JPH0558533B2 - - Google Patents

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material containing a polymerized stabilizer to prevent fogging during storage over time. .

[Background of the Invention] Even when light-sensitive silver halide photographic materials are not exposed to light, they tend to generate nuclei that induce development and cause fog, and especially during storage over time, the formation of fog can lead to a decrease in sensitivity. , or deterioration of gradation in extremely many cases. Many compounds have been proposed for the purpose of improving this phenomenon, such as 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene or 1-phenyl-5-mercaptotetrazole. Heterocyclic compounds in which the mercapto group of is substituted are widely known. However, these compounds do not always sufficiently suppress fog during storage of photographic materials over time, and when used in large quantities with the expectation of effectiveness, they result in decreased sensitivity and softening of gradations. Moreover, the use of a large amount of this type of stabilizer can lead to a decrease in spectral sensitivity due to the desorption of the sensitizing dye, and also lead to undesirable and disadvantageous changes as a result of diffusion into the adjacent photosensitive layer. It is to suffer from a defect. Under these circumstances, attempts have been made to improve desensitization or diffusibility by polymerizing the stabilizer. For example, U.S. Pat. No. 3,598,599 uses thiazoles, and U.S. Pat. Examples of using imidazoles in JP-A No. 3598600, tetrazaindenes in JP-A-57-211142, and benzotriazoles in JP-A No. 59-90844 as polymeric compounds with repeating stabilizer residues. is disclosed. However, all of these polymerization technologies can improve the above-mentioned spectral sensitivity inhibition or diffusion to other layers, and the important fog suppression ability, especially for color photosensitive materials at high temperatures and high humidity. The ability to suppress fog at the bottom is not necessarily sufficient,
There has been a strong demand for a fog suppressant that can withstand long-term storage of silver halide photosensitive materials.

[Purpose of the invention]

The present invention has been made in view of the above-mentioned circumstances, and its first purpose is to maintain stable photographic properties of silver halide photographic materials (hereinafter referred to as "photosensitive materials") during storage over time. An object of the present invention is to provide a photosensitive material containing a fog suppressor, that is, a stabilizer. The second object of the present invention is to contain a fog suppressant that can provide antifogging properties with little desensitization even when used in large amounts in photosensitive materials, does not inhibit spectral sensitivity, and does not diffuse into adjacent layers. The purpose of the present invention is to provide a photosensitive material with improved characteristics.

[Structure of the invention]

The above object is achieved by a photosensitive material characterized in that at least one of the constituent layers of the photosensitive material contains at least one polymeric compound having a repeating unit represented by the following general formula []. General formula []

[Formula] However, R ₁ in the formula represents a hydrogen atom, a chlorine atom, or a lower alkyl group, and J represents a divalent linking group. A represents an atomic group necessary to form an oxadiazole ring, a thiadiazole ring, a selenadiazole ring, and a triazole ring. To explain the general formula [] in more detail, R ₁ in the formula represents a hydrogen atom, a chlorine atom, or a lower alkyl group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom or a methyl group. . J is a divalent linking group that connects A and is preferably selected from the following. -CONH-, -CONH( _CH2 ) ^n- (n; 1 to 3),

[Formula] −CONHCH ₂ CONH −, −CONH・CH ₂ CH ₂ NHCO−, −
NHCONH−,

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] -CO, -COS-, etc. Among the above J, the most preferred is a divalent linking group represented by -CONH( _CH2 ) ^n- (n: 0 or 1-2). A represents a diazole ring or triazole ring as described above, for example, the following general formula [] or [-
a], [-b], and [-c]. General formula []

[Formula] However, in the formula, Z represents an oxygen atom, a sulfur atom or a selenium atom. R ₂ is a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group (preferably up to 12 carbon atoms, such as methyl, ethyl, propyl, hexyl, hydroxyethyl, carboxyethyl, chloropropyl, benzyl) group, 2-(methoxycarbonyl)ethyl group, cyanopropyl group,
trichloromethyl group, etc.), substituted or unsubstituted aryl groups (preferably having 6 to 12 carbon atoms, such as phenyl group, naphthyl group, p-tolyl group, p-chlorophenyl group, 0-carboxyphenyl group, etc.), substituted substituted or unsubstituted carbamoyl group (e.g. carbamoyl group, methylcarbamoyl group, etc.), mercapto group, cyano group, halogen atom (chlorine, bromine), alkoxy group (for example, methoxy group, ethoxy group, propioxy group, etc.), alkoxycarbonyl group (for example, methoxycarbabonyl group, butoxycarbamoyl group, etc.), alkylthio group (for example, methylthio group, ethylthio group, butylthio group, etc.), and particularly in the present invention. Preferred R ₂ is a mercapto group, and the mercapto group may be in the form of sodium or potassium salts. General formula [-a] General formula [-b] General formula [-c]

