JPS626252A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material containing an antifogging, that is, a stabilizer capable of retaining stable photographic characteristics during long storage by incorporating at least one of polymers having specified repeating units in at least one of the constituent layers of the photosensitive material. CONSTITUTION:At least one of the constituent layers of the silver halide photographic sensitive material contains at least one of polymers having repeating units each represented by the formula shown on the right in which R1 is H, Cl, or lower alkyl; J is a divalent bonding group; and A is an atomic group necessary to form a pyrimidine ring, a triazine ring, or a tetrazole ring together with an N atom. The polymer is used generally in an amount of 1X10<-6>-1mol per mol of silver halide in terms of molarity of the azole ring residue.

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 which contains a polymerized stabilizer to prevent the occurrence of fog during storage over time. be.

[Background of the invention]

Light-sensitive silver halide photographic materials tend to generate fog that induces development even when not exposed to light.
Decreased sensitivity due to fogging, especially during storage over time.
Otherwise, it very often causes deterioration of gradation. Many compounds have been proposed for the purpose of improving such development, including mercapto compounds such as 4-hydroxy-6-methyl-1,3,3a, 7-titrazaindene or 1-phenyl-5-mercaptotetrazole. Group-substituted heterocyclic compounds 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 a decrease in 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 the desensitization or diffusivity of the stabilizer by polymerizing it.
For example, in U.S. Patent No. 3,598,599, thiazoles are
JP-A-57-211142 describes tetrazaindenes, and JP-A No. 59-90844 describes benzotriazoles, with repeating stabilizer residues. A polymer compound having the following properties 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. It cannot be said that the ability to inhibit fog in the underlayer is necessarily sufficient, and there has been a strong demand for a fog inhibitor 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 during storage of silver halide photographic materials (hereinafter referred to as "photosensitive materials") over time. An object of the present invention is to provide a photosensitive material containing such a fog suppressor, that is, a stabilizer. A second object of the present invention is to obtain fog suppressing properties with little desensitization even when used in large amounts in silver halide photosensitive materials, and to suppress fog without inhibiting spectral sensitivity and without diffusion transfer to adjacent layers. An object of the present invention is to provide a photosensitive material containing the agent.

[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 polymer compound having a repeating unit represented by the following general formula (1). be done. , +-\ General formula CI) R. (-CHrC±" ■ ^ However, R1 in the formula represents a hydrogen atom, a chlorine atom, or a lower alkyl group, and J represents a divalent linking group. A represents a nitrogen atom, a pyrimidine ring, a tri7one ring, and a tetrazole ring. represents a group of atoms necessary to form the formula (1). To explain the general formula (1) in more detail, R1 in the formula can preferably be a hydrogen atom or a methyl group. J connects A Jr:2 The connecting group is preferably selected from the following: -CONH-1-CONH(CH2)n-1(n:1-
3), -0-C-CI! 2-3--coo-4C>-s
o□NH-1←(=ΣState old-between CO-1-C>CII
□N11- Among the above J, the most preferable is -C0N
II(C1lz) is a divalent linking group represented by n-(n: 0 or 1-2). Preferred heterocyclic monovalent groups formed by A include the following. However, in the above formula, M represents a hydrogen atom, an alkali metal (eg, sodium, potassium, etc.), or ammonium. Each of the bicyclic rings may have a substituent, and preferred substituents include the following. For example, a substituted or unsubstituted alkyl group (preferably a C1-C12 group such as a methyl group, an ethyl group, a propyl group, a hexyl group, a hydroxyethyl group, a carboxyethyl group, a benyl group, a 2-(methoxycarbonyl)ethyl group) , cyanopropyl group, trichloromethyl group, etc.), substituted or unsubstituted 7-aryl group (e.g. 7enyl group, P-
(chlorophenyl group, etc.), amide 7 group, hydroxyl group,
Examples include a mercapto group, a cya 7 group, a halogen atom (chlorine, bromine, etc.), an alkoxy group (eg, methoxy group, ethoxy group, etc.), an alphkyl dicarbonyl group (eg, methoxycarbonyl group, etc.). Among these, the most preferred substituents include a hydrogen atom, a lower alkyl group (for example, a methyl group), and a hydroxy group. The polymer compound according to the present invention may be a so-called homopolymer consisting only of repeating units represented by the general formula [1], or may be a so-called copolymer with other copolymers. However, in the present invention, preferred is a polymerized polymer. Kobo I+
Examples of comonomers used when synthesizing - include the following. Acrylamides, such as acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, t-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide
Allyl compounds such as allyl acetate, allyl caproate, heptalyl laurate, allyl benzoate, etc. Vinyl ethers such as methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl Vinyl ether, dimethyl 7/ethyl ether, etc.; Vinyl ketones, such as methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, etc.; Vinyl heterocyclic compounds, such as vinyl pyridine, N-vinyl triazole, N-vinyl oxazolidone, N- Vinyl triazole, N-vinylpyrrolidone, etc.; glycyl esters, such as glycidyl 7-acrylate, glycidyl methacrylate, etc.; unsaturated nitriles, such as acrylonitrile, methacrylatetril, etc.; polyfunctional monomers, such as divinylbenzene, methylene bisacryl 7-mide, etc. , ethylene glycol dimethacrylate, etc. Furthermore, acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconates such as monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, etc.; monoalkyl maleates such as monomethyl maleate, monoethyl maleate, maleic acid, etc. monobutyl acids, etc.; citraconic acid, styrene sulfonic acid, vinylbenzyl sulfonic acid, vinyl sulfonic acid, acryloyloxyalkyl sulfonic acid, such as acryloyloxymethylsulfonic acid, acryloyloxyethylsulfonic acid, etc.; methacryloyloxyalkyl sulfonic acid, such as methacryloyl Oxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid, etc.; acrylamide alkylsulfonic acid, such as 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido- 2-methylbutanesulfonic acid, etc.; methacrylamide alkyl sulfonic acids, such as 2-methacrylamido-2-methylethanesulfone 2-methylpropanesulfonic acid, 2-methacrylamido-2-methylbutanesulfonic acid, etc.; acryloino-oxyalkyl phosphates , such as acryloyloxyethyl phosphate, 3-acryloyloxybucopyru-2-phosphate, etc.; methacryloyloxyalkyl phosphate, such as methacryloyloxyethyl phosphate, 3-methacryloyloxypropyl-
Examples include 2-phos-7ate and the like. These acids may be salts of alkali metals (eg, Nu, Ni, etc.) or ammonium ions. Other copolymerizable co-7mers include acrylic esters, methacrylic esters, crotonic esters, vinyl esters, maleic diesters, 7malic acid noesters, itaconic acid diesters, olefins, and styrenes. Among these comonomers, preferably acrylamide, methacrylamide, vinylbenzenesulfonate,
Preferred are vinylbenzenesulfinate, N-vinylpyrrolide, hydroxyethyl acrylate, and the like. The polymer of the high molecular compound of the present invention can be arbitrarily selected, but the present invention can be carried out as long as the molar ratio of repeating units represented by the general formula [1] is at least 0.1 mol% or more, preferably 1 mol% or more. effect can be obtained. Specific examples of monomers serving as repeating units of the polymer compound according to the present invention are listed below, but the present invention is not limited thereto. I13 (17)C)12=c11 YN II Specific examples of the polymer compound of the present invention are shown below. The polymer compound according to the present invention is synthesized by the following and similar synthesis methods. Synthesis of Polymer Compound (1) 8.6 g of Monomer 1 was dissolved in 400n+Q of water containing 4 g of potassium carbonate. Next, 13g of acrylamide and 0.
