JPS6410820B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an image forming method, and more particularly to a method for forming extremely high-contrast negative gradation photographic images. A method of adding a hydrazine compound to a silver halide photographic emulsion to obtain photographic characteristics of high contrast negative gradation is known from US Pat. No. 2,419,975. The patent specification states that by adding a hydrazine compound to a silver chlorobromide emulsion and developing it with a developer with a high pH of 12.8, extremely high-contrast photographic characteristics with a gamma (γ) exceeding 10 can be obtained. has been done. However, strong alkaline developers with a pH close to 13 are unstable and susceptible to air oxidation, and cannot withstand long-term storage or use. The ultra-high contrast photographic characteristics with a gamma of over 10 are extremely useful for photographic reproduction of continuous tone images or line drawings using dot images, which are useful in printing plate making, whether negative or positive tone. Useful. Conventionally, for this purpose, a silver chlorobromide photographic emulsion with a silver chloride content exceeding 50 mol%, preferably 75 mol%, is used, and the effective concentration of sulfite ions is kept extremely low (usually 0.1 mol%). A method of developing with a hydroquinone developing solution (hereinafter) was generally used. However, in this method, since the concentration of sulfite ions in the developer is low, the developer is extremely unstable and cannot be stored for more than 3 days. Since both of these methods require the use of silver chlorobromide emulsions with relatively high silver chloride contents,
It was not possible to obtain high sensitivity. Therefore, there has been a strong desire to obtain ultra-high contrast photographic characteristics useful for reproducing halftone images and line drawings by using a highly sensitive emulsion and a stable developer. The first object of the present invention is to provide a method for forming photographic images having extremely high contrast negative gradation photographic characteristics using a stable developer. A second object of the present invention is to provide a photographic image forming method that provides photographic characteristics of high sensitivity and extremely high contrast negative gradation. It is a further object of the present invention to provide a method for forming extremely high contrast negative photographic images with little fog. The above objects of the invention consist of monodisperse silver halide grains having an average grain size of not more than 0.7 microns and of substantially surface latent image type, and not more than 250 grams per mole of silver halide. A photographic light-sensitive material having at least one silver halide photographic emulsion layer containing a binder, and containing a compound represented by the general formula [] in the emulsion layer or at least one other hydrophilic colloid layer. After imagewise exposure, development was carried out at pH 11.0 to 12.3 with a developer containing benzotriazoles and 0.15 mol/or more of sulfite ion. R ¹ NNHHCOR ² [] In the formula, R ¹ represents a monocyclic or bicyclic aryl group.
The above aryl group may be substituted, such as a non-electron-withdrawing substituent, such as an alkyl group having 1 to 20 carbon atoms (which may have a branch), an aralkyl group having 1 to 3 carbon atoms in the alkyl moiety, It may have an alkoxy group (1 to 20 carbon atoms), an amino group mono- or di-substituted with an alkyl group (1 to 20 carbon atoms), an aliphatic acylamino group (2 to 21 carbon atoms), an aromatic acylamino group, etc. can. ^R2 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms which may be branched, or a phenyl group. Desirably, the alkyl group is unsubstituted.
