.), and an optionally substituted amino group (for example, an amino group, an ethylamino group, a diethylamino group, a dioctylamino group, etc.) ) Unsubstituted or alkylthio group (e.g. methylthio group, ethylthio group, etc. benzylthio group) include an optionally substituted arylthio group (e.g., phenylthio group).

R ₁ , R ₂ , R ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ ,
The alkyl group represented by R ₂₂ , R ₂₃ , R ₂₄ , R ₃₁ , R ₃₂ , R ₃₃ , and R ₃₄ is a substituted or unsubstituted alkyl group, and an alkyl group having 1 to 8 carbon atoms (for example, , Methyl, ethyl, isopropyl, butyl, hexyl, octyl, methoxyethyl, phenethyl, benzyl, o-carboxybenzyl, etc.), preferably having 1 to 5 carbon atoms. It is an alkyl group. Examples of the alkenyl group include an alkenyl group having 2 to 6 carbon atoms (eg, a vinyl group, an allyl group, and a 1-butenyl group), preferably a vinyl group and an allyl group.

R ₁ , R ₂ , R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ ,
The aryl group represented by R ₂₃ , R ₃₁ , R ₃₂ and R ₃₃ is a substituted or unsubstituted aryl group, having 6 to 1 carbon atoms.
Up to two aryl groups (eg, phenyl, tolyl, 4
-Chlorophenyl group, m-cyanophenyl group, p-chlorophenyl group, naphthyl group, etc.). Preferably, it is an aryl group having 6 to 10 carbon atoms. The heterocyclic group is a substituted or unsubstituted heterocyclic group having 2 to 10 carbon atoms (for example, a pyrrolyl group, a thienyl group, an imidazolyl group, a furanyl group, a pyridinyl group, a benzothiazolyl group, a thiadiazolyl group, Benzothiazolyl group, oxadiazolyl group, etc.).

Examples of cations represented by M ₁ , M ₁₁ , M ₂₁ and M ₃₁ include sodium ion, potassium ion,
Examples include lithium ion, calcium ion, ammonium ion, triethylammonium ion, and pyridinium ion. Preferred cations include sodium ion, potassium ion, triethylammonium ion, pyridinium ion and the like. M _2, M
_12, as a counter ion necessary to neutralize the charge represented by M _32, examples of the cation is the same as that of M _1. Examples of anions include, for example, chloride ion, bromine ion, iodine ion, tetrafluoroborate ion,
Examples include perchlorate ion, acetate ion, benzenesulfonate ion, and tosyl ion. Preferred anions include iodine ion, tetrafluoroborate ion, perchlorate ion and tosyl ion.

Examples of methine dyes formed by D include styryl dyes, hemicyanine dyes, cyanine dyes, merocyanine dyes, and the like.

The compound represented by the general formula (1) of the present invention is preferably a compound represented by the above general formula (2), (3) or (4)
The compound represented by these is mentioned.

In the general formulas (2), (3) and (4), the methine group represented by L ₁₁ , L ₁₂ , L ₁₃ , L ₂₁ , L ₂₂ , L _{31 to} L ₃₅ has a substituent Examples of the substituent may include an alkyl group having 1 to 6 carbon atoms (eg, a methyl group, an ethyl group, an isopropyl group, and a butyl group), and an aryl group having 6 to 10 carbon atoms (eg, a phenyl group). Group, tolyl group, m-bromophenyl group, etc.), halogen atom (eg, fluorine atom, chlorine atom, etc.), amino group (eg, dimethylamino group, diphenylamino group, etc.), heterocyclic group having 2 to 10 carbon atoms (eg, Morpholino group, N, N-diethylbarbituric acid group, 2-furyl group, 2-thienyl group, etc., alkoxy group (eg, methoxy group, ethoxy group), aryloxy group (eg, phenoxy group, etc.), Lucio groups (such as methylthio,
An ethylthio group); an arylthio group (eg, a phenylthio group); Further, a ring (for example, a pentene ring, a cyclohexene ring, etc.) may be formed using two methine groups. Further, the formed ring may have a substituent.

In the general formulas (2) and (4), the alkyl group represented by R ₁₃ and R ₃₄ is preferably a methyl group, an ethyl group or a substituted alkyl group having 1 to 5 carbon atoms. Examples of preferred substituted groups include — (CH ₂ ) —C (R ₁ ) described in the general formula ( ₁ ).
A group represented by (R ₂ ) —COO (M ₁ ) p ₁ , an ethoxyethyl group, a trifluoromethyl group, a sulfoethyl group, a sulfopropyl group, a 3- or 4-sulfobutyl group, a 3-sulfopentyl group, Hydroxysulfopropyl group, carboxymethyl group, carboxybutyl group, hydroxyethyl group, methanesulfonylaminosulfonylmethyl group, acetoacetylmethyl group, acetaminosulfonylmethyl group, methanesulfonylaminocarbonylmethyl group, 3-
Sulfo-3-phenylpropyl group).