【formula】

【formula】

[Formula] However, R ₃ in the formula is a hydrogen atom, an alkyl group up to the number of carbon atoms (e.g. methyl group, propyl group, etc.),
It represents an aryl group (for example, a phenyl group), a substituted or unsubstituted amino group, or a substituted or unsubstituted carbamoyl group (for example, an amino group, a dimethylamino group, a methylcarbamoyl group, etc.). Among these, hydrogen atoms are particularly preferred in the present invention. R ₄ , R ₅ , R ₆ , R ₇ and R ₈ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group (preferably up to 12 carbon atoms, such as a methyl group, an ethyl group, propyl group, hexyl group, hydroxyethyl group, carboxyethyl group, chloropropyl group, benzyl group, 2-)methoxycarbonyl)ethyl group, cyanopropyl group, trichloromethyl group, etc.), substituted or unsubstituted aryl group (preferably C6 to C12 (e.g., phenyl, naphthyl, p-tolyl, p-chlorophenyl, o-carboxyphenyl, etc.), substituted amino groups (e.g., dimethylamino, acetylamino, etc.), substituted or unsubstituted carbamoyl group (e.g. carbamoyl group, methylcarbamoyl group, etc.), hydroxy group, mercapto group, cyano group, halogen atom (chlorine, bromine), alkoxy group,
(e.g. methoxy group, ethoxy group, propioxy group, etc.), alkoxycarbonyl group (e.g. methoxycarbonyl group, butoxycarbonyl group, etc.),
It represents an alkylthio group (for example, a methylthio group, an ethylthio group, a butylthio group, etc.), and among these, the most preferred is a mercapto group, and the mercapto group may be in the form of a sodium or potassium salt. Next, examples of repeating units (monomers) that can be particularly preferably used in the present invention include the following general formula []. General formula [] However, Z in the formula is a carbon atom, a sulfur atom, or -NH
-, n represents 0 or 1-2. The polymer compound according to the present invention may be a so-called homopolymer consisting only of repeating units represented by the general formula [], or a so-called copolymer with other copolymerizable comonomers, In the present invention, copolymerized polymers are preferred. Examples of comonomers used when synthesizing copolymers include: Acrylamides, such as acrylamide, methylacrylamide, ethyl acrylamide, propylacrylamide, butylacrylamide,
t-butylacrylamide, cyclohexylacrylamide, benzyl acrylamide, hydroxymethyl acrylamide, methoxyethylacrylamide, dimethoxyaminoethylacrylamide, phenyl acrylamide, dimethyl acrylamide, diethylacrylamide, β-cyanoethylacrylamide, etc.; allyl compounds such as allyl acetate, allyl caproate , allyl laurate, allyl benzoate, etc.; Vinyl ethers, such as methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl ether, etc.; Vinyl ketones, such as methyl vinyl ketone,
phenyl vinyl ketone, methoxyethyl vinyl ketone, etc.; vinyl heterocyclic compounds such as vinyl pyridine,
N-vinylimidazole, N-vinyloxazolidone, N-vinyltriazole, N-vinylpyrrolide, etc.; Glycidyl esters, such as glycidyl acrylate, glycidyl methacrylate, etc.; Unsaturated nitriles, such as acrylonitrile,
methacrylonitrile etc.; polyfunctional monomers such as divinylbenzene,
Methylene bisacrylamide, ethylene glycol dimethacrylate, etc. Furthermore, acrylic acid, methacrylic acid, itaconic acid,
Maleic acid, monoalkyl itaconate, e.g.
Monomethyl itaconate, monoethyl itaconate,
Monobutyl itaconate, etc.; monoalkyl maleates, such as monomethyl maleate, monoethyl maleate, monobutyl maleate, etc.; citraconic acid, styrene sulfonic acid, vinylbenzyl sulfonic acid, vinyl sulfonic acid, acryloyloxyalkyl sulfonic acid, such as acryloyl Oxymethylsulfonic acid, acryloyloxyethylsulfonic acid, acryloyloxypropylsulfonic acid, etc.; Methacryloyloxyalkylsulfonic acid, such as methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid, etc.; Acrylamidoalkylsulfonic acid, e.g. 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid, etc.; methacrylamide alkylsulfonic acid, such as 2-methacrylamido-2-methylethane Sulfonic acid, 2-methacrylamide
2-methylfuropanesulfonic acid, 2-methacrylamido-2-methylbutanesulfonic acid, etc.; acryloyloxyalkyl phosphate, e.g.
Acryloyloxyethyl phosphate, 3-acryloyloxypropyl-2-phosphate, etc.; methacryloyloxyalkyl phosphate, such as methacryloyloxyethyl phosphate, 3-methacryloyloxypropyl-2-
Examples include phosphate, etc. These acids may be salts of alkali metals (eg, Na, K, etc.) or ammonium ions. Other comonomers that can be copolymerized include acrylic esters, methacrylic esters, crotonic esters, vinyl esters, maleic diesters, fumaric acid diesters, itaconic acid diesters, olefins, and styrenes. Among these comonomers, acrylamide, methacrylamide, vinylbenzenesulfonate, vinylbenzenesulfinate, N
-Vinylpyrrolide, hydroxyethyl acrylate, etc. are preferred. The polymer of the polymer compound of the present invention can be arbitrarily selected, but the molar ratio of repeating units represented by the general formula [] is at least 0.1 mol% or more, preferably 1
If the amount is mol % or more, the effects of the present invention can be obtained. Next, specific examples of monomers serving as repeating units of the polymer compound according to the present invention will be shown, but the present invention is not limited thereto. Specific examples of the polymer compounds of the present invention are listed below.

