JPS6327832A - Silver halide photosensitive material having improved contrast, dots quality and storage life - Google Patents

Abstract

PURPOSE:To obtain the titled material having a stabilized performance (such as dots quality) at the time of storing it at high temp. and humidity conditions by incorporating a specific compd. contg. a tetrazolium compd. to a hydrophilic colloid layer. CONSTITUTION:The titled material comprises a substitute body and the hydrophilic colloid layer contg. at least one layer of the photosensitive silver halide emulsion layers mounted on the substrate body. The hydrophilic colloid layer contains the tetrazolium compd. shown by formula I and a compd. shown by formula II. In formula I, R<1>-R<3> are each hydrogen atom or a substituent, X<-> is an anion. In formula II, R<4>-R<7> are each hydrogen atom, halogen atom, carboxyl, alkyl, alkoxy, alkylthio or hydroxyalkyl group, etc., R<4> and R<5>, and R<6> and R<7>, together with each other, may form 5-6 membered sulfur contg. heterocyclic ring. Thus, the titled material having the improved contrast, dots quality and storage performance at the high temp. and humidity is obtd.

Description

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

The present invention relates to a silver halide photographic material used for forming ultra-high contrast photographic images, and more specifically to a printing plate that can form a high-contrast halftone image using a developer with good stability. This article relates to silver halide photographic materials that have high utility value in the field.

[Conventional technology]

It is conventionally known that photographic images with extremely high contrast can be formed using silver halide photosensitive materials. For example, the average grain size of silver halide grains is approximately 0.
．． Fine particles of 5 μl or less, narrow particle size distribution, uniform particle shape, and silver chloride content of, for example, 50 mol%.
As described above, by processing a silver halide photosensitive material having an emulsion layer consisting of a high silver chlorobromide or silver chloroiodide emulsion with an alkaline developer containing only hydroquinone as a developing agent and having a low concentration of sulfite ions. A method of obtaining a halftone image or line drawing with high image contrast is known. This type of silver halide light-sensitive material is known as a lithium-type silver halide photographic light-sensitive material, and has an area of a size proportional to the continuous tone density change of the original during the photolithography process. It is used to convert to a set of halftone dots. Such conversion uses a lithium-type silver halide photographic light-sensitive material, photographs the original through a cross-line screen or a direct screen, and then changes the sulfite ion concentration. A halftone dot image is formed by developing with a so-called Lith type developer which contains only a hydroquinone developing agent and which has a very low oxidation rate. This lithium-type silver halide photographic light-sensitive material itself does not have sufficient high contrast; for example, even if it is processed with a commercially available developer for photographic paper, the mm is only 5 to 6;
Since 7-linone, which must be most avoided in forming halftone dots, occurs frequently, it is said that combination with the above-mentioned Lith type developer is essential for halftone negative/positive use. Regarding this lithium type developer, please refer to
Neil's Journal of the Franklin Institute (J, ^, CYule: J, Frankl
In Intrute), Vol. 239, p. 221 (1945), it contains essentially only hydroquinone as a developing agent, and the concentration of sulfite ion, which acts as an antioxidant for the developing agent, is It is a low developer. Such developers have poor storage stability and are susceptible to auto-oxidation, so in order for platemakers to consistently obtain high-quality halftone negative or halftone positive images, the developer's activity, which decreases in II10, must be It is necessary to manage the developer in order to maintain a constant value, but this operation inevitably becomes complicated. The benefits of improving the stability of Lith-type developers are extremely large, and a great deal of effort has been made to do so. It is completely inadequate compared to Therefore, a method using a phenidone-hydroquinone type developer with a high sulfite ion concentration to form a high-contrast image comparable to Lith development was proposed in Japanese Patent Publication No. 59-17825, No. 5
No. 9-17818, No. 59-17819, No. 59-1
No. 7820, No. 59-17821, No. 59-1782
No. 6, No. 59-17822, etc. disclose silver halide photographic materials containing a tetrazolium compound.

[Problems to be solved by the invention]

Although these technologies allow the formation of high-contrast halftone dot images using long-lasting developers, they require even greater contrast and halftone dots to be fully compatible with the remarkable quality improvement movement in the printing and platemaking field. Improvements in dot quality are needed, and improvements in the stability of performance (dot quality) when stored under high temperature and high temperature conditions are desired for these technologies. Therefore, an object of the present invention is to solve the above-mentioned problems in silver halide photographic materials using tetrazolium compounds. That is, it is an object of the present invention to provide a silver halide photographic light-sensitive material in which images comparable to Lith development can be formed using a developing solution with good stability and improved high contrast, halftone dot quality, and storage performance under high temperature and high humidity conditions. It is.

