JPH04294346A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To give a silver picture of cold-black tone without decreasing sensitivity by incorporating a specified compd. into a structural layer. CONSTITUTION:The above silver halide photographic sensitive material has a silver halide emulsion layer on the one side of a supporting body, and the emulsion layer has photosensitive silver halide particles having <=0.4mum diameter in terms of sphere volume, and the whole gellatin amt. on one side of the supporting body including the emulsion layer is <=3.3g/m<2>. The emulsion layer or other structural layers contain a compd. expressed by formula. In formula, M is hydrogen atom, alkali metal atom, ammonium group, or group which cleaves under alkali condition, L is bivalent org. group comprising single or combination of alkylene, -CO-, etc., X is amino ammonium group, etc., which may be subtd. with alkyl group, and (n) is 0 or 1. The amt. of the compd. used is preferably 1X10<-5>-1X10<-1> to 1mol of silver of the photosensitive silver halide. The compd. is added to the photosensitive silver halide emulsion layer or adjacent layers.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and particularly a silver halide photographic material having high covering power and suitability for rapid processing when processed using an automatic processor. The present invention relates to a silver halide photographic material which also provides a cool black tone. [0002] In recent years, high-temperature rapid processing has rapidly become popular in the development process of silver halide photographic light-sensitive materials (hereinafter referred to as "sensitive materials"), and even in the automatic processing of various light-sensitive materials, Processing times have been significantly reduced. In order to achieve rapid processing, it is necessary to use a sensitive material that can provide sufficient blackening density in a short period of time, and to have characteristics that allow fixing, washing, and drying to be completed in a short period of time. In particular, various methods have been studied to quickly complete drying, but one method that is commonly used to improve the drying properties of sensitive materials is to apply a sufficient amount of hardness in advance during the coating process of the sensitive material. There is a method of reducing the water content in the sensitive material before drying by adding a film agent and reducing the amount of swelling of the emulsion layer and surface protective layer during the development, fixing, and water washing steps. In this method, the drying time can be shortened by using a large amount of hardener, but due to the decrease in swelling, development and fixing are delayed, low sensitivity and tone, a decrease in covering power, and a decrease in the amount of residual silver. cause undesirable phenomena such as increase in Another method for improving drying properties is to reduce the water content in the sensitive material before drying by reducing the amount of binder in the coating film. This method involves developing,
Although this method is excellent in that it does not delay the penetration and diffusion of the processing solution during the fixing process, the high silver/gelatin ratio in the emulsion layer makes it difficult to handle the sensitive material (scratches, roller marks, and nicks). It has the disadvantage of getting worse. In order to prevent this, covering and
Research is being actively conducted to reduce the amount of coated silver and lower the silver/gelatin ratio by increasing the power. However, as the grain size of the silver halide emulsion becomes smaller, the color of the developed silver image becomes yellowish and loses its cool black tone. Such yellowish silver images are disliked because they give an unpleasant feeling to the observer who directly observes them. SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photographic material that can be rapidly processed and provides a silver image with a cool black tone even when using fine-grain photosensitive silver halide. It is. [0004] The above problems have been solved by the present invention as described below. That is, the equivalent spherical volume diameter of the photosensitive silver halide grains used in the photosensitive silver halide emulsion layer is 0.4 μm or less, and the total amount of gelatin on the side of the support containing the emulsion layer is 3.3 g/m2. The following silver halide photographic material is characterized in that a compound represented by the following general formula (I) is contained in an emulsion layer or another constituent layer on the same side as the emulsion layer when viewed from the support. . General formula (I) [Formula 2] (wherein M represents a hydrogen atom, an alkali metal atom, an ammonium group, or a group that cleaves under alkaline conditions, and L represents an alkylene, alkenylene, ether, thioether, -
Represents a divalent organic group composed of CO-, -CS-, -NR- [R represents a hydrogen atom or an optionally substituted alkyl group] alone or in combination, and X may be substituted with alkyl. Represents an amino group, an alkyl-substituted ammonio group, a hydroxy group, and an optionally substituted heterocyclic residue. n represents 0 or 1. ) Hereinafter, general formula (I)
I will explain in detail. In the formula, M represents a hydrogen atom, an alkali metal atom, an ammonium group, or a group that cleaves under alkaline conditions. L is alkylene, alkenylene, ether, thioether, -CO-, -CS-, -NR- [
R represents a hydrogen atom or an optionally substituted alkyl group] alone or in combination. A preferred example of L is alkylene, and this alkylene group may have a substituent. X
