JPH0518090B2 - - Google Patents

Description

[Detailed description of the invention]

(Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material and a method for producing the same, and more particularly to a silver halide photographic light-sensitive material containing a stably dispersed hydrophobic hydrazine compound and a method for producing the same. be. (Prior Art) The presence of hydrazine compounds in silver halide emulsion layers for various purposes is described, for example, in "The Theory of the Photographic Process" by Mees.
3rd edition, (1966) 281 pages, Research Disclosure Magazine 23510 (1983), U.S. Patent No. 4224401,
No. 4243739, No. 4272614, No. 4323643, No. 4243739, No. 4272614, No. 4323643, No.
It is known as No. 4385108, No. 4268969, etc.
That is, the hydrazine compound is sometimes used in combination with internal latent image type silver halide to directly form a positive image, and separately in combination with surface latent image type silver halide to form a high-sensitivity image. It is sometimes used to form ultra-high contrast negative images. When hydrazine compounds are used in silver halide light-sensitive materials for these various purposes, the hydrazine compounds may elute into the developer and cause contamination of the solution, or may have an adverse effect on the silver halide in the nearby emulsion layer. It is desirable to use a hydrazine compound that has been made diffusion-resistant, that is, water-insolubilized, in order to prevent this from occurring. However, it is not easy to stably disperse the water-insolubilized hydrophobic hydrazine compound in a hydrophilic silver halide emulsion. Conventionally, as a method for dispersing hydrophobic photographic additives in silver halide emulsions, dibutyl phthalate was dissolved in a water-miscible organic solvent such as methanol and added to the emulsion in combination with a surfactant if necessary. A method of dissolving in a high boiling point organic solvent such as or tricresyl phosphate, stirring and dispersing it in a hydrophilic colloid using a surfactant if necessary, and mixing this emulsion with an emulsion, or Japanese Patent Publication No. 58-35214 A known method is to impregnate a loadable polymer latex and mix it with an emulsion, as described in No. However, when a hydrophobic hydrazine compound is dissolved in a water-miscible organic solvent and added to a silver halide emulsion, the hydrazine compound aggregates and crystallizes in the coating solution between the time of addition and coating. (this crystallization cannot be prevented even if the crystallization is used), the desired effect on silver halide grains will no longer be exhibited. Furthermore, methods using high boiling point organic solvents and methods using loadable polymer latexes are difficult to avoid due to the use of diffusible active species (color developing agents) generated during processing, such as dye-forming couplers and color mixing inhibitors in color photography. Although it is effective for dispersing substances that perform their mission by reacting with oxidized forms of silver halide (oxidized form of There is a point. That is, the amount of dispersant (high-boiling organic solvent,
If a polymer latex or the like is used, there is a problem in that the hydrazine compound is encapsulated in these dispersants and cannot directly interact with the silver halide grains. (Object of the Invention) Therefore, the first object of the present invention is to provide a silver halide photographic material containing a hydrophobic hydrazine compound stably dispersed so that its purpose of use can be fully achieved. The second object is to provide a method for stably dispersing a hydrophobic hydrazine compound in a silver halide emulsion so that its purpose of use can be fully achieved. (Structure of the Invention) The objects of the present invention have been achieved by the following (1) and (2). (1) A hydrazine compound represented by the following general formula () that is substantially insoluble in water and has a melting point of 25°C or higher, and a hydrazine compound that is substantially insoluble in water and has the effect of lowering the melting point when mixed with the hydrazine compound. 1. A silver halide photographic light-sensitive material, comprising at least one light-sensitive silver halide emulsion layer containing a mixture with an organic compound represented by the following general formula () having a molecular weight of 1000 or less. (2) A hydrazine compound represented by the following general formula () that is substantially insoluble in water and has a melting point of 25°C or higher, and a substantially water-insoluble compound that has the effect of lowering the melting point when mixed with the hydrazine compound. 1. A method for producing a silver halide photographic material, which comprises adding an organic compound represented by the following general formula () having a molecular weight of 1000 or less to a light-sensitive silver halide emulsion coating solution and coating. General formula () R ₁ -G ₁ -NHNH-G ₂ -R ₂ In the formula, R ₁ represents an alkanamide group having 8 to 70 carbon atoms, and R ₂ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or represents an unsubstituted aryl group or a substituted or unsubstituted aryloxy group, G ₁ represents a substituted or unsubstituted phenylene group, G ₂ represents a carbonyl group, a sulfonyl group,
