JPH053571B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] 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 green light sensitivity. [Background of the Invention] Conventionally, since a photosensitive silver halide emulsion alone has a narrow sensitive wavelength range, spectral sensitizers have been used for the purpose of expanding the sensitive wavelength range to longer wavelengths. For example, Japanese Patent Publications No. 38-7828, No. 40-392,
No. 43-10251, No. 43-22884, British Patent No. 815172
No. 955912, No. 955961, No. 142228, U.S. Pat.
No. 2238231, No. 2521705, No. 2647059, No.
No. 2839403, No. 2839404, Special Publication No. 43-2606, No. 2839404,
44-3644, 48-15032, 49-33782, 49-33782, 48-15032, 49-33782,
No. 54-34252, No. 58-52574, U.S. Patent No. 3567458
Examples include cyanine dyes and merocyanine dyes described in specifications and publications such as No. 3,625,698. These spectral sensitizers not only increase the sensitivity in a specific wavelength range, but also: (1) are not affected by other additives or affect the effects of other additives; (2) No change in photographic characteristics such as a decrease in sensitivity or increase in fog occurs even over time. (3) No color staining should occur after treatment. The following characteristics are required. However, the current situation is that none of the conventionally developed spectral sensitizers has been found that satisfies all of these conditions. [Object of the Invention] The first object of the present invention is to produce a product that is not affected by additives;
Moreover, it is an object of the present invention to provide a silver halide photographic material containing a novel merocyanine dye having 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, and does not cause color staining. [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 group of nonmetallic atoms necessary to form a 5-membered or 6-membered heterocycle. R ₁ represents an alkyl group. R ₂ represents a pyridyl group. _R3
is a cyanoalkyl group, an alkylsulfonylalkyl group, a sulfamoylalkyl group, an alkylsulfonylaminoalkyl group, an alkoxyalkyl group, an alkoxycarbonylalkyl group, a hydroxyalkyl group, a hydroxyalkoxyalkyl group, a carbamoylalkyl group, a hydroxyphenyl group, or a hydroxy Represents an alkylphenyl group. L ₁ and L ₂ represent methine groups. ] [Specific structure of the invention] In the general formula [], Z represents a group of nonmetallic atoms necessary to form a 5-membered or 6-membered heterocycle. The heterocycle includes, for example, a thiazoline nucleus,
Thiazolidine nucleus, selenazoline nucleus, oxazolidine nucleus, oxazoline nucleus, benzothiazoline nucleus, benzoselenazoline nucleus, benzoxazoline nucleus, naphthothiazoline nucleus, naphthoselenazoline nucleus, naphthoxazoline nucleus, etc., which may be substituted with a substituent. . Examples of the substituent include halogen atoms (e.g., fluorine atom, chlorine atom, bromine atom, etc.), alkyl groups, preferably alkyl groups having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, n-propyl group, etc.), alkoxy group, preferably an alkoxy group having 1 to 4 carbon atoms (e.g. methoxy group, ethoxy group,
n-propyloxy group, etc.), alkoxycarbonyl group, preferably an alkoxycarbonyl group having 2 to 5 carbon atoms (e.g., methoxycarbonyl group, ethoxycarbonyl group, etc.), hydroxy group, aryl group (e.g., phenyl group, etc.). . In the general formula [ ], the alkyl group represented by R ₁ is preferably an alkyl group having 1 to 6 carbon atoms (e.g., methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, etc.) Ten
substituted alkyl groups (e.g. methoxymethyl group, carboxymethyl group, 2-methoxyethyl group, 2-
hydroxyethyl group, 2-carboxyethyl group,
2-sulfoethyl group, 2-chloroethyl group, 3-
Sulfopropyl group, 3-carboxypropyl group,
3-sulfobutyl group, 4-sulfobutyl group, 3-
Carboxybutyl group, 4-carboxybutyl group,
2-chloro-3-methoxypropyl group, vinylmethyl group, benzyl group, 4-sulfophenethyl group,
2-carbamoylethyl group, 2-sulfamoylethyl group, 2-methylsulfonylethyl group, etc.)