represents an amino group which may be substituted with alkyl, an ammonio group which may be substituted with alkyl, a hydroxy group, or a heterocyclic residue which may be substituted. The alkyl substituent is preferably an alkyl group having 1 to 10 carbon atoms, and may be further substituted with a hydrophilic substituent such as a hydroxyl group, a carboxy group, or a sulfo group. A preferred example of X is an amino group which may be substituted with alkyl. n represents 0 or 1. Specific examples of the compound represented by general formula (I) are shown below. However, the present invention is not limited to this. [Formula 3] [Formula 4] [Formula 5] [Formula 5] The amount of the compound of general formula (I) used is 1×10 per mole of silver for photosensitive silver halide. -5 mol to 1 x 10-1 mol, especially 1 x 1 mol.
The amount is preferably 0-4 mol to 1 x 10-2 mol. The compound of general formula (I) is added to the photosensitive silver halide emulsion layer or a layer adjacent thereto, but it is particularly preferable to add it to the surface protective layer. Although the compound of general formula (I) can be added as is, it is preferably adsorbed onto substantially non-photosensitive silver halide fine grains before adding it to the emulsion layer or its adjacent layer. This non-photosensitive fine grain silver halide will be described later. The photosensitive silver halide grains used in the present invention are composed of chlorine, bromine, and iodide, such as silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide, and silver chloroiodobromide. Any silver halide may be used, but silver bromide, silver iodobromide, silver chloride, silver chlorobromide, and silver chloroiodobromide are particularly preferred. The particle shape may be so-called regular particles having regular crystal bodies such as cubes, octahedrons, and tetradecahedrons, and may also be potato-shaped, spherical, plate-shaped, tabular with a particle diameter of 5 times or more the particle thickness, etc. It may be one having an irregular crystal form or a complex thereof. The grain size of the silver halide may be a monodisperse emulsion with a narrow distribution, or a polydisperse emulsion with a wide distribution. The grain size of silver halide can be determined by a commonly used method using an electron microscope. The average value of particle size is determined by number averaging. The light-sensitive material used in the present invention is not limited to one silver halide emulsion layer, but may have two or more layers, and two or more types of emulsions with different grain sizes, sensitivities, etc. may be mixed or used in separate layers. Even if the crystal structure of silver halide grains is uniform throughout the interior, there are also those with a layered structure with different interior and exterior structures, as described in British Patent No. 635,841 and U.S. Patent No. 3,622,318. It may also be of the so-called conversion type as described in . Further, either a type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside the particle may be used. The emulsion of the present invention may contain metal ions such as iridium ions and iron ions. Metal ions may be added in the same aqueous solution as silver halide for grain formation, or may be added before grain formation, during grain formation, or after grain formation until chemical sensitization. However, addition at the time of particle formation is particularly preferred. During the formation of silver halide grains, for example, ammonia, rhodanpotash, rhodanammonium, thioether compounds, thione compounds, amine compounds, etc. can be used as silver halide solvents to control grain growth. In addition to silver halide solvents, compounds that adsorb to the grain surface to control crystal habit, such as cyanine sensitizing dyes, tetrazaindene compounds, and mercapto compounds, can be used during grain formation. Various commonly used chemical sensitization methods such as gold sensitization, sulfur sensitization, reduction sensitization, and sensitization using thioether compounds can be applied to the silver halide emulsion. The silver halide emulsion used in the present invention is spectrally sensitized with a known spectral sensitizing dye, if necessary. Spectral sensitizing dyes that can be used include, for example, Hamer, “
"Heterocyclic Compounds - The Cyanine Soybean and Related Compounds", John Wiley and Sons (1964) (F.
M. Hamer, “Heterocyclic Com.
Pounds The Cyanine Dyes a
nd Related Compounds”, John
Wiley & Sons (1964) and Starmer, “Heterocyclic Compounds - Special Topics in Heterocyclic Chemistry,” John Wiley & Sons (1977).
Annual)D. M. Sturmer, “Heterocy
clic Compounds-Special To
pics in Heterocyclic Chemi
John Wiley & Sons
(1977)], cyanine, merocyanine, rhodacyanine, styryl, hemicyanine, oxonol, benzylidene, holopolar, etc. can be used, and cyanine and merocyanine are particularly preferred. Sensitizing dyes that can be preferably used in the present invention include JP-A-60-133442 and JP-A-61-7533.
No. 9, No. 62-6251, No. 59-212827,
Examples include cyanine dyes and merocyanine dyes represented by the general formulas described in No. 50-122928 and No. 59-1801553. Specifically, JP-A-60-1
No. 33442, pages (8) to (11), JP-A-61-
No. 75339, pages (5) to (7), (24) to
Page (25), No. (10) to (10) of JP-A-62-6251.
Page 15), No. (5) of JP-A No. 59-212827 ~
(7) Page, No. (7) of JP-A-50-122928
~ (9) pages, No. (7) of JP-A-59-180553
Sensitizing dyes that spectrally sensitize silver halide in the blue region, green region, red region, or infrared region of the spectrum as described in pages 1 to 18 can be mentioned. Representative examples of infrared sensitizing dyes are described in JP-A-63-96476. These sensitizing dyes may be used alone, but
Combinations thereof may also be used, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, aminostilbene compounds substituted with a nitrogen-containing heterocyclic ring group (e.g., U.S. Pat. No. 2,933,390, U.S. Pat. No. 3,6