Add 22g of 7zobissia7valeric acid and heat for 50 minutes under nitrogen stream.
The mixture was heated at ℃ for 24 hours and stirred. The resulting pale yellow viscous solution was neutralized with diluted hydrochloric acid, then dialyzed, and then freeze-dried. 20. A polymer compound (■) was obtained. Synthesis of polymer compound (1) 3.7 g of monomer 3 was dissolved in 200 + aQ of water containing 2 g of potassium carbonate. Next, 15 g of acrylamide and 0.18 g of azobiscyanokilic acid were added, and the mixture was heated and stirred at 60° C. for 20 hours under a nitrogen stream. The resulting orange viscous solution was neutralized with diluted hydrochloric acid, then dialyzed, and then freeze-dried. 17 g of polymer compound (2) was obtained. Synthesis of polymer compound (1) 11 g of monomer 4 was dissolved in 600 tn Q of water containing 60 g of potassium carbonate. Next, 26 g of acrylamide and o, aeg of 7zobisci7/valeric acid were added, and heating and stirring were continued at 60° C. for 20 hours under a nitrogen stream. The resulting red viscous solution was neutralized with diluted hydrochloric acid, then dialyzed, and then freeze-dried. 34 g of polymer compound (2) was obtained. Synthesis of polymer compound [phase] 50 g of n-butyl acrylate and 50 g of monomer 10
was heated and dissolved in 100J of Nooxaso, 5g of dimethyl 7zobisisobutyrate was added, and the mixture was reacted at 80°C for 6 hours under a nitrogen stream. After the reaction, nooxane was distilled off under heating and reduced pressure using a band continuous vacuum dryer (manufactured by Okawara Seisakusho Co., Ltd.) to obtain 96 g of a polymer compound [phase]. The amount of the polymer compound used in the present invention can be used within a wide range, but is generally 10-6 per mol of silver halide, calculated from the number of moles of 7-zole ring residue contained in the polymer.
The amount may range from 1 mole to 1 mole, and when converted into a polymer compound, the amount is 10 (h) per 1 mole of silver halide in terms of weight.
g to 200g, preferably 200II1g to 100
Use within the g range. Further, the amount per support 1+s2 ranges from about 1111 g to about 2 g, preferably from 10 oz to 1 g. The layer to be added may be added to any layer of the light-sensitive material, and the timing of addition is in the chemical hot acid of the silver denide emulsion, at the end of ripening and/or before coating the emulsion after completion of ripening. . A preferred form is to add it at the end of chemical ripening of the silver halide emulsion. 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 [I] of the present invention. As the antifoggant and stabilizer, U.S. Patent No. 2.71
No. 3,541, No. 2,743.180, No. 2,743
, US Pat. No. 2,716,062, US Pat. No. 2,444,607, US Pat.
, No. 444,605, No. 2,756,147, No. 2,
No. 835.581, No. 2,852,375, Research Disc + - (Research Disc+
7-zaindenes such as tetrazaindenes described in US Pat. No. 14851, triazaindenes described in U.S. Pat. Class: U.S. Patent No. 2,131,038, U.S. Patent No. 3,342.5
Quaternary onium salts such as thiazolium salts described in U.S. Pat. No. 96 and No. 3,954.478, biryllium salts described in U.S. Pat. Salts; US special mention 2I
No. 403.927, No. 3,266.897, No. 3,7
No. 08,303, JP-A-55-135835, JP-A No. 59
-71047, mercaptotetrazoles, mercaptotriazoles, mercaptodiazoles, mercaptothiazoles described in U.S. Pat. No. 2,824,001, mercapto described in U.S. Pat. No. 3,397,987. Benzthiazoles, mercaptobenzthiazoles, mercaptooxanoazoles described in U.S. Pat. No. 2,843,491, U.S. Pat.
364,028; mercapto-substituted heterocyclic compounds such as mercaptothyanazoles; US Pat.
, 236,652, catechols described in Japanese Patent Publication No. 43-10256, resorcinols described in Japanese Patent Publication No. 56-44413 'IL tf Japanese Patent Publication No. 43-413
Polyhydroxybenzenes such as el gallate described in No. 3; tetrazoles described in West German Patent No. 1,189,380; triazoles described in U.S. Patent No. 3,157,509; ,704,721
17 Azoles, U.S. Patent No. 3)
, urazoles described in U.S. Pat. No. 3,106.467, indazoles described in U.S. Pat. No. 2,271.229, and JP-A-59-90844. Heptazoles such as polymerized benztriazoles described in U.S. Pat.