Represents a sulfoxy group, phosphoryl group, or N-substituted or unsubstituted iminomethylene group. General formula () Z ₁ -Q In the formula, Z ₁ represents an alkyl-substituted phenoxyalkanamide having 8 to 20 carbon atoms, and Q is a hydrogen atom, a substituted or unsubstituted alkyl group having 20 or less carbon atoms, or a carbon number Represents a substituted or unsubstituted phenyl group of 20 or less. However, Z ₁ and Q do not have a hydrazino group as a substituent. In the present invention, "substantially insoluble in water" means that the solubility in water at 0° C. to 100° C. and pH 5 to 8 is 0.01% by weight or less. The most preferred R ₁ is an alkyl-substituted phenoxyalkanamide group. G ₁ in the general formula () is preferably a paraphenylene group. The phenylene group of G ₁ may have a substituent other than R ₁ . However, the algebraic sum of the sigma values of R ₁ and other substituents is +0.3
Hereinafter, it is particularly preferable that the substituent group is selected to be 0 or less. The alkyl group represented by R ₂ in the general formula () is preferably an alkyl group having 10 or less carbon atoms, and may have a substituent such as a halogen atom, a cyano group, an alkoxy group, or a phenyl group. In the general formula (), the optionally substituted aryl group among the groups represented by R ₂ is a monocyclic or bicyclic aryl group, and includes, for example, a benzene ring. This aryl group is, for example, a halogen atom,
It may be substituted with an alkyl group, a cyano group, etc. Among the groups represented by R ₂ in the general formula (), the optionally substituted alkoxy group is an alkoxy group having 12 or less carbon atoms, and may be substituted with a halogen atom, an aryl group, or the like. Among the groups represented by R ₂ in the general formula (), the optionally substituted aryloxy group is preferably a monocyclic one, and examples of the substituent include a halogen atom. Among the groups represented by R ₂ , preferred are G ₂
is a carbonyl group, a hydrogen atom, a methyl group,
A methoxy group, an ethoxy group, a substituted or unsubstituted phenyl group, and a hydrogen atom is particularly preferred. When _G2 is a sulfonyl group, _R2 is preferably a methyl group, an ethyl group, a phenyl group, or a 4-methylphenyl group, with a methyl group being particularly preferred. When G ₂ is a phosphoryl group, R ₂ is preferably a methoxy group, an ethoxy group, a butoxy group, a phenoxy group, or a phenyl group, and a phenoxy group is particularly preferred. When G ₂ is a sulfoxy group, R ₂ is preferably a cyanobenzyl group or a methylthiobenzyl group, and when G ₂ is an N-substituted or unsubstituted iminomethylene group, R ₂ is preferably a methyl group, an ethyl group, or a substituted or unsubstituted iminomethylene group. It is a substituted phenyl group. Most preferably, G ₂ is a carbonyl group. Substituents for Q in general formula () include halogen atoms, aryl groups (for alkyl groups),
Examples include alkyl groups (relative to aryl groups), alkoxy groups, aryloxy groups, and the like. Among the compounds represented by the general formula (), those having a solubility in a water-miscible organic solvent described below of 0.1% by weight or more, particularly 1% by weight or more, and a melting point of 200°C or less, particularly 170°C or less are preferred. In the present invention, when determining the combination of the compound of general formula () and the compound of general formula (), it is particularly advantageous to combine compounds in which the difference in carbon atoms in each compound is 6 or less. This provides excellent dispersion stability. Specific examples and combinations of the compound of the general formula () and the compound of the general formula () of the present invention are listed below, but the present invention is not limited thereto. Specific examples of compounds represented by general formula () Examples of combinations of compounds of general formula () and compounds of general formula () -2 and -1 -3 and -1 -4 and -2 -5 and -3, -4, -5, -6,
-7, -8, -9 -6 and -10 -7 and -11 -8 and -3 or -12 Many of the compounds used in the present invention are known compounds, and those skilled in organic synthesis techniques can It can be easily synthesized. In the present invention, the compound represented by the general formula () is usually 10 ^-6 to 5 x 10 ^-2 mol per mol of silver,