etc., and more preferably R ₁ has 1 to 6 carbon atoms.
substituted alkyl groups (e.g. methoxyethyl group, carboxymethyl group, 2-carboxyethyl group, 2-carboxyethyl group,
-Sulfoethyl group, 3-sulfopropyl group, 2-
sulfamoylethyl group, etc.). Examples of the pyridyl group represented by R ₂ include a 2-pyridyl group, a 3-pyridyl group, and a 4-pyridyl group, and the pyridyl group may be substituted with a substituent. The substituent includes an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms (for example, a methyl group,
ethyl group, etc.), alkoxy group (preferably an alkoxy group having 1 to 4 carbon atoms (e.g., methoxy group, ethoxy group, etc.), halogen atom (e.g., chlorine atom,
(bromine atom, etc.), carboxy group, hydroxy group, etc. R ₃ is a cyanoalkyl group, preferably having 1 carbon number
-5 cyanoalkyl groups (e.g. cyanomethyl group, 2-cyanomethyl group, 3-cyanopropyl group, 2-cyanopropyl group, etc.), alkylsulfonylalkyl groups, preferably with a total number of carbon atoms of 2
-8 alkylsulfonylalkyl groups (e.g. methylsulfonylmethyl group, 2-methylsulfonylethyl group, 2-ethylsulfonylethyl group, etc.),
A sulfamoyl alkyl group, preferably a sulfamoyl alkyl group having a total number of carbon atoms of 2 to 6 (for example, a 2-N-methylsulfamoylethyl group, a 2-
N,N-dimethylsulfamoylethyl group, etc.),
Alkylsulfonylaminoalkyl group, preferably an alkylsulfonylaminoalkyl group having a total number of carbon atoms of 2 to 6 (e.g. methylsulfonylaminomethyl group, 2-methylsulfonylaminoethyl group, etc.), an alkoxyalkyl group, preferably a total number of carbon atoms is 2 to 6 alkoxyalkyl groups (e.g. methoxymethyl group, 2-methoxyethyl group, 2
-propyloxyethyl group, etc.), alkoxycarbonylalkyl group, preferably an alkoxycarbonylalkyl group having a total of 3 to 7 carbon atoms (e.g., methoxycarbonylmethyl group, ethoxycarbonylmethyl group, ethoxycarbonylethyl group, etc.), hydroxyalkyl group , preferably a hydroxyalkyl group having 1 to 4 carbon atoms (e.g. 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group,
-hydroxypropyl group, 2,3-dihydroxypropyl group, etc.), hydroxyalkoxyalkyl group, preferably hydroxyalkoxyalkyl group having a total of 2 to 6 carbon atoms {e.g., hydroxymethoxymethyl group, 2-(2-hydroxyethoxy)
ethyl group, 2-hydroxyethoxymethyl group, etc.}, carbamoyl alkyl group, preferably carbamoyl alkyl group having a total number of carbon atoms of 2 to 8 {N
-alkyl substitution, N,N-dialkyl substitution, N-
Includes substituted carbamoyl alkyl groups with hydroxyalkyl substitution, N-alkyl-N-hydroxyalkyl substitution, or N,N-di(hydroxyalkyl) substitution, and carbamoyl alkyl groups of 5- or 6-membered cyclic amines. For example, 2-carbamoylethyl group, 2-N-(2-hydroxyethyl)carbamoylethyl group, N-hydroxyethylcarbamoylmethyl group, N,N-di(2-hydroxyethyl)carbamoylmethyl group, 2-N,N- Ji (2
-hydroxyethyl) carbamoylethyl group,
N,N-dimethylcarbamoylmethyl group, morpholinocarbamoylmethyl group, piperidinocarbamoylmethyl group}, hydroxyphenyl group, or hydroxyalkylphenyl group, preferably a hydroxyalkylphenyl group having 7 to 9 carbon atoms {e.g. 4-(2-hydroxyethyl)phenyl group,
3-(1-hydroxyethyl)phenyl group, etc.}
represents. L ₁ and L ₂ represent a methine group, and the methine group may be substituted with an alkyl group or an aryl group, such as -CH=, -C( _CH3 )=,

Examples include [Formula]. Next, typical examples of the compound represented by the above general formula [] used in the present invention will be listed, but the compounds used in the present invention are not limited to these. The compound represented by the general formula [] used in the present invention is disclosed in Japanese Patent Publication No. 46-549, No. 46-18105.