【table】

【table】

[Table] Although the amount of the polymer compound used in the present invention is used in a wide range, it is generally calculated based on the number of moles of azole ring residue contained in the polymer.
The amount may be in the range of 10 ^-6 mol to 1 mol per mol, and when converted into a polymer compound, it is preferably 100 mg to 200 g per mol of silver halide in terms of weight.
Use between 200mg and 100g. Also, support 1
About 1 mg to about 2 g, preferably 10 mg per cm ²
The range is from 1g to 1g. The layer to be added may be added to any layer of the light-sensitive material, and the time of addition is during, after, and/or after the chemical ripening of the silver halide emulsion and/or before coating the emulsion. A preferred form is to add it at the end of chemical ripening of the silver halide emulsion. Synthesis of polymer compound 1 Monomer 1 was added to 500 ml of water containing 3 g of potassium carbonate.
4g was dissolved. Next, 36g of acrylamide and
Add 0.4g of azobiscyanovaleric acid under nitrogen stream.
Heated at 50°C for 24 hours. The resulting viscous solution was neutralized with diluted hydrochloric acid, dialyzed, and then freeze-dried. 35 g of polymer compound 1 was obtained. Monomer 1 was synthesized as follows. 20 g of 5-amino-2-mercapto-1,3,
4-thiadiazole was dispersed in 600 ml of acetonetrile, and 23 g of β-chloropropionyl cloide was added dropwise. Thereafter, the mixture was heated under reflux for 1 hour and cooled. The precipitated crystals were filtered and 14.7g of 5-(β-
Chloropropionylamino)-2-mercapto-
1,3,4-thiadiazole was obtained. this crystal
In addition to 100 ml of methanol, 100 ml of a methanol solution containing 13 g of potassium hydroxide was added dropwise under ice cooling. After the reaction, the mixture was poured into 600 ml of water, adjusted to pH 2-3 with concentrated hydrochloric acid, and the precipitated crystals were filtered. 1.8 g of Monomer 1 was obtained by recrystallization from acetonitrile. The structure is IR,
Confirmed by NMR and Mass spectrum.
mp230℃. Synthesis of Polymer Compound 2 3 g of Monomer 2 was dissolved in 500 ml of water containing 1.7 g of potassium carbonate. Next, 27g of acrylamide and
Add 0.3g of azobiscyanovaleric acid under nitrogen stream.
Heated at 55°C for 16 hours. The resulting viscous solution was neutralized with dilute hydrochloric acid, dialyzed, and then freeze-dried. 25 g of polymer compound 2 was obtained. Monomer 2 was synthesized as follows. 10 g of 5-(p-aminophenyl)-2-mercapto-1,3,4-oxadiazole and 7.3 g of β-chloropropionyl chloride were added to 200 ml of ethyl acetate, heated under reflux for 2.5 hours, and then cooled.
The precipitated crystals were filtered. The filtrate was added to 200 ml of methanol, and 130 ml of a methanol solution containing 9.5 g of potassium hydroxide was added dropwise under ice cooling. Add the reaction solution to water
1.2, the pH was adjusted to 2-3 with concentrated hydrochloric acid, and the precipitated crystals were filtered. Recrystallization from ethanol/water yielded 5.2 g of monomer 2. Structure is IR, NMR
and confirmed by Mass spectrum. mp260
~265℃(dec). Synthesis of polymer compound 15 Dissolve 40 g of n-butyl acrylate and 10 g of monomer 2 in 500 ml of dimethylformamide,
0.25 g of dimethyl azobisinbutyrate was added, and the mixture was heated at 60° C. for 10 hours under a nitrogen stream. After the reaction, reprecipitation was repeated with n-hexane, and 42 g of polymer compound 15 was obtained by heating and drying under reduced pressure. A known antifoggant or stabilizer can be added to the light-sensitive material of the present invention in combination with the compound represented by the general formula [] of the present invention. As the antifoggant and stabilizer, the antifoggant and stabilizer are
Pentazaindenes described in No. 2713541, No. 2743180, and No. 2743181, U.S. Patent No. 2716062,
Same No. 2444607, No. 2444605, No. 2756147, Same No.
Tetrazaindenes described in No. 2835581, No. 2852375, Research Disclosure No. 14851, triazaindenes described in U.S. Patent No. 2772164, and JP-A-57
-Azaindenes such as polymerized azaindenes described in US Pat. No. 211142: US Pat.
Quaternary onium salts such as thiazolium salts described in U.S. Patent No. 3342596 and No. 3954478, biryllium salts described in U.S. Pat.
No. 2403927, No. 3266897, No. 3708303, JP-A-Sho
Mercaptotetrazoles, mercaptotriazoles, and mercaptodiazoles described in No. 55-135835 and No. 59-71047, US Patent
Mercaptothiazoles described in No. 2824001,
Mercapto-substituted heterocyclic compounds such as mercaptobenzothiazoles and mercaptobenzimidazoles described in US Pat. No. 3,397,987, mercaptooxadiazoles as described in US Pat. No. 2,843,491, and mercaptothiadiazoles as described in US Pat. No. 3,364,028. Class; U.S. Patent No. 3236652,
Catechols listed in Special Publication No. 43-10256,
Resorcinols described in Special Publication No. 56-44413,
and polyhydroxybenzenes such as gallic acid esters described in Japanese Patent Publication No. 43-4133; West German patent
Tetrazoles described in US Pat. No. 1189380, triazoles described in US Pat. No. 3,157,509, benzotriazoles described in US Pat. No. 2,704,721, urazoles described in US Pat. pyrazoles, indazoles described in U.S. Pat. No. 2,271,229, azoles such as polymerized benzotriazoles described in JP-A-59-90844, pyrimidines described in U.S. Pat. No. 3,161,515, and U.S. Pat. Heterocyclic compounds such as 3-pyrazolidones described in No. 2751297 and polymerized pyrrolidones or polyvinylpyrrolidones described in U.S. Pat.
Various inhibitor precursors described in No. 137945, No. 140445, British Patent No. 1356142, U.S. Pat. , No. 2839405, No. 2488709,
There are inorganic salts described in No. 2728663. The silver halide emulsion according to the present invention includes any silver halide used in conventional silver halide emulsions, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. You can use things. Furthermore, even if the silver halide grains have a uniform silver halide composition distribution within the grain, the core/silver halide composition may differ between the grain interior and the surface layer.
They may also be shell particles. The silver halide emulsion used in the present invention is, for example, British Patent No. 618061, British Patent No. 1315755, British Patent No.
No. 1396696, Special Publication No. 15748, US Patent