In particular, it is used in a range of 10 ^-5 to 2×10 ^-2 mol. In the present invention, the amount of the compound represented by the general formula () to be used is not particularly limited, but it may be a relatively small amount, and usually the amount of the compound represented by the general formula () is 5 to 80% by weight relative to the compound of the general formula (). %, especially from 10 to 60% by weight, good results are obtained. This amount is less than the amount of high-boiling organic solvent required to stably disperse the compound of general formula () in a hydrophilic colloid using a high-boiling organic solvent, and therefore the presence of the compound of general formula () does not inhibit the direct interaction between the compound of general formula () and silver halide grains. In order to produce the silver halide photographic light-sensitive material of the present invention, (a) a hydrazine compound that is substantially insoluble in water and has a melting point of 25°C or higher is mixed with (b) the hydrazine compound to reduce its melting point. It is mixed into a silver halide emulsion together with an organic compound that is substantially insoluble in water and has a molecular weight of 1000 or less, and the resulting coating solution is applied onto the support or other layers provided on the support. The coating may be applied using a known coating means. More specifically, a solution of the compound of general formula () and a water-miscible organic solvent containing the compound of general formula () is prepared, and this solution is mixed with a silver halide emulsion coating solution. The coating liquid thus prepared is stable, and the compound of general formula () does not aggregate or crystallize. The water-miscible organic solvents used here include methanol, ethanol, propanol, isopropyl alcohol, acetone, acetonitrile,
Examples include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, dioxane, trimethyl phosphate, etc., which can dissolve the compound of general formula () and the compound of general formula (). Water may be contained in a proportion that does not interfere with the composition. Among these water-miscible organic solvents, its boiling point is 100℃ at normal pressure.
The following (methanol, ethanol, isopropyl alcohol, acetone, etc.) are preferred. When dissolving the compound of general formula () and the compound of general formula () above in a water-miscible organic solvent, or when adding the dissolved solution to a silver halide emulsion, a surfactant may be used in combination. I can do it. According to the invention, in order to use a compound of general formula (),
The amount of surfactant used can be significantly reduced compared to conventional methods, and the negative effects (such as contamination of the processing liquid and occurrence of coating failures) caused by using a large amount of surfactant can be prevented. Surfactants suitable for use in the present invention are anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, and phosphate ester groups, among which 8 to 14 in particular.
HLB value (Here, HLB value is determined by the organic/inorganic method. For details, see Tsuji Kono's "Emulsification/Solubilization Techniques" 3rd edition (1979) No. 10-11 published by Kogyo Tosho Co., Ltd.
(see page) is preferred. For example, 2-
Examples include (N-methyl-N-oleoylamino)ethanesulfonic acid sodium salt. The silver halide emulsion used in the present invention is not particularly limited, and in addition to silver chloride and silver bromide, mixed silver halides such as silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. may be used. I can do it. However, when silver iodobromide or silver chloroiodobromide is used, the content of silver iodide is 5
The range is preferably mol % or less. If surface latent image type silver halide is used, which forms a latent image mainly on the surface, an ultra-high contrast negative image can be obtained, while if internal latent image type silver halide, which forms a latent image mainly inside the grain, is used, it can be directly imaged. A positive image is obtained. Here, the surface latent image type silver halide is defined, for example, in US Pat. No. 4,224,401. The present invention is particularly effective for silver halide photosensitive materials for ultra-high contrast negative images that use surface latent image type silver halide emulsions which are more susceptible to the dispersion state of the hydrazine compound. Although there are no particular limitations on the morphology, crystal habit, size distribution, etc. of the silver halide grains, a monodisperse emulsion with a grain size of 0.7 μm or less is preferred for forming ultra-high contrast negative images. Alternatively, two or more types of silver halide photographic emulsions formed separately may be mixed. Furthermore, even if the crystal structure of silver halide grains is uniform inside,
Also, those with a layered structure with different interior and exterior,
It may be of a so-called convergence type as described in British Patent No. 635,841 and US Pat. No. 3,622,318. These photographic emulsions are from ``The Theory of the Photographic Process'' by Mees.