In the general formula (3), the acidic nucleus formed by Z ₂₃ generally represents an atomic group necessary for forming a merocyanine dye, but may take any form of a merocyanine dye. The term "acid nucleus" used here refers to James ed., "The Theory of the Photographic
Process, 4th Edition, Macmillan Publishing Company, 1977, 1
Refers to the nucleus defined by page 98. Preferably, 2
-Pyrazolin-5-one or thione, pyrazolidine-
3,5-dione or dithione, imidazolin-5-one or thione, hydantoin, 2 or 4-thiohydantoin, 2,4-dithiohydantoin, rhodanine, isorhodanine, 2-thiazolin-4-one or thione, thiazolidine-2, 4-dione or dithione, oxazoline-4-one or thione, oxazolidin-2,4-dione or dithione, 2-iminooxazoline-4-one or thione, isoxazolin-5-one or thione;
Indoline-2 or 3-one or thione, 6,7-dihydrothiazolo [3,2-a] pyrimidine-1,3-dione or dithione, 1,2,3,4-tetrahydroquinoline-2,4-dione Or dithione, barbituric acid, 2
Or, 4-thiobarbituric acid, 2,4-dithiobarbituric acid and the like can be mentioned. Further, in the above examples, pyrazolidine-3,5-dione or dithione is replaced with pyrazolidine-
As in 3-one-5-thione, a ketone group and a thioketone group may be mixed. More preferably, hydantoin,
2 or 4-thiohydantoin, rhodanine, isorhodanine, 2-thiazolidin-4-one or thione, thiazolidine-2,4-dione, oxazolidin-4-one or thione, oxazolidin-2,4-dione, oxazolidin-4-one -2-thione and the like.

In formulas (3) and (4), the acidic nucleus formed by Z ₂₂ and Z ₃₂ means that one ketone group or one thioketone group is removed from the acidic nucleus represented by Z ₂₃ . Things. Preferably, 2-pyrazolin-5-one or thione, pyrazolidin-3,5-dione or dithione, imidazolin-5-one or thione, hydantoin, 2 or 4-thiohydantoin, 2,4-dithiohydantoin, rhodanine, isorhodanine , 2-thiazolin-4-one or thione, thiazolidine-2,4-dione or dithione, oxazoline-4-one or thione,
Oxazolidine-2,4-dione or dithione, 2-iminooxazoline-4-one or thione, isoxazolin-5-one or thione, indoline-2 or 3-one or thione, 6,7-dihydrothiazolo [3, 2-
a] pyrimidine-1,3-dione or dithione, 1,
One ketone group or one thioketone group from 2,3,4-tetrahydroquinoline-2,4-dione or dithione, barbituric acid, 2 or 4-thiobarbituric acid, 2,4-dithiobarbituric acid, or the like Are excluded. More preferably, hydantoin, 2 or 4-thiohydantoin, rhodanine, isorhodanine, 2-thiazodilin-4-one or thione, thiazolidine-2,
4-dione, oxazolidin-4-one or thione, oxazolidin-2,4-dione, oxazolidin-4-
One in which one ketone group or one thioketone group is removed from on-2-thione is exemplified.

Hereinafter, the compounds of the present invention will be exemplified.

[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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The compounds of the present invention are described in "Heterocyclic Compounds Cyanine Soybeans and Related Compounds" by FM Hammer, John
Wheely and Science (1964), Day
The compound can be synthesized by a method described in M. Sturmer, "Heterocyclic Compounds Special Topics in Heterocyclic Chemistry", John Wiley and Science Co., Ltd. (1977).

Synthesis Example 1) 5-Chloro-3-carboxyphenylmethyl-2-
Synthesis of methylbenzothiazolium bromide 3.9 g of 5-chloro-2-benzothiazole (20 m
mol) and 4.7 g of phenylbromoacetic acid in a pressure bottle and heated at 140 ° C. for 48 hours. 50 ml of isopropyl ether is added to the obtained oil, and the resulting tar is removed by decantation. The tar was purified by column chromatography to obtain 2.1 g (yield 26%) of 5-chloro-3-carboxyphenylmethyl-2-methylbenzothiazolium bromide.

2) Synthesis of Compound (1-9) 2.0 g (5 mmol) of 5-chloro-3-carboxyphenylmethyl-2-methylbenzothiazolium bromide
l) and anhydro-5-chloro-2- (2-ethoxy-
1.95 g (5 mmol) of 1-butenyl) -3- (3-sulfopropyl) benzothiazolium hydroxide
Was dissolved in 5 ml of m-cresol, and when the solution temperature reached 120 ° C., 1.5 g of triethylamine (15 mmol
1) is added quickly, and the mixture is heated and stirred for 30 minutes. After cooling,
30 ml of diisopropyl ether is added, and the resulting tar is removed by decantation. Acetone was added to the tar and stirred, and the precipitated red crystals were collected by filtration.
0.83 g (yield 20%) of -9 was obtained. Purified by column chromatography, and λmax 55
It was 2 nm and ε10.7 × 10 ⁴ .

The above-mentioned intermediate and target compound are each NM
The structure was confirmed from the R spectrum and the mass spectrum. Other compounds of the present invention can be similarly synthesized.