No. 1574944, No. 1623499, No. 1673522, No.
No. 2278942, No. 2399083, No. 2410689, No.
No. 2419974, No. 2448060, No. 2487850, No.
No. 2518698, No. 2521926, No. 2642361, No. 2518698, No. 2521926, No. 2642361, No.
No. 2694637, No. 2728668, No. 2983609, No.
No. 2983610, No. 3021215, No. 3297446, No. 3297446, No.
No. 3297447, No. 3411914, No. 3554757, No.
No. 3565631, No. 3565633, No. 3591385, No.
No. 3656955, No. 3761267, No. 3772031, No. 3772031, No. 3761267, No. 3772031, No.
No. 3857711, No. 3901714, No. 3904415, No. 3904415, No. 3901714, No. 3904415, No.
No. 3930867, No. 4054457, No. 4067740, Research Disclosure No. 12008, No. 13452, No.
No. 13452, TH James, The Theory of the Photographic Process.
(4th Ed. 1977), pages 67 to 76, etc., it is preferable to sensitize using a chemical sensitizer or sensitization method. Sensitizing dyes used in the silver halide emulsion according to the present invention include cyanine dyes, merocyanine dyes,
Complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxanol dyes are used. Particularly useful dyes are cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus,
Thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus,
Tetrazole nucleus, pyridine nucleus, nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei, and nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, i.e., indolenine nucleus, benzindolenine nucleus, indole nucleus, benzo Oxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus,
benzoselenazole nucleus, benzimidazole nucleus,
Such as quinoline nucleus. These nuclei may be substituted on carbon atoms. The merocyanine dye or composite merocyanine dye includes a nucleus having a ketomethylene structure such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, A 5- to 6-member heterologous nucleus such as a thiobarbituric acid nucleus can be applied. Useful sensitizing dyes used in blue-sensitive silver halide emulsion layers include, for example, West German Patent No. 929080;
U.S. Patent No. 2231658, U.S. Patent No. 2493748, U.S. Patent No. 2503776,
Same No. 2519001, No. 2912329, No. 3656959, Same No.
No. 3672897, No. 3694217, No. 4025349, No. 3672897, No. 3694217, No. 4025349, No.
No. 4046572, British Patent No. 1242588, Special Publication No. 1977-
Examples include those described in No. 14030 and No. 52-24844. In addition, useful sensitizing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Pat.
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in US Pat. No. 2,945,763 and US Pat. No. 5,059,79. Furthermore, useful sensitizing dyes used in red-sensitive silver halide emulsions include, for example, U.S. Pat.
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in Japanese Patent No. 2454629, No. 2776280, and the like. Furthermore, U.S. Patent No. 2213995,
Cyanine dyes, merocyanine dyes, or composite cyanine dyes such as those described in No. 2493748, No. 2519001, and West German Patent No. 929080 can be advantageously used in green-sensitive silver halide emulsions or red-sensitive halogen emulsions. These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization. Typical examples are Special Publication No. 43-4932 and No. 43-4932.
No. 4933, No. 43-4936, No. 44-32753, No. 45-
No. 25831, No. 45-26474, No. 46-11627, No. 46
−18107, No. 47-8741, No. 47-11114, No. 47
-25379, 47-37443, 48-28293, 47-37443, 48-28293,
No. 48-38406, No. 48-38407, No. 48-38408,
No. 48-41203, No. 48-41204, No. 49-6207,
No. 50-40662, No. 53-12375, No. 54-34535,
No. 55-1569, JP-A No. 50-33220, No. 50-33828
No. 50-38526, No. 51-107127, No. 51-
No. 115820, No. 51-135528, No. 51-151527, No. 115820, No. 51-135528, No. 51-151527, No.
No. 52-23931, No. 52-51932, No. 52-104916,
No. 52-104917, No. 52-109925, No. 52-110618
No. 54-80118, No. 56-25728, No. 57-1438
No. 58-10753, No. 58-91445, No. 58-
No. 153926, No. 59-114533, No. 59-116645, No.
No. 59-116647, U.S. Patent No. 2688545, U.S. Patent No. 2977229
No. 3397060, No. 3506443, No. 3578447,
3672898, 3679428, 3769301, 3672898, 3679428, 3769301,
It is described in No. 3814609 and No. 3837862. Binder (or protective colloid) according to the present invention
Although it is advantageous to use gelatin,
Hydrophilic colloids such as synthetic hydrophilic polymeric substances such as gelatin derivatives, graft polymers of gelatin and other polymers, and single or copolymers can also be used. Gelatin includes lime-processed gelatin, acid-processed gelatin, Bull, Soc, Sci, Phot, Japan.No.
16, 30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. Examples of gelatin derivatives include gelatin and various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acids, alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkyleonoxides, and epoxy compounds. The product obtained by reacting is used. A specific example is a US patent
No. 2614928, No. 3132945, No. 3186846, No. 3186846, No. 3132945, No. 3186846, No.
3312553, British Patent No. 861414, British Patent No. 1033189, British Patent No.
It is described in No. 1005784, Special Publication No. 42-26845, etc. In addition, typical synthetic hydrophilic polymer substances include:
Single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc., for example, West German patent application (OLS) No. 2312708, U.S. Pat. No. 3,620,751, U.S. Pat. In addition to the above-mentioned antifoggants and stabilizers, the present invention also uses hardeners, antistatic agents, matting agents, surfactants, etc. used in the photographic industry to improve physical properties, photographic properties, or developability. Various additives can be used. As a hardening agent, aldehyde type, aziridine type (for example, PB Report, 19921, US Patent No. 2950197)
No. 2964404, No. 2983611, No. 3271175,
those described in Japanese Patent Publication No. 46-40898 and Japanese Patent Application Publication No. 50-91315), isoxal series (for example, those described in U.S. Pat.
331609), epoxy systems (e.g. US patent 3047394, West German patent 1085663, British patent
No. 1033518, those described in Special Publication No. 1973-35495),
Vinyl sulfones (e.g. PB Report 19920,
West German Patent No. 1100942, German Patent No. 2337412, German Patent No. 2545722,
No. 2635518, No. 2742308, No. 2749260, British Patent No. 1251091, Patent Application No. 54236, No. 48-
No. 110996, US Pat. No. 3,539,644, US Pat.
−27949, as described in U.S. Pat. No. 3,640,720),
Carbodiimides (e.g., U.S. Pat. No. 2,938,892,
No. 4043818, No. 4061499, Special Publication No. 46-38715,