35,721), aromatic organic acid formaldehyde condensates (e.g., U.S. Pat. No. 3,743,510)
(described in the above issue), cadmium salts, azaindene compounds, etc. U.S. Patent No. 3,615,613, U.S. Patent No. 3,615,641, U.S. Patent No. 3,617,295
Particularly useful are the combinations described in No. 3,635,721. The above sensitizing dye is 5 x 10-7 mol to 5 x 10-2 mol per mol of silver halide, preferably 1 x
10-6 mol to 1x10-3 mol, particularly preferably 2x
It is contained in the silver halide photographic emulsion layer in a proportion of 10-6 to 5 x 10-4 mol. Various compounds can be added to the photographic light-sensitive material of the present invention in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the light-sensitive material. These compounds include nitrobenzimidazole, ammonium chloroplatinate, 4-hydroxy-6-methyl-
A large number of compounds have been known for a long time, including 1,3,3a,7-tetraazaindene, 1-phenyl-5-mercaptotetrazole, many heterocyclic compounds, mercury-containing compounds, mercapto compounds, and metal salts. An example of a compound that can be used is C. E. K. “TheT” by Mees
theory of the Photographic
Process" 3rd edition, 1966), pages 344 to 349, list the original documents. For example, U.S. Patent No. 2,131,038 and U.S. Patent No. 2,694,716
Thiazolium salts described in U.S. Patent No. 2, etc.
, 886,437 and 2,444,605; U.S. Patent No. 3,287
, 135; sulfocatechols described in U.S. Patent No. 3,236,652; oximes described in British Patent No. 623,448; U.S. Patent No. 2,403,927
No. 3,266,897, No. 3,397,98
Mercaptotetrazoles described in No. 7, etc.
Nitrones, nitroindazoles; U.S. Patent No. 2,83
Polyvalent metal salts (Pol
yvalent metal salts; described in U.S. Patent No. 3,220,839, etc. Thiuronium salts; These include palladium, platinum and gold salts. The silver halide photographic material of the present invention includes:
Developing agents, such as hydroquinones; catechols; aminophenols; 3-pyrazolidones; ascorbic acid and its derivatives; reductones;
s), phenylenediamines, or a combination of developing agents. In the present invention, as matting agents, US Pat. Nos. 2,992,101, 2,701,245,
Homopolymers of polymethyl methacrylate or polymers of methyl methacrylate and methacrylic acid as described in 4,142,894 and 4,396,706, organic compounds such as starch, silica, titanium dioxide, sulfuric acid Fine particles of inorganic compounds such as strontium, barium, etc. can be used. The particle size is 1.
It is preferably 0 to 10 μm, particularly 2 to 5 μm. The surface layer of the photographic light-sensitive material of the present invention may contain silicone compounds described in U.S. Pat. No. 3,489,576, U.S. Pat.
In addition to the colloidal silica described in the publication, paraffin wax, higher fatty acid esters, starch derivatives, etc. can be used. Polyols such as trimethylolpropane, pentanediol, butanediol, ethylene glycol, and glycerin can be added as plasticizers to the hydrophilic colloid in the constituent layers of the photographic material of the present invention. Further, it is preferable that the hydrophilic colloid layer of the photographic material of the present invention contains a polymer latex for the purpose of improving pressure resistance. As the polymer, a homopolymer of an alkyl ester of acrylic acid or a copolymer with acrylic acid, a styrene-butadiene copolymer, and a polymer or copolymer consisting of a monomer having an active methylene group can be preferably used. The photographic emulsions and non-light-sensitive hydrophilic colloids of this invention may contain inorganic or organic hardeners. For example, aldehydes (formaldehyde, glyoxal, glitaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), activated vinyl compounds (1,3,5- triacryloyl-hexahydro-s-triazine, bis(
(vinylsulfonyl) methyl ether, N,N'-methylenebis-[β-(vinylsulfonyl)propionamide], etc.), active halogen compounds (2,4-dichloro-6
-Hydroxy-s-triazine, mucohalogen acids (mucochloric acid, mucophenoxychloric acid, etc.), and the like can be used alone or in combination. Among them, JP-A-53-41220, JP-A-53-57257, JP-A-5
Preferred are the active vinyl compounds described in US Pat. No. 9-162,546 and US Pat. No. 60-80,846 and the active halides described in US Pat. The amount of hardening agent added is 0.02 to 1 g of the hydrophilic binder constituting the layer.
0.10g is preferred. The silver halide emulsion layer may have two or more layers.
The sensitivity, gradation, etc. of the silver halide emulsion layers may be different from each other. The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic agents, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (for example, development acceleration). Various surfactants may be included for various purposes such as increasing contrast, increasing contrast, and increasing sensitization. Examples of the surfactant used in the present invention include "Surfactants and Their Applications" by Ryohei Oda (Maki Shoten, 1964), "New Surfactants" by Hiroshi Horiguchi (Sankyo Publishing Co., Ltd., 1975), or ``Mac Cation's Detergent and E
MC CUTCHEON'S (MC CUTCHEON'S, MC PUBLISHING COMPANY 1985)
Detergents & Emulsifiers”
(MC Cutcheon Divisions, M
C Publishing Co. 1985))
It is described in Japanese Patent Application Laid-Open No. 60-76741, Japanese Patent Application No. 13398/1982, Japanese Patent Application No. 61-16056, Japanese Patent Application No. 61-32462, etc. As antistatic agents, in particular, fluorine-containing interfaces described in U.S. Pat. Activator or polymer, JP-A-60-76742, JP-A-60-808
No. 46, No. 60-80848, No. 60-80839, No. 60-76741, No. 58-208743, Japanese Patent Application No. 61-13398, No. 61-16056, No. 6
Nonionic surfactants described in JP-A No. 1-32462, or JP-A-57-204540,