4th edition, published by MacMillan (1976); P.
“Chimie et Photographi−que” by Grafkides,
Published by Paul Montel (1957); written by GFDuffin,
"Photo-graphic Emulsion Chemistry",
Published by The Focal Press (1966); VLZslikman
“Making and Coat−ing Photographic” by et al.
It can be adjusted using the method described in "Emul-sion", published by The Focal Press (1964). In the process of silver halide grain formation or physical ripening, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or iron complex salts, etc. may be present. After the emulsion is precipitated or physically ripened, soluble salts are usually removed. For this purpose, the long-known Nudel water washing method, which involves gelatinization, may be used. Inorganic salts such as sodium sulfate,
Precipitation methods using anionic surfactants, anionic polymers (e.g. polystyrene sulfonic acid), or gelatin derivatives (e.g. aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.) ) may be used. The process of removing soluble salts may be omitted. Although a so-called immature emulsion (primitive emulsion) which is not chemically sensitized may be used as the silver halide emulsion, it is usually chemically sensitized. For chemical sensitization, the above-mentioned book by Glafkides or Zelikman et al., or "Die
Grundlagender Photographischen Proze−sse
mit Silberhalogeni−den”, Akademische
The method described in Verla-GSGESELL SCHAFT (1968) can be used. That is, sulfur-containing compounds that can react with activated gelatin and silver (e.g. thiosulfates, thioureas,
mercapto compounds, rhodanines), reduction sensitization methods using reducing substances (e.g. stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds), noble metal compounds (e.g. gold In addition to compounds, a noble metal sensitization method using complex salts of group metals of the periodic table, such as platinum, iridium, and palladium, can be carried out alone or in combination. As the hydrophilic colloid binder used in the non-photosensitive upper layer, emulsion layer or other constituent layers of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters, sugar derivatives such as sodium alginate and starch derivatives, and polyvinyl Alcohol, polyvinyl alcohol partial acetal,
Poly-N-vinylpyrrolidone, polyacrylic acid,
A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like. In addition to lime-processed gelatin, acid-processed gelatin, Bull.Soc.Sci.Phot.Japan, No. 16,
Oxygen-treated gelatin such as that described on page 30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The pigments used include cyanine pigments, merocyanine pigments,
Included are complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used, especially 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. Binders or protective colloids that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention include:
Although gelatin is advantageously used, other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl Various synthetic hydrophilic polymeric substances such as single or copolymers of alcohol, polyvinyl alcohol acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be used. In addition to lime-processed gelatin, acid-processed gelatin, Bull.Soc.Sci.Phot.Japan, No. 16,
Oxygen-treated gelatin as described in P30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. such as benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; Zaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3,
3a, 7) tetraazaindenes), pentaazaindenes, etc.; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfonic acid, benzenesulfonic acid amide, etc. can be added. Among these, particularly preferred are benzotriazoles (eg, 5-methylbenzotriazole) and nitroindazoles (eg, 5-nitroindazole). Further, these compounds may be included in the treatment liquid. The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.),
Dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,3-dihydroxydioxane, etc.), (4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), and the like can be used alone or in combination. The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced using the present invention contains coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, high contrast , sensitization)
Various surfactants may be included for various purposes. For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols Nonionic interfaces such as alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Activator: Alkyl carboxylate, alkyl sulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfate, alkyl phosphate, N-acyl-N-alkyl taurine, sulfosuccinic acid Contains acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc., such as esters, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphate esters, etc. Anionic surfactants; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts Cationic surfactants such as heterocyclic quaternary ammonium salts such as , pyridinium, imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used. When polyalkylene oxides are used in the present invention, polyalkylene oxides having a molecular weight of 600 or more described in Japanese Patent Publication No. 58-9412 are preferred. The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl (meth)acrylate, alkoxyalkyl (meth)
Acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or together with acrylic acid, methacrylic acid, α,β-unsaturated dicarboxylic acid, Hydroxyalkyl (meth)
Polymers containing a combination of acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as monomer components can be used. When an internal latent image type silver halide emulsion is used as the silver halide emulsion of the present invention, the light-sensitive material of the present invention can also be used in a color diffusion transfer method. In that case, Research Disclosure Magazine 17643
(1978, November) various additives described in Chapter XX can be used. Any known method can be used for the photographic processing of the light-sensitive material of the present invention. Depending on the purpose, development processing for forming a silver image (black and white development processing), color development processing for forming a color image, and development processing for color diffusion transfer (viscous development processing) can be used. The present invention is particularly suitable for use in silver halide photosensitive materials that form ultra-high contrast negative images in combination with surface latent image type silver halide grains. In order to obtain high-speed photographic properties, it is not necessary to use a conventional infectious developer or a highly alkaline developer with a pH close to 13 described in US Pat. No. 2,419,975, and a stable developer can be used. In other words, this type of silver halide photosensitive material is
By using a developing solution containing 0.15 mol/l or more of sulfite ion as a preservative and having a pH of 9.5 to 12.3, particularly 10.5 to 12.3, a sufficiently high contrast negative image can be obtained. There are no particular restrictions on the developing agents that can be used, such as dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone, 4,4-dimethyl-1-
phenyl-3-pyrazolidone), aminophenols (for example, N-methyl-p-aminophenol), etc. can be used alone or in combination. In particular, a developing solution containing dihydroxybenzenes as a main developing agent and 3-pyrazolidones or aminophenols as an auxiliary developing agent is preferred. Preferably, in this developer, dihydroxybenzenes are contained in an amount of 0.05 to 0.5 mol/l, and 3-pyrazolidones or aminophenols are contained in an amount of 0.06 mol/l.
Used in combination within the following ranges. Amines can also be used to increase development speed and reduce processing time, as described in US Pat. No. 4,268,969. The developer also contains alkali metal sulfites,
PH buffering agents such as carbonates, borates, and phosphates, development inhibitors or antifoggants such as bromides, iodides, and organic antifoggants (particularly preferably nitroindazoles or benzotriazoles), etc. can include. If necessary, water softeners, solubilizers, color toning agents, development accelerators, surfactants (especially preferably the aforementioned polyalkylene oxides), antifoaming agents, hardeners, and film silver stain preventive agents may be added. (for example, 2-mercaptobenzimidazole sulfonic acids). Specific examples of these additives are described in Research Disclosure No. 176, No. 17643. The cations contained in the developer are sodium ions and potassium ions, but it is important to select additives so that potassium ions account for 60 mol% or more, especially 75 mol%, of the total cations to concentrate the developer. advantageous for. As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used. The fixing solution may also contain a water-soluble aluminum salt or the like as a hardening agent. The treatment temperature is usually selected between 18°C and 50°C, but it may also be lower than 18°C or above 50°C. It is preferable to use an automatic processor for photographic processing. In the present invention, the total processing time from the time the photosensitive material is put into the automatic processor until it comes out is 90 seconds or more.
Even when set to 120 seconds, you can still obtain ultra-high contrast and high-sensitivity negative tone photographic characteristics. The present invention will be explained in more detail with reference to Examples below. Example 1 (1) Preparation of hydrazine compound mixture Solution A: 0.8 g of compound-4 and 0.24 g of compound-3 were dissolved in 40 c.c. of methanol. Solution B: 0.8 g of compound-5 and 0.24 g of compound-3 were dissolved in 40 c.c. of methanol. Solution C: 0.8 g of compound-5 and 0.24 g of compound-4 were dissolved in 40 c.c. of methanol. Solution D: 0.8 g of compound-5 was dissolved in 40 c.c. of methanol. Solution E: 0.8 g of Compound-5 was dispersed in an aqueous gelatin solution with ethyl acetate, N,N-diethyllautamide in an amount twice the weight of Compound-5, and sodium dodecylbenzenesulfonate under high-speed stirring. (2) Preparation of photosensitive material sample A cubic monodisperse silver iodobromide emulsion (silver iodide content 2 mol %) with an average grain size of 0.3 μm was prepared, and after washing with water in a conventional manner to remove soluble salts, Chemical sensitization was performed by adding sodium thiosulfate and potassium chloroaurate. This emulsion contained gelatin in an amount such that the gelatin/silver nitrate (weight ratio) was 0.30. Anhydro-5 was added to this emulsion as a sensitizing dye.
