JPH0516576B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a silver halide photographic material spectrally sensitized with a novel merocyanine dye, and particularly to a silver halide photographic material having high sensitivity to green light. [Prior Art] Conventionally, since a photosensitive silver halide emulsion alone has a narrow sensitive wavelength range, a spectral sensitizer has been used for the purpose of expanding the sensitive wavelength range to longer wavelengths. For example, as a device that imparts sensitivity to green light,
No. 43-10251, No. 43-22884, British Patent
No. 815172, No. 955961, No. 955912, No. 142228
No. 1942854, U.S. Patent No. 1950876, U.S. Pat.
No. 1957869, No. 2238231, No. 2521705, No. 2521705, No.
No. 2647059, Special Publication No. 43-2606, No. 44-3644,
46-18106, 46-18108, 48-15032, 46-18108, 48-15032,
No. 49-33782, No. 54-34252, No. 58-52574,
Examples include cyanine dyes and merocyanine dyes described in specifications such as US Pat. No. 2,839,403, US Pat. No. 3,567,458, and US Pat. These spectral sensitizers increase the sensitivity in a specific wavelength range, and at the same time, (1) are not affected by other additives or affect the effectiveness of the additives, and (2) date and time. (3) Properties such as not causing dye staining after processing are required. However, among the many conventionally developed spectral sensitizers, no one has yet been found that satisfies all of these conditions. [Object of the Invention] The first object of the present invention is to provide a silver halide photographic material containing a novel merocyanine dye that is not affected by additives and has a high spectral sensitizing effect. A second object of the present invention is to provide a silver halide photographic material that exhibits little change in photographic properties such as a decrease in sensitivity or an increase in fog even with the passage of time. [Structure of the Invention] The above object of the present invention is to provide a silver halide photographic material having at least one silver halide emulsion layer on a support, in which the silver halide grains contained in the silver halide emulsion layer are as follows: General formula []
This was achieved by providing a silver halide photographic material which has been spectrally sensitized with the compound represented by: General formula [] [In the formula, Z represents a nonmetallic atomic group necessary to form an oxazolidine ring, a 3(H) oxazole ring, a 3(H) benzoxazole ring, or a 3(H) naphthoxazole ring. R ₁ represents an alkyl group, R ₂ represents a halogen atom, an alkyl group, an alkoxy group, or a hydrogen atom, and A represents a nitrile group, an alkylsulfonyl group, a sulfonamido group, an alkylsulfonylamino group, or a lower alkoxy group. n is 1
Represents an integer value of ~4. ] In the general formula [], substituted on the carbon atom of the oxazolidine ring, 3(H) oxazole ring, 3(H) benzoxazole ring, or 3(H) naphthoxazole ring formed by the nonmetallic atom group of Z It can have a group. Examples of substituents include halogen atoms (specifically chlorine atoms, bromine atoms, fluorine atoms, etc.), alkyl groups, preferably carbon atoms of 1 to 4.
alkyl groups (specifically methyl, ethyl, n-propyl, etc.), alkoxy groups, preferably alkoxy groups having 1 to 4 carbon atoms (specifically methoxy, ethoxy, n-propoxy) base, etc.),
Alkoxycarbonyl group, preferably carbon number 1-
4 alkoxycarbonyl groups (specifically methoxycarbonyl group, ethoxycarbonyl group, etc.),
and a phenyl group. Specific examples of the oxazolidine ring, 3(H) oxazole ring, 3(H) benzoxazole ring or 3(H) naphthoxazole ring having or not having such a substituent include 4,4-dimethyl-oxazole Dinylidene, 2(3H)oxazolidene, 5,6-diphenyl-2(3H)-oxazolidene, 6-phenyl-2(3H)-oxazolidene, 4-methyl-2
(3H)oxazolidene, 2(3H)benzoxazolidene, 5-chloro-2(3H)-benzoxazolidene, 5-methyl-2(3H)benzoxazolidene, 5-methoxy-2(3H)benzo Oxazolidene, 5-chloro-6-methyl-2(3H) benzoxazolidene, 5-bromo-2(3H) benzoxazolidene, 5-ethoxycarbonyl-2
(3H)Benzoxazolidene, 6-ethoxy-2
(3H)Benzoxazolidene, 6-chloro-5-
Methyl-2(3H)benzoxazolidene, 5-phenyl-2(3H)benzoxazolidene, 2
(1H) naphtho[1,2-d]oxazolidene, 2
Examples include (3H) naphtho[2,3-d]oxazolidene. R ₁ represents an alkyl group, preferably an alkyl group having 10 or less carbon atoms. This alkyl group may be linear or branched, and may be, for example, a methyl group, an ethyl group, an n-propyl group, an isobutyl group, an n-butyl group, or the like. These alkyl groups may have a substituent, and examples of the substituent include a sulfo group, a carboxyl group, an alkoxy group (specifically, a methoxy group, an ethoxy group, etc.),
Examples include a carbamoyl group, a halogen atom (specifically a chlorine atom, a fluorine atom, etc.), a sulfate group, an alkylsulfonyl group (specifically a methylsulfonyl group, an ethylsulfonyl group, etc.). The halogen atom represented by R ₂ is, for example, a chlorine atom, a fluorine atom, a bromine atom, etc., and the alkyl group is preferably an alkyl group having 1 to 2 carbon atoms (for example, a methyl group, an ethyl group, etc.). Yes, and the alkoxy group is preferably an alkoxy group having 1 to 2 carbon atoms (e.g., methoxy group, ethoxy group, etc.)