No. 46-18106, No. 46-18108, No. 47-4085
No. 58-52574, U.S. Patent No. 2839403, Id.
No. 2839404, No. 3384486, No. 3625698, No.
It can be synthesized according to the method for synthesizing dimethine merocyanine described in No. 3480439, No. 3567458, etc. Next, specific synthesis examples will be shown, but other compounds represented by the general formula [] can also be synthesized according to the synthesis method below. [Synthesis Example] Synthesis of Exemplified Compound (1) 9 g of N-(2-pyridyl)aminoacetic acid ethyl ester and 6 g of 2-methoxyethyl isothiocyanate were heated to 150° C. for 60 minutes. The product has 2
-[2-(2-piperidino)-3-penzooxazolio]ethanesulfonate 5.5g and ethanol 50g
ml, and while stirring at room temperature, a solution of 1.7 g of potassium hydroxide dissolved in 50 ml of ethanol was added, reacted for 30 minutes, and then left to stand. Filter the precipitated crystals,
Exemplary compound (1) was recrystallized from aqueous methanol solution.
1.1 g of orange crystals were obtained. The methanol solution of this compound had a λmax of 483 nm. The merocyanine dye represented by the general formula [] used in the present invention can be added and dispersed in a silver halide emulsion by a conventionally known method. For example, special public service in 1977-
44895 and JP-A-50-11419, the method of dispersing and adding with a surfactant, JP-A-Sho.
53-16624, 53-102732, and 53-102733, the method of adding as a dispersion with a hydrophilic substrate described in the specifications of U.S. Patent Nos. 3469987 and 3676147, East German patent Examples include the method of adding as a solid solution described in the specification of No. 143324. In addition, the merocyanine dye represented by the above general formula [] is dissolved in a water-soluble solvent such as water, ethanol, methanol, acetone, n-propanol, fluorinated alcohol, pyridine, etc. alone or in a mixture thereof to form an emulsion. May be added to. It can be added at any time during the emulsion manufacturing process, but
Preferably, during or after chemical ripening. The amount of the merocyanine dye represented by the general formula [] used in the present invention is the amount that spectrally sensitizes the silver halide emulsion, for example, 1 x 10 ^-5 to 2 x 10 ^-2 mol per 1 mol of silver halide. , preferably 1×
10 ⁻⁴ to 2×10 ⁻³ mol. Further, the merocyanine dye represented by the general formula [] used in the present invention can be, for example,
No. 4933, No. 43-4936, No. 46-18107, No. 46-
No. 1999, No. 47-11114, No. 48-1762, No. 48-
38408, 56-38937, 58-52574, U.S. Patent No. 2519001, U.S. Pat. can. Silver halides used in the silver halide photographic emulsion of the silver halide photographic light-sensitive material according to the present invention include silver iodobromide, silver bromide, silver chloride, silver chlorobromide, silver chloroiodobromide, and silver chloroiodide. Silver etc. 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 emulsion used in the present invention can be prepared by any of forward mixing, back mixing, semi-back mixing, and simultaneous mixing, but the most preferred method is the simultaneous mixing method. In addition, methods for preparing emulsions include the ammonia method,
Although there are neutral methods and acidic methods, it is particularly preferable to use 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 shape. 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. Chemical sensitizers used in this chemical sensitization include, for example, active gelatin, sulfur sensitizers (sodium thiosulfate, allylthiocarbamide, thiourea, N-ethyl-N'-2-thiazolylthiourea, allyl thiocyanate, etc.), selenium sensitizers (N,N-dimethylselenourea, selenourea, etc.), reduction sensitizers (triethylenetetramine, stannic chloride, etc.), such as potassium chlorooolite, potassium aurithiocyanate, potassium Various noble metal sensitizers represented by chloroaurate, 2-oresulfobenzothiazole methyl chloride, ammonium chloroparadate, potassium chloroplatinate, sodium chloroparadite, etc. can be used alone or in combination of two or more. Can be used. 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 for example 4-
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, 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 No. 2217153 and West German Application No. 2217895 can also be used in the silver halide emulsion used in the present invention. Particularly preferably 1-phenyl-
When used in combination with 5-mercaptotetrazole,
The amount added is 1 mg to 5 mg per mole of silver halide.