[Means to solve problem α]

As a result of intensive research, the present inventors have found that the present inventors have a support and a hydrophilic colloid layer coated on the support, including at least one photosensitive silver halide emulsion layer, and the hydrophilic colloid layer is The above problems are solved by a silver halide photographic material containing a compound represented by the following general formula (1) and a compound represented by the following general formula (II), and a high-contrast and stable photographic material is obtained. I found out that it is possible. General Formula (1) In the formula, R', R2 and R3 each represent a hydrogen atom or a substituent, and xe represents an anion. General formula (II) In the formula, R4, R5J! and R? each represents a hydrogen atom, a halogen atom, a carboxyl group, an alkyl group, an alkoxy group, an alkylthio group, a hydroxyalkyl group, an alkoxyalkyl group, a cyanoalkyl group, a hydroxyalkyl group, or a mercapto group)l4, R5 and R
6 and R7 may each be bonded to each other to form a 5- to 6-shell sulfur-containing heterocycle. The present invention will be explained in detail below. Preferred examples of the substituents represented by R1 to R3 in the general formula (1) include alkyl groups (e.g., methyl, ethyl, cyclopropyl, propyl, isopropyl, cyclobutyl, butyl, isobutyl, pentyl, cyclohexyl, etc.), ami7 groups, acylamine groups, etc. 7 groups (e.g. acetylamino), hydroxyl groups, alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, pentoxy, etc.),
Acyloxy groups (e.g. acetyloxy), halogen atoms (e.g. fluorine, chlorine, bromine, etc.), carbamoyl groups,
Examples include groups such as acylthio groups (e.g. acetylthio), alkoxycarbonyl groups (e.g. ethoxycarbonyl), carboxyl groups, acyl groups (e.g. 7 cetyl), cyano groups, nitro groups, mercapto groups, sulfoxy groups, aminosulfoxy groups. . Examples of the anion represented by x0 include halogen ions such as chloride ion, bromide ion, and iodide ion, acid groups of inorganic acids such as nitric acid, sulfuric acid, and perchloric acid, and acid groups of organic acids such as sulfonic acid and carboxylic acid. , anionic activators, specifically lower alkylbenzenesulfonate anions such as p-)luenesulfonate 7-anion, higher alkylbenzenesulfonate anions such as p-dodecylbenzenesulfonate anion, and higher alkyls such as latulylsulfonate anion. Sulfate ester anion, boric acid anion such as tetraphenylboron, cyfurkylsul7oxacinate anion such as no-2-ethylhexylsulfosuccinate anion, polyether alcohol sulfate ester anion such as cetylboriethe/xysal7ate anion, stearin Examples include higher aliphatic anions such as acid anions, and polymers with acid groups such as polyacrylic acid anions. Specific examples of the compound represented by the general formula ([) used in the present invention are listed below, but the compound of the present invention is not limited thereto. (Exemplary Compounds) Tetrazolium compounds used in the present invention are, for example, CheIIlical Revie.
It can be easily synthesized according to the method described in Vol. 155, pp. 1335-483. The tetrazolium compound represented by the general formula (1) of the present invention is contained in the silver halide photographic light-sensitive material of the present invention in an amount of about 9 to 10 mg, preferably about 10 mg, per liter of silver halide contained in the silver halide photographic light-sensitive material of the present invention. It is preferable to use the amount up to about 2 g. In the general formula (It), the halogen atom at which P to R7 is atom is, for example, a fluorine atom, a chlorine atom, a bromine atom, etc., and the alkyl group may be linear or branched, such as a methyl group, an ethyl group, an isopropyl group, Examples of the alkoxy group include methoxy group and ethoxy group; examples of the alkylthio group include methylthio group and ethylthio group; examples of the hydroxylalkyl group include hydroxymethyl group; examples of the alkoxyalkyl group include methoxymethyl group. Preferred examples of the cyanofurkyl group include a cyanomethyl group, and examples of the sulfur-containing polycyclic ring formed by bonding R4 and R5 and R6 and R7 include, for example, 2゜3-dihydro-1, Examples include rings such as 4-dithiacyclohexene ring and 2-hydro-1,3-dithiacyclopentene ring. Next, specific examples of the compound represented by the general formula (I[) used in the present invention will be listed, but the compound of the present invention is not limited to these. II -2 II -3 II -4 II -6 II -7 t -8 [-9 General formula (