(described in Japanese Patent Application No. 49-15095), triazine type (for example, those described in West German Patent No. 2410973, West German Patent No. 2553915, U.S. Pat. , U.S. Patent No. 822061, U.S. Patent No. 3623878, U.S. Patent No. 3396029, U.S. Patent No. 3226234,
(Those described in Japanese Patent Publication Nos. 47-18578, 18579, and 47-48896), maleimide-based, acetylene-based, methanesulfonic acid ester-based (N-methylol-based) hardening agents alone or in combination. Can be used. Examples of useful combination techniques include West German patents 2447587, 2505746, 2514245,
U.S. Patent No. 4047957, U.S. Patent No. 3832181, U.S. Patent No. 3840370,
JP-A No. 48-43319, No. 50-63062, No. 52-
Examples include combinations described in Japanese Patent Publication No. 12739 and Japanese Patent Publication No. 48-32364. Examples of antistatic agents include compounds described in Research Disclosure No. 17643. The antistatic agent may be added to the layer on the side of the support on which the emulsion is not laminated, and the antistatic agent may be added to the layer on the side of the support on which the emulsion is not laminated.
Alternatively, it may be used in a protective colloid layer other than the emulsion layer on the side where the emulsion layer is laminated on the support. When the present invention is used as a color photographic light-sensitive material, various materials and techniques conventionally used for color photography can be used. First, as the coupler, various couplers are used, such as a dye-forming coupler that forms a dye image or a DIR coupler that adjusts photographic characteristics and image quality characteristics. As the yellow dye-forming coupler, known acylacetanilide couplers can be preferably used. Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. Specific examples of yellow couplers that can be used include U.S. Patent No. 1077874, Japanese Patent Publication No. 45-40757,
JP-A-47-1031, JP-A No. 47-26133, JP-A No. 48-94432
No. 50-87650, No. 51-3631, No. 52-
No. 115219, No. 54-99433, No. 54-133329, No. 115219, No. 54-99433, No. 54-133329, No.
56-30127, U.S. Patent No. 2875057, U.S. Patent No. 3253924,
Same No. 3265506, No. 3408194, No. 3551155, Same No.
No. 3551156, No. 3664841, No. 3725072, No.
No. 3730722, No. 3891445, No. 3900483, No.
No. 3929484, No. 3933500, No. 3973968, No.
No. 3990896, No. 4012259, No. 4022620, No. 4022620, No. 4012259, No. 4022620, No.
No. 4029503, No. 4057432, No. 4106942, No. 4029503, No. 4057432, No. 4106942, No.
No. 4133958, No. 4269936, No. 4286053, No. 4286053, No. 4269936, No. 4286053, No.
No. 4304845, No. 4314023, No. 4336327, No.
It is described in No. 4356258, No. 4386155, No. 4401752, etc. As a magenta dye-forming coupler, known 5
- Pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, and closed acylacetonitrile couplers can be preferably used. Specific examples of magenta couplers that can be advantageously used are disclosed in Japanese Patent Application No. 58-164882;
No. 58-167326, No. 58-206321, No. 58-214863
No. 58-217339, No. 59-24653, Special Publication No. 1973
−6031, No. 40-6035, No. 45-40757, No. 47
-27411, 49-37854, JP-A-50-13041,
No. 51-26541, No. 51-37646, No. 51-105820
No. 52-42121, No. 53-123129, No. 53-
No. 125835, No. 53-129035, No. 54-48540, No. 54-48540, No.
No. 56-29236, No. 56-75648, No. 57-17950,
No. 57-35858, No. 57-146251, No. 59-99437
No., UK Patent No. 1252418, US Patent No. 2600788,
No. 3005712, No. 3062653, No. 3127269, No. 3005712, No. 3062653, No. 3127269, No.
No. 3214437, No. 3253924, No. 3311476, No. 3214437, No. 3253924, No. 3311476, No.
No. 3419391, No. 3519429, No. 3558319, No.
No. 3582322, No. 3615506, No. 3658544, No. 3658544, No. 3615506, No. 3658544, No.
No. 3705896, No. 3725067, No. 3758309, No.
No. 3823156, No. 3834908, No. 3891445, No.
No. 3907571, No. 3926631, No. 3928044, No.
No. 3935015, No. 3960571, No. 4076533, No. 3935015, No. 3960571, No. 4076533, No.
No. 4133686, No. 4237217, No. 4241168, No. 4241168, No. 4237217, No. 4241168, No.
These are described in No. 4264723, No. 4301235, No. 4310623, etc. As the cyan dye-forming coupler, known naphthol couplers and phenol couplers can be preferably used. Specific examples of cyan couplers that can be advantageously used are British Patents Nos. 1038331 and 1543040.
No., Special Publication No. 48-36894, Japanese Patent Publication No. 48-59838, same.
No. 50-137137, No. 51-146828, No. 53-105226
No. 54-115230, No. 56-29235, No. 56-
No. 104333, No. 56-126833, No. 57-133650, No.
No. 57-155538, No. 57-204545, No. 58-118643
No. 59-31953, No. 56-31954, No. 59-
No. 59656, No. 59-124341, No. 59-166956, U.S. Patent No. 2369929, No. 2423730, No. 2434272,
Same No. 2474293, No. 2698794, No. 2772162, Same No.
No. 2801171, No. 2895826, No. 3253924, No.
No. 3311476, No. 3458315, No. 3476563, No.
No. 3591383, No. 3737316, No. 3758308, No. 3758308, No. 3737316, No. 3758308, No.
No. 3767411, No. 3790384, No. 3880661, No.
No. 3926634, No. 4004929, No. 4009035, No.
No. 4012258, No. 4052212, No. 4124396, No. 4012258, No. 4052212, No. 4124396, No.
No. 4134766, No. 4138258, No. 4146396, No. 4134766, No. 4138258, No. 4146396, No.
No. 4149886, No. 4178183, No. 4205990, No. 4149886, No. 4178183, No. 4205990, No.
No. 4254212, No. 4264722, No. 4288532, No. 4288532, No. 4264722, No. 4288532, No.
No. 4296199, No. 4296200, No. 4299914, No. 4296199, No. 4296200, No. 4299914, No.
No. 4333999, No. 4334011, No. 4386155, No. 4333999, No. 4334011, No. 4386155, No.
It is described in No. 4401752, No. 4427767, etc. As a colored coupler, for example, a British patent
No. 937621, No. 1035959, No. 1255111, Japanese Patent Application Publication No. 1973
−22028, No. 52-42121, Special Publication No. 38-22335,
No. 44-2016, No. 44-15754, U.S. Patent No. 2449966
No. 2521908, No. 2543691, No. 2801171,
Same No. 2983608, No. 3005712, No. 3034892, Same No.
No. 3061432, No. 3419391, No. 3476560, No. 3476560, No. 3419391, No. 3476560, No.
No. 3476563, No. 3481741, No. 3519429, No.
No. 3583971, No. 3622328, No. 3684514, No.
No. 4004929, No. 4070191, No. 4138258, No. 4004929, No. 4070191, No. 4138258, No.
No. 4138264, No. 4163670, No. 4292400, No. 4138264, No. 4163670, No. 4292400, No.
Those described in No. 4369248 etc. can be used. As a DIR coupler, for example, British patent 953454
No., U.S. Patent No. 3227554, U.S. Patent No. 3615506, U.S. Pat.
No. 3617291, No. 3701783, No. 3933500, No.