The amount of the compound of the present invention (hereinafter also referred to as the photosensitive dye of the present invention) varies greatly depending on the conditions used and the type of emulsion, but is preferably 1 × 10 ⁻ per mol of silver halide. ⁶ to 5 × 10 ^-3 mol, more preferably 2 ×
It is in the range of 10 ^{-6 to} 2 × 10 ^-3 mol.

The photosensitive dye of the present invention can be added to a silver halide emulsion by a conventionally known method. For example, the protonated dissolution addition method described in JP-A-50-80826 and 50-80827, U.S. Pat.
No. 35, JP-A-50-11419, a method of dispersing and adding together with a surfactant, US Pat.
6,147, 3,469,987, 4,24
7,627, JP-A-51-59942, and JP-A-5-59942.
No. 3-16624, No. 53-102732, No. 53-
Nos. 102733 and 53-137131, the method of dispersing and adding to a hydrophilic substrate, East German Patent No. 143,
No. 324, or a water-soluble solvent dissolving a dye represented by Research Disclosure 21, 802, JP-B-50-40659, and JP-A-59-148053 (for example, ,water,
Low-boiling solvents such as methanol, ethanol, propyl alcohol, acetone, and fluorinated alcohol; high-boiling solvents such as dimethylformamide, methylcellosolve, and phenylcellosolve) alone or in the form of a mixture thereof. Kaihei 5-297496, 6-186
No. 657, No. 7-253626 and the like, and the like.

The photosensitive dye of the present invention may be added at any stage during the emulsion production process from physical ripening to completion of chemical ripening, but is added between physical ripening and completion of chemical ripening. Is preferred.

The addition of the compound according to the present invention during physical ripening, prior to the addition of the chemical sensitizer in the chemical ripening step, or immediately after the addition of the chemical sensitizer, has the effect of obtaining higher spectral sensitivity. And is preferably used.

The photosensitive dye of the present invention can be used in combination with another photosensitive dye.

These photosensitive dyes may be added to the emulsion at the same time or separately at different times, and the order and time interval at that time may be arbitrarily determined depending on the purpose.

The spectral sensitivity of the photosensitive dye of the present invention can be further improved by using a compound having another supersensitizing effect. Compounds having such a supersensitizing effect include, for example, US Pat. No. 2,933,390,
Nos. 3,416,927, 3,511,664, 3,615,613, 3,615,632, 3,635,721, etc., and JP-A-3-15042.
Having a pyrimidinylamino group or a triazinylamino group described in JP-A Nos. 3-110545, 4-2555841, etc., British Patent No. 1,137,580, JP-A-61-169833. Organic Formaldehyde Condensate described in Japanese Patent Application Laid-Open No. 4-18433
No. 2; calixarene derivatives described in U.S. Pat. No. 4,030,927; halogenated benzotriazole derivatives described in U.S. Pat. No. 4,030,927;
Bispyridinium compounds described in JP-A-9-18641, an aromatic heterocyclic quaternary salt compound described in JP-A-59-191332, an electron-donating compound described in JP-A-60-79348, U.S. Pat. No. 4,307 Polymer containing aminoallylidenemalononitrile unit described in JP-A-183183, hydroxytetrazaindene derivative described in JP-A-4-149937, U.S. Pat. No. 3,615,633.
1,3-oxadiazole derivative described in US Pat. No. 4,780,404, amino-1,
2,3,4-thiatriazole derivatives and the like.
The timing of addition of these supersensitizers is not particularly limited, and they can be arbitrarily added according to the timing of the addition of the photosensitive dye. The amount of addition is selected in the range of 1 × 10 ^-6 to 1 × 10 ^-1 mol per mol of silver halide, and it is used in a molar ratio of 1/10 to 10/1 with the photosensitive dye.

The silver halide used in the light-sensitive material of the present invention is arbitrarily selected from silver iodobromide, silver bromide, silver chlorobromide, silver chloroiodobromide, silver chloride and silver chloroiodide. . The silver halide grains may be of any type such as cubic, octahedral, tetradecahedral, spherical, or tabular having an aspect ratio of 5 or more. Average value) x 10
0] is preferable. The average grain size of the silver halide grains is not particularly limited, but is preferably 0.05 to 2.0 μm, and more preferably 0.1 to 2.0 μm.
１．２1.2 μm.

These silver halides may introduce a transition line into the silver halide crystals as needed. In order to introduce a transition line into a silver halide crystal, it is necessary to irregularly disrupt the periodic structure of the crystal. That is, a halogen ion used for silver halide growth during the crystal growth process and a different ion or an organic compound different from the silver ion are introduced so that the lattice constant changes discontinuously at a certain position of the crystal lattice. Alternatively, if a halogen ion and a silver ion are supplied so that the halogen composition changes rapidly, a transition line can be introduced. If an organic compound is added for this purpose, it is preferred that it interacts in some way with the silver halide. Specifically, sensitizing dyes and stabilizers commonly used in the art can be used for this purpose. Examples of a method of rapidly changing the composition of silver halide include a method of adding a KI solution during the formation of AgBr grains, and a method of adding AgI or Ag during the formation of AgBr grains.
Cl is grown and then aged or subsequently Ag
There is a method of further adding the particle formation of Br. Alternatively, on the contrary, there is a method in which Ag ⁺ and Br ⁻ are added to a system of small-sized core particles having an extremely high iodine composition to cause significant recrystallization. In short, the crystallization may be performed such that when the silver halide minimizes the formation energy of the crystal lattice during the growth process, the lattice constant is stabilized in a state where the lattice constant is suddenly changed in a certain region.