5'-dichloro-9-ethyl-3,3'-bis-(3
- Add sulfopropyl)oxacarbocyanine hydroxide sodium salt, add 2-(N-methyl-N-oleoylamino)ethanesulfonic acid sodium salt corresponding to 60 mol% of the hydrazine compound, and then add the above solution A. or F solution, the amount of hydrazine compound is 4.6×10 ^-3 per silver/mol.
immediately or after adding the dispersion of polyethyl acrylate.
After stirring at ℃ for 6 hours, 2-hydroxy-4,6-dichloro-1,3,5-triazine sodium salt was added as a hardening agent so that the amount of silver coated on the polyethylene terephthalate film was 3.6 g/m ² . It was applied to. At this time, a protective layer was applied at the same time. (3) Evaluation method The sensitivity and gamma were evaluated by sensitometry in which each sample was exposed for 1 second under a light wedge. The processing was performed by developing with the following developer at 38° C. for 30 seconds, stopping, fixing, washing with water, and drying. Developer Hydroquinone 40.0g 4,4-dimethyl-1-phenyl-3-pyrazolidone 0.4g Sodium hydroxide 13.0g Anhydrous potassium sulfite 90.0g Tertiary potassium phosphate 74.0g Disodium ethylenediaminetetraacetate 1.0g Potassium bromide 6.0g 5 -Methylbenzotriazole 0.6g 1-diethylamino-2,3-dihydroxypropane 17.0g Water was added (adjusted to pH 11.5 with potassium hydroxide) The results are shown in Table 1. As is clear from Table 1, when the hydrazine compound was added alone (No. 4), the sensitivity and gamma significantly decreased as the coating solution aged after addition. Moreover, this drawback cannot be solved by simply using a large amount of surfactant (No. 5); on the contrary, if the coating is applied immediately after addition, the sensitivity and gamma will decrease. Furthermore, when a gelatin dispersion of a hydrazine compound is used with the amount of high-boiling organic solvent necessary to obtain a stable dispersion (No. 6), even if it is added just before coating, the sensitivity and gamma are insufficient. I can't get it. In contrast, samples of the present invention (No. 1 to No. 3)
shows good sensitivity and gamma both when the mixture of the hydrazine compound and the compound of formula () is added immediately before coating, and when it is added 6 hours before coating. That is, it can be seen that according to the present invention, stable dispersion of the hydrazine compound can be achieved without inhibiting the direct interaction between the hydrazine compound and silver halide grains.

[Table] Example 2 (1) Preparation of a mixed solution of hydrazine compounds Solution G: Same as Solution A in Example 1 except that methanol was replaced with isopropyl alcohol. Solution H: Same as Solution B in Example 1 except that methanol was changed to ethanol. Solution I; methanol in Solution C of Example 1 was changed to ethanol, and further 2-(N-oleoyl-
Same as Solution C except that 0.8 g of N-methylamino)ethanesulfonic acid sodium salt was added. Solution J: Same as Solution D in Example 1. K solution; 1-formyl-2-(4-methylphenyl)
0.26 g of hydrazine was dissolved in 40 c.c. of methanol. (2) Preparation of light-sensitive material sample After adding the sensitizing dye and surfactant to the same emulsion as in Example 1, the above G, H,
One of the J solutions was added in an amount such that the hydrazine compound was 4.6×10 ⁻³ mol per mol of silver. Further, the same sensitizing dye as in Example 1 was added to the same emulsion as in Example 1, and then either of the above-mentioned solutions I and K was added in an amount such that the hydrazine compound was 4.6×10 ^-3 mol per mol of silver. A dispersion of polyethyl acrylate was added to these emulsions in the same manner as in Example 1, and then a hardening agent was added and coated in the same manner as in Example 1, followed by development. The results are shown in Table 2. As shown in Table 2, according to the present invention, there is almost no decrease in sensitivity and gamma due to aging of the coating liquid. It is also understood that as long as component (b) of the present invention is used, the surfactant may be added to the solution of components (a) and (b) in a water-miscible organic solvent or to the emulsion. No. 13 is an example using a non-hydrophobic hydrazine compound, but it can be seen that the problem that was addressed in the present invention does not occur in the case of a non-hydrophobic compound (However, in this case, contamination of the processing There are other problems such as