No. 4095984, No. 4149886, No. 2866054, No. 4095984, No. 4149886, No. 2866054, No.
No. 4359521, Japanese Patent Publication No. 52-90932, No. 56-116029
No. 57-151944, etc., and U.S. Pat.
No. 58-162949, No. 58-205150, No. 59-
No. 195643, No. 59-206834, No. 59-206836, No.
Timing DIR couplers described in No. 59-210440, No. 60-7429, etc. can be preferably used. As a DIR compound, for example, US Pat. No. 3,632,345
No. 3928041, No. 3938996, No. 3958993,
Same No. 3961959, No. 4046574, No. 4052213, Same No.
No. 4171223, No. 4186012, JP-A-52-65433,
Compounds described in No. 52-130327, No. 57-128335, etc. can be preferably used. As the colorless coupler, so-called Weis couplers described in US Pat. No. 2,998,314, US Pat. No. 1,284,649 and West German Pat. No. 1,168,769 can be used for gradation adjustment and prevention of color turbidity and fogging. The high boiling point oil agent used to disperse oil droplets of the coupler or oil-soluble additive in the hydrophilic solution includes phenol derivatives, phthalate alkyl esters, phosphate esters, citric acid esters, which do not react with the oxidized form of the developing agent. Organic solvents with a boiling point of 150° C. or higher, such as benzoic acid esters, alkylamides, fatty acid esters, and trimesic acid esters, are used. Examples of high-boiling organic solvents that can be used in the present invention include U.S. Pat.
No. 2835579, No. 3287134, No. 2353262, No.
No. 2852383, No. 3554755, No. 3676137, No. 3676137, No.
No. 3676142, No. 3700454, No. 3748141, No. 3748141, No.
No. 3779765, No. 3837863, British Patent No. 958441, No. 3837863, British Patent No. 958441,
No. 1222753, OLS2538889, JP-A-47-1031,
No. 49-90523, No. 50-23823, No. 51-26037,
No. 51-27921, No. 51-27922, No. 51-26035,
No. 51-26036, No. 50-62632, No. 53-1520,
No. 53-1521, No. 53-15127, No. 54-119921,
No. 54-119922, No. 55-25057, No. 55-36869
No. 56-19049, No. 56-81836, Special Publication No. 1977-
It is described in issues such as No. 29060. Also, low boiling point or water-soluble organic solvents that can be used with or in place of high boiling point solvents are disclosed in U.S. Pat.
Examples include those described in No. 2801171 and No. 2949360. Organic solvents with low boiling points that are substantially insoluble in water include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane, and benzene, and water-soluble organic solvents include acetone and methyl. Examples include isobutyl ketone, β-ethoxyethyl acetate, methoxyglycol acetate, methanol, ethanol, acetonitrile, dioxane, dimethylformamide, dimethyl sulfoxide, hexamethylphosphoformamide, diethylene glycol monophenyl ether, phenoxyethanol, and the like. Examples of the surfactant used as a dispersion aid for the oil droplets include alkylbenzene sulfonate,
Anionic surfactants such as alkylnaphthalene sulfonates, alkyl sulfonates, alkyl sulfates, alkyl phosphates, sulfosuccinates and sulfoalkyl polyoxyethylene alkyl phenyl ethers; steroidal saponins, Nonionic surfactants such as alkylene oxide derivatives and glycidol derivatives; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, and alkyl betaines; and cationic surfactants such as quaternary ammonium salts. It is preferable to use an agent. Specific examples of these surfactants are described in ``Surfactant Handbook'' (Sangyo Tosho, 1966) and ``Emulsifiers, Emulsification Equipment Research, Technical Data Collection'' (Kagakuhanrinsha, 1978). Further, as a color antifogging agent for color photographic light-sensitive materials, hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives, ascorbic acid derivatives, etc. are preferable, and specific examples thereof include US Pat. No. 2,360,290.
No. 2336327, No. 2403721, No. 2418613,
Same No. 2675314, No. 2701197, No. 2704713, Same No.
No. 2728659, No. 2732300, No. 2735765, No. 2735765, No. 2732300, No. 2735765, No.
No. 3700453, Japanese Patent Application Publication No. 50-92988, No. 50-92989,
No. 50-93928, No. 50-110337, No. 50-156438
No. 52-146235, No. 55-95948, No. 59-
It is described in No. 5247, Special Publication No. 50-23813, etc. Furthermore, image stabilizers include, for example, hydroquinone derivatives, gallic acid derivatives, phenol derivatives and their bis forms, hydroxycoumarans and their spiro forms, hydroxychroman and their spiro forms, piperazine derivatives, aromatic amine compounds, benzodioxane derivatives, and benzodioxane derivatives. Dioxole derivatives, silicon atom-containing compounds, thioether compounds, etc. are preferred. A specific example is British Patent No. 1410846,
JP-A-49-134326, JP-A No. 52-35633, JP-A No. 52-
No. 147434, No. 52-150630, No. 54-145530, No. 52-150630, No. 54-145530, No.
No. 55-6321, No. 55-21004, No. 55-124141,
No. 59-3432, No. 59-5246, No. 59-10539,
Special Publication No. 48-31625, No. 49-20973, No. 49-
No. 20974, No. 50-23813, No. 52-27534, U.S. Patent No. 2360290, No. 2418613, No. 2675314,
No. 2701197, No. 2704713, No. 2710801, No. 2701197, No. 2704713, No. 2710801, No.
No. 2728659, No. 2732300, No. 2735765, No. 2735765, No. 2732300, No. 2735765, No.
No. 2816028, No. 3069262, No. 3336135, No. 3336135, No.
No. 3432300, No. 3457079, No. 3573050, No. 3432300, No. 3457079, No. 3573050, No.
No. 3574627, No. 3698909, No. 3700455, No.
No. 3764337, No. 3935016, No. 3982944, No. 3982944, No. 3935016, No. 3982944, No.
No. 4013701, No. 4113495, No. 4120723, No. 4113495, No. 4120723, No.
No. 4155765, No. 4159910, No. 4254216, No. 4155765, No. 4159910, No. 4254216, No.
No. 4268593, No. 4279990, No. 4332886, No. 4268593, No. 4279990, No. 4332886, No.