Examples of the dislocation introduction site include a main surface and an apex of a grain, and in the case of a tabular grain, a twin plane can be cited. However, these may be limited to these positions or may be combined. .

In the present invention, the silver halide emulsion is usually chemically sensitized. As the chemical sensitizer, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer, or the like can be used.

The silver halide emulsion may be optionally used
It is sensitized by a combination of chemical sensitization, noble metal sensitization and reduction sensitization.

The chalcogen sensitization includes sulfur sensitization, selenium sensitization, and tellurium sensitization. Examples of the sulfur sensitizer include thiosulfates, thioureas (diphenylthiourea, triethylthiourea, allylthiourea). , Allyl isothiocyanate, cystine, p-toluenethiosulfonate, rhodanines and mercapto compounds.

The selenium sensitizer is described in JP-B-43-1.
Nos. 3489 and 44-15748,
Specific examples are described in -25832, 4-109240 and the like. Tellurium sensitizers are described in U.S. Pat. Nos. 2,518,698 and 3,201,254.
No. 3,411,917, No. 3,779,77
7, No. 3,930,867, JP-A-4-2046
40, JP-A-4-271341, 4-3
No. 33043, and the like.

The noble metal sensitization is typically gold sensitization, but platinum, palladium, iridium and rhodium may be used in some cases. These noble metals are used as metal salts or metal complexes.

The reduction sensitization is carried out by adding a reducing agent to a silver halide emulsion or a mixed solution for growing grains. Preferred reducing agents include thiourea dioxide, ascorbic acid and its derivatives, borane compounds,
Hydrazine derivatives, formamidinesulfinic acid, silane compounds, amines and polyamines, sulfites and the like are used.

In addition, these sensitization methods may be used in various combinations. Regarding these methods, JP-A-7-219093, JP-A-7-225438,
Nos. 7,191,426 and 8,212,524 and U.S. Pat. No. 5,576,170.

The amount of the sulfur sensitizer, selenium sensitizer, and tellurium sensitizer to be added is not uniform depending on the type of silver halide emulsion, the type of compound used, the ripening conditions and the like. It is preferably from 1 × 10 ⁻⁴ to 1 × 10 ⁻⁹ mol per mol. More preferably, 1 × 10 ⁻⁵ to 1 × 1
^0-8 mol.

Depending on the properties of the compound to be used, the above-mentioned various sensitizers may be added by dissolving them in water or an organic solvent such as methanol or ethanol, alone or in a mixed solvent, or by adding a gelatin solution. And a method disclosed in JP-A-4-140739, that is, a method in which the mixture is added in the form of an emulsified dispersion of a mixed solution with a polymer soluble in an organic solvent.

The hydrophilic protective colloid used for preparing the silver halide photographic light-sensitive material of the present invention includes, in addition to the gelatin used in ordinary silver halide emulsions, gelatin derivatives such as acetylated gelatin and phthalated gelatin. , Water-soluble cellulose derivatives and other synthetic or natural hydrophilic polymers.

Various techniques and additives known in the art can be used in the silver halide photographic light-sensitive material of the present invention, if necessary. For example, in addition to the photosensitive silver halide emulsion layer, auxiliary layers such as a protective layer, a filter layer, an antihalation layer, a crossover light cut layer, and a backing layer can be provided. Boiling point solvent,
Antifoggants, stabilizers, development inhibitors, bleaching accelerators, fixing accelerators, color mixture inhibitors, formalin scavengers, color tones, hardeners, surfactants, thickeners, plasticizers, slippers,
An ultraviolet absorber, an irradiation preventing dye, a filter light absorbing dye, a polymer latex, a heavy metal, an antistatic agent, a matting agent and the like can be contained by various methods.

The support usable in the silver halide photographic light-sensitive material of the present invention includes polyesters such as cellulose triacetate, cellulose nitrate, polyethylene terephthalate, polyethylene-2,6-naphthalate, polyolefins such as polyethylene, and the like. Polystyrene, baryta paper, paper laminated with polyethylene or the like, glass, metal and the like can be mentioned. Further, a magnetic recording layer may be provided on the support as needed.

These supports may be optionally provided, for example,
An undercoating process such as corona discharge treatment and installation of a subbing polymer adhesive layer is performed.

These additives described above are described in more detail in Research Disclosure, Vol. 176, Item.
/ 17643 (December 1978), 184 Volume
m / 18431 (August 1979) and 187 It.
em / 18716 (November 1979).