It is. A represents a nitrile group, an alkylsulfonyl group, a sulfonamido group, an alkylsulfonylamino group, or a lower alkoxy group, and among these, the alkylsulfonyl group is preferably an alkylsulfonyl group having 1 to 4 carbon atoms (for example, methylsulfonyl group, ethylsulfonyl group, etc.), and the sulfonamide group is preferably a sulfonamide group having 1 to 4 carbon atoms (for example, N-methylsulfonamide group, N,N-dimethylsulfonamide group, etc.), The sulfonylamino group is preferably an alkylsulfonylamino group having 1 to 4 carbon atoms (for example, a methylsulfonylamino group),
The lower alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms (eg, methoxy group, ethoxy group, etc.). Particularly preferred in the compound represented by the above general formula [] is a case where R ₁ represents a linear or branched alkyl group having 1 to 4 carbon atoms substituted with a sulfo group or a carboxyl group and/or a hydroxyl group. , specifically, a sulfoethyl group, a sulfopropyl group, a 3-sulfobutyl group, a 4-sulfobutyl group, a carboxymethyl group, a carboxyethyl group, a hydroxyethyl group, a 3-sulfo-2-hydroxypropyl group, and the like. Next, typical examples of the compound represented by the above general formula [] used in the present invention will be listed, but it goes without saying that the compounds used in the present invention are not limited to these. The compound represented by the above general formula [] used in the present invention is disclosed in Japanese Patent Publication No. 46-549, No. 46-549,
No. 18105, No. 46-18106, No. 46-18108, No. 47
-4085, 58-52574, U.S. Patent No. 2839403,
No. 3384486, No. 3625698, No. 3480439, No. 3480439, No.
It can be synthesized according to the method for synthesizing dimethine merocyanine described in No. 3567458 and the like.
Next, specific synthesis examples will be shown, but other compounds represented by the above general formula [] can also be synthesized according to the following synthesis method. [Synthesis example] Synthesis of exemplified compound (1-5) N-cyanoethylglycine ethyl ester 7g
and ethyl-2-pyridyldithiocarbamate 5.9g
were mixed in 30 ml of toluene and heated under reflux for 4 hours. The reaction product was subjected to B--O silica gel column chromatography, and the fractions distilled out with ethyl acetate were collected and evaporated under reduced pressure. The precipitate was washed with ether to obtain 5.6 g of 1-(2-cyanoethyl-3-(2-pyridyl)-2-thiohydantoin. 4.9 g of this thiohydantoin compound and 2-[2-(2-anilinovinyl) -3-Benzoxazolio]ethanesulfonate (3.4 g) is stirred in 30 ml of morpholine at room temperature. 200 ml of ether is added to the reaction mixture, stirred for 1 hour, and left to stand. The supernatant liquid is decanted. A small amount of the residue is Dissolve by heating with methanol,
Add a solution of 4 g of potassium acetate in 50 ml of methanol, stir and cool. The precipitated crystals were collected by filtration, and recrystallization from water-containing methanol was repeated twice to obtain 2.5 g of red-orange exemplified compound (1-5). The maximum absorption wavelength of the obtained compound in methanol solvent was 485 nm. The merocyanine dye represented by the above general formula [] used in the present invention can be added and dispersed in a silver halide emulsion by a conventionally known method. For example, the
No. 44895, a method of adding by dispersing with a surfactant described in the specification of JP-A-50-11419, JP-A-Sho.