Examples include No. 4360589, No. 4430425, and No. 4452884. The black-and-white developer used in the black-and-white development process of the present invention is commonly known as a developer for black-and-white photographic light-sensitive materials or a black-and-white first developer for color reversal light-sensitive materials. Various additives can be included. Typical additives include developing agents such as 1-phenyl-3-pyrazolidone, metol and hydroquinone, preservatives such as sulfites, accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate and potassium carbonate; Inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole, and methylbenzothiazole, water softeners such as polyphosphate, and trace amounts of iodide and mercapto compounds to prevent surface overdevelopment. can be mentioned. When the present invention is used as a color photographic light-sensitive material, the color development processing step is a step of forming a color image as in the conventional method. This is a process of forming an image. Therefore, in the color development processing process, it is usually necessary to include a color developing agent in the color developing solution, but a color developing agent containing the color developing agent is created by incorporating the color developing agent into the color photographic material. Alternatively, treatment with an alkaline solution (activator solution) is also included. The color developing agent contained in the color developing solution is an aromatic primary amine color developing agent, and includes aminophenol derivatives and p-phenylenediamine derivatives. These color developing agents can be used as salts of organic acids and inorganic acids; for example, hydrochloric acid, sulfate, p-toluenesulfonate, sulfite, oxalate, benzenesulfonate, etc. can be used. can. These compounds are generally used at a concentration of about 0.1 g to about 30 g per color developer, more preferably from about 1 g to 15 g per color developer. If the amount added is less than 0.1 g, sufficient color density cannot be obtained. In addition, the temperature of the processing solution in the color developing tank is 10°C to 65°C,
More preferably, the treatment is carried out at 25°C to 45°C. Examples of the aminophenol-based developer include o-aminophenol, p-aminophenol, 5-amino-2-hydroxytoluene, 2-aminophenol, and p-aminophenol.
These include amino-3-hydroxytoluene, 2-hydroxy-3-amino-1,4-dimethylbenzene, and the like. Particularly useful primary aromatic amine color developers are N-N'-dialkyl-p-phenylenediamine compounds, in which the alkyl and phenyl groups may be substituted or unsubstituted. good. Among them, an example of a particularly useful compound is N
-N'-dimethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N'-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-(N- Ethyl-N-
dodecylamino)-toluene, N-ethyl-N-
β-Methanesulfonamidoethyl-3-methyl-
4-aminoaniline sulfate, N-ethyl-N-β
-Hydroxyethylaminoaniline, 4-amino-3-methyl-N,N'-diethylaniline, 4
-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate and the like. Further, the above color developing agents may be used alone or in combination of two or more. Furthermore, the color developing agent may be incorporated into the light-sensitive material. for example,
A method of incorporating a color developing agent in the form of a metal salt, such as in U.S. Pat. No. 3,719,492, and a method of incorporating a color developing agent in the form of a Schiff salt, as shown in U.S. Pat. No. 3,342,559 and Research Disclosure No. 15159 of 1976. , JP-A-58-65429 and JP-A No. 58-
A method of incorporating it as a dye precursor as shown in US Pat. No. 24137, a method of incorporating it as a color developing agent precursor as shown in US Pat. No. 3,342,597, etc. can be used. In this case, it is also possible to treat the photosensitive material with an alkaline solution (activator solution) instead of a color developing solution, and the bleach-fixing process is carried out immediately after the alkaline solution treatment. The color developing solution used in the present invention may contain alkaline agents commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, or borax. Furthermore, it may contain various additives such as benzyl alcohol, alkali metal halides such as potassium bromide or potassium chloride, development regulators such as citrazic acid, and preservatives such as hydroxylamine or sulfites. It's okay. Furthermore, various antifoaming agents and surfactants, as well as organic solvents such as methanol, dimethylformamide or dimethyl sulfoxide, etc. can be appropriately contained. The pH of the color developer used in the present invention is usually 7 or more, preferably about 9-13. In addition, the color developing solution used in the present invention may contain antioxidants such as diethylhydroxyamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, pentose, or Hexose, pyrogallol-1,3-dimethyl ether, etc. may be contained. In the color developing solution used in the present invention, various chelating agents can be used in combination as metal ion sequestering agents. For example, the chelating agent may be an aminopolycarboxylic acid such as ethylenediaminetetraacetic acid or diethylenetriaminepentaacetic acid, an organic phosphonic acid such as 1-hydroxyethylidene-1,1'-diphosphonic acid, or an aminopolycarboxylic acid such as aminotri(methylenephosphonic acid) or ethylenediaminetetraphosphoric acid. Polyphosphonic acid, oxycarboxylic acid such as citric acid or gluconic acid, 2-phosphonobutane-1,2,4
- Phosphonocarboxylic acids such as tricarboxylic acid, polyphosphoric acids such as tripolyphosphoric acid or hexametaphosphoric acid, and polyhydroxy compounds. Supports used in photosensitive materials using the silver halide emulsion of the present invention include flexible paper such as paper laminated with α-olefin polymers (e.g., polyethylene, polypropylene, ethylene/butene copolymers), synthetic paper, etc. Reflective support, cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride,
Examples include films made of semi-synthetic or synthetic polymers such as polyethylene terephthalate, polycarbonate, and polyamide, flexible supports prepared by providing reflective layers on these films, glass, metals, ceramics, and the like. Particularly useful coating methods are extrusion coating and curtain coating, which allow two or more layers to be applied simultaneously.
Further, the coating speed can be arbitrarily selected, but from the viewpoint of productivity, a speed of 50 m/min or more is preferable. The photographic light-sensitive material of the present invention can also be applied to the following various types of light-sensitive materials. For example, they are photosensitive materials for general-purpose black and white use, X-ray recording, plate making, color positive use, color paper use, color negative use, color reversal use, direct positive use, heat development use, and the like. It can also be used in the light-sensitive material described in Japanese Patent Publication No. 41-2068, which uses a combination of internal latent image type and surface latent image type silver halide grains. In particular, it is advantageously used in color photosensitive materials having a multilayer structure.