The amount of the compound represented by II) is in the range of 5X 10-' to 5X 10-2 mol, particularly 5X 10-2 per mole of silver dendide contained in the silver dendide photographic material of the invention. A range of '-' to LX 10-' moles is preferred. In addition, when the compound of general formula (n) is contained in a hydrophilic colloid layer adjacent to an emulsion layer, such as an emulsion protective layer or an undercoat layer, 1. A range of 1 to 5 g per w2, particularly a range of 10IIF to 500B is preferred. It is also possible to contain it in the backing layer, but in this case, even if it is contained in an amount of 100zy to 11000z per m', the effect is extremely low. The compound represented by general formula (II) can be easily synthesized and is also available as a commercial product. The silver halide photographic material of the present invention comprises a support and a hydrophilic colloid layer including at least one silver halide emulsion layer coated on the support. The silver halide emulsion layer is coated directly or coated via a hydrophilic colloid layer that does not contain a silver halide emulsion, and a hydrophilic colloid layer is coated as the 11th layer on top of the silver halide emulsion layer. The silver halide emulsion layer may also be divided into silver halide emulsion layers of different sensitivities, e.g. high and low sensitivity, and the silver halide emulsion layer may contain hydrophilic colloids between the layers. An intermediate layer may be provided between the layers, or an intermediate layer may be provided between the silver halide emulsion layer and the protective layer. The layer containing the tetrazolium compound represented by the general formula (1) and the compound represented by the general formula (II) of the present invention is a hydrophilic colloid layer, preferably a silver halide emulsion layer and/or the halogen It is a wood-philic colloid layer adjacent to the silver oxide emulsion layer. The most preferred embodiment of the invention is the general formula CI
) and general formula (II)
This is a halide photographic light-sensitive material in which the compound represented by is contained in the silver halide emulsion layer, and the hydrophilic colloid is gelatin or a gelatin derivative. In order to incorporate the tetrazolium compound represented by the general formula (1) and the compound represented by the general formula [II] of the present invention into the hydrophilic colloid layer, both are dissolved in appropriate water and/or an organic solvent. The present invention includes a method of adding the compound, a method of dispersing a solution in an organic solvent in a hydrophilic colloid matrix such as gelatin or a gelatin derivative, and then adding the compound, or a method of adding the compound after dispersing it in latex. Any of these methods may be used. The tetrazolium compound represented by the general formula (1) used in the present invention may be used alone or in combination of two or more in an appropriate ratio. Tetrazolium compounds may be used in combination in an appropriate ratio. One preferred embodiment of the present invention is to add the tetrazolium compound according to the present invention and the compound represented by the general formula (It) to a silver halide emulsion layer. In another preferred embodiment of the present invention, it is added to a non-photosensitive hydrophilic colloid layer directly adjacent to the silver halide emulsion layer, or to a non-photosensitive hydrophilic colloid layer adjacent via an intermediate layer. In another embodiment, the tetrazolium compound according to the present invention and the compound represented by the general formula [■] are dissolved in a suitable organic solvent, such as water, alcohols such as methanol and ethanol, ethers, and esters. It may be incorporated into the silver halide photographic material by directly coating the outermost layer on the silver halide emulsion layer side of the silver halide photographic material using an overcoating method or the like. In the present invention, particularly favorable results can be obtained when an anion that binds to the tetrazolium compound of the present invention and lowers the hydrophilicity of the tetrazolium compound of the present invention is used in combination. Examples of such anions include acid groups of inorganic acids such as perchloric acid, acid groups of organic acids such as sulfonic acids and carboxylic acids, anionic activators, and p-)luenesulfonic acid anions in the A form. lower alkylbenzenesulfonate anions, p-dotecylbenzenesulfonate anions, alkylnaphthalenesulfonate anions, laurylsulfonate anions, tetraphenylborons, no 2-
dialkyl sulfosuccinate anions such as ethylhexyl sulfosuccinate anions, polyether alcohol sulfate ester anions such as cetyl polyethenoxysal 7 ate anions, stearic acid anions, etc.
Examples include polyacrylic acid anions. Such anions may be added to the hydrophilic colloid layer after being premixed with the tetrazolium compound of the present invention, or may be added alone to silver halide pores, shavings, or chips containing or not containing the tetrazolium of the present invention. It can be added to the hydrophilic floid layer. There are no particular limitations on the S silver halide (used in the silver halide photographic material of the present invention), but silver chloride or silver chlorobromide is preferred. The composition of silver chlorobromide may be ^gcl/^gr = 10010-2/98, but preferably ^, ci7^gBr = 1oO10-50150
The molar ratio of The average grain size of the silver halide grains is 0.
10 μl to 0.40 μl is preferable, and the coefficient of variation expressed by (standard deviation of particle size)/(average particle size) x 100 is 15%.