No. 53-16624, No. 53-102732, No. 53-102733,
A method of adding it as a dispersion with a hydrophilic substrate as described in the specifications of U.S. Patent Nos. 3,469,987 and 3,676,147
Examples include the method of adding as a solid solution described in the specification of East German Patent No. 143324. Other merocyanine dyes can be used in water-soluble solvents such as water, ethanol,
It may be added to the emulsion by being dissolved in a solvent such as methanol, acetone, n-propanol, fluorinated alcohol, pyridine, etc. or a mixture thereof. It may be added at any time during the emulsion manufacturing process, but preferably during or after chemical ripening.
The amount of the merocyanine dye used in the present invention is the amount for spectral sensitization of the silver halide emulsion, for example, 10 ^-5 to 2 x 10 ^-2 mol per mol of silver halide, preferably 10 ^-4 to 2 x It is 10 ^-3 mol. In addition, the merocyanine dye used in the present invention is
For example, Special Publication No. 43-4933, No. 43-4936, No. 46
−18107, No. 46-1999, No. 47-11114, No. 48
−1762, No. 48-38408, No. 56-38937, No. 58
Supersensitization can be achieved by using it in combination with other dyes disclosed in specifications such as No. -52574, US Pat. No. 2,519,001, and US Pat. Silver halide used in the silver halide photographic emulsion of the light-sensitive material according to the present invention includes silver iodobromide,
Silver bromide, silver chloride, silver chlorobromide, silver chloroiodobromide, silver chloroiodide, and the like are used. In particular, when used as a printing sensitive material, it is preferable that the silver chloride content is 50 mol% or more. The method for preparing the emulsion used in the present invention is as follows:
Forward mixing, back mixing, semi-back mixing, and simultaneous mixing are all possible, but the most preferred method is the simultaneous mixing method, and the emulsion preparation method is the ammonia method,
Although there are neutral methods and acidic methods, it is preferable to prepare by the neutral method or the acidic method. The distribution of silver halide grains in the emulsion may be either monodisperse or polydisperse, but monodisperse is preferable for uniform grain sensitivity. Further, the grain crystal habit may be cubic, octahedral, dodecahedral, spherical, or any other form. As particle size
It is preferably 2μ or less, preferably 1.0μ or less. More preferably, it is 0.8μ or less. This is because it is necessary to make the grains finer in order to prevent the developing silver grains from becoming rough and to achieve the required photographic density with a small amount of silver in order to save resources. The emulsion thus prepared is subjected to chemical sensitization (for example, sulfur sensitization, gold-sulfur sensitization, reduction sensitization, etc.) using a chemical sensitizer. Examples of chemical sensitizers used in this chemical sensitization include active gelatin, sulfur sensitizers (sodium thiosulfate, allylthiocarbamide, thiourea, allyl isothiacyanate, etc.), selenium sensitizers (N, N-dimethylselenourea, selenourea, etc.) reduction sensitizers (triethylenetetramine, stannic chloride, etc.), such as potassium chloroaurate,
Various noble metal sensitizers represented by potassium aurithiocyanate, potassium chloroaurate, 2-oresulfobenzothiazole methyl chloride, ammonium chloroparadate, potassium chloroplatinate, sodium chloroparadite, etc. are used alone or in combination. More than one species can be used in combination. When using a metal sensitizer, rhodanammonium can also be used as an auxiliary agent. Further, the silver halide emulsion used in the present invention is disclosed in, for example, U.S. Pat.
No. 1189380, West German Publication No. 2058626, West German Publication No.
No. 2118411, Special Publication No. 43-4133, U.S. Patent No. 3342596
No., Special Publication No. 47-4417, West German Application Publication No. 2149789
Compounds described in Japanese Patent Publication No. 39-2825 and Japanese Patent Publication No. 49-13566, preferably, e.g.
-Hydroxy-6-methyl-1,3,3a,7-
Tetrazaindene, 5,6-trimethylene-7-
hydroxy-s-triazolo(1,5-a)pyrimidine, 5,6-tetramethylene-7-hydroxy-s-triazolo(1,5-a)pyrimidine,
5-Methyl-7-hydroxy-s-triazolo(1,5-a)pyrimidine, 7-hydroxy-s
-triazolo(1,5-a)pyrimidine, 5-methyl-6-bromo-7-hydroxy-s-triazolo(1,5-a)pyrimidine, gallic acid esters (e.g. isoamyl gallate, dodecyl gallate, gallic acid) propyl acid, sodium gallate),
Stabilization using mercaptans (1-phenyl-5-mercaptotetrazole, 2-mercaptobenzthiazole), benztriazoles (5-bromobenztriazole, methylbenztriazole), benzimidazoles (6-nitrobenzimidazole), etc. can do. In addition, latent image stabilizers such as sulfur-containing amino acid compounds described in West German Application Publication No. 2217153 and West German Application No. 2217895 can also be used in the silver halide emulsion used in the present invention. Particularly preferably, when 1-phenyl-5-mercaptotetrazole is used in combination, the amount added is 1 mg to 1 mg per mole of silver halide.