The phenyl group may be substituted, but the substituent is preferably an electron-withdrawing substituent such as a halogen atom (chlorine, bromine, etc.), a cyano group, a trifluoromethyl group, a carboxy group, a sulfo group, etc. Specific examples of the substituent represented by R ¹ include phenyl group, α-naphthyl group, β-naphthyl group, p-tolyl group, m-tolyl group, o-tolyl group, p-methoxyphenyl group, m-methoxy phenyl group, p-dimethylaminophenyl group, p-diethylaminophenyl group, p-(acetylamino)phenyl group,
p-(capryloylamino)phenyl group, p-
(benzoylamino)phenyl group, p-benzylphenyl group, etc. Specific examples of substituents other than hydrogen atoms represented by R ² are methyl group, ethyl group, n-propyl group, isopropyl group, phenyl group, 4-chlorophenyl group, 4-promophenyl group, 3-chlorophenyl group, 4-cyanophenyl group. group, 4-carboxyphenyl group, 4-sulfophenyl group, 3,5-dichlorophenyl group, and 2,5-dichlorophenyl group. Among the substituents represented by R ¹ , monocyclic aryl groups are preferred, and unsubstituted phenyl groups and tolyl groups are particularly preferred. Among the substituents represented by R ² , preferred are a hydrogen atom, a methyl group, and a phenyl group including substituted ones. Particularly preferred is a hydrogen atom. Among the compounds represented by the general formula [], preferred are the compounds represented by the general formula [a]. R ¹ NNHHCOR ¹² [a] In the formula, R ¹ has the same meaning as in the general formula [], and R ¹² represents a hydrogen atom, a methyl group, an unsubstituted phenyl group, or a phenyl group substituted with an electron-withdrawing group. Among the compounds represented by the general formula [a], particularly preferred are the compounds represented by the general formula [a]. R ¹¹ NHNHCHO [b] In the formula, R ¹¹ represents an unsubstituted phenyl group or a tolyl group. The silver halide grains used in the present invention are substantially of the surface latent image type. In other words,
Not substantially internal latent image type. In the present invention, "substantially surface latent image type" means that the surface development ( It is defined as the sensitivity obtained in A) being greater than the sensitivity obtained in internal development (B). Here, sensitivity is defined as follows. S100/Eh S is sensitivity, Eh is density 1/2 (Dmax +
Indicates the amount of exposure required to obtain Dmin). Surface development (A) Develop at 20°C for 10 minutes in the following developer solution. N-methyl-p-aminophenol (hemisulfate) 2.5g Ascorbic acid 10g Sodium metaborate tetrahydrate 35g Potassium bromide 1g Add water 1 Internal development (B) Red blood salt 3g/and phenosafranin 0.0125 g/
20°C for 10 minutes, then washed with water for 10 minutes, and developed in a developer having the following formulation at 20°C for 10 minutes. N-Methyl-p-aminophenol (hemisulfate) 2.5 g Ascorbic acid 10 g Sodium metaborate tetrahydrate 35 g Potassium bromide 1 g Sodium thiosulfate 3 g Add water 1. If it is not an image type, positive gradation will be given in addition to negative gradation. The silver halide grains used in the present invention must not have an average grain size larger than 0.7 microns. Average grain size is a term commonly used and easily understood by those skilled in the field of silver halide photographic science. Particle size means the particle diameter in the case of particles that are spherical or can be approximated to a sphere. When the particle is cubic, the particle size is defined as the edge length x √4/π. The average is determined by a representative average or geometric average based on the particle projected area. For more information on how to determine average particle size, see
CEKMeeS and THJames: The Theory of the Photographic Process
theory of the photographic process), 3rd ed.
+P.36 to p.43, (1966, published by McMillan).If the average grain size exceeds 0.7μ in the silver halide emulsion layer essential for the method of the present invention, γ It is not possible to obtain a high contrast in which the average grain size of the emulsion exceeds 10.It is more preferable that the average grain size of the emulsion in the present invention is 0.4μ or less.According to the method of the present invention, even though the average grain size of the silver halide is small, figure,
It is characterized by high sensitivity. The silver halide grains in the photographic emulsion of the present invention need to have a narrow grain size distribution, and in particular, in terms of weight or number of silver halide grains, the size of grains that account for 90% of the total is the average grain size. (Such emulsions are generally called monodisperse emulsions). As the silver halide, any of silver chloride, silver chlorobromide, silver iodochlorobromide, silver bromide, and silver iodobromide can be used, but in the case of silver chloride bromide or silver iodochlorobromide, silver chloride The content of silver preferably does not exceed 80 mol%, and in the case of silver iodobromide or silver iodochlorobromide, the content of silver iodide is 10% by mole.