g, preferably 10 mg to 500 mg. 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, water-soluble rhodium salts, etc. Particular examples of water-soluble rhodium salts include rhodium dichloride, rhodium trichloride, ammonium hexachlorodate, etc. can be mentioned, but
Preferred is a complex compound of rhodium trichloride and a halogen, preferably chlorine or bromine. 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 silver halide photographic 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 cellulose acetate, acrylamide, imidized polyamide, polyvinyl alcohol, hydrolyzed polyvinyl acetate, e.g. British Patent
No. 523661, West German Application Publication No. 2255711, West German Application No. 2046682
water-soluble polymers, gelatin derivatives, such as phenylcarbamyl gelatin, acylated gelatin, phthalated gelatin, as described in US Pat. Or US Patent
Examples include gelatin graft polymerized with polymerizable monomers having ethylene groups such as styrene acrylate, acrylic ester, and methacrylic ester as described in No. 2548520 and No. 2831767, etc. These hydrophilic colloids can also be applied to hydrophilic colloid layers that do not contain silver halide, such as antihalation layers, protective layers, intermediate layers, 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.
g/m ² , preferably 1 g/m ² to 5 g/m 2 . In that case, the amount of gelatin as hydrophilic colloid is preferably from 0.1 g to 10 g/m ² , particularly preferably:
It is 1 g to 5 g/ ^m2 . The silver halide photographic light-sensitive material according to the present invention is formed by coating the above-mentioned silver halide emulsion layer on a suitable photographic support.
Typical examples include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass paper, cellulose acetate, cellulose nitrate, polyester films such as polyethylene terephthalate, polyamide films, polypropylene films, polycarbonate films, and polystyrene films. Each of these supports is appropriately selected depending on the intended use of the silver halide photographic material. The silver halide photographic material according to the present invention is typically formed by coating on a support at least one hydrophilic colloid layer containing silver halide. It is desirable that the silver photographic light-sensitive material be coated with a protective layer of gelatin having an appropriate thickness, preferably 0.1 to 10 .mu.m, particularly preferably 0.8 to 2 .mu.m. 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
Conditioners, 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. be able to. For example, thickeners or plasticizers include US Pat. Substances described in Patent No. 3767410, Belgian Patent No. 558143, etc., such as styrene-sodium maleate copolymer, dextran sulfate, etc. Hardening agents include aldehyde-based, epoxy-based, ethyleneimine-based, active Various hardening agents such as halogen type, vinyl sulfone type, isocyanate type, sulfonic acid ester type, calphodiimide, mucochloric acid type, and acyloyl type can be used. The silver halide photographic light-sensitive material according to the present invention can also be used as a color photographic silver halide light-sensitive material. Contains a coupler that releases a development inhibitor (so-called DIR coupler) and a color fog preventive agent. As the yellow coloring coupler, a known closed ketomethylene coupler can be used. Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. A specific example of a yellow coupler that can be used is U.S. Pat. No. 2,875,057.
No. 3255506, No. 3408194, No. 3408194, No. 3255506, No. 3408194, No.
3551155, 3582322, 3725072, 3891445, West German Patent No. 2547868, West German Patent Application (OLS) No. 2213461, 2219917, 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. 1810494,
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 color-forming coupler, a phenol compound, a naphthol compound, 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. As a colored coupler, for example, U.S. Patent No.
No. 3476560, No. 2521908, No. 3034892, Tokko Akira
No. 44-2016, No. 38-22335, No. 42-11304, No. 42-11304, No.