The following narrow particle size distributions are more preferable. The silver halide used in the present invention can be sensitized with various chemical sensitizers. Examples of sensitizers include activated gelatin, sulfur sensitizers (sodium thiosulfate, allylthiocarbamide, thiourea,
7lylisothiacyanate, etc.), selenium sensitizers (N, N
-dimethylselenourea, selenourea, etc.), reduction sensitizers (
(triethylenetetramine, stannous chloride, etc.), such as potassium chlorooleite, potassium aurithiocyanate, potassium chlorooleate, 2-ourosulfobenzothiazolemethyl chloride, ammonium chlorobarate, potassium chlorooleate, sodium, Various noble metal sensitizers such as umchloroparagite can be used alone or in combination of two or more. When a metal sensitizer is used, rogammon may be used as an auxiliary agent. Further, the silver halide emulsion used in the present invention may be optically sensitized using one or more sensitizing dyes in order to impart photosensitivity in a desired wavelength range. Various sensitizing dyes can be used, but optical sensitizing dyes that can be advantageously used in the present invention include:
Examples include cyanines, 70 cyanines, trinuclear or tetranuclear merocyanines, trinuclear or tetranuclear cyanines, styryls, holopolar cyanines, hemicyanines, oxonols, hemioxonols, etc. Optical sensitizing dyes are nitrogen-containing heterocyclic nuclei with basic groups such as thiazoline, thiazole, etc.
Those containing a nucleus such as gummy, thiohyguntoin, oxazolidinedione, barbylic acid, thiobarbital acid, bilasolone, etc. are preferable, and such a nucleus can be substituted with alkyl, hydroxyalkyl, halogen, phenyl, cyano, or alkoxy, and the optical The sensitizing dye may be fused with a carbocyclic or heterocyclic ring. In addition, when the above-mentioned optical sensitizing dyes, especially merocyanine-based sensitizing dyes, are used, not only optical sensitization but also the effect of widening the development latitude can be obtained. Further, the silver halide emulsions used in the present invention are disclosed in, for example, U.S. Pat. No. 2,444,607, U.S. Pat.
No. 82, West German Application Publication No. 1,189.380, P.
jS2,058.626, 2,118,411,
Japanese Patent Publication No. 43-4133, U.S. Patent No. 3,342,59
No. 6, Special Publication No. 47-4417, West German Application Publication No. 2.
No. 149.789, Special Publication No. 39-2825, Special Publication No. 4
9-13566, preferably for example 5.6-)rimethylene-7-hydroxy-5
-177zoa (1,5-a)pyrimidine, 5,6-teFramethylene-7-hydroxy-S-triazolo(1,
5-a) Pyrimidine, 5-methyl-7-hydroxy-5
-) Riazolo(1,5-a)pyrimidine, 7-hydroxy-5-) Riazolo(1,5-a)pyrimidine, 5-methyl-6-promotyroxy-S-triazolo(
1,5-a) Pyrimidine, gallic acid ester (e.g. isoamyl gallate, dodecyl gallate, propyl gallate, sodium gallate), mercaptanic acid (1-phenyl-5-mercaptotetrazole, 2-mercaptobenzthiazole), benzotriazole (5-bromobenzotriazole, 5-methylbenzotriazole),
Benrai Migzor! (6-nitrobenzimiguzole) and the like can be used for stabilization. The silver halide and tetrazolium compounds according to the present invention and the compound represented by the general formula (It) are added to the hydrophilic colloid layer. The woody colloid particularly advantageously used in the present invention is gelatin, but hydrophilic colloids other than gelatin include, for example, colloidal albumin, agar, gum arabic, alginic acid, hydrolyzed cellulose acetate, acrylamide, imidized Polyamide, polyvinyl alcohol, hydrolyzed polyvinyl acetate, gelatin derivatives, such as U.S. Pat. No. 2,614,928, q @ 2,525,753%
As stated in each memorandum! ! Phenylcarbamyl gelatin, acylated gelatin, heptalated gelatin, or U.S. Patent No. 52.548.520, No. 2,
831,767, styrene acrylate, acrylic ester, methacrylic acid,
Examples include graph F polymerization of gelatin with a polymerizable monomer having an ethylene group such as methacrylic acid ester, and these hydrophilic colloids are coated with layers that do not contain silver halide, such as a halide prevention layer, a protective layer, etc. It can also be applied to layers, intermediate layers, etc. Examples of the support used in the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, and glass glue.
．． Cellulose acetate, cellulose nitrate, polyester films such as polyethylene terephthalate, polyamide films, polypropylene films,
Typical examples include polycarbonate film, polystyrene film, and the like. These supports are appropriately selected depending on the intended use of the silver halide photographic material. As described above, the photosensitive material of the present invention has a hydrophilic colloid layer containing at least INJ silver halide on the support, and at least one hydrophilic colloid layer on the side of the layer containing the layer. The tetrazolium compound of the present invention and the compound represented by the general formula CII) are contained therein, and the layer side has an appropriate thickness. layer, i.e. preferably from 0.1 to 10 μl, particularly preferably from 0.8 to 2 μl