It is preferable that it does not exceed mol%. Silver chloride content is
It is particularly preferred that the content of silver iodide does not exceed 50 mol %, and it is especially preferred that the content of silver iodide does not exceed 6 mol %. Since the method of the present invention can use a wide range of silver halides, it
It is possible to obtain much higher sensitivity than a method using ("lith") type development. The monodisperse silver halide emulsions used in this invention must not contain more than 250 grams of binder per mole of silver halide. If silver halide 1
If more than 250 g of binder is contained per mole, the extremely high contrast photographic properties which are the object of the present invention cannot be obtained. In particular, it is absolutely impossible to obtain γ greater than 10. It is a general tendency of photographic emulsions that the smaller the amount of binder in the emulsion, the higher the contrast, but this is an effect based on the amount of silver halide contained in the emulsion layer of unit thickness. The influence of the silver halide content in the present invention differs from such known effects, and the effect on gradation changes significantly near the above-mentioned limit value. This change is shown in Example 4. The effects of the present invention can only be achieved by having an average grain size not exceeding 0.7 μm and a high silver halide content in the emulsion as described above. Gelatin is advantageously used as binder or protective colloid in photographic emulsions. 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 sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. ,
Polyvinyl alcohol partial acetal, poly-N
- A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like. As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin may be used, and gelatin hydrolysates and gelatin enzymatically decomposed products can also be used.
As gelatin derivatives, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acids, alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds can be added to gelatin. The product obtained by the reaction is used. Specific examples are U.S. Patent No. 2614928, U.S. Patent No. 3132945,
3186846, 3312553, British Patent No. 861414,
It is described in No. 1033189, No. 1005784, and Japanese Patent Publication No. 42-26845. The gelatin graft polymer is a gelatin grafted with a single (homo) or copolymer of vinyl monomers such as acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, acrylonitrile, styrene, etc. can be used. In particular, polymers with some degree of compatibility with gelatin, such as acrylic acid,
Graft polymers with polymers such as methacrylic acid, acrylamide, methacrylamide, hydroxyalkyl methacrylate are preferred. Examples of these are U.S. Pat.
It is described in issues such as No. 2956884. Typical synthetic hydrophilic polymer substances include West German patent applications (OLS)
No. 2312708, U.S. Patent No. 3620751, U.S. Patent No. 3879205,
This is described in Japanese Patent Publication No. 7561/1973. The silver halide emulsion used in the method of the present invention does not need to be chemically sensitized, but is preferably chemically sensitized. Sulfur sensitization, reduction sensitization, and noble metal sensitization are known as methods for chemically sensitizing silver halide emulsions. Among the noble metal sensitization methods, the gold sensitization method is a typical method and uses a gold compound, mainly a gold complex salt. It may also contain complex salts of noble metals other than gold, such as platinum, palladium, and iridium. The reduction sensitization method may be used as long as it does not cause fogging which is a practical problem. A particularly preferred chemical sensitization for the practice of this invention is sulfur sensitization. As the sulfur sensitizer, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines, etc. can be used. Specific example is a US patent
No. 1574944, No. 2278947, No. 2410689, No.
It is described in No. 2728668, No. 3501313, and No. 3656955. Specific examples of the compound represented by the general formula [] are shown below. However, the invention is not limited thereto. The compound represented by the general formula [] can generally be synthesized by the reaction of hydrazines and formic acid, or the reaction of hydrazines and acyl halides. Next, a specific synthesis method will be described. <Synthesis of Compound 2> 110 g of formic acid was stirred at 25 to 30°C, and p
- Add 107 g of tolylhydrazine little by little.