No. 44-32461, specification of patent application No. 49-98469, 50-
Specification No. 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.
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.
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, US Patent No. 4310618, UK Patent No.
No. 2083640, Research Disclosure No.
18360 (1979), No. 14850 (1980), No. 19033 (198
0
year), No.19146 (1980), No.20525 (1981), No.
21728 (1982) may 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 (diphthyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (dibutyl nyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (such as acetyl tributyl citrate), benzoic acid 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, such as lower alkyl acetates such as ethyl acetate, butyl acetate, propion After being dissolved in ethyl acid, 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 a 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. As a color fog preventive agent, for example, U.S. Patent No.
No. 2360290, No. 2336327, No. 2403721, No. 2360290, No. 2336327, No. 2403721, No.
No. 2418613, No. 2675314, No. 2701197, No.
No. 2704713, No. 2728659, No. 2732300, No.
No. 2735765, Japanese Patent Application Publication No. 50-92988, No. 50-92389,
No. 50-93928, No. 50-110337, Special Publication No. 50-
Hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives, ascorbic acid derivatives, etc. described in No. 23813 and the like are used. 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 polyalkylene oxide chains and at most 200 or less polyalkylene oxide chains in the molecule, such as polyalkylene oxide and aliphatic alcohol, phenols, fatty acids, aliphatic Condensation reaction products with compounds having active hydrogen atoms such as mercaptans and organic amines, or aliphatic mercaptans with polyols such as polypropylene glycol and polyoxytetramethylene polymers,
It is a condensation product of organic amines, ethylene oxide, propylene oxide, etc., and also includes block copolymers in which the polyalkylene oxide chain in the molecule is split into two or more locations instead of one. The total polymerization degree of polyalkylene oxide is 10 or more.
100 or less is preferable. Specific examples of the polyalkylene oxide compound used in the present invention include the following compounds.

【table】

【table】 ‖
(CH ₂ CH ₂ O) _o CCH ₂ CH ₂ COOH
〓l+n=15, m=15〓

【table】 \
(CH ₂ CH ₂ O) _l H
〓l＋n＝30〓
In the present invention, the amount of the optionally used polyalkylene oxide compound added is 0.01 to 10 g, preferably 0.1 to 3 g per mole of silver halide.
is within the range of 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 non-photosensitive layer.
The lower layer is preferred. As a light source for exposing the silver halide photographic light-sensitive material according to the present invention, natural light, laser light such as argon light, a light emitting diode, a xenon lamp, a metal halide lamp, a tungsten lamp, a fluorescent lamp, etc. are used. As the developer for the silver halide photographic light-sensitive material according to the present invention, either a developer used for general silver halide photographic light-sensitive materials or a lithium developer can be used. As developing agents, hydroquinone, chlorohydroquinone, dihydroquinobenzenes such as catechol, 1-phenyl-3
-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone,
3-pyrazolidones such as 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, N-methyl-p-aminophenol, N-
Para-aminophenols such as (4-hydroxyphenyl)glycine, N-β-methanesulfonamidoethyl-N-ethyl-3-methyl-4-aminoaniline, N,N-diethyl-p-phenylenediamine, etc. Examples include p-phenylene diamines and ascorbic acids, and an aqueous solution containing one or more of these developing agents is used as the developer, and potassium sulfite, formaldehyde sodium hydrogen sulfite, hydroxyamine, ethylene urea, etc. preservatives such as potassium bromide, development inhibitors such as potassium iodide, 1'-phenyl-5
-Mercaptotetrazole, 5-nitrobenzimidazole, 5-nitrobenztriazole, 5
- Organic antifoggants such as nitroindazole, 5-methyl-benztriazole, 4-thiazoline-2-thione, alkaline agents such as sodium carbonate, potassium hydroxide, borax, diethanolamine, triethanolamine, and buffers. agents, salts such as sodium sulfate, sodium acetate, sodium citrate, water softeners such as EDTA-disodium salt, nitrotriacetic acid, hydroxyethylenediaminetriacetic acid, developer hardeners such as glutaraldehyde, diethylene glycol,