Preferably, a protective layer of gelatin is applied. The hydrophilic colloid layer used in the present invention may optionally contain various photographic additives, such as gelatin plasticizers, hardeners, surfactants, image stabilizers, ultraviolet m absorbers, antistain agents, and p11 adjusters. Agents, antioxidants, antistatic agents, thickeners, graininess improvers, dyes, mordants, brighteners, development speed igtI agents, matting agents, etc. should be used within the range that does not impair the effects of the present invention. Can be done. Among the various additives mentioned above, those that can be particularly preferably used in the present invention are those used as thickeners or plasticizers, such as those disclosed in U.S. Pat.
No., West German Application Publication No. 1,904,604, Japanese Unexamined Patent Publication No. 4
No. 8-63715, Japanese Patent Publication No. 45-15462, Belgian Patent No. 762,833, U.S. Patent No. 3,767.
No. 410, Belgian Patent No. 558. -143, such as styrene-sodium maleate copolymer, dextran sulfate, etc. Hardening agents include aldehy V-based, epoxy-based, ethyleneimine-based, active halogen-based, vinyl sulfone-based, cyanate type,
Various hardeners and ultraviolet absorbers such as sulfonic acid ester, carbodiimide, mucochloric acid, and acyloyl are described in, for example, U.S. Patent No. 3,253,921, British Patent No. 1,309°349, etc. Compounds that are
In particular, 2-(2'-hydroxy-5-tertiary butylphenyl)benzotriazole, 2-(2'hydroxy-3',
5'-ditertiary butylphenyl)benzotriazole, 2
(2-hydroxy-3'-3mbutyl-5'-butylphenyl, 2-(2'-hydroxy-3',5'-no-tertiary butylphenyl)-5-chlorobenzotriazole, etc. , and as a dye, U.S. Patent No. 2,
No. 072,908, German Patent No. 107,990, US Patent No. 153,048,487, US Patent No. 515,9
Compounds described in No. 88 and the like can be used, and these compounds may be contained in the preservative IN1 emulsion layer or intermediate layer. Furthermore, coating aids, emulsifiers, permeability improvers for processing liquids, antifoaming agents, and surfactants used to control various physical properties of photosensitive materials include British Patent No. 548, No. 532, No. 1,
No. 216,389, U.S. Patent No. 3,026,202;
No. 3,514,293, Japanese Patent Publication No. 44-26580, No. 43-131f36, No. 48-20785, Buddhist Patent J@202, 588, Belgian Patent No. 773
Anionic, cationic, nonionic, or amphoteric compounds described in JP-A-48-10111, No. 459, etc. can be used, and among these, 7-ionic surfactants having a sulfo group are particularly suitable. For example, succinic acid ester sulfonated 4kl, alkylnaphthalene sulfonated products, alkylbenzene sulfonated products, etc. are preferable. In addition, as an antistatic agent, Japanese Patent Publication No. 46-24159,
JP 48-89979, U.S. Patent No. 2,882,1
No. 57, No. 2,972, No. 535, Japanese Unexamined Patent Publication No. 1973-
No. 20785, No. 48-43130, No. 48-903
No. 91, Special Publication No. 46-24159, No. 46-3931
No. 2, No. 48-43809, JP-A-47-33627
Examples of matting agents include compounds described in British Patent No. 1,221,980, U.S. Pat. No. 2,992,101, and U.S. Pat. No. 956,884, Inter-French Patent PtS1,396,544
Compounds described in Japanese Patent Publication No. 48-43125, etc., especially silica sol with a particle size of 0.5 to 20 μl, 0
．． Examples include polymers of polymethyl methacrylate having a particle size of 5 to 20 microns. The /% silver lodenide photographic light-sensitive material containing the tetrazolium compound of the present invention and the compound represented by general formula (II) is preferably developed in the presence of the compound represented by general formula (1) below. . [In the formula, R1 represents a nitro group at the 5th or 6th position, and R12 represents an aqueous atom or a C, to C, lower alkyl group. M
represents a cation such as a hydrogen atom, an alkali metal atom, an alkaline earth gold S atom, or an ammonium ion. ] As a specific compound represented by the general formula (I[[), 5-
Examples include nitroindazole and 6-nitroindazole, but the present invention is not limited thereto. The compound represented by the general formula (I[I) can be used in organic solvents such as noethylene glycol, triethylene glycol, ethanol, noethanolamine and triethanolamine, alkalis such as sodium hydroxide, and acetic acid. It may be dissolved in an acid or the like and added to the developer, or it may be added as is. The compound represented by general formula (III) is preferably contained in a concentration range of about 111 g to 1,000 JIF, more preferably about 50 JIg to 300 JIF, per 11 developer solutions. The following developing agents may be used in the development of the silver halide photographic material of the present invention. This developing agent can be used together with the compound represented by the above-mentioned general formula (III). 110 (CIl= Cll +n 011 Representative examples of type developing agents include hydroquinone, as well as catechol, pyrogol and its derivatives, ascorbic acid, chlorohydroquinone, promohydroquinone, isopropylhydroquinone, toluhydroquinone, methyl Hydroquinone, 2,3-dichlorohydroquinone, 2,5-tumethylhydroquinone, 2,3-dibromohydroquinone, 2,5-dihydroxyacetophenone, 2,5-dimethylhydroquinone, 2,5-di-p-7enethyl Hydroquinone, 2.