After the addition is complete, heat and stir at 50°C for 20 minutes. After cooling on ice, take the crystals and dilute with acetonitrile 550
Recrystallize in ml. 54.5 g of colorless needle-shaped crystals with a melting point of 176 DEG -177 DEG C. are obtained. <Synthesis of Compound 5> Add 15 g of p-tolylhydrazine to 100 ml of acetonitrile while stirring at 25-30°C. Then, 15 g of benzoyl chloride is gradually added dropwise at 25 to 30°C. After the addition is complete, stirring is continued for 6 hours at 25-30°C. After cooling on ice, the resulting crystals are collected and recrystallized from benzene. 7 g of colorless needle-shaped crystals with a melting point of 146° C. are obtained. The compound of general formula [] is usually contained in the photographic emulsion of the present invention in an amount of 10 ^-4 to ^{10 -1} mol/molAg. The preferred concentration is 10 ^-3 to 5 x 10 ^-2 mol/molAg, particularly preferably 5 x 10 ^-3 to 5 x 10 ^-2 mol/molAg. To add the compound of general formula [] to the emulsion, a conventional method for adding additives in photographic emulsions can be used. For example, water-soluble compounds should be prepared as an aqueous solution with an appropriate concentration, and compounds that are insoluble or sparingly soluble in water should be prepared using suitable organic solvents that are miscible with water, such as alcohols, ethers, glycols, acetones, esters, and amides. Among these, those that have no adverse effect on photographic properties are dissolved and added to the emulsion as a solution. It is also possible to use the well-known methods for adding water-insoluble (so-called oil-soluble) couplers into the emulsion in the form of a dispersion. Among the benzotriazoles used in the present invention, preferred compounds are represented by the following general formula []. In the formula, Y is an alkyl group having 1 to 12 carbon atoms (e.g., methyl group, hebutyl group, heptadecyl group), a halogen atom (e.g., chlorine atom, bromine atom), or an alkyl group having 1 to 12 carbon atoms.
~12 alkoxy groups (e.g. methoxy group, lauryloxy group), C2-13 acyl groups (e.g. acetyl group, benzyl group), C2-13 acylamino groups (e.g. acetylamino group, capryloylamino group) , benzoylamino group, benzenesulfonylamino group), carbamoyl group optionally substituted with an aliphatic or aromatic group having 1 to 12 carbon atoms (e.g. methylcarbamoyl group, phenylcarbamoyl group), aliphatic group having 1 to 12 carbon atoms represents a sulfamoyl group (eg, methylsulfamoyl group, phenylsulfamoyl group) or a monocyclic or bicyclic aryl group (eg, phenyl group) which may be substituted with a group or an aromatic group. Y does not represent a nitro group. n represents 0.1 or 2.
When n is 2, the two Y may be two different substituents. The number of carbon atoms in the alkyl group contained in Y is particularly preferably 1 to 3. X is hydrogen atom, halogen atom (e.g. chlorine atom, bromine atom)
Or it represents an acyl group having 1 to 10 carbon atoms (eg, acetyl group, propionyl group). Specific examples of the compound represented by the general formula [] are shown below. The benzotriazole compound represented by the general formula [] is described in, for example, Organic Synthesis, Volume 3, p. 106; Journal of the Chemical Society (J.
Chem.Soc.) Volume 119 (1921) Pages 2088-94;
Same magazine, 1931, pp. 1143-53; Same magazine, C category,
1969, pp. 1474-78, etc., for synthesis. Benzotriazoles are added to the developer solution. Water-miscible organic solvents or alcohols (e.g. methanol,
It may be added as a solution dissolved in ethanol) ketones (eg, acetone, methyl ethyl ketone), esters (eg, ethyl acetate), or water during the preparation of the developer solution, or in the completed developer solution. These solvents can also be used as alkaline or acidic, if necessary. The light-sensitive material can also be treated with a bath containing benzotriazoles after exposure and before development. The amount added to the developer is 10 ^-6 ~
10 ^-1 mol/l developer is suitable. Especially 3×10 ^-5
~3×10 ⁻² mol/l of developer is preferred. The photographic emulsion of the present invention is based on Chimie et al. by P. Glafkides.
Physique Photographique (published by Paul Montel)
1967), Photographic Emulsion by GFDuffin
Chemistry (The Focal Press, 1966), VL
Making and Coating by Zelikman et al
Photographic Emulsion (published by The Focal Press)
(1964) and others. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt and soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. . It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).