To develop the silver halide photographic light-sensitive material of the present invention, for example, H. The Theory of the Photographic Process by James 4
Edition (The Theory of the Photo)
graphic Process, fourth Ed
Ition) Pages 291-334 and Journal of
The American Chemical Society (Journa)
l of the American Chemical
Society) 73, 3,100 (195
The developer as described in 1) can be used effectively.

[0074]

Next, the present invention will be described based on examples.
Embodiments of the present invention are not limited to these.

Example 1 The amount of addition in the silver halide photographic light-sensitive material is the number of grams per 1 m ² unless otherwise specified. Incidentally, silver halide and colloidal silver are shown in terms of silver, and photosensitive dyes are shown in moles per mole of silver halide in the same layer.

(Preparation of silver halide photographic emulsion) <Preparation of seed emulsion-1> Seed emulsion-1 was prepared as follows.

A1 ossein gelatin 100 g potassium bromide 2.05 g 11.5 l in water B1 ossein gelatin 55 g potassium bromide 65 g potassium iodide 1.8 g 0.2N sulfuric acid 38.5 ml 2.6 l in water C1 ossein gelatin 75 g Potassium bromide 950 g Potassium iodide 27 g 3.0 l with water D1 95 g silver nitrate 2.7 l with water E1 1410 g silver nitrate 3.2 l with water Control solution A1 solution B1 and solution D1 are kept at 60 ° C. The solution was added over 30 minutes by the jet method, and then the C1 and E1 solutions were added over 105 minutes by the control double jet method. Stirring is 50
Performed at 0 rpm.

The flow rate was such that no new nuclei were generated with the growth of the particles, and so-called Ostwald ripening was performed. At the time of adding the silver ion solution and the halide ion solution, pAg was adjusted to 8.3 ± 0.05 using an aqueous potassium bromide solution, and pH was adjusted to 2.0 ± 0.1 using sulfuric acid.

After completion of the addition, the pH was adjusted to 6.0, and then extraneous salts were removed to remove extraneous salts.
A desalting treatment was performed by the method described in No. 6.

When this seed emulsion was observed with an electron microscope, it was a cubic monodisperse emulsion having an average grain size of 0.27 μm and a grain size distribution of 17%, and the corners were slightly chipped.

<Preparation of silver halide emulsion C> Seed emulsion-1
And seven kinds of solutions shown below were used to prepare monodisperse core / shell emulsions.

A2 ossein gelatin 10 g ammonia water (28%) 28 ml glacial acetic acid 3 ml seed emulsion-1 0.119 mole equivalent 11.5 l with water B2 ossein gelatin 0.8 g potassium bromide 5 g potassium iodide 3 g water 110 ml C2 Ossein gelatin 2.0 g Potassium bromide 90 g 240 ml with water D2 silver nitrate 9.9 g ammonia water (28%) 7.0 ml 110 ml with water E2 130 g silver nitrate 130 g ammonia water (28%) 240 ml with water F2 94 g potassium bromide water 165 ml G2 silver nitrate 9.9 g ammonia water (28%) 7.0 ml 110 ml A2 solution was kept at 40 ° C. with water, and stirred at 800 rpm with a stirrer. The pH of Solution A2 was adjusted to 9.90 using acetic acid, and Seed Emulsion-1 was collected and dispersed and suspended. Then, Solution G2 was added at a constant speed over 7 minutes to adjust the pAg to 7.3. Further, solution B2 and solution D2 were added simultaneously over 20 minutes. At this time, the pAg was kept constant at 7.3. Further, pH = 8.8 using an aqueous solution of potassium bromide and acetic acid over 10 minutes.
3. After adjusting the pAg to 9.0, the C2 solution and the E2 solution were simultaneously added over 30 minutes.

At this time, the flow ratio between the start of addition and the end of addition was 1:10, and the flow rate was increased with time.
Further, the pH was lowered from 8.83 to 8.00 in proportion to the flow rate ratio. Further, when the C2 solution and the E2 solution were added in only ／ of the total amount, the F2 solution was additionally injected and added at a constant speed over 8 minutes. At this time, the pAg was 9.0 to 11.
It has risen to zero. Further, acetic acid was added to adjust the pH to 6.0.

After completion of the addition, precipitation and desalting were carried out using an aqueous solution of Demol (manufactured by Kao Atlas) and an aqueous solution of magnesium sulfate to remove excess salts.
5, an emulsion having an average silver iodide content of about 2.0 mol% at pH 5.85 was obtained at 40 ° C.

When the obtained emulsion was observed with an electron microscope, the average particle size was 0.55 μm, and the size distribution was 14%.
This was a rounded tetradecahedral monodisperse core / shell emulsion.

<Preparation of Seed Emulsion-2> Seed emulsion-2 was prepared as follows.

A3 ossein gelatin 24.2 g water 9657 ml polypropyleneoxy-polyethyleneoxy-disuccinate Na salt (10% aqueous ethanol) 6.78 ml potassium bromide 10.8 g 10% nitric acid 114 ml B3 2.5N silver nitrate aqueous solution 2825 ml C3 bromide Potassium 824 g Potassium iodide 23.5 g Water 2825 l D3 1.75 N Potassium bromide aqueous solution Silver potential control amount at 35 ° C: JP-B-58-58288, 58-5828
Using a mixing stirrer described in the specification of No. 9, 464.3 ml of each of the solution B3 and the solution C3 was added to the solution A3 by the simultaneous mixing method over 2 minutes to form nuclei.