5-Nobenzoylamine/hydroquine, catechol,
4-chlorocatefur, 3-phenylcatechol, 4-
Phenylcatechol, 3-nodoxycatechol, 4-7
Examples include cetylvirolol, 4-(2'-hydroxybenzoyl)pyrogallol, and sodium ascorbate. Also, HO+ CH= CI! +-n Nl! Typical Z-type developers include ortho and rose ami/phenol or ami/pyrazolone, including 4-7 minophenol, 2-7 mino 6-phenyl 7er/-ol, 2-amino-4- Chloro-phenylphenol, 4-ami/-
2-phenylphenol, 3,4-diamino7er/-l, 3-/thi-4,6-tzaminophenol, 2,4-
diami/resorcinol, 2,4.6-)su7mino7er/-l, N-methyl-p-amino/phenol, N-β-
Examples include hydroxyethyl-p-7minol, p-hydroxyphenylamide/acetic acid, and 2-aminonaphthol. Further, as the 112N-+C=C+-n Ntlz type developer, for example, 4-7 minnow 2-methyl-N,N-;
/ethylreaniline, 2゜4-diamino-N, N-noethylaniline, N-(4-7minor 3-methylphenyl)-morpholine, p-phenylenediamine, 4-7minor N, N-dimethyl-3 -Hydroxyaniline, N, N
, N', N'-tetramethylbaraphenylenediamine,
4-7 minnow N-ethyl-N-(β-hydroxyethyl)aniline, 4-7 minnow 3-methyl-N-ethyl-N
-(β-hydroxyethyl)aniline, 4-ami/-
N-ethyl(β-nodoxyethyl)-3-methylaniline, 4-7mi/-3-methyl-N-ethyl-N-(β-
methylsulfonamidoethyl)aniline, 4-amino-
N-butyl-N-γ-sulfobutylaniline, 1-(4
-7mi/phenyl)pyrrolidine, 6-amino-1-ethyl-1,2,3,4-tetrahydroquinone, 9-7minoylolidine, and the like. Examples of the heterogeneous developer include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-methyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, l-phenyl -4-methyl-
3- such as 4-hydroxymethyl-3-pyrazolidone
Pyrazolidones, 1-phenyl-4-7 minnow 5-pyrazolone, 1-(p-aminophenyl)-3-7 minnow 2
-pyrazolone, 1-722-3-methyl-4-7mi/
-5-pyrazolone, 5-ami/uracil, etc. can be mentioned. Other books include The Theory of the Photographic Process, 4th edition, by T. H. James.
ory of tbe PhotographicPe
ocess+ Fourth Edition) No. 291
~334 pages and Journal of the American
Chemical Society (Journal of the
American C1+emical 5ociet
y) The developer described in Vol. 73, p. 31100 (1951) can be effectively used in the present invention. These developers may be used alone or in combination of two or more, but it is preferable to use two or more in combination. Even if a sulfite salt such as sodium sulfite or potassium sulfite is used as the agent, the effects of the present invention will not be impaired and this can be mentioned as one of the features of the present invention. Furthermore, hydroxylamine and hydranoid compounds may be used as preservatives. In addition, caustic alkali, carbonate alkali, or amine, etc., which are used in general Hakushi developers, are used. I+ adjustment and buffer function, inorganic development inhibitors such as brompotali, organic development inhibitors such as benzotriazole, metal rice 20M promoters such as ethylenenoaminetetraacetic acid, methanol, ethanol, benzyl alcohol, polyalkylene oxide. Development accelerators such as sodium alkylaryl sulfonate,
It is optional to add surfactants such as natural saponins, saccharides, or alkyl esters of the above compounds, hardening agents such as glutaraldehyde, formalin, glyoxal, and ionic strength regulators such as sodium sulfate. The developing solution used for developing the photosensitive material of the present invention may contain alkali/amino compounds or glycol M as an organic solvent. Examples of the alkanolamine mentioned above include monoethanolamine, jetanolamine, and triethanolamine, and triethanolamine is preferably used. The preferred amount of these alkanolamines used is 5 to 500 g, more preferably 20 to zoog, per 11 of the developer. In addition, the above-mentioned glycols include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, 1,4-butanol, 1g5
-bentanediol and the like, but diethylene glycol is preferably used. The amount of these glycols used is 5 to 500 g per 11 of the developer, more preferably 2
It is 0-200g. These organic solvents can be used alone or in combination. The silver halide photographic material of the present invention can be developed with a challenge solution containing a development inhibitor as described above to obtain a light-sensitive material with extremely excellent storage stability. The pH value of the developer having the above composition is 9 to 12,
From the viewpoint of stability and photographic properties, the pH value is preferably in the range of 10 to 11. The silver halide photographic material of the present invention can be processed under various conditions. The processing temperature is, for example, the development temperature is 5
A temperature of 0'C or less is preferable, and a temperature of about 30C is particularly preferable, and the development time is generally completed within 3 minutes, but particularly preferably within 2 minutes, which often brings about good results. Processing steps other than development, such as washing, stopping,
It is optional to adopt steps such as stabilization, fixation, and if necessary, preduration and neutralization, and these steps can be omitted as appropriate. Furthermore, these treatments may be so-called manual development treatments such as dish development and suki development, or mechanical development such as roller development and hanger development.