, 3-pyrazolidones described in U.S. Pat. No. 2,751,297, and polymerized pyrrolidones or polyvinylpyrrolidones described in U.S. Pat. No. 3,021,213, etc. heterocyclic compounds; JP-A-54-130924, JP-A-54-130924;
-137945, 140445, British patents 1 and 3
No. 56.142, U.S. Pat. No. 3,575,699, No. 3
, 649, 267, etc.; sulfinic acids and sulfonic acid derivatives described in U.S. Pat. No. 3,047,393; U.S. Pat.
56゜263, 2,839,405, 2,48
There are inorganic salts described in No. 8,709 and No. 2,728゜663. In the silver halide emulsion according to the present invention, any of silver bromide, silver iodobromide, silver iodochloride, and chlorobromide can be used as the silver halide. Further, the silver halide grains may have a uniform 7N silver lodenide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside of the grain and the surface layer. The silver lodenide emulsion used in the present invention is, for example, British Patent No. 618,061, British Patent No. 1,315,755, British Patent No. 1,396, British Patent No. 898, Japanese Patent Publication No. 44-15748.
No. 1,574,944, U.S. Pat. No. 1,623,4
No. 99, No. 1,673,522, No. 2,278,94
No. 2, No. 2.399,083, No. 2,410,689
No. 2,419.974, No. 2448.060, No. 2,487,850, No. 2,518,698,
2,521.926, 2,642.361, 2,852.375, 2,728゜668, 2,
No. 983,609, No. 2,983,610, No. 3,0
No. 21,215, 3. , No. 297, 446, 3, 2
No. 97,447, No. 3,411,914, No. 3,55
No. 4,757, No. 3,565,631, No. 3,565
．． No. 1333, No. 3,591,385, No. 3,656
, No. 955, No. 3,761.267, No. 3.772,
No. 031, ll, 857,711, 3,901
, No. 714, No. 3904.415, No. 3,930,
No. 867, No. 4,054,457, No. 4,067.7
No. 40, Research Disclosure No. 12008,
No. 13452, No. 13452, T. H. James, TI+e Theory of the Photographic Ink Process (TI+e Theory of
tbe Photographic Proc
It is preferable to carry out sensitization using a chemical sensitizer or a sensitization method described in ess) (4Ll+ Ed, 1977) p. 67-76. The sensitizing dyes used in the silver halide emulsion according to the present invention include cyanine dyes, merocyanine dyes, composite cyanine dyes, composite merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, sterin color cords, and hemioxa/
- color dyes are used. Particularly useful dyes include cyanine dyes, merocyanine dyes,
and a complex merocyanine pigment. For these dyes, any of the nuclei commonly used in cyanide dyes can be used as the basic heterocyclic nucleus. Namely, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, virol nucleus, oxazole nucleus, thiazole nucleus, seven? Nazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei, and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, i.e., indolenine nucleus, benzindolenine These include a nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, etc. These nuclei may be substituted on carbon atoms. Merocyanine dyes or complex merocyanine dyes include a pyrazolin-5-one nucleus, a thiohyguntoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, logenine nucleus, thiobarbic acid nucleus, etc. can be applied. Useful sensitizing dyes that can be incorporated into blue-sensitive silver halide emulsion layers include, for example, West German Patent No. 929,080, US Pat. No. 2,231,658, US Pat. No. 776, No. 2,519,001, No. 2
, No. 912,329, No. 3,656,959, No. 3,
No. 672,897, No. 3,694,217, No. 4.0
No. 25,349, No. 4,046,572, British Patent 1
, No. 242,588, Special Publication No. 44-14030, No. 5
Examples include those described in No. 2-24844. Further, useful sensitizing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Pat.
No. 1, No. 2,072,908, No. 2,739,149
No. 2,945,763, U.S. Patent No. 505,979
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. Furthermore, useful sensitizing dyes used in red-sensitive silver halide emulsions include, for example, U.S. Pat. Representative examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in U.S. Pat. No. 2,493,748,
Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in German Pat. 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 Publications No. 43-4932, No. 43-4933, No. 4
No. 3-4936, No. 44-32753, No. 45-25
No. 831, No. 45-26474, No. 46-11627
No. 46-18107, No. 47-8741, No. 4
No. 7-11114, No. 47-25379, No. 47-3
No. 7443, No. 48-28293, No. 48-3840
No. 8, No. 48-38407, No. 48-38408,
No. 48-41203, No. 48-41204, No. 49
-6207, 50-40662, 53-12'
No. 375, No. 54-34535, No. 55-1569, JP-A No. 50-33220, No. 50-33828,
No. 50-38526, No. 51-107127, No. 5
No. 1-115820, No. 51-135528, No. 51
-151527, 52-23931, 52-5
No. 1932, No. 52-104916, No. 52-104
No. 917, No. 52-109925, No. 52-1106
No. 18, No. 54-80118, No. 56-25728, No. 57-1438, No. 58-10753, No. 58-
No. 91445, No. 58-153926, No. 59-11
No. 4533, No. 59-116645, No. 59-116
No. 647, U.S. Patent 2. 'ass, No. 545, 2,9
No. 77.229, No. 3,397,080, No. 3.5 (
! No. 6,443, No. 3,578.447, No. 3,67
No. 2,898, No. 3,679.428, No. 3,769
．． No. 301, No. 3,814.609, No. 3,837,
It is described in No. 862. As the binder (or protective colloid) according to the present invention, it is advantageous to use gelatin, but synthetic hydrophilic polymeric substances such as gelatin derivatives, graft polymers of gelatin and other polymers, single or copolymers, etc. Hydrophilic colloids such as, for example, can also be used. Gelatin includes lime-processed gelatin, acid-processed gelatin, Bull, Soc, Sci, Phot, Japa.
Enzyme-treated gelatin such as that described in J. N., No. 16*30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. Gelatin derivatives include gelatin, for example, acid halides, acid anhydrides,
Incyanates, bromoacetic acid, alkanesultones,
Those obtained by reacting various compounds such as vinyl sulfonamides, maleimide compounds, polyalkyleonoxides, and evoquin compounds are used. Specific examples are U.S. Patent Nos. 2,614,928 and 3,132.9.