Conductive polymers or latexes (nonionic, anionic, cationic, amphoteric) described in Japanese Patent Application No. 61-32462 can be preferably used. Examples of inorganic antistatic agents include ammonium, alkali metal, and alkaline earth metal halogen salts, nitrates, perchlorates, sulfates, acetates, phosphates, and thiocyanates. Composite oxides prepared by doping conductive tin oxide, zinc oxide, or these metal oxides with antimony or the like, as described in Japanese Patent No. 118242, etc., can be preferably used. Furthermore, various charge transfer complexes, π-conjugated polymers and their doped compounds, organometallic compounds, intercalation compounds, and the like can also be used as antistatic agents, such as TCNQ/TTF, polyacetylene, and polypyrrole. These are Morita et al., Chemistry and Industry 59 (3), 103-111 (1985),
59(4), 146-152 (1985). A hydrophilic colloid is used as a protective colloid in the silver halide photographic emulsion layer, back layer, etc. in the present invention, and gelatin can be used as the hydrophilic colloid. In addition, acylated gelatins such as phthalated gelatin and malonated gelatin, cellulose compounds such as hydroxyethyl cellulose and carboxymethyl cellulose; solubilized starches such as dextrin; polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide and polystyrene sulfonic acid Hydrophilic polymers such as hydrophilic polymers can be added. Among these, it is preferable to use dextran and polyacrylamide together with gelatin. Also, U.S. Patent No. 3,411
, No. 911, No. 3,411,912, No. 3,14
No. 2,568, No. 3,325,286, No. 3,5
47,650, Japanese Patent Publication No. 45-5331, etc., a polymer latex consisting of a homopolymer or copolymer of alkyl acrylate, alkyl methacrylate, acrylic acid, glycidyl acrylate, etc. is used to improve the dimensional stability of photographic materials. It can be included for purposes such as improving membrane materials. The substantially non-photosensitive fine silver halide grains used in the present invention preferably have an average size (volume equivalent spherical diameter) of 0.3 μm or less. If the thickness is 0.3 μm or more, optical scattering effects cannot be ignored, resulting in deterioration of image sharpness. For the present invention, it is preferred that the average particle size is less than 0.2 μm, particularly preferably ultrafine particles of less than 0.10 μm. Particle size can be determined by a commonly used method using an electron microscope. The average value of particle size is determined by number averaging. Although there is no particular restriction on the grain size distribution, it is preferable for the present invention to use a so-called monodispersed emulsion having a narrow size distribution. A preferred size distribution has a coefficient of variation of 20% or less, more preferably 15% or less, particularly preferably 10% or less. The shape of the particle is a cube consisting of (100) planes, (1
11) Octahedron consisting of faces, dodecahedron consisting of (110) faces, and (hh1), (hk1) faces (h, k, 1>1
) may be any polyhedron with a high-order surface index. Further, particles having multiple faces such as tetradecahedral grains in which (100) and (111) faces coexist may also be used. Further, tabular grains having twin planes or potato-like grains having an amorphous shape may be used. It is preferable that the non-photosensitive silver halide fine particles used in the present invention mainly consist of silver bromide, silver chlorobromide, or silver chloride. [0020] In the method for preparing silver halide fine grains having a small average grain size, it is necessary to stabilize the generated core grains at the initial stage of grain formation, that is, at the time of nucleation at the beginning of addition of silver salt and/or halide. , generation of a large number of core particles is a fundamental matter in the formation of fine particles. As the number of stable nuclei increases, silver halide, which is added later and is formed, is deposited on these nuclei, so that the size of the grains becomes finer after the addition is completed. In order to form stable nuclei, it is important to minimize physical ripening during particle formation, that is, to prevent the formed nuclei from redissolving. Therefore, the temperature during particle formation should be as low as possible, preferably 45° C. or lower. Also, the potential at the time of preparation (comparison potential: saturated Calomelo electrode) is -80
It is best to carry out in the range of mV to +600 mV, and especially in the time of nucleation, it is preferably in the range of -50 mV to +600 mV. Further, the concentration of the binder is important for stabilizing the core particles, and it is preferably used in a range of 0.2% to 4%. Furthermore, in order to generate a large number of nuclei, it is important to add a highly concentrated solution (for example, 1 to several moles/liter) in a short period of time. For that, the addition time is 3
It is best to complete within 0 minutes, preferably within 20 minutes,
More preferably, the time is within 15 minutes. Although any stirring method may be used, it is preferable to use a method that has good stirring efficiency and uniformly stirs. The particle shape method is Sin
Any method may be used, such as the gle jet method, the double jet method, or a combination thereof, and the controlled double jet method. [0021] Silver halide emulsions usually have a desalting step to remove unnecessary salts after grain formation. The pH in the desalting step is preferably 3.2 to 4.8, more preferably 3.