Solvents for developing agents and organic inhibitors such as dimethylformamide, ethyl alcohol, benzyl alcohol, methylimidazoline, methylimidazole, polyethylene glycol with an average molecular weight of 1540,
A development accelerator such as dodecylpyridinium bromide can be added. Although the pH of the developer is not subject to any restrictions, a pH of 8 to 13 is usually used, preferably 9 to 12. Further, the development processing temperature is usually selected between 20°C and 50°C. [Examples] The present invention will be explained in more detail below with reference to Examples. Example 1 0.2μ cubic monodisperse silver chloroiodobromide emulsion (composition
AgCl:AgBr:AgI=69:30:1) was prepared according to a conventional method and subjected to gold-sulfur sensitization. This emulsion was divided into 22 parts, 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 mole of silver), 1-phenyl-5-mercaptotetrazole (10 mg/1 mole of silver), 3% saponin as a coating aid, polyethyl acrylate as a softener, and a polyalkylene oxide compound as a halftone improver (as described above). Exemplary compound [2-5]) (600
mg/1 mole of silver), and gelatin was added so that the amount of gelatin in the emulsion layer was 2 g/m ² and the amount of silver was 3.5 g/m ² , and the mixture was coated on the polyester base simultaneously with the protective layer solution shown below and dried. did. The above protective layer liquid consists of gelatin, succinic acid octyl ester as a coating aid, 4μ silica as a matting agent, and mucochloric acid as a hardening agent, and as mentioned above, the amount of gelatin attached is 2 g/m ² It was simultaneously coated on the emulsion layer 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 ( Wedge exposure was performed through a lattice film (58). After exposure, develop using the following composition 38
℃ 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 Ethylenediaminetetraacetic acid Sodium 2g 5-methylbenzotriazole 0.2g The solution was adjusted to 1 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.
Relative sensitivity is displayed with the green light sensitivity of sample No. 18 stored at 23°C and 40% RH as 100.
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, samples (No. 2 to 13) spectrally sensitized using the merocyanine dye according to the present invention
Compared to the comparative samples (Nos. 14 to 22) that were similarly spectrally sensitized using comparative sensitizing dyes, the sensitivity decreased significantly even when stored under high temperature and high humidity conditions.
Furthermore, there is almost no increase in fog or decrease in gradation,
It can be seen that it is extremely stable. 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, and a sensitizing dye, sodium thiosulfate, and gold chloride were added to each emulsion as shown in Table 2.
Chemical ripening and spectral sensitization were performed under optimal conditions. Next, each emulsion was used as a stabilizer with 2-methyl-4-hydroxy-1,3,3a,7-tetrazaindene (2 g/1 mole of silver) and 1-phenyl-5-mercaptrazole (150 mg/1 mole of silver). ), exemplified polyalkylene oxide compound (2-10) (900 mg/mol silver), 2% sabonin as a coating aid, polyethylene acrylate as a softener (based on gelatin),
100% by weight), etc., 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 , and layered on the polyester base at the same time as a protective layer solution with the following composition. Apply and dry. The above protective layer liquid consists of gelatin, phthalated gelatin, 2% saponin, polymethyl 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 80% relative humidity and 50°C as in Example 1, and this sample was compared with the above sample that had been stored under the conditions of 40% relative humidity and 23°C. A 10 ⁻⁵ second wedge exposure was performed using a xenon light source through a green light filter. 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-2) Hydroquinone 25g Sodium sulfite 3g Sodium ethylenediaminetetraacetate 3g Potassium carbonate 40g Potassium bromide 3g 5-nitroindazole 3mg Diethylene glycol 40g The solution 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 expressed as a relative sensitivity, with the green light sensitivity of sample No. 28 stored at 23°C and 40% RH as 100.