After stopping the addition of the solution B3 and the solution C3, it takes 60 minutes to raise the temperature of the solution A3 to 60 ° C., adjust the pH to 5.0 with a 3% KOH aqueous solution, and then again. The solution B3 and the solution C3 were added at a flow rate of 55.4 ml / min for 42 minutes by the simultaneous mixing method. The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the temperature rise from 35 ° C. to 60 ° C. and the re-simultaneous mixing with the solutions B3 and C3 was +8 mV using the solution D3. And +16 mV.

After completion of the addition, p is added with a 3% aqueous KOH solution.
H was adjusted to 6, and immediately desalting and washing were performed.

In this seed emulsion, 90% or more of the total projected area of the silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0, and the average thickness of the hexagonal tabular grains is 0.06.
It was confirmed by an electron microscope that the average particle size (in terms of salt diameter) was 0.59 μm.

<Preparation of silver halide emulsion D> Seed emulsion-2
And three kinds of solutions shown below were used to prepare tabular emulsions.

A4 ossein gelatin 5.26 g Polypropylene oxy-polyethylene oxy-disuccinate Na salt (10% aqueous ethanol) 1.4 ml seed emulsion-2 equivalent to 0.094 mol 569 ml with water B4 ossein gelatin 15.5 g potassium bromide 114 g Potassium iodide 3.19 g 658 ml with water C4 166 g with silver nitrate 889 g with water 10 ml of B4 and C4 solutions in A4 solution stirred vigorously at 60 ° C
It was added by the double jet method in 7 minutes. During this time, the pH was kept at 5.8 and the pAg was kept at 8.7 throughout. B4 liquid and C4
The addition rate of the liquid was linearly increased so as to be 6.4 times at the beginning and at the end.

After completion of the addition, precipitation and desalting were carried out using an aqueous solution of Demol (manufactured by Kao Atlas) and an aqueous solution of magnesium sulfate to remove excess salts.
5, an emulsion having an average silver iodide content of about 2.0 mol% at pH 5.85 was obtained at 40 ° C.

When the obtained emulsion was observed with an electron microscope, a tabular halide having a projection area of 82% of the average grain size of 0.98 μm, a grain size distribution of 15%, and an average aspect ratio of 4.5 was obtained. It was silver particles. The average of the ratio (t / l) of the distance between twin planes (l) to the thickness (t) of tabular grains is 11
Met. The crystal plane was composed of a (111) plane and a (100) plane, the main planes were all (111) planes, and the ratio of the (111) plane to the (100) plane in the edge plane was 78:22.

These emulsions were subsequently adjusted to pH 5.8 and pAg to 7.0 with citric acid and sodium chloride.
Several kinds of dyes shown in Tables 1 and 2 were added, and after optimal chemical ripening at 60 ° C. using ammonium thiocyanate, sodium thiosulfate pentahydrate and chloroauric acid, 4-hydroxy-6- The ripening was stopped by adding 1.0 g of methyl-1,3,3a, 7-tetrazaindene per mole of silver.

(Preparation of silver halide photographic light-sensitive material) One side (surface) of a triacetylcellulose film support is subjected to an undercoating process, and the surface opposite to the undercoated process is sandwiched between the supports. On the (back side), layers having the following compositions were sequentially formed from the support side.

Back First Layer Alumina Sol AS-100 (Aluminum Oxide) (Nissan Chemical Industries, Ltd.) 0.8 g Back Second Layer Diacetylcellulose 100 mg Stearic acid 10 mg Silica fine particles (average particle size 0.2 μm) 50 mg Subbing process On the surface of the triacetyl cellulose film support thus formed, layers having the following compositions were sequentially formed from the support side to produce color photographic light-sensitive materials (samples 1-1 to 1-42).

First layer: Antihalation layer (HC) Black colloidal silver 0.15 g UV absorber (UV-1) 0.20 g Dye (CC-1) 0.02 g High boiling solvent (Oil-1) 0.20 g High boiling point solvent (Oil-2) 0.20 g Gelatin 1.6 g Second layer: Intermediate layer (IL-1) Gelatin 1.3 g Third layer: Silver halide photosensitive layer Silver halide emulsion C (sample 1-1) 1-20) and silver halide emulsion D (samples 1-21 to 1-42) 0.9 g Photosensitive dye (described in Tables 1 and 2) 2.7 × 10 ⁻⁴ mol / mol AgX magenta coupler (M-1) ) 0.30 g Magenta coupler (M-2) 0.13 g Colored magenta coupler (CM-1) 0.04 g DIR compound (D-1) 0.004 g High boiling solvent (Oil2) 0.35 g Gelatin 1.0 g Fourth layer: First protective layer (Pro-1) Fine grain silver iodobromide emulsion (average particle size 0.08 μm) 0.3 g UV absorber (UV-1) 0.07 g UV absorber (UV-2) 0.10 g Additive 1 (HS-1) 0.2 g Additive 2 (HS-2) 0.1 g High boiling solvent (Oil-1) 0.07 g High boiling solvent (Oil-3) 0.07 g Gelatin 0.8 g Fifth layer: Second protective layer (Pro-2) Additive 3 (HS-3) 0.04 g Additive 4 (HS-4) 0.004 g Polymethyl methacrylate (average particle size 3 μm) 0.02 g Methyl methacrylate: ethyl methacrylate: methacryl Acid copolymer (3: 3: 4 weight ratio) (average particle size 3 μm) 0.13 g Gelatin 0.5 g In addition, the above-mentioned coated samples further include activators SA-2 and SA-
3, viscosity modifier, hardener H-1, H-2, stabilizer ST-
3, ST-4, ST-5 (weight average molecular weight 10,000)
And 1,100,000) dyes F-4, F
-5 and the additive HS-5 (9.4 mg / m ² ).