．． It is preferably 4 to 4.8. The gelatin used in preparing the non-photosensitive fine silver halide grains used in the present invention may be any gelatin such as lime-treated gelatin, acid-treated gelatin, phthalated gelatin, etc., or a combination thereof. To remove soluble salts from the emulsion after grain formation or physical ripening (desalting step), anionic surfactants, anionic polymers (e.g. polystyrene sulfonic acid), or gelatin derivatives (e.g. acylated gelatin, carbamoylated It is preferable to use a sedimentation method (flocculation method) using gelatin, etc. Exposure to obtain a photographic image using the light-sensitive material of the present invention may be carried out using a conventional method. i.e. natural light (sunlight), tungsten electric lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, cathode ray tube flying spot, light emitting diode, laser light (e.g. gas laser), dye laser, YAG laser, semiconductor laser, etc.) Any of various known light sources including infrared light can be used. Alternatively, exposure may be performed using light emitted from a phosphor excited by electron beams, X-rays, γ-rays, α-rays, or the like. Exposure times include not only 1/1000 second exposure times that are normally used with cameras, but also exposure times shorter than 1/1000 seconds, such as exposures of 1/10 to 1 to 108 seconds using xenon flash lamps or cathode ray tubes. can. If necessary, the spectral composition of the light used for exposure can be adjusted using a color filter. The photosensitive material of the present invention is particularly suitable for use in scanners using semiconductor lasers, helium-neon lasers, or the like. The developing agent used in the developer for processing the light-sensitive material of the present invention is mainly hydroquinone, but since it is easy to obtain good performance, hydroquinone and 1-
A combination of phenyl-3-pyrazolidones or a combination of hydroquinones and p-aminophenols is preferred. Hydroquinone-based developing agents used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,5-dimethyl Examples include hydroquinone and hydroquinone monosulfonate, with hydroquinone being particularly preferred. The p-aminophenol developing agent used in the present invention includes N-methyl-p-aminophenol, p-
Aminophenol, N-(β-hydroxyethyl)-p
-aminophenol, N-(4-hydroxyphenyl)
Examples include glycine, 2-methyl-p-aminophenol, and p-benzylaminophenol, among which N-methyl-p-aminophenol is preferred. As the 3-pyrazolidone developing agent used in the present invention, 1-phenyl-3
-pyrazolidone, 1-phenyl-4,4-dimethyl-3
-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,
4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-
p-Tolyl-4,4-dimethyl-3-pyrazolidone, 1
-p-tolyl-4-methyl-4-hydroxymethyl-3
-pyrazolidone, etc. The hydroquinone developing agent is usually 0.01 mol/liter to 1.5 mol/liter, preferably 0.05 mol/liter to 1.2 mol/liter.
Used in liter quantities. In addition, the p-aminophenol developing agent or 3-pyrazolidone developing agent is usually 0.0005 mol/liter to 0.2 mol/liter, preferably 0.001 mol/liter to 0.1 mol/liter.
It is used in amounts of moles/liter. Sulfites used in the developer of the present invention include sodium sulfite, potassium sulfite, lithium sulfite,
These include ammonium sulfite, sodium bisulfite, potassium metabisulfite, etc. The amount of sulfite is preferably 0.1 mol/liter or more, particularly 0.3 mol/liter or more. Further, the upper limit is preferably up to 2.5 mol/liter in the developer concentrate. The pH of the developer used in the development process of the present invention is preferably in the range of 9 to 18. More preferably, the pH range is from 10 to 12. Alkaline agents used for setting pH include pH adjusting agents such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, tribasic sodium phosphate, and tribasic potassium phosphate. Buffers such as JP-A-62-186259 (borates), JP-A-60-93433 (e.g., sucrose, acetoxime, 5-sulfosalicylic acid), phosphates, carbonates, etc. may be used. In the present invention, the developer preferably contains a chelating agent having a chelate stability constant of 8 or more with respect to iron ions. Here, the chelate stability constant is defined as L. G. Sillen, A. E.
．． H “Stability C” by Martell.
instants of Metal-ion Com
plexes", The Chemical Soci
ety, London (1964). S. Chaberek, A. E. Written by Martell,
“Organic Sequestering Agent
ts'', Wiley (1959). In the present invention, the chelating agent having a chelate stability constant of 8 or more for iron ions includes an organic carboxylic acid chelating agent and an organic phosphoric acid chelating agent. , inorganic phosphoric acid chelating agents, polyhydroxy compounds, etc.The above-mentioned iron ion refers to ferric ion (
Fe3+). In the present invention, specific examples of compounds of chelating agents having a chelate stability constant of 8 or more with ferric ions include the following compounds, but are not limited thereto. Namely, ethylenediamine diorthohydroxyphenylacetic acid, triethylenetetraminehexaacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, Hydroxyethyliminodiacetic acid, 1
, 3-diamino-2-propanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine-N,N,N',N'tetrakismethylenephosphonic acid, nitrilo-N,N,N -trimethylenephosphonic acid, 1
-Hydroxyethylidene-1,1-diphosphonic acid, 1,
1-diphosphonoethane-2-carboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,3-tricarboxylic acid, catechol-3,5-disulfonic acid, Examples include sodium pyrophosphate, sodium tetrapolyphosphate, and sodium hexametaphosphate. Further, a dialdehyde hardener or its bisulfite adduct is used in the developer, and specific examples thereof include glutaraldehyde and its bisulfite adduct. Additives used in addition to the above components include development inhibitors such as sodium bromide, potassium bromide, and potassium iodide; ethylene glycol, diethylene glycol, triethylene glycol, dimethyl formamide, methyl cellosolve, hexylene glycol, ethanol, and methanol. Organic solvents such as: 1-phenyl-