No. 45, No. 3,186,846, No. 3,312,55
No. 3, British Patent No. 8 (No. 31,414, British Patent No. 1,033,1
No. 89, No. 1,005,784, Special Publication No. 42-268
It is described in No. 45 etc. Typical synthetic hydrophilic polymer substances include polyvinyl alcohol, polyvinyl alcohol partial acetal,
Poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl alcohol
For example, West German Patent Application (OLS) 2,312,7
No. 08, U.S. Patent No. 3,620,751, U.S. Patent No. 3,87
No. 9,205 and Japanese Patent Publication No. 43-7561. In addition to the antifoggants and stabilizers mentioned above, in the present invention, hardeners, antistatic agents, matting agents, surfactants, etc. used in the photographic industry to improve physical properties, photographic properties, or developability are used. It is possible to use various additives. Hardening agents include aldehyde type, aziridine type (e.g. P[3revo-), 19,921, US Patent 2,950
, No. 197, No. 2.964, 404, No. 2,983,
No. 611, No. 3,271,175, Special Publication No. 1977-40
No. 898, JP-A No. 50-91315)
, inoxal series (e.g., U.S. Pat. No. 331,609
), epoxy systems (e.g. U.S. Pat. No. 3,0
47,394, West German Patent No. 1,085,663, British Patent No. 1,033,518, and Japanese Patent Publication No. 48-35495), vinyl sulfone type (e.g. PE REVO) 19,920. West German Patent No. 1,100,942,
2,337,412, 2,545.722, 2,635.518, 2,742,308, 2
, 749, 260, British Patent No. 1,251°091
No., Patent Application No. 45-54236, No. 48-110996
No. 3,539,644, U.S. Patent No. 3,490,9
11), acryloyl type (e.g., those described in Japanese Patent Application No. 48-27949 and US Pat. No. 3,640,720), carbodiimide type (e.g., US Pat. No. 2,938,892, US Pat. No. 3,640,720), No. 4,043,818, same 4
, No. 061.499, Japanese Patent Publication No. 46-38715, and Japanese Patent Application No. 15095-1983), triazine-based (
For example, West German Patent No. 2.410, 973, West German Patent No. 2.55
No. 3,915, U.S. Pat. No. 3,325.287, and JP-A-52-12722), polymer type (e.g., U.S. Pat. No. 822,061, U.S. Pat. No. 3,623,8)
No. 78, No. 3,396.029, No. 3,228,23
No. 4, Japanese Patent Publication No. 47-18578, No. 18579, No. 47-48896), maleimide-based, acetylene-based, methanesulfonic acid ester-based (tomethylol-based) hardening agents alone or Can be used in combination. As a useful combination technique, 84*t!
N Sh v#k 2.447.587% -rM 2
．． No. 505.746, No. 2 514.245, U.S. Patent No. 4,047,957, U.S. Pat. No. 3,832,181, U.S. Pat. No. 52-12739, Special Publication No. 4
Examples of the combination antistatic agent described in No. 8-32364 include compounds described in Research, Disclosure No. 17643, X■. The antistatic agent may be added to the layer on the side of the support on which the emulsion is not laminated, and the protective colloid may be added to the emulsion layer and/or the emulsion layer on the side on which the emulsion layer is laminated to the support. It may be used in layers. 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, various couplers are used as couplers, such as dye-forming couplers that form dye images and DIR couplers that adjust photographic characteristics and image quality characteristics. As the yellow dye-forming coupler, known 7-syl acetanilide couplers can be preferably used. Among these, benzoylaceto-7dilide and pivaloylacetanilide compounds are advantageous. A specific example of a yellow coupler that can be used is U.S. Pat. No. 1,077.874.
No., Special Publication No. 45-40757, Japanese Patent Publication No. 47-1031
No. 47-26133, No. 48-94432, No. 50-87650, No. 51-3631, No. 52-1
No. 15219, No. 54-99433, No. 54-133
No. 329, No. 56-30127, United States vfW'f L
No. 875-057, No. 3,253,924, No. 3,2
No. 85,506, No. 3,408. lj No. 4, 3,55
No. 1,155, No. L55L156, No. 1,664,
No. 841, No. 3,725,072, No. 3,730,7
No. 22, No. 3,891,445, No. 3,900,48
No. 3, No. 3,929,484, No. 3,933,500
No. 3.973,968, No. 3,990.896, No. 4,012,259, No. 4゜022.620,
No. 4,029,508, No. 4,057,432, No. 4,106.942, No. 4,133,958, No. 4
, 269, No. 938, No. 4,286°053, No. 4,304,845, No. 4,314.023, No. 4
, No. 336,327, No. 4,356,258, No. 4,
It is described in No. 386.155, No. 4,401,752, etc. As the magenta dye-forming coupler, known 5-pyrazolone couplers, virazolobenlimigzole couplers, pyrazolotriazole couplers, and closed acylacetonitrile couplers can be preferably used. A specific example of a magenta coupler that can be advantageously used is disclosed in the patent application filed in 1973.
No. 8-164882, No. 58-187326, No. 58
-206321, 58-214863, 58-
No. 217339, No. 59-24853, Special Publication No. 1973-
No. 6031, No. 40-6035, No. 45-40757
No. 47-27411, No. 49-37854, JP-A No. 50-13041, No. 51-26541, No. 5
No. 1-37648, No. 51-105820, No. 52-
No. 42121, No. 53-123129, No. 53-12
No. 5835, No. 53-129035, No. 54-485
No. 40, No. 56-29236, No. 56-75648, No. 57-17950, No. 57-35858, No. 5
No. 7-146251, No. 59-99437, British Patent No. 1,252.418, U.S. Patent No. 2,600,788, No. 3,005,712, No. 3.062,653,
3,127,289, 3,214,437, 3゜253.924, 3,311,476, 3
, No. 419,391, No. 3,519.429, No. 3,
No. 558,319, No. 3,582,322, No. 3,6
15゜506, 3,658,544, 3,70
No. 5.898, No. 3,725,087, No. 3,758
, No. 309, No. 3,823.156, No. 3,834,
No. 908, No. 3,891,445, No. 3,907,5
No. 71, No. 3,926.631, No. 3,928,04
No. 4, No. 3,935,015, No. 3,960,571
No. 4, 076, 533, No. 4,133,68
No. 6, No. 4,237,217, No. 4゜241, 16
No. 8, No. 4,264,723, No. 4,301,235
No. 4,310.623, etc. As the cyan dye-forming coupler, known 7-tall couplers and phenol couplers can be preferably used. Specific examples of cyan couplers that can be advantageously used include British Patent No. 1,038,331, British Patent No. 1.543.040, Japanese Patent Publication No. 48-36894, and Japanese Patent Publication No. 48-59838.