【Example】

The present invention will be explained in more detail with reference to Examples below. Example 1 A silver iodobromide emulsion containing 2.5 mol% of silver iodide and the rest consisting of silver bromide was chemically thermally formed to the highest sensitivity by gold and sulfur sensitization to obtain a high-sensitivity silver iodobromide emulsion. . Next, the emulsion was divided into equal parts, and the compounds of the present invention and comparative compounds were added as shown in Table 1 below, and appropriate amounts of formalin as a hardening agent and saponin as a coating aid were added, respectively. These emulsions were uniformly coated onto a subbed polyester support so that the amount of silver was 3 g/m ² and dried to obtain Samples 1 to 13. One set of the obtained samples was left in a refrigerator set at 5°C, and the other two sets were left in a high temperature, low humidity environment and a high temperature, high humidity environment (Table 1) for 5 days, and then these three sets were incubated in the usual manner. I exposed it to light. The film was then developed with Kodatsu D-72 developer at 20°C for 4 minutes, fixed, washed with water and dried, followed by sensitometry. The sensitivity in the table is calculated using the reciprocal of the logarithm of the exposure amount required to obtain a density of fog density + 0.5.
It is expressed as a relative sensitivity set to 100, and the fog value is expressed as a value obtained by subtracting the base density. As is clear from Table 1, it can be seen that the compounds according to the present invention suppress the occurrence of fogging and the decrease in sensitivity is smaller than the comparative compounds even when left under severe storage conditions.

[Table] Example 2 In this example, the diffusibility of compounds was tested. Anhydrous 5,5'-dichloro-9-ethyl-3,3'-di-(3-sulfobutyl)-oxacarbocyanine hydroxide was added as a green-sensitive emulsion onto the emulsion layer of the sample prepared in Example-1. spectrally sensitized, and 4
-Hydroxy-6-methyl-1,3,3a,7-
A silver iodobromide emulsion similar to that in Example 1 stabilized with tetrazaindene and containing only a hardening agent and a coating aid was coated in multiple layers. The 13 samples obtained were immediately exposed through a green filter through a wedge, and then subjected to the same treatment as in Example 1 and subjected to sensitometry. The results obtained are shown in Table 2 below. Note that the gamma value indicates the slope of the straight line portion of the characteristic curve.

[Color developer]

4-amino-3-methyl-N-ethyl-N-
(β-hydroxyethyl)-aniline sulfate
4.75g Anhydrous sodium sulfite 4.25g Hydroxylamine 1/2 sulfate 2.0g Anhydrous potassium carbonate 37.5g Sodium bromide 1.3g Nitrilotriacetic acid trisodium salt (monohydrate)
2.5g Potassium hydroxide 1.0g Add water to make 1. [Bleach solution] Ethylenediaminetetraacetic acid iron ammonium salt
100.0g Ethylenediaminetetraacetic acid diammonium salt
10.0g ammonium bromide 150.0g glacial acetic acid 10.0g Add water to make 1 and use ammonium water
Adjust to PH6.0. [Fixer] Ammonium thioacetate 175.0g Anhydrous sodium sulfite 8.6g Sodium metasulfite 2.3g Add water to make 1, and adjust to PH6.0 using acetic acid. [Stabilizing liquid] Formalin (37% aqueous solution) 1.5ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.)
Add 7.5ml water to make 1. Table 3 shows the results of the storage test on the blue-sensitive layer, and these results show that the compound according to the present invention does not deteriorate photographic properties over time and can obtain a fog suppressing effect with little desensitization. Recognize.

[Table] Example 4 Samples No. 36 and 37 were prepared by using compounds [6] and [7] in place of compound [] in sample No. 6 of Example 1 of the present invention, and A similar evaluation was made. The results are shown in Table 4.

[Table] As is clear from Table 4, the effects of the present invention can be obtained even when compounds [6] and [7] of the present invention are used.

【Effect of the invention】

As is clear from the above examples, according to the present invention, it is possible to obtain a silver halide photographic material that does not cause fogging or decrease in sensitivity or gamma even when placed under severe storage conditions, and also has a multilayer structure. In the case of photosensitive materials, it is possible to provide photosensitive materials that are free from the harmful effects of diffusion into adjacent layers.

Claims (1)

[Scope of Claims] 1. A halogen characterized by containing at least one of the polymer compounds having a repeating unit represented by the following general formula [] in at least one of the constituent layers of a silver halide photographic light-sensitive material. Silver chemical photographic material. General formula [] [Formula] [In the formula, R ₁ represents a hydrogen atom, a chlorine atom, or a lower alkyl group, and J represents a divalent linking group. A is an oxadiazole ring, a thiadiazole ring,
Represents the atomic group necessary to form a selenadiazole ring or triazole ring. ]