Antifoggants such as mercapto compounds such as 5-mercaptotetrazole and 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, indazole compounds such as 5-nitroindazole, and benztriazole compounds such as 5-methylbenztriazole. May contain, Research Disclosure No. 176
Volume, No. 17643, Section XXI (December Issue, 1
Development accelerators described in 1978) and, if necessary, color toning agents, surfactants, antifoaming agents, water softeners, and JP-A-56
It may also contain the amino compound described in No.-106244. In the development process of the present invention, known silver stain inhibitors, such as the compounds described in JP-A-56-24347, can be used in the developer. The developer of the present invention includes European Patent Publication No. 136582, British Patent No. 95
No. 8678, U.S. Patent No. 3,232,761, JP-A-56
Amino compounds such as alkanolamines described in No. 106244 can be used for the purpose of accelerating development, increasing contrast, and other purposes. Besides this, L. F. A. "Photographic Processing Chemistry" by Mason
, Focal Press (1966), 226-22.
9 pages, U.S. Patent No. 2,193,015, 2,592
, No. 364, JP-A No. 48-64933, etc. may be used. [0027] The fixing solution is an aqueous solution containing thiosulfate;
It has a pH of 3.8 or higher, preferably 4.2 to 7.0. Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, and ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed. The amount of the fixing agent used can be varied as appropriate, and is generally about 0.1 to about 6 mol/liter. The fixer may also contain water-soluble aluminum salts that act as hardeners, such as aluminum chloride, aluminum sulfate, potassium alum, and the like. In the fixing solution, tartaric acid, citric acid, gluconic acid, or their derivatives can be used alone or in combination of two or more. 0.0 of these compounds per liter of fixer
Those containing 0.05 mol or more are effective, and particularly 0.01 mol/liter to 0.03 mol/liter are particularly effective. The fixing solution may optionally contain preservatives (e.g., sulfites, bisulfites), pH buffers (e.g., acetic acid, boric acid), pH adjusters (e.g., sulfuric acid), chelating agents with hard water softening ability, and It can contain the compound described in No. 62-78551. In the present invention, the term "developing process time" or "developing time" refers to the time from when the leading edge of the photosensitive material to be processed is immersed in the developing tank solution of the automatic processing machine until it is immersed in the next fixing solution. "Fixing time" is the time from immersion in the fixing tank liquid until immersion in the next washing tank liquid (stabilizing liquid). "Washing time" refers to the time during which the film is immersed in the washing tank liquid. In addition, "drying time" is usually 35℃ to 100℃ for automatic processors.
A drying zone is installed in which hot air, preferably 40°C to 80°C, is blown, and the term refers to the time spent in the drying zone. In the development process of the present invention, the development time is 5 seconds to 18 seconds, preferably 5 seconds to 12 seconds, and the development temperature is 2 seconds.
5°C to 50°C is preferable, and 30°C to 40°C is more preferable. Fixing temperature and time are approximately 20℃ to approximately 50℃ for 4 seconds to 1
5 seconds is preferable, and 5 seconds to 12 seconds at 30°C to 40°C is more preferable. Water washing or stabilization bath temperature and time are 0 to 50℃
The heating time is preferably 4 seconds to 15 seconds at a temperature of 15°C to 40°C, and more preferably 4 seconds to 10 seconds at a temperature of 15°C to 40°C. According to the method of the present invention, development,
The fixed and washed (or stabilized) photographic material is dried by squeezing out the washing water, ie passing through a squeeze roller. Drying is performed at a temperature of about 40°C to about 100°C, and the drying time can be changed as appropriate depending on the surrounding conditions, but it is usually about 4 seconds to
It may be 15 seconds, particularly preferably about 5 seconds to 10 seconds at 40°C to 80°C. [Example] Next, the present invention will be specifically explained with reference to Examples. Example 1 Preparation of silver halide emulsion 40 g of gelatin was dissolved in 1 liter of H2O,
After putting 6 g of sodium chloride, 0.4 g of potassium bromide, and 60 mg of [Chemical 6] into a container heated to 3°C, 600 ml of an aqueous solution containing 100 g of silver nitrate and 56 g of potassium bromide were added. and 600 ml of an aqueous solution containing 7 g of sodium chloride were added by the double jet method to create a core containing 20 mol% silver chloride, and then 500 ml of an aqueous solution containing 100 g of silver nitrate was added.
, 40 g of potassium bromide, 14 g of sodium chloride, and potassium hexachloroiridate(III) (1
500 ml of an aqueous solution containing 0-7 mol/mol silver) was added by the double jet method to form a shell portion of 40 mol % silver chloride, resulting in a so-called core/shell type cubic monodisperse with an average particle size of 0.35 μm. Silver chlorobromide particles were prepared. After desalting this emulsion, 40 g of gelatin was added and p
2 mg of triethylthiourea, 4 mg of chloroauric acid, and 0.2 g of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene were added in accordance with H6.0 and pAg8.5, and chemical amplification was carried out at 60°C. I gave it a feeling. The yield of emulsion is 950
It was g. Preparation of Emulsion Coating Solution A container in which 850 g of the emulsion was weighed out was heated to 40° C., and additives were added in the following manner to prepare an emulsion coating solution. (Emulsion coating liquid formulation) a. emulsion