One type of simultaneous mixing method is a method in which the pAg in the liquid phase in which silver halide is produced is kept constant, that is, the so-called controlled double jet method. According to this method, the crystal form is regular. A silver halide emulsion with nearly uniform grain size can be obtained. The silver halide grains in the photographic emulsion may have regular crystals such as cubic or octahedral, or irregular crystals such as spherical or plate-like. , or a composite form of these crystal forms.
It may also consist of a mixture of particles of various crystalline forms. The interior and surface layers of the silver halide grains may have uniform phases or may have different phases. In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present. Two or more types of silver halide emulsions formed separately may be mixed and used. The soluble salts are usually removed from the emulsion after precipitation or physical ripening, and the long-known Nudel water washing method in which gelatin is gelatinized may be used as a means for this purpose. Utilizing inorganic salts such as sodium sulfate, anionic surfactants, anionic polymers (e.g. polystyrene sulfonic acid), or gelatin derivatives (e.g. aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.) A sedimentation method (flocculation) may also be used. The process of removing soluble salts may be omitted. Although a silver halide emulsion that is not chemically sensitized (so-called primitive emulsion) may be used, it is usually chemically sensitized. For chemical sensitization, there are sulfur sensitization methods that use active gelatin and compounds containing sulfur that can react with silver ions, reduction sensitization methods that use reducing substances, and noble metal sensitization methods that use noble metal compounds such as gold. Can be used in combination. For these see Glafkides or
Zelikman et al.'s book or H. Frieser's Die
Grundlagen der photographischen Prozesse
mit Silberhalogeniden (Akademische
Verlagsgesellschaft, 1968).
Specific examples of sulfur sensitizers include US Pat. No. 1,574,944;
Described in Nos. 2410689, 2278947, 2728668, and 3656955. As the reduction sensitizer, stannous salts, amines, formamidine sulfinic acid, silane compounds, etc. can be used, and specific examples thereof include U.S. Pat.
No. 2983610, No. 2694637. For noble metal sensitization, complex salts of metals in the periodic table group such as gold platinum, iridium, and paldium can be used, and specific examples thereof are described in US Pat. No. 2,448,060, British Patent No. 618,061, and the like. In the method of the present invention, when photographically processing the image-exposed silver halide photographic light-sensitive material, benzotriazoles and 0.15 mole/
It can be carried out in the same manner as known methods, except that it contains the above sulfite ions and is developed at a pH of 11 to 12.3. Known processing liquids other than the developer can be used. Depending on the purpose, either a development process that forms only a silver image (black and white photographic process) or a color photographic process that consists of a development process that forms a dye image can be applied. The processing temperature is usually chosen between 18°C and 50°C, but temperatures below 18°C or above 50°C may also be used. The developer used in black-and-white photographic processing can contain known developing agents. Examples of developing agents include dihydroxybenzenes (for example, hydroquinone), 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone), aminophenols (for example, N-methyl-p-aminophenol), and 1-phenyl-3-pyrazoline. You can choose from among the following. The developing solution generally contains other well-known preservatives, alkaline agents, PH buffers, antifoggants, etc., and, if necessary, solubilizing agents, color toners, development accelerators, surfactants, antifoaming agents, etc. It may also contain water softeners, hardeners, viscosity-imparting agents, and the like. According to the method of the present invention, even when developed with a developer containing 0.15 mol/sulfite ion or more, it is possible to obtain a γ of more than 10. In the present invention, the pH of the developer needs to be 11.0 to 12.3. 11.5
~12.0 is preferred. When the pH is low, it is difficult to obtain the sensitization and contrast enhancement effects of the present invention. PH is
If it exceeds 12.3, the developer becomes unstable even if the concentration of sulfite ions is high, and stable photographic characteristics cannot be maintained for more than 3 days. When developing the photographic emulsion of the present invention, a developer containing a fogging agent (development nucleating agent) in an amount that substantially causes fog is not used. 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 contain a water-soluble aluminum salt as a hardening agent. The photosensitive material used in the present invention may contain an antifoggant. Antifoggants which are advantageous for use in the emulsions of the invention are, for example, 1,2,4-triazole compounds substituted with methylcapto in the 3-