【Example】

A silver chlorobromide emulsion was prepared using the following solutions of Solution ^, Solution B, and Solution C. (Solution^) Ossein gelatin 17g Polyisopropylene-polyethylene oxynosuccinate ester sodium salt 10%' Ethanol solution
5xl adenine 2
0B distilled water 1280 shoulders! (
Dissolved silver nitrate 170g distilled water
4LOx1 (Solution C) Sodium chloride 38.0g Potassium bromide 41.7゜Potassium hexachloroylininate 100μs Rhodium trichloride trihydrate 60μg Polyisopropylene-polyethyleneoxydisuccinate ester sodium salt 10% Ethanol solution 311 Ossein gelatin 1g Bennoratenin 20zg Distilled water
407 ml of the solution^ was kept at 40'C, and solutions B and C were added thereto by a double jet method while stirring using a mixing stirrer described in JP-A-57-92523 and JP-A-57-92524. The addition flow rate of each solution B and C was changed incrementally over 80 minutes as shown in Table 1 to form halogenated root particles. During the first 5 minutes of mixing, the [^g of the emulsion was set to 160 mV.
After 5 minutes from the start of mixing, a 3 mol/l aqueous sodium chloride solution was used to adjust the voltage to 120 mVl:g, and thereafter this value was maintained using the aqueous sodium chloride solution. Further, during mixing, the pH was adjusted to 3.0 with IN nitric acid aqueous solution.
It was held at 0. After addition of solutions B and C, Ostwald ripening was carried out for 10 minutes, followed by desalting and washing with water in the usual manner, followed by 600 ml of an aqueous solution of ossein gelatin inactivated by hydrogen peroxide treatment (ossein gelatin). (contains 30g of gelatin),
After dispersion by stirring at 55°C for 30 minutes, 750zz!
Adjusted to. The average particle size of the obtained particles was 0.20 μl, and the coefficient of variation of the particle size distribution was 10. A metal silver electrode and a double junction saturated ^g/^gc1 comparison electrode were used to measure the EAg value. (The double-shank dithane disclosed in Japanese Patent Application Laid-Open No. 57-197534 was used as the electrode structure.) A variable flow rate roller tube metering pump was used to add solutions B and C. Furthermore, during the addition of liquids B and C, sampling of the emulsion revealed that no new particles were observed using an electron microscope. We have confirmed that the amount added does not exceed the critical growth rate in the system. This emulsion was subjected to sulfur-containing sensitization, and as a stabilizer,
6-Methyl-4-hydroxy-1=L3a-7-chitrazaindene was added, and 1-(β-hydroxyethyl)-3-7znyl-5-((3-γ-sulfopropyl-a- Benzoxazolilidene)-ethylidene]thiohydentoin was added at 15 (h+9) per mole of silver lodenide contained in the emulsion for optical sensitization.
μmg, compound of general formula [■] shown in Table 2 15
0B, p-)' Add 400xg of sodium decylbenzenesulfonate and 2g of styrene-maleic acid copolymer, 8gm3, sg712, amount of gelatin 2.0
It was applied onto the base so that the ratio was 0/II2. At that time, add 1 as a spreading agent so that the gelatin it, Og/z2.
-decyl-2-(3-inpentyl)succinate-2
- A protective layer containing 30zg/x" of sodium sulfonate and 25B/z2 of formalin as a hardening agent was simultaneously coated in multiple layers. Table 2 (margin below) Triphenyltetrazolium compound (compound of general formula (1)) Sample 1 The tetrazolium compounds used in , 2 and 3.4 are the exemplified compounds 1-2. I -1 and I -, respectively.
7,! -6. Each sample was divided into two parts, one half was kept as it was, and the other half was kept at 23℃ and relative humidity 5 to evaluate the stability of performance.
Humidify at 5% for 24 hours and use polyvinyl acetate (J!7).
100 μm) and sealed in laminated wrapping paper.
After being left in a thermostat at 58° C. and 80% relative temperature for 48 hours, both samples were exposed to light using an optical wedge with a tungsten light source. The above test sample was processed using a rapid processing automatic developing machine using a developing solution and a fixing solution according to the following formulation for a total processing time of 5 minutes.