850g B. embedded image 1.2×10 −4 mol C. embedded image 0.8×10 −3 mol D. embedded image 1×10 −3 mol E. Polyacrylamide (molecular weight 40,000)
7.5g f.
trimethylolpropane
1.6
g. Sodium polystyrene sulfonate
2.
4g chi. Poly(ethyl acrylate/methacrylic acid) latex

16g li. N,N'-ethylenebis-(vinylsulfone acetamide)

1.2g [0
039 Preparation container of surface protective layer coating solution-A for emulsion layer
The mixture was heated to 0° C., and additives were added according to the formulation shown below to prepare a coating solution. (Formulation of coating solution for surface protective layer of emulsion layer) a. gelatin

100g lo. Polyacrylamide (molecular weight 40,000)
10g c. Sodium polystyrene sulfonate (molecular weight 600,000) 0.6
gni. N,N'-ethylenebis-(vinylsulfone)
acetamide)

1.5g e. Polymethyl methacrylate fine particles (average particle size 2.0μm)

2.2g f. t-Octylphenoxyethoxyethanesulfo
Sodium phosphate
1
．． 2g g. C16H33O-(CH2CH2O)10-
H
2.7g chi. Sodium polyacrylate
4g ri.
C8F17SO3K

70mg Nu. C8F17SO2N
(C3H7)(CH2CH2O)4(CH2)4-SO
3Na
70mg le. NaOH (1N)

4ml. methanol

60 ml Preparation of Back Layer Coating Solution A container was heated to 40° C., and additives were added in the following formulation to prepare a back layer coating solution. (Back layer coating liquid formulation) a. gelatin

80g [0041]B. [Chemical formula 10] 3.1g [0042] c. Sodium polystyrene sulfonate
0.6g ni. Poly(ethyl acrylate/methacrylic acid) latex 15g e. N,N'-ethylenebis-(vinylsulfone acetamide)
4.3g [0
043: Preparation container for bag surface protective layer coating solution at 40°C.
The mixture was heated to 100°C, and additives were added according to the formulation shown below to prepare a coating solution. (Back surface protective layer coating solution formulation) a. gelatin

80g c. Sodium polystyrene sulfonate
0.3g ni. N,N'-ethylenebis-(
vinyl sulfone acetamide)

1.7g e. Polymethyl methacrylate fine particles (average particle size 4.
0μm)
4.0g
F. t-Octylphenoxyethoxyethanesulfo
Sodium phosphate

3.6g. NaOH (1N)

6ml chi. Sodium polyacrylate
2g
Li. C16H33O-(CH2CH2O)10-H

3.6g Nu. C8F17SO3K


50mg le. C8F17SO2N(C3H7)(CH
2CH2O)4(CH2)4-SO3Na
50 mg. methanol

130 ml Preparation of Coating Sample The above-mentioned back layer coating solution was coated on the side of the polyethylene terephthalate support together with the back layer surface protective layer coating solution so that the total coating amount of gelatin was 3 g/m 2 . Subsequently, on the opposite side of the support, the above-mentioned emulsion coating solution and surface protective layer coating solution were applied so that the amount of Ag applied was 2.5 g/m2 (the amount of gelatin was 1.2 g), and the amount of gelatin applied in the surface protective layer was is 1g
/m2 (coating sample 1-1). Preparation of surface protective layer coating solution-B for emulsion layer Exactly the same composition as coating solution-A except that 0.1 g of Compound Example 3 of the present invention was added to surface protective layer coating solution-A per 100 g of gelatin. A solution was prepared and designated as surface protective layer coating solution-B. In the structure of coating sample 1-1, the surface protective layer-A of the emulsion layer
Coated sample 1-2 was prepared using the same composition and coating amount as coated sample 1-1 except that the surface protective layer-B was used. Processing (developer composition) Potassium hydroxide