No. 50-137137, No. 51-146828, No. 53-105226, No. 54-115230,
No. 56-29235, No. 56-104333, No. 5
No. 6-126833, No. 5 Hu 131650, No. 57
-No. 155538, No. 57-204545, No. 5B-
No. 118643, No. 59-31953, No. 56-31
No. 954, No. 59-59856, No. 59-12434
No. 1, No. 59-168956, U.S. Patent No. 2,369,
No. 929, No. 2,423,730, No. 2,434,2
No. 72, No. 2,474,293, No. 2,698,79
No. 4, No. 2,772.162, No. 2,801,171
No. 2,895,826, No. 3,253.924, No. 3,311,476, No. 3,458.315,
3,476.563, 3゜591, 383,
Same 3. F3F, No. 316, No. 3,758,308, No. 3,767.411, No. 3,790,384, No. 3
, No. 880,661, No. 3,926゜634, No. 4,
No. 004,929, No. 4,009,035, No. 4,0
No. 12,258, No. 4,052,212, No. 4,12
No. 4,398, No. 4,134,786, No. 4,138
．． No. 258, No. 4,146,396, No. 4,149,
No. 886, No. 4,178.183, No. 4,205,9
No. 90, No. 4,254,212, No. 4.264,72
No. 2, No. 4,288,532, No. 4,296,199
No. 4゜298.200, No. 4,299,914, No. 4,33L999, No. 4,334.011, No. 4,386,155, No. 4,401,752, No. 4
, 427°767, etc. As a colored coupler, for example, British patent 937,8
No. 21, No. 1,035,959, No. 1, 255,
No. 111, JP-A-48-22028, JP-A No. 52-421
No. 21, Special Publication No. 38-22335, No. 44-2016
No. 44-15754, U.S. Patent No. 2,449,96
No. 6, No. 2゜521.908, No. 2,543,691
No. 2,801,171, No. 2,983.608, No. 3,005,712, No. 3,034,892,
3,061゜432, 3,419,391, 3,476.560, 3,476.563, 3
, No. 481,741, No. 3,519,429, No. 3,
No. 583,971, No. 3,622,328, No. 3,6
No. 84,514, No. 4,004,929, No. 4,07
No. 0,191, No. 4,138,258, No. 4,138
, No. 264, No. 4.163,670, No. 4,292,
400, No. 4,369,248, etc. can be used. As a DIR coupler, for example, British patent 953, 4
No. 54, U.S. Patent No. 3,227,554, U.S. Patent No. 3,615
, No. 506, No. 3,617゜291, No. 3,701,
No. 783, No. 3,933.500, No. 4, 095
, No. 984, No. 4,149,886, No. 2,866.
No. 054, No. 4,359,521, JP-A-52-90
No. 932, No. 56-116029, No. 57-1519
No. 44, etc., and U.S. Patent No. 4,248,9
No. 62, No. 4,409,323, JP-A-57-154
No. 234, No. 58-162949, No. 58-2051
No. 50, No. 59-195843, No. 59-20683
No. 4, No. 59-206836, No. 59-210440
The timing DIR coupler described in No. 60-7429 and the like can be preferably used. As a DIR compound, for example, U.S. Patent No. 3,632,3
No. 45, No. 3,928,041, No. 3,938,99
No. 6, No. 3,958,993, No. 3,961,959
No. 4,046,574, No. 4,052,213, No. 4.171,223, No. 4,186,012,
JP 52-65433, JP 52-130327,
Compounds described in No. 57-128335 and the like can be preferably used. As colorless couplers, U.S. Pat. No. 2,998,314 and U.S. Pat.
, 284,649 and DE 1,168,769 can be used. The high-boiling fish oil agent used to disperse oil droplets of the coupler or oil-soluble additive in the hydrophilic solution includes phenol derivatives that do not react with the oxidized form of the developing agent, heptata alkyl esters, phosphate esters, and citric acid. ester, breath
Organic solvents having a boiling temperature of 150° C. or higher, such as acid esters, alkylamides, fatty acid esters, and trimesic acid esters, are used. High boiling point organic solvents that can be used in the present invention include:
US patent! ! n 2,322,027, 2,533
．． 51; No. 1, No. 2,835,579, No. 3,287
, No. 134, No. 2,353,262, No. 2.852,
No. 383, No. 3,554,755, No. 3,678,1
No. 37, No. 3゜876.142, No. 3,700,45
No. 4, 3,748. '141, 3,779.76
No. 5, No. 3,837,863, British Patent No. 958.44
No. 1, No. 1゜222.753, 0LS2,538,8
89, ty Kaisho No. 47-1031, No. 49-90523
No. 50-23823, No. 51-26037, No. 51-27921, No. 51-27922, No. 51-
No. 26035, No. 51-26036, No. 50-626
No. 32, No. 53-1520, No. 53-1521, No. 53-15127, No. 54-119921, No. 54
-119922, 55-25057, 55-3
No. 6869, No. 56-19049, No. 56-8183
No. 6, Japanese Patent Publication No. 48-29060, etc. 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.
No. 1, No. 2,949,360, etc. can be mentioned. 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, benzene, etc.