5g, preferably 10mg to 500mg. Further, the silver halide emulsion used in the present invention can also contain a Group 8 metal salt. Examples of the Group 8 metal salts include platinum chloride, hexahalogenoiridium complex salts, and water-soluble rhodium salts. Particular examples of water-soluble rhodium salts include rhodium dichloride, rhodium trichloride, and ammonium hexachlorodate. Preferably, a complex compound of rhodium trichloride and a halogen, preferably chlorine or bromine, is used. The amount added is 10 ^-9 to 10 ^-3 mol per mol of silver halide, particularly preferably 10 ⁷ to 10 ^-5 mol. Furthermore, covering power improvers, anti-irradiation agents, wetting agents, latexes, polyalkylene oxides, other spreading agents, hardening agents, etc. can be added to the silver halide emulsion. The hydrophilic colloid particularly advantageously used in the silver halide emulsion layer of the light-sensitive material according to the present invention is gelatin, but hydrophilic colloids other than gelatin include, for example, colloidal albumin, agar, gum arabic, alginic acid, hydrolyzed colloids, etc. Cellulose acetate, acrylamide, imidized polyamide, polyvinyl alcohol, hydrolyzed polyvinyl acetate, such as British patent no.
Water-soluble polymers such as those described in US Pat. No. 3,341,332, gelatin derivatives, such as US Pat.
Phenylcarbamyl gelatin, acylated gelatin, phthalated gelatin as described in US Patent No. 2525753, etc., or US Patent No. 2548520, US Pat.
Examples include gelatin graft polymerized with polymerizable monomers having ethylene groups, such as styrene acrylate, acrylic ester, and methacrylic ester, as described in No. 2831767, etc., and these hydrophilic The colloids can be applied in hydrophilic colloid layers that do not contain silver halide, such as antihalation layers, protective layers, interlayers, etc. In the present invention, when coating the above-mentioned silver halide emulsion layer, the amount of coated silver is usually 0.01 g to 10 g/m ² ,
Preferably, it is 1 g to 5 g/ ^m2 . In that case, the preferred amount of gelatin as a hydrophilic colloid is 0.1
~10 g/ ^m2 , particularly preferably 1 g/ ^m2 to 5 g/m2. The light-sensitive material according to the present invention is formed by coating the silver halide emulsion layer on a suitable photographic support. Examples of the support used in the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, Typical examples include glass paper, cellulose acetate, cellulose nitrate, polyester films such as polyethylene terephthalate, polyamide films, polypropylene films, polycarbonate films, and polystyrene films. be selected accordingly. The light-sensitive material according to the present invention typically comprises at least one silver halide containing silver halide on a support.
The photosensitive material according to the present invention includes a protective layer having an appropriate thickness,
That is, preferably from 0.1 to 10μ, particularly preferably from 0.8 to
Preferably, a 2μ gelatin protective layer is applied. In the present invention, the hydrophilic colloid layer including the emulsion layer may contain various photographic additives such as those described in Research Disclosure No. 17643, such as hardeners, surfactants, and image forming agents. Stabilizer, UV absorber, anti-stain agent, PH
H regulators, antioxidants, antistatic agents, thickeners, graininess improvers, dyes, mordants, brighteners, development speed regulators, matting agents, etc. are used within the range that does not impair the effects of the present invention. can do. For example, thickeners or plasticizers include US Pat. No. 2,960,404;
Special Publication No. 43-4939, West German Application Publication No. 1904604,
Substances described in JP-A-48-63715, JP-A-45-15462, Belgian Patent No. 762833, US Pat. No. 3767410, Belgian Patent No. 558143, etc., such as styrene-sodium maleate copolymer, dextran Sulfate, etc., and various hardening agents such as aldehyde, epoxy, ethyleneimine, active halogen, vinyl sulfone, isocyanate, sulfonic acid ester, carbodiimide, mucochloric acid, acyloyl, etc. Film agents can be used. Furthermore, the silver halide photographic material according to the present invention can also be used as a color photographic silver halide light-sensitive material, in which case yellow, magenta,
Contains color-forming couplers such as cyan, colored couplers that have a color correction effect, couplers that release a development inhibitor during development (so-called DIR couplers), color antifoggants, etc. As the yellow coloring coupler, a known open-chain ketomethylene coupler can be used. Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. Specific examples of yellow couplers that can be used include U.S. Pat.