24g sodium sulfite

40g potassium sulfite

50g diethylenetriaminepentaacetic acid

2.4g boric acid

10g hydroquinone

35g diethylene glycol

11g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone

6g 5-methylbenzotriazole

60mg potassium bromide

2g acetic acid


1.8g

upto 1000ml


pH 10.5 (Fixer composition) Ammonium thiosulfate

140g sodium sulfite

15g Ethylenediaminetetraacetic acid disodium dihydrate
25mg sodium hydroxide

6g


upto 1000ml

pH 5.
10 [0048] A roller conveyance type automatic processing machine (FPM-9000 manufactured by Fuji Photo Film Co., Ltd.) was filled with the above-mentioned developer and fixer, and coated sample 1-1 (comparative sample) and coated sample 1-2 ( the present invention) was developed. Coating sample 1-1,
1-2 was exposed using a semiconductor laser having an emission maximum at 780 nm while changing the exposure amount stepwise. The development processing steps are as follows. The automatic processing machine FPM-9000 was modified to enable the following processing. Development process (total process 35.5 seconds) Development
35℃ 11 seconds
Fixation 32℃
9.5 seconds Wash with water
6 seconds squeeze
Drying 9 seconds 0050
] Result Comparison Sample The silver image of coated sample 1-1 was a yellowish black, whereas the silver image of coated sample 1-2 of the present invention was a cool black with a bluish tinge. . Example 2 Preparation of coating sample 2-1 (invention) 1) Preparation of substantially non-photosensitive fine silver bromide emulsion Water 1
Dissolve 15 g of gelatin in 1 liter, heat to 40°C, and then prepare 500 ml of an aqueous solution containing 100 g of silver nitrate and 500 ml of an aqueous solution containing 75 g of potassium bromide while keeping the pAg value at 7.0.
00ml was added in 15 minutes and the average particle size was 0.15.
Cubic monodisperse silver bromide particles of μm size were prepared. After desalting this emulsion, 15 g of gelatin was added and dispersed. After dispersion, 10 g of Compound Example-3 of the present invention was added. Yield was 500g. 2) Preparation of surface protective layer coating solution-C of emulsion layer 5 g of a substantially non-photosensitive fine silver bromide emulsion to which the above compound example 3 was added per 100 g of gelatin of the surface protective layer coating solution-A. A liquid having the same composition as surface protective layer coating liquid-A except for the addition of was prepared as surface protective layer coating liquid-C. In the structure of coating sample 1-1, the surface protective layer-A of the emulsion layer
Coated sample 2-1 was prepared using the same structure and coating amount as coated sample 1-1 except that the surface protective layer-C was used. Treatment Coated samples 1-1, 1-2, and 2-1 were exposed and developed in exactly the same manner as in Example 1. Results Table 1 shows the results. [Table 1] Among Samples 1-2 and 2-1 of the present invention, Sample 2-1 is particularly preferable because it provides a desirable silver tone with a cool black tone and almost no decrease in sensitivity. I understand that. Effects of the Invention In the present invention, photosensitive silver halide grains have a particle size of 0.
By incorporating the compound represented by the general formula (I) into a light-sensitive material having a diameter of 4 μm or less and a total gelatin content of 3.3 g/m2 or less on the side with the photosensitive emulsion layer, cooling can be achieved without deterioration in sensitivity. A black-toned silver image could be obtained.

Claims (2)

[Claims] Claim 1: A support has a silver halide emulsion layer on one side, and the photosensitive silver halide grains in the emulsion layer have a sphere volume equivalent diameter of 0.4 μm or less, and the emulsion layer has a silver halide emulsion layer on the side containing the emulsion layer. A silver halide photographic material having a total gelatin content of 3.3 g/m2 or less, which contains a compound represented by the following general formula (I) in the emulsion layer or other constituent layers. Photographic material. General formula (I) [Formula 1] (wherein M represents a hydrogen atom, an alkali metal atom, an ammonium group, or a group that cleaves under alkaline conditions, and L represents alkylene, alkenylene, ether, thioether, -
Represents a divalent organic group composed of CO-, -CS-, -NR- [R represents a hydrogen atom or an optionally substituted alkyl group] alone or in combination, and X may be substituted with alkyl. Represents an amino group, an alkyl-substituted ammonio group, a hydroxy group, and an optionally substituted heterocyclic residue. n represents 0 or 1. ) [Claim 2] Substantially no photosensitivity, with an average particle size of 0.3 μm or less, in which the compound represented by the general formula (I) is adsorbed in constituent layers other than the emulsion layer on the side containing the emulsion layer. 2. The silver halide photographic material according to claim 1, further comprising silver halide fine particles.