[0099]

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[0100]

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[0101]

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[0102]

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Each of the prepared samples was divided into two parts, and one of them was left for 3 days in an atmosphere of 80% RH and 40 ° C. in order to evaluate the stability under high temperature and high humidity. And forcedly deteriorated.

<< Evaluation of Photographic Properties >> Samples 1-1 to 1-1
Samples 1-42 were each exposed to wedge with white light for 1/100 second, and then developed, bleached,
Fixing process was performed. The density of the processed sample was measured using an optical densitometer (PDA-65 manufactured by Konica), and the sensitivity is shown in Tables 1 and 2 as the sensitivity, using the reciprocal of the exposure at fog density +0.03 as usual.

In Tables 1 and 2, Samples 1-1 to 1-9 are expressed as relative sensitivities, with the sensitivity of Sample 1-1 being 100. Hereinafter, similarly, Sample 1-10 to Sample 1-15, Sample 1-16 to Sample 1-20, Sample 1-21 to Sample 1-2
4. Samples 1-25 to 1-32, Samples 1-33 to 1-35, Samples 1-36 to 1-39, and Samples 1 to 40
Samples 1-42 are Samples 1-10, 1-16, 1
The sensitivity of the instant photographic performance of -21, 1-25, 1-33, 1-36 and 1-40 was expressed as a relative sensitivity with 100 as the sensitivity.

Tables 1 and 2 show the sensitivities and fog of the photographic material immediately and the aging sample. In addition, as a substitute test evaluation of the performance fluctuation that appears when the photosensitive material is stored for a long period of time, from the obtained data, the sensitivity change rate and the fog increase value of the sample after the forced deterioration treatment with respect to the sample immediately after coating and drying Are shown in Tables 1 and 2.

(Processing step) Step Processing time Processing temperature Replenishment amount * Color development 3 minutes 15 seconds 38 ± 0.3 ° C. 780 ml Bleaching 45 seconds 38 ± 2.0 ° C. 150 ml Fixing 1 minute 30 seconds 38 ± 2.0 830 ml Stability 60 seconds 38 ± 5.0 ° C. 830 ml Drying 60 seconds 55 ± 5.0 ° C.-* The replenishing amount is a value per 1 m ² of the photosensitive material.

<Preparation of Processing Agent> (Composition of Developer) Water 800 ml Potassium carbonate 30 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxyamine sulfate 2.5 g 4 -Amino-3-methyl-N-ethyl N- (β-hydroxyethyl) aniline sulfate 4.5 g Diethylenetetraamine pentaacetic acid 3.0 g Potassium hydroxide 1.2 g Potassium or 20
The pH is adjusted to 10.06 with% sulfuric acid.

(Development replenisher composition) Water 800 ml Potassium carbonate 35 g Sodium hydrogen carbonate 3.0 g Potassium sulfite 5.0 g Sodium bromide 0.4 g Hydroxyamine sulfate 3.1 g 4-Amino-3-methyl-N-ethyl N -(Β-hydroxyethyl) aniline sulfate 6.3 g diethylenetetraaminepentaacetic acid 3.0 g potassium hydroxide 2.0 g Water was added to make up to 1.0 liter, and potassium hydroxide or 20
The pH is adjusted to 10.18 with% sulfuric acid.

(Composition of bleaching solution) Water 700 ml 1,3-diaminopropanetetraacetic acid iron (III) ammonium 125 g ethylenediaminetetraacetic acid 2 g sodium nitrate 40 g ammonium bromide 150 g glacial acetic acid 40 g Alternatively, the pH is adjusted to 4.4 using glacial acetic acid.

(Composition of bleach replenisher) Water 700 ml 1,3-diaminopropanetetraacetate ammonium (III) ammonium 175 g ethylenediaminetetraacetic acid 2 g sodium nitrate 50 g ammonium bromide 200 g glacial acetic acid 56 g Adjust to pH 4.0 with water or glacial acetic acid.

(Formulation of Fixing Solution) Water 800 ml Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g Water was added to make up to 1.0 liter, and the pH was adjusted to 6.2 with aqueous ammonia or glacial acetic acid.