2875057, 3265506, 3408194, 3551155, 3582322, 3725072,
West German Patent Application No. 3891445, West German Patent No. 1547868, West German Patent Application (OLS) No. 2213461, OLS No. 2219917,
It is described in No. 2261361, No. 2414006, No. 2263875, etc. As the magenta coloring coupler, pyrazolone compounds, indazolone compounds, cyanoacetyl compounds, etc. can be used, and pyrazolone compounds are particularly advantageous. Specific examples of magenta coloring couplers that can be used include U.S. Pat. No. 2,600,788;
No. 2983608, No. 3062653, No. 3127269, No.
No. 3314476, No. 3419391, No. 3519429, No.
No. 3558319, No. 3582322, No. 3615506, No. 3582322, No. 3615506, No.
No. 3834908, No. 3891445, West German Patent No. 1810464,
West German Patent Application (OLS) No. 2468665, OLS No. 2417945
No. 2418959, No. 2424467, Special Publication No. 40-6031
This is what is listed in the issue. As the cyan coloring coupler, phenol compounds, naphthol compounds, etc. can be used. Specific examples include U.S. Patent No. 2,369,929;
No. 2434272, No. 2474293, No. 2521908, No.
No. 2895826, No. 3034892, No. 3311476, No. 3311476, No.
No. 3458315, No. 3476563, No. 3583971, No.
No. 3591383, No. 3767411, West German patent application (OLS)
It is described in No. 2414830, No. 2454329, and JP-A-48-59838. Examples of colored couplers include U.S. Patent No. 3476560, U.S. Patent No. 2521908, U.S. Pat.
Patent Application No. 44-32461, Specification of Patent Application No. 49-98469, No. 50
−118029, West German Patent Application (OLS) No.
The one described in No. 2418959 can be used. As a DIR coupler, for example, U.S. Patent No.
No. 3227554, No. 3617291, No. 3701783, No. 3227554, No. 3617291, No. 3701783, No.
No. 3790384, No. 3632345, West German patent application (OLS)
Those described in No. 2414006, No. 2454301, No. 2454329, British Patent No. 953454, and Japanese Patent Application No. 146570-1988 can be used. In addition to the DIR coupler, the light-sensitive material may also contain a compound that releases a development inhibitor during development; for example, U.S. Pat. No. 3,297,445, U.S. Pat.
The one described in West German Patent Application (OLS) No. 2417914 can be used. Others: JP-A No. 55-85549;
No. 57-94752, No. 56-65134, No. 56-135841,
No. 54-130716, No. 56-133734, No. 56-135841
No. 4,310,618, UK Patent No. 2,083,640
Research Disclosure No. 18360 (1979
), No.14850 (1980), No.19033 (1980), No.
19146 (1980), No.20525 (1981), No.21728 (198
2
Couplers described in 2010) can also be used. In order to introduce the coupler into the silver halide emulsion layer, a known method such as the method described in US Pat. No. 2,322,027 can be used. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl phosphate), tributyl acid), benzoate esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), etc., or organic solvents with a boiling point of about 30°C to 150°C, e.g. lower alkyl acetates such as ethyl acetate, butyl acetate, propionic acid. After being dissolved in ethyl, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used. When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution. These couplers are generally added in an amount of 2 x 10 ^-3 mol to 5 x 10 -1 mol, preferably 1 x 10 ^-2 mol to 5 x ^{10 -1 mol} , per mol of silver in the silver halide emulsion layer. Furthermore, the silver halide photographic material according to the present invention is widely applicable not only to the above-mentioned color photography, but also to silver salt dye bleaching, reversal, diffusion transfer, X-ray, microfilm, black and white general use, etc. Although it can be done,
Particularly preferably, it can be used as a silver halide photographic material for plate making in printing. When used as a silver halide photographic light-sensitive material for plate making, a polyalkylene oxide compound can be contained as a halftone dot improver. The polyalkylene oxide compound used in the present invention refers to a compound containing at least 10 or more and at most 200 polyalkylene oxide chains in the molecule, such as polyalkylene oxide and aliphatic alcohols, phenols, fatty acids, etc.