[Table] Example 3 The following liquids M to R were used in place of liquids A to E in Example 1, and evaluation was conducted in the same manner as in Example 1. The results are shown in Table 3. Preparation of hydrazine compound mixture Solution M: 0.8 g of compound-4 and 0.24 g of tricresyl phosphate were dissolved in 40 c.c. of methanol. N solution: 0.8 g of compound-4 and 0.24 g of dibutyl phthalate were dissolved in 40 c.c. of methanol. O liquid: 0.8g of compound-4 and 0.24g of N,N-
Diethyl lauramide was dissolved in 40 c.c. of methanol. Solution P: 0.8 g of compound-4 and 0.24 g of 1-octanol were dissolved in 40 c.c. of methanol. Q solution: 0.8 g of compound-4 and 0.24 g of ethylene glycol monobutyl ether were dissolved in 40 c.c. of methanol. R solution: 0.8 g of compound-4 and 0.24 g of benzyl benzoate were dissolved in 40 c.c. of methanol. From the results in Table 3, it can be seen that instead of the compound represented by the general formula () of the present invention, a typical high boiling point oil used when dispersing a hydrophobic organic compound such as a photographic coupler in a hydrophilic colloid is used. It can be seen that even if the hydrazine compound of general formula () is used, the hydrazine compound of general formula () cannot be stably dispersed. General formula of the present invention ()
It can be seen that a compound having a specific structure represented by is useful for stable dispersion of the hydrazine compound of general formula ().

【table】

Claims (1)

[Claims] 1. A hydrazine compound represented by the following general formula () that is substantially insoluble in water and has a melting point of 25°C or higher, and a substantially hydrazine compound that has the effect of lowering the melting point when mixed with the hydrazine compound. 1. A silver halide photographic material comprising at least one light-sensitive silver halide emulsion layer containing a mixture of water and an organic compound represented by the following general formula () having a molecular weight of 1000 or less. General formula () R ₁ -G ₁ -NHNH-G ₂ -R ₂ In the formula, R ₁ represents an alkanamide group having 8 to 70 carbon atoms, and R ₂ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or represents an unsubstituted aryl group or a substituted or unsubstituted aryloxy group, G ₁ represents a substituted or unsubstituted phenylene group, G ₂ represents a carbonyl group, a sulfonyl group,
Represents a sulfoxy group, phosphoryl group, or N-substituted or unsubstituted iminomethylene group. General formula () Z ₁ -Q In the formula, Z ₁ represents an alkyl-substituted phenoxyalkanamide having 8 to 20 carbon atoms, and Q is a hydrogen atom, a substituted or unsubstituted alkyl group having 20 or less carbon atoms, or a carbon number Represents a substituted or unsubstituted phenyl group of 20 or less. However, Z ₁ and Q do not have a hydrazino group as a substituent. 2. A hydrazine compound represented by the following general formula () that is substantially insoluble in water and has a melting point of 25°C or higher, and a molecular weight substance that is substantially insoluble in water and has the effect of lowering the melting point when mixed with the hydrazine compound. 1. A method for producing a silver halide photographic material, which comprises adding an organic compound represented by the following general formula () of 1000 or less to a light-sensitive silver halide emulsion coating solution and coating. General formula () R ₁ -G ₁ -NHNH-G ₂ -R ₂ In the formula, R ₁ represents an alkanamide group having 8 to 70 carbon atoms, and R ₂ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or represents an unsubstituted aryl group or a substituted or unsubstituted aryloxy group, G ₁ represents a substituted or unsubstituted phenylene group, G ₂ represents a carbonyl group, a sulfonyl group,
Represents a sulfoxy group, phosphoryl group, or N-substituted or unsubstituted iminomethylene group. General formula () Z ₁ -Q In the formula, Z ₁ represents an alkyl-substituted phenoxyalkanamide having 8 to 20 carbon atoms, and Q is a hydrogen atom, a substituted or unsubstituted alkyl group having 20 or less carbon atoms, or a carbon number Represents a substituted or unsubstituted phenyl group of 20 or less. However, Z ₁ and Q do not have a hydrazino group as a substituent.