(Formulation of Fixing Replenisher) Water 800 ml Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g Add water to finish to 1.0 liter, and adjust to pH 6.5 using aqueous ammonia or glacial acetic acid.

(Preparation of Stabilizing Solution and Stabilizing Replenishing Solution) Water 900 ml p-octylphenol / ethylene oxide / 10 mol adduct 2.0 g dimethylolurea 0.5 g hexamethylenetetramine 0.2 g 1,2-benzoisothiazolin-3-one 1 g Siloxane (UCC L-77) 0.1 g Ammonia water 0.5 ml Add water to make up to 1.0 liter, ammonia water or 50%
Adjust to pH 8.5 with sulfuric acid.

[0115]

[Table 1]

[0116]

[Table 2]

[0117]

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[0118]

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Tables 1 and 2 show that the silver halide photographic light-sensitive materials using the compounds of the present invention gave good photographic performance with less fog and excellent storage stability as compared with the comparative samples.

[0120]

Industrial Applicability According to the present invention, a silver halide photographic light-sensitive material excellent in storage stability without deteriorating photographic performance, in particular, reduced in sensitivity and increase in fog even after long-term storage under high temperature and high humidity. I got

Claims (2)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support,
A silver halide photographic light-sensitive material characterized in that the silver halide emulsion layer contains at least one compound represented by the following general formula (1). Embedded image [In the formula, Z represents a nonmetallic atom group necessary to form a 5- or 6-membered nitrogen-containing heterocyclic ring. R ₁ and R ₂ each represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. Here, at least one of R ₁ and R ₂ is an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. D represents a group of nonmetallic atoms necessary for forming a methine dye. M ₁ represents a hydrogen atom or a monovalent cation. M ₂ represents a counter ion necessary for neutralizing the charge.
m represents 0 or 1. n represents an integer from 0 to 3.
p ₁ represents 0 or 1. p ₂ is an integer of 0 or more necessary for neutralizing the molecular charge. ] 2. A compound represented by the general formula (1):
From the following general formula (2), general formula (3) or general formula (4)
The compound according to claim 1, which is a selected compound.
Silver halide photographic material. Embedded image[Wherein, Z₁₁And Z₁₂Is synonymous with Z. L₁₁, L₁₂,
L₁₃Each represents a methine group. R₁₁, R₁₂Are each
R₁, R_TwoIs synonymous with R₁₃Is an alkyl group or aryl
Represents a group. M₁₁, M₁₂Is M₁, M_TwoSynonymous with
You. m₁₁, M₁₃Represents 0 or 1, respectively. m₁₂Is 0
Represents an integer from 1 to 4. m₁₂When m is 2 to 4, m₁₂Pieces
L₁₁, L₁₂May be the same or different. p₁₁Is
Represents 0 or 1. p₁₂Is required to neutralize the molecular charge
Represents an integer of 0 or more. n₁₁Represents an integer from 0 to 3
You. [Chemical formula 3][Wherein, Z_{twenty one}Is synonymous with Z. Z_{twenty two}, Z_{twenty three}Are each
Represents the group of atoms necessary to form an acidic nucleus. L_{twenty one}, L_{twenty two}
Each represents a methine group. R_{twenty one}, R_{twenty two}Are each
R₁, R_TwoIs synonymous with M_{twenty one}Is M₁Is synonymous with_{twenty four}
Is R₁₃Is synonymous with R_{twenty three}Is an alkyl group, alkenyl
Represents a group, an aryl group or a heterocyclic group. Z_{twenty four}, Z _{twenty five}Haso
Represents an oxygen atom or a sulfur atom, respectively. n_{twenty one}Is from 0 to 3
Represents an integer. m_{twenty one}Represents 0 or 1. m_{twenty two}Is 0 to 2
Represents an integer up to. m_{twenty three}Represents an integer from 0 to 2.
m_{twenty two}, M_{twenty three}Is 2, two L_{twenty one}, L_{twenty two}AndMay be the same or different. p_{twenty one}Is the molecular charge
Represents an integer of 0 or more necessary to neutralize [Chemical formula 5][Wherein, Z₃₁, Z₃₃Is synonymous with Z. Z₃₂Is
Z_{twenty two}Is synonymous with L₃₁~ L₃₅Each represents a methine group
You. R₃₁, R₃₂Is R₁And R_TwoIs synonymous with M
₃₁, M₃₂Is M₁And M_TwoIs synonymous with R₃₃Is
R_{twenty three}Is synonymous with₃₄Is R₁₃Is synonymous with Z₃₄Is an acid
Represents an elementary atom or a sulfur atom. m₃₁, M₃₄Are 0 or
Represents 1. n₃₁Represents an integer from 0 to 3, and m₃₂,
m₃₃Each represents an integer from 0 to 2. m₃₂, M₃₃
Is 2, two L₃₁, L₃₂And L₃₄, L₃₅Each
They may be the same or different. p₃₁Represents 0 or 1. p
₃₂Represents an integer of 0 or more necessary to neutralize the molecular charge.
You. ]