Condensation reaction products with compounds having active hydrogen atoms such as aliphatic mercaptans and organic amines, or condensation products of polyols such as polypropylene glycol and polyoxytetramethylene polymers with aliphatic mercaptans, organic amines, ethylene oxide, propylene oxide, etc. It includes block copolymers in which the polyalkylene oxide chain in the molecule is divided into two or more locations instead of one. The total weight of polyalkylene oxide is
It is preferably 10 or more and 100 or less. Specific examples of the polyalkylene oxide compound used in the present invention include the following compounds. (2-1) HO(CH ₂ CH ₂ O) nH [n=35] (2-2) n-C ₄ H ₃ O(CH ₂ CH ₂ O) lH [l=20] (2-3) n −C ₈ H ₁₇ O(CH ₂ CH ₂ O) lH [l=30] (2-4) n−C ₁₂ H ₂₅ O(CH ₂ CH ₂ O) lH [l=30] _{( 2-7} ) _{C4H9S ( CH2CH2O} ) _{nCOCH2CH2COOH}
[n=50] (2-8) HO (CH ₂ CH ₂ O) l (CH ₂ ) m (CH ₂ CH ₂ O)
nCOCH ₂ CH ₂ COOH [l+n=70, m=5] ( _2-13 ) HO( _CH2CH2O ) _{l ( CH2CH2CH2CH2O} ) _m
−(CH ₂ CH ₂ O) nH [l+n=23, m=21] (2-14) HO(CH ₂ CH ₂ O) l(CH ₂ CH ₂ CH ₂ CH ₂ O) m
−(CH ₂ CH ₂ O) nH [l+n=38, m=15] In the present invention, the amount of the optional polyalkylene oxide compound added is in the range of 0.01 to 10 g, preferably 0.1 g to 3 g, per mole of silver halide. The addition position may be either the silver halide emulsion layer and/or the non-photosensitive layer, but preferably the silver halide emulsion layer and/or the layer below it. The silver halide photographic material according to the present invention includes:
Various light sources are used, such as natural light, laser light such as argon light, a light emitting diode, a xenon lamp, a metal halide lamp, a tungsten lamp, and a fluorescent lamp. As the developer for the silver halide photographic light-sensitive material according to the present invention, either a developer used for a general silver halide photographic light-sensitive material or a lithium developer can be used. As developing agents, hydroquinone, chlorohydroquinone, dihydroquinobenzenes such as catechol, 1-phenyl-
3-pyrazolidones such as 3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, N-methyl-p-
para-aminophenols such as aminophenol, N-(4-hydroxyphenyl)glycine,
N,N-β-methanesulfonamidoethyl, ethyl-3-methyl-4-aminoaniline, N,N-
p- such as diethyl-p-phenylenediamine
Examples include phenylene diamines and ascorbic acids, and an aqueous solution containing one or more of these developing agents is used, as well as preservatives such as potassium sulfite, formaldehyde sodium bisulfite, hydroxyamine, ethylene urea, and odor. Development inhibitors such as potassium chloride, potassium iodide, 1-
organic fog suppressants such as phenyl-5-mercaptotetrazole, 5-nitrobenzimidazole, 5-nitrobenztriazole, 5-nitroindazole, 5-methyl-benztriazole, 4-thiazoline-2-thione, sodium carbonate, Alkaline and buffering agents such as potassium hydroxide, borax, diethanolamine, triethanolamine, salts such as sodium sulfate, sodium acetate, sodium citrate, EDTA
- Water softeners such as 2-sodium salts, nitrotriacetic acid, hydroxyethylenediaminetriacetic acid, developer hardeners such as glutaraldehyde, developing agents and organic inhibitors such as diethylene glycol, dimethylformamide, ethyl alcohol, benzyl alcohol. Solvents such as methyl imidazoline, methyl imidazole, polyethylene glycol with an average molecular weight of 1540, development accelerators such as dodecylpyridinium bromide, etc. can be added. Although the pH of the developer is not subject to any restrictions,
Usually 8 to 13 are used, preferably 9 to 12
It is. Further, the treatment temperature is usually selected between 20°C and 50°C. Preferred embodiments of the invention are as follows. (1) In the dye represented by the following general formula [] in the claims, the general formula [] [Z in the formula represents a nonmetallic atomic group necessary to form an oxazolidine ring, a 3(H) oxazole ring, a 3(H) benzoxazole ring, or a 3(H) naphthoxazole ring. R ₁ represents an alkyl group, and R ₂ represents a halogen atom, an alkyl group, an alkoxy group, or a hydrogen atom. A represents a nitrile group, an alkylsulfonyl group, a sulfonamide group, an alkylsulfonylamino group, or a lower alkoxy group, and n is an integer value of 1 to 4. ] (2) In embodiment (1), R ₁ in the general formula [] represents a carboxyalkyl group, a hydroxyalkyl group, a sulfate alkyl group, or a sulfonalkyl group. (3) In embodiment (2), R ₂ in the general formula [] represents a hydrogen atom, a methyl group, a methoxy group, or a chlorine atom. (4) In embodiment (3), Z in the general formula [ ] is 3