【table】

[Table] From the above results, it can be seen that the samples (Nos. 24 to 27) spectrally sensitized using the merocyanine dye according to the present invention are the same as the comparative samples (No. .28-30), the green light sensitivity is higher during high-intensity exposure, and the characteristics such as green light sensitivity, fog, and gradation change during storage at high temperature and high humidity are also reduced and stabilized. Furthermore, dye staining was also improved in the present invention compared to the comparative sample. Example 3 A 0.30μ 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, and a sensitizing dye, sodium thiosulfate, and gold chloride were added to each emulsion as shown in Table 2.
Chemical ripening and spectral sensitization were performed under optimal conditions. Next, each emulsion was stabilized with 2-methyl-4-hydroxy-1,3,3a,7-tetrazaindene (2 g/1 mole of silver) and 1-phenyl-5-mercaptotetrazole (150 mg/1 mole of silver). , exemplified polyalkylene oxide compound (2-10) (900 mg/1 mole of silver), 2% saponin as a coating aid, polyethyl acrylate (100% by weight based on gelatin) as a softener, and gelatin in the emulsion layer. Gelatin was added so that the coating amount was 1.8 g/m ² and the silver coating amount was 3 g/m ² , and a protective layer solution having the following composition was coated on the polyester base at the same time and dried. The above protective layer liquid consists of gelatin, phthalated gelatin, 2% saponin, polymethyl methacrylate with an average particle size of 3μ, and bis(vinylsulfonylmethyl).
It contained ether, dye 1, etc., and was simultaneously coated on the emulsion layer in a gelatin coverage of 2 g/m ² as described above. The above coating sample was coated at relative humidity in the same manner as in Example 1 above.
This sample and the above sample, which had been stored at 40% relative humidity and 23°C, were exposed at 10 ^-5 through a green light filter using a xenon light source. A second wedge exposure was performed.
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-2) Hydroquinone 25g Sodium sulfite 3g Sodium ethylenediaminetetraacetate 3g Potassium carbonate 40g Potassium bromide 3g 5-nitroindazole 3mg Diethylene glycol 40g The solution was adjusted to 1 with water, and the pH was adjusted to 10.2 with caustic potassium. Relative change in color sensitization sensitivity over time, fog,
Table 3 shows the gradation evaluation results. The method of displaying fog and gradation is the same as in the first embodiment. In addition, the change in sensitivity over time (ΔS) was evaluated at the point on the characteristic curve showing a concentration of 3.0, and the sensitivity of the sample stored at 23°C and 40% RH (S ₁ ) was compared with that of the sample stored at 50°C and 80% RH. It is expressed as the relative difference in sensitivity (S ₂ ) of samples with the same number aged for days. ΔS=S ₁ [23℃, 40%RH sample] −S ₂ [50℃, 80%RH 3-day sample]

【table】

[Table] From the above results, the samples (No. 31 to 36) spectrally sensitized using the merocyanine dye according to the present invention are compared to the comparative samples (No. 31 to 36) spectrally sensitized using the comparative sensitizing dye. It can be seen that compared to .37-39), characteristics such as green light sensitivity, fog, and gradation fluctuate less and are more stable during storage at high temperatures and high humidity. Furthermore, in the present invention, green light sensitivity was high during high-intensity exposure, and pigment staining was improved compared to comparative samples.

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 are represented by the following general formula []. A silver halide photographic material characterized by being spectrally sensitized with the compound shown below. General formula [] [In the formula, Z represents a nonmetallic atomic group necessary to form a thiazoline nucleus, thiazolidine nucleus, oxazolidine nucleus, benzothiazoline nucleus, benzoselenazoline nucleus, benzoxazoline nucleus, or naphthoxazoline nucleus. R ₁ represents an alkyl group. R ₂ represents a pyridyl group. R ₃ is a cyanoalkyl group, an alkylsulfonylalkyl group, a sulfamoylalkyl group, an alkylsulfonylaminoalkyl group,
Alkoxyalkyl group, alkoxycarbonylalkyl group, hydroxyalkyl group, hydroxyalkoxyalkyl group, carbamoylalkyl group,
Represents a hydroxyphenyl group or a hydroxyalkylphenyl group. L ₁ and L ₂ represent methine groups. ]