Water-soluble organic solvents include acetone, methyl isobutyl ketone, β-ethoxyethyl acetate, methoxy glycol acetate, methanol, ethanol, acetonitrile, nooxane, trimethylformamide, dimethyl sulfoxide, hexamethylphosphoramide, diethylene glycol. Examples include monophenyl ether, 7eth7xinitanol, and the like. The surfactant used as a dispersion aid for the oil droplets includes:
For example, alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkylsulfonates, alkylsulfates, alkylphosphates, sulfosuccinates, and sulfoalkylpolyokine ethylene alkyl 7-enyl ethers; steroidal saponins, alkylene oxides 7-ionic surfactants such as derivatives and glycidol derivatives; amphoteric surfactants such as ami-7N1s, ami/alkyl sulfonic acids and alkyl betaines;
and cationic surfactants such as quaternary ammonium salts (preferably 1 lucoton). Eight examples of these surfactants can be found in the "Surfactant Handbook" (Sangyo Tosho, 196
6) and [Emulsifiers, Emulsifier Research, Technical Data Collection J (Kagakuhanrinsha, 1978). Further, as a color antifogging agent for color photographic light-sensitive materials, hydroquinone derivatives, amyl/7-ethyl derivatives, gallic derivatives, ascorbic acid derivatives, etc. are preferable, and specific examples thereof include U.S. Pat. ,336,
No. 327, No. 2,403.721, No. 2,418,6
No. 13, No. 2,675,314, No. 2,701,19
No. 7, No. 2,704,713, No. 2,728,659
No. 2,732,300, No. 2. No. 35,765, No. 3700.453, JP-A No. 50-92988, No. 50-92989, No. 50-93928, No. 5
No. 0-110337, No. 50-158438, No. 52
-146235, 55-95948, 59-5
No. 247, Japanese Patent Publication No. 50-23813, etc. Furthermore, image stabilizers include, for example, hydroquinone derivatives, gallic derivatives, heptanols derivatives and their bis forms, hydroxycoumaran and its spiro forms, human mixichroman and its spiro forms, piperidine derivatives, aromatic amine compounds, pendinooxane derivatives, Preferred are penzenoxole derivatives, silicon atom-containing compounds, thioether compounds, and the like. A specific example is British Patent No. 1,410,
No. 846, JP-A-49-134326, JP-A No. 52-35
No. 633, No. 52-147434, No. 52-1506
No. 30, No. 54-145530, No. 55-6321, No. 55-21004, No. 55-124141, No. 59-3432, No. 59-5246, No. 59-10
No. 539, Special Publication No. 48-31625, No. 49-209
No. 73, No. 49-20974, No. 50-23813, No. 52-27534, U.S. Patent No. 2,360.290
No. 2,418,813, No. 2,875,314, No. 2,701.197, No. 2,704,713,
No. 2,710,801, No. 2,728,659, No. 2,732,300, No. 2, 735, 765,
2.816,028, 3,069,262, 3,336,135, 3゜432.300, 3
, No. 457+079, No. 3,573,050, No. 3,
No. 574.627, No. 3,1398.909, No. 3,
No. 700,455, No. 3,764゜337, No. 3,9
No. 35,016, No. 3,982,944, No. 4,01
No. 3,701, No. 4,113,495, No. 4,120
, No. 723, No. 4,155,765, No. 4,159,
No. 910, No. 4,254,216, No. 4,268,5
No. 93, No. 4,279,990, No. 4,332,88
No. 6, No. 4,360,589, No. 4.430,425
No. 4,452,884, etc. The black-and-white developer used in the black-and-white development process of the present invention is commonly known as a black-and-white first developer used in processing color photographic materials, or is used in processing black-and-white photographic materials. It can contain various additives that are generally added to black and white developers. Typical additives include developing agents such as 1-7enyl-3-pyrazolidone, methol and hydroquinone, preservatives such as sulfites, accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate and potassium carbonate; Surface overdevelopment consisting of neutral or organic inhibitors such as potassium bromide, 2-methylbenlimigsol, methylbenzthiazole, water softeners such as polyphosphates, and trace amounts of iodides and mercapto compounds. Examples include prevention. 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, and specifically, a color image is formed by a coupling reaction between an oxidized product of a color developing agent and a color coupler. This is the process of forming. Therefore, in the color development processing process, it is usually necessary to incorporate a color developing agent into the color developing solution, but it is necessary to incorporate the color developing agent into the color photographic material, and use a color developing solution or a color developing agent containing the color developing agent. It also includes treatment with alkaline R (activator liquid). The color developing agent contained in the color developing solution is an aromatic 1a amine color developing agent, aminophenol type and p-7
Our color developing agents containing unilene diamine derivatives can be used as salts of organic acids and **acids.
For example, hydrochloric acid, sulfate, P-)luenesulfonate, sulfite, oxalate, benzenesulfonate, etc. can be used. These compounds generally have a color developer IQ of about 0.
Concentrations of Ig to about 30 g, more preferably color development 8!
Use a concentration of about 1 g-15 g for IQ. If the amount added is less than 0.1 g, sufficient color density cannot be obtained. Further, the temperature of the processing solution in the color developing tank is 10°C to 65°C, more preferably 25°C to 45°C. Examples of the above-mentioned amino 7-ether-based developer include 0-7
mino7er/-, p-7 monophenol, 5-7er/-
Included are 2-oxy-toluene, 2-7 minnow-3-oxy-toluene, 2-oxy-3-7 minnow-1,4-methyl-benzene, and the like. A particularly useful fJS primary aromatic amine color developer is N-
N'-noalkyl-p-phenylenenoamine compound 4 &
1, and the alkyl group and phenyl group may be substituted or unsubstituted. Among them, examples of particularly useful compounds include N-N'-tumethyl-9-phenylenenoamine tMIsRtiA, N-mef loop
-phenylenediamine hydrochloride, N,N'-dimethyl-p
-7 Unilenediamine hydrochloride, 2-amine-5-(N-
Ethyl-N-dodecylamine)-) toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-7thyl-
4-7 mino/aniline sulfate, N-ethyl-N-β-hydroxyethylamino 7-niline, 4-7 minnow 3-methyl-N, N'-noethylaniline, 4-7 minnow N-(2
-7toxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate. 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, U.S. Patent 3,719
, 492, and a method of incorporating a color developing agent in the form of a metal salt, as shown in U.S. Pat. Method for incorporating the main drug, JP-A-58-65429 and JP-A-58-241
A method of incorporating the pigment as a dye precursor as shown in US Pat. No. 37, etc., a method of incorporating as a color developing agent precursor as shown in U.S. Pat. In this case, the photosensitive material can be treated 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 is
It 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, and may further contain various additives, such as Bennol alcohol, alkali halide I
It may contain a J metal such as potassium bromide or potassium chloride, a development regulator such as citranedic acid, and a preservative such as hydroxylamine or sulfite. Plus 111 each! ? It is possible to appropriately contain a foaming agent, a surfactant, and an organic solvent such as methanol, metalformamide or dimethyl sulfoxide. I)H of the color developing solution 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 optionally contain antioxidants such as diethylhydroxyamine, tetronic acid, tetronimide, 2-7 nylinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, and benthic acid. - large or hexose, pyroprole-1.
3-methyl 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, as the chelating agent, amine polycarboxylic acid such as ethylene-7minetetraacetic acid, diethylenetriaminepentaacetic acid, 1
-Organic phosphonic acids such as hydroxyethylidene-1,1'-diphosphonic acid; Examples include phospho/carboxylic acids such as phosphonobutane-1,2,4-)licarboxylic acid, polyphosphoric acids such as tripolyphosphoric acid or hexametaphosphoric acid, and polyhydroxy compounds. The support used in the light-sensitive material using the silver halide emulsion of the present invention includes an a-olefin polymer (for example, polyethylene, polypropylene, ethylene/butene copolymer).
Flexible reflective supports such as paper laminated with synthetic paper, etc.
Films made of semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, flexible supports with reflective layers on these films, laths, and metals. , pottery, etc. Particularly useful coating methods are extrusion coating and curtain coating, which allow two or more layers to be applied simultaneously. Also, the coating speed can be arbitrarily selected and can be set to 3ζ, but from the viewpoint of productivity it is 50+n/fain.
A speed higher than that 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, for general black and white, for X-ray recording, for plate making, for color positive, for color paper, for color printing, for color reversal,
It is a photosensitive material for direct positive use and heat development use. 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 ripened to the highest sensitivity by gold and sulfur sensitization to obtain a high-sensitivity silver iodobromide emulsion. Obtained. 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 coated uniformly on a pre-subbed polyester support to a silver content of 3 g/m2 and dried to form samples 1 to 1.
I got 3. One set of the obtained samples was placed in a cold M&R set at 5°C, and the other 2 and 11 were placed under high temperature and low humidity, and under high temperature and high humidity (first stage).
After being left for 5 days, the three sets were subjected to wedge exposure in the usual manner. Then I added 20 ml of Kodak D-72 developer.
Table 1 shows the results of sensitometry after developing for 4 minutes at ℃, fixing, washing with water and cooking. The sensitivity in the table is expressed as a relative sensitivity using the reciprocal of the logarithm of the exposure amount required to obtain a density of fog density + 0.5, with the comparison sample set as 100, and is the value obtained by subtracting the base density above the fog value of 1. Indicated. As is clear from the m1 table, the compound according to the present invention suppresses the occurrence of fog even when left under harsh storage conditions, and the decrease in sensitivity is small compared to the comparative compound. Examples test the diffusivity of compounds. Anhydrous 5,5'-dichloro-9-ethyl-3,3'- was added as a green-sensitive emulsion on the emulsion layer of the sample prepared in Example-1.
Spectrally sensitized with no (3-sulfobutyl)-oxacarbocyanine hydroxide and stabilized with 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene and coating aid only. A silver iodobromide emulsion similar to that of Example 1 in which . The 13 samples obtained were immediately exposed to wedge light through a green filter, and then subjected to the same treatment as in Example 1 for sensitometry. The results obtained are shown in Table 2 below. Note that the comma value indicates the slope of the linear part of the characteristic curve, and as is clear from Table 2, the influence of photographic properties on the upper layer emulsion due to diffusion transfer from the lower layer to the upper layer is The fact that it is hardly seen in the compound indicates that the diffusivity of the compound is suppressed and improved. Example 3 Multilayer color photosensitive material sample 1 was prepared by sequentially providing each layer having the composition shown below on a cellulose triacetate film support.
(Comparison) was made. 1st layer: antihalation layer black gelatin layer containing colloidal silver 2nd layer: intermediate gelatin layer 3rd KJ: red sensitivity low sensitivity? L l'Ij 1-layer silver iodobromide emulsion (silver iodide: 5 mol %) (average grain size 0.5 μto) Silver coating amount: bow, 79 g/+n2 Sensitizing dye ■... 1 mol of silver 6X 10-
5 mol sensitizing dye ■・・・1.5×1 per 1 mol of silver
0-5 moles Coupler A...0.06 moles per 1 mole of silver Coupler C...0.003 moles per 1 mole of silver Coupler D...largely equal to 1 mole of silver・1 then 0.0
03 Moltricresyl 7 Male 7 A) fill Fabric amount 0.3 cc/m2 4th WJ: Red-sensitive high-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide: 4 mol% Average grain size 0.7 μ'n Silver coating amount... ...1.4g/+n2 sensitizing dye■...