(H) represents a benzoxazole ring. (5) In embodiment (4), n in the general formula [ ] is 1
or an integer value of 2. (6) In embodiment (5), A in the general formula [] is a nitrile group, a sulfonamide group, or a methoxy group. [Examples] The present invention will now be described in more detail with reference to Examples. Example 1 A 0.2μ cubic crystal monodisperse silver chloroiodobromide emulsion (composition (AgCl:AgBr:AgI=69:30:1) is prepared according to a conventional method and subjected to gold-sulfur sensitization. This emulsion is 25
A sensitizing dye was added to each emulsion as shown in Table 1, and 2-methyl-4-hydroxy-1,3,3a,7-tetrazaindene (3 g/1 mol of silver) was added to each emulsion. , 1-phenyl-5-mercaptotetrazole (10 mg/1 mol of silver), 3% saponin as a coating aid, polyethyl acrylate as a softener, and a polyalkylene oxide compound as a halftone dot improver (the above-mentioned exemplified compound [2-5)] ] (600mg/
1 mole of silver), plus 2 g of gelatin in the emulsion layer/
The above-mentioned gelatin was added to give a coating weight of 3.5 g/m 2 and a silver coating amount of 3.5 g/m ² , and the gelatin was coated on a polyester base at the same ^weight as the protective layer solution described below and dried. The above protective layer liquid is
It consists of gelatin, succinic acid octyl ester as a coating aid, 4μ silica as a matting agent, and mucochloric acid as ^a hardening agent. Coated on top and dried. The applied sample obtained as above was heated to relative humidity.
This sample and the above sample, which had been stored at 40% relative humidity and 23°C, were placed together using a green light filter ( It was exposed to light through a latten-58). After exposure, at 38℃ using a developer with the following composition,
It was developed for 20 seconds and fixed using Sakura Fixer Type 821. (Developer 1) Hydroquinone 25g 4,4-dimethyl-3-pyrazolidone 0.5g Potassium sulfite 100g Potassium bromide 3g Triethylene glycol 30g Polyethylene glycol (average molecular weight 1500)
3g 5-Nitroindazole 0.1g Potassium carbonate 30g Sodium ethylenediaminetetraacetate 2g 5-Methylbenzotriazole 0.2g It was diluted with water, and the pH was adjusted to 10.7 with caustic potassium. The obtained results are shown in Table 1 below. In the table, sensitivity is evaluated by the point showing a concentration of 3.0 on the characteristic curve.
When sample No. 21 is stored at 23°C and 40% RH, the green light sensitivity is set as 100 and the relative sensitivity is displayed.
Fog is also displayed including base density.
Furthermore, the gradation is expressed by the slope of the straight line on the characteristic curve. In addition, the numbers of the sensitizing dyes in the table are indicated by the numbers of the above-mentioned exemplified compounds.

【table】

[Table] From the above results, the samples (No. 2 to 16) spectrally sensitized using the merocyanine dye according to the present invention are as follows:
It can be seen that sensitivity, fog, and gradation are stable even when stored under high temperature and high humidity compared to comparative samples (Nos. 17 to 25) that were similarly spectrally sensitized using comparative sensitizing dyes. Example 2 A 0.25μ monodisperse silver chlorobromide emulsion (silver chloride: silver bromide = 80:20) was prepared in the presence of iridium chloride (10 ⁻⁶ mol/silver 1 mol). The prepared emulsion was divided into parts, and a sensitizing dye, sodium thiosulfate, and gold chloride were added to each emulsion as shown in Table 2, and each emulsion was subjected to chemical ripening and spectral sensitization under optimal conditions. Next, each emulsion was added with 2-methyl-4- as a stabilizer.
Hydroxy-1,3,3a,7-tetrazaindene (2 g/1 mole of silver), 1-phenyl-5-methylcaptotetrazole (150 mg/1 mole of silver), Exemplary polyalkylene oxide compound (2-10) (900
mg/mol silver), 2% saponin as a coating aid,
In addition to polyethyl acrylate (100% by weight based on gelatin) as a softener, gelatin was added so that the amount of gelatin in the emulsion layer was 1.8 g/m ² and the amount of silver was 3 g/m ² . A protective layer solution having the following composition was simultaneously coated onto the base and dried. The above protective layer liquid consists of gelatin, phthalated gelatin, 2% saponin, olymethyl methacrylate with an average particle size of 3μ, and bis(vinylsulfonylmethyl).