Processed in 0 seconds. Development processing conditions Development processing conditions (process) (temperature) (time) Development
33℃ 15 seconds fixation 28°
C Wash with water for about 10 seconds, dry at room temperature for about 10 seconds
50'0 15 seconds development! Composition (to composition) Pure water (ion-exchanged water) 150zf engineered tylennoaminetetraacetic acid disodium salt g Diethylene glycol 50g Potassium sulfite (55% w/v aqueous solution) 100z1 Potassium carbonate 50g Hydroxylate/
1595-Methylbenzotriazole 200ml 1'1-Phenyl-5-mercaptotetrazole 30B Potassium hydroxide Potassium monobromide to bring the pi of the working solution to 10.4
4.5g (composition) Pure water (ion-exchanged water) 31g Diethylene glycol 50° Ethylenenoaminetetraacetic acid disodium salt 25z, g Acetic acid (90% aqueous solution) 0.3zf
5-nitroingzole 110zy1
-Phenyl-3-pyrazolidone 500 g When using a developer, the above composition was dissolved in 500 i+f in the order of the above composition, and the composition was finished to 11 and used. Fixer formulation (composition^) Ammonium thiosulfate (72.5% w/v aqueous solution) 24
0zffi Sodium sulfite 17g Sodium acetate trihydrate 6.5grIAP11
6g Sodium citrate dihydrate 2g Acetic acid (9
0%-7w aqueous solution) 13. f3tj
! (Similar) Pure water (ion-exchanged water) 17xl sulfur 1!1 (50%-/chia water solution)
4.79 Aluminum sulfate (aqueous solution with a content of 8.1% w/w)
When using 26.5 g of fixer solution, the above composition was dissolved in 500 ml of water in the order of the composition, and the final composition was used. The pH of this fixer was about 4.3. Draw a photographic characteristic curve for the developed sample and determine the sensitivity,
Measurements were made to measure the distance between the two legs of the curve and the characteristic curve. The sensitivity was determined from the reciprocal of the exposure amount required to form an optical density of 2.5, and was expressed as relative sensitivity with Sample No. 1 as 100. 〃The mass was determined from the straight line portion of the concentration from 0.5 to 4.0. In addition, the breakage of the legs was shown in the exposure range (t'ogE value) from optical density 0.1 to 0.5. This value indicates a desirable characteristic of small and sharp legs. The results are summarized in the m3 table. From Table ff13 in the margin below, it can be seen that the present invention improves the high contrast, sharpness, and the shelf life under high-temperature and high-humidity conditions in the technology using a tetrazolium compound. Effects of the Invention The present invention improves the high contrast and halftone performance of conventional halogenated photographic materials using a tetrazolium compound that allows ultra-high contrast images to be obtained using a stable developing solution with a high sulfite ion concentration, as well as the high-temperature performance of these materials. Storage stability under high humidity conditions is improved.

Claims (1)

[Scope of Claims] A support comprising a support and at least one photosensitive colloid layer coated on the support, and at least one of the hydrophilic colloid layers is represented by the following general formula [I] A silver halide photographic light-sensitive material characterized by containing a compound and a compound represented by the following general formula [II]. General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1, R^2 and R^3 each represent a hydrogen atom or a substituent, and X^■ represents an anion. ] General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. are included▼ [In the formula, R^4, R^5, R^6 and R^7 are each a hydrogen atom, a halogen atom, a carboxyl group, an alkyl group,
Represents an alkoxy group, alkylthio group, hydroxyalkyl group, alkoxyalkyl group, cyanoalkyl group, hydroxyalkyl group, or mercapto group, and R^4 and R
^5, R^6 and R^7 may each be bonded to each other to form a 5- to 6-membered sulfur-containing heterocycle. ]