...3XiO-5 moles per mole of silver sensitizing dye ■...1.2X per mole of silver 1
0-5 mole coupler F...0.012 for 1 mole of silver
5 mole coupler C...0.0016 per mole of silver
Moltricresyl 7 male 7 ate Coating amount: 0.2 cc/parrot 2 5th layer: Intermediate layer Same as 2nd layer 6th layer: Green-sensitive low-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide: 4 mol% ゛ Average grain size 0.5μIn Silver coating amount...1. Og/m2 Sensitizing dye■...3X per mole of silver 10-
5 mol sensitizing dye ■... IX 10- for 1 mol of silver
5 mole coupler l3-1...0.0 per mole of silver
8 mole coupler M: o, oos mole coupler D: 0.0015 per mole of silver
Malt Resil 7 Male 7z-)! Fabric weight + 141-, /IA2 7th layer: Green-sensitive highly emulsion layer Silver iodobromide emulsion Silver iodide: 5 mol% Average grain size 0.75 μ'0 Silver coating amount...1.6 g/ [f12 sensitizing dye ■・
...2.5X 10-5 mole sensitizing dye for 1 mole of silver...0.8X 1 for 1 mole of silver
0-5 mole coupler B-1...0.02 per mole of silver
Mol coupler M: 0.003 mole tricresyl 7male 72t coating amount per mole of silver 0.8cc/m2 No. 81 VJ: Yellow filter single layer A gelatin layer containing yellow colloidal silver in an aqueous gelatin solution. m9 layer: Blue-sensitive low-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide 6 mol% Average grain size 0.7 g/l112 Silver coating amount...0.5 g/+n2 coupler Y-1
・・・・・・0.125 mol tricresyl 7 osphene per 1 mol of silver) a Fabric weight 0, 3ce/2 10th layer: Blue-sensitive high-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide 20 mol% Average particle size 0.8μ "Ω Silver coating amount...0.6H/+a2 coupler Y-1
・・・・・・0.04 mol of triclenol 7A per 1 mol of silver) a Cloth mO, ice/+
a2 111N: Protective layer trimethyl meth/acrylate particles (diameter 1.5 μII
Apply a gelatin layer containing I). The coupler in each layer was prepared by adding the coupler to a solution of tricresyl 7m 7ate and ethyl acetate and using it as an emulsifier.
Dodecylbenzenesulfonic acid sorg was added, dissolved by heating, mixed with a heated 10% gelatin solution, and emulsified in a colloid mill. In addition to the above composition, a gelatin hardener and a surfactant were added to each layer. The sample prepared as described above was designated as Sample 1. Compound Sensitizing Dye I used to prepare the sample: Anhydro-5,5'-dichloro-3,3
'-di(γ-sulfopropyl)-9-ethyl-thiacarbocyanine hydroxide pyridium salt sensitized color code: Anhydro-9-ethyl-3,3'-(
γ-sulfopropyl)-4,5,4',5'-dibenzothiacarbocyanine hydroxide triethylamine salt sensitizing dye ■: Anhydro-9-ethyl-5,5'-dichloro-3,3'-cy(γ -sulfopropyl)oxacarbocyanine sodium salt sensitizing dye
β-(γ-sulfopropoxy)ethoxy]ethylimidazolocarbocyanine hydroxide sodium salt coupler AC Majiro 461] Coupler 8-1 (MW!=;700) 2H5 Shimi coupler C [opening'': 922) H coupler DL Sleeve = 850] The red-sensitive layers of the third WI and fourth layers, which are the silver halide emulsion layers, and the green-sensitive layers of the sixth and seventh layers are all stabilized in a known manner after adding a sensitizing dye. 3 g of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene per mole of silver halide and 1-phenyl-5-
mercaptotetrazole per mole of silver halide
It was stabilized by adding 10ll1. The ninth and tenth layers of the next blue-sensitive emulsion layer contain coupler Y.
Before adding -1, the comparative compound and the compound of the present invention were added as shown in Table 3 below, and the mixture was prepared and multilayered. The obtained multilayer color light-sensitive material was subjected to high temperature and high humidity processing for the storage test in the same manner as in Example 1, followed by ordinary wedge exposure and then the following color processing. Processing process [Processing temperature: 38℃] Color development during processing
Bleach for 3 minutes and 15 seconds
Wash with water for 6 minutes and 30 seconds
Fixed for 3 minutes and 15 seconds
Wash with water for 6 minutes and 30 seconds
Stabilization for 3 minutes and 15 seconds Drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is as follows. [Color developer] 4-7 minnow 3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfur fi [4.75g Anhydrous sodium sulfite 4.25g Hydroxylamino 1/2 sulfate 2.0g Anhydrous potassium carbonate
37.5g sodium bromide
Add 1.3g nitrilotriacetic acid trisodium salt (monohydrate) 2.5g potassium hydroxide 1.0g water to make 19. [) White liquid] Ethylenediaminetetraacetic acid iron ammonium salt 100,
Og Ethylenediaminetetraacetic acid diammonium salt 10.0
g Ammonium bromide 150.0g Glacial acetic acid 10.0g Add water to make IQ, and adjust to pl+6.0 using ammonium water. [Fixer] Ammonium thioacetate 175.0g Anhydrous sodium sulfite 8.6g Sodium metasulfite 2.3g Add water to make IQ, and adjust to PL+6.0 using acetic acid. [Stabilizing liquid] Formalin (37% aqueous solution) 1.5m
Q Funigux (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5m
Add Mimizu to make one party. Table 3 shows the results of the storage test on the blue-sensitive layer, and these results show that the compound of the present invention does not deteriorate photographic properties when administered orally, and can obtain a fog suppressing effect with little desensitization. . (Be

【Effect of the invention】

As is clear from the above Examples, according to the present invention, a silver halide photographic material that does not cause fogging or decrease in sensitivity or mass even when placed under severe storage conditions can be obtained; In a multilayer photosensitive material, it is possible to provide a photosensitive material that does not have any adverse effects due to diffusion into adjacent layers. Applicant Roku Konishi Photo Industry Co., Ltd. Procedural Amendment June 11, 1985 1985 Patent M No. 146185 2 Name of invention Silver halide photographic light-sensitive material 3.111 Relationship to the case of person making corrections Patent application Person Address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Contact Address 1-1 Sakuracho, Hino-shi, Tokyo 191 Konishiroku Photo Industry Co., Ltd. (Telephone 0425-83-152)
1) 5. Column 6 of "Detailed Description of the Invention" of the specification to be amended, contents of the amendment We will make the following amendments. Procedural amendment July 11, 1986

Claims (1)

[Scope of Claims] A silver halide photographic material is characterized in that at least one of its constituent layers contains at least one polymeric compound having a repeating unit represented by the following general formula [I]. Silver halide photographic material. General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼ [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 represents an atomic group necessary to form a pyrimidine ring, a triazine ring and a tetrazole ring together with a nitrogen atom. ]