Containing ether etc., this was simultaneously coated on the emulsion layer so that the amount of gelatin attached was 2 g/m ² as described above. The above coated sample was left for 5 days under the conditions of relative humidity 80% and temperature 50°C as in Example-1, and this sample was compared with the above sample stored under the conditions of relative humidity 40% and temperature 23°C. the green light through the filter
A 10 ^-5 second exposure was applied. After exposure, development was carried out at 32° C. for 1 minute using a developer having the composition shown below, and further fixation was carried out. (Developer Solution 2) Hydroquinone 25g Sodium sulfite 3g Sodium ethylenediaminetetraacetate 3g Potassium carbonate 40g Potassium bromide 3g 5-nitroindazole 3mg Diethylene glycol 40g The pH was adjusted to 1 with water, and the pH was adjusted to 10.2 with caustic soda. The results obtained are shown in Table 2, and the display methods for sensitivity, fog, and gradation were the same as in Example-1. However, the sensitivity is sample No. The green light sensitivity when stored at 23℃ and 40% RH of 33 is expressed as relative sensitivity as 100.

[Table] From the above results, the samples (No. 27 to 32) spectrally sensitized using the merocyanine dye according to the present invention are as follows:
Compared to comparative samples (Nos. 33 to 36) that were similarly spectrally sensitized using comparative sensitizing dyes, the green light sensitivity is higher during high-intensity exposure, and the properties are stable with less variation during storage at high temperatures and high humidity. It can be seen that it has been modified. Furthermore, in the present invention, the pigment stain was also used as comparative sample 33.
It was improved compared to 35 and 35. Example 3 A silver iodobromide emulsion (silver bromide: silver iodide = 98:2) with an average grain size of 0.3 μm was prepared in the same manner as in Example 1, and then gold chloride, sodium thiosulfate, and rhodan ammonium were added. was added for chemical ripening. The prepared emulsion was divided into five parts, each was subjected to spectral sensitization by adding 30 x 10 ^-5 moles of sensitizing dye per mole silver as shown in Table 3, and then 2-methyl-4-hydroxy -1,
3,3a,7-tetrazaindene (3g/1 mole of silver)
was added, and each emulsion was further divided into four. To each of the redivided emulsions was added each hardening agent (H1 to H4) equivalent to 10 mg per g of gelatin as shown in Table 3.
Furthermore, 3% saponin was added as a coating aid, and polyethyl acrylate was added as a softener, and the amount of gelatin on the emulsion layer was 2 g/m ² and the amount of silver was 3.6 g/m 2 .
Gelatin was added to give an amount of m ² and applied onto a polyester base, followed by drying. The obtained coated samples were left for 1 day and 30 days at a temperature of 23 DEG C. and a relative humidity of 50%, and then exposed, developed and fixed in the same manner as in Example-1. Table 3 shows the specific sensitivity and fog density change of the samples left for 30 days, with the sensitivity of each sample left for 1 day as 100. The change in fog density was determined using the following equation. [Fog density of sample left for 30 days] - [Fog density of sample left for 1 day]

[Table] As is clear from Table 3, in the comparative samples to which the comparative sensitizing dye was added, a decrease in sensitivity and a change in fog density were observed depending on the hardening agent used (specifically, sample No. 49, 51, 53, 55). In contrast, in the present invention, the decrease in sensitivity and change in fog density due to the type of hardening agent are very small, which suggests that the sensitizing dye used in the present invention is not easily affected by additives. . [Effects of the Invention] As explained in detail above, the silver halide photographic material of the present invention contains a novel merocyanine dye and exhibits a high spectral sensitization effect without being affected by additives. Further, the silver halide photographic material of the present invention shows little change in photographic properties such as a decrease in sensitivity or an increase in fog even with the passage of time.

Claims (1)

[Scope of Claims] 1 In a silver halide photographic material having at least one silver halide emulsion layer on a support, the silver halide grains contained in the silver halide emulsion layer have the following general formula [] A silver halide photographic material characterized by being spectrally sensitized with a compound represented by: General formula [] [Wherein, Z represents a nonmetallic atomic group necessary to form an oxazolidine ring, a 3(H) oxazole ring, a 3(H) benzoxazole ring, or a 3(H) naphthoxazole ring. R ₁ represents an alkyl group, R ₂ represents a halogen atom, an alkyl group, an alkoxy group or a hydrogen atom, and A represents a nitrile group, an alkylsulfonyl group, a sulfonamido group, an alkylsulfonylamino group or a lower alkoxy group. n is 1
Represents an integer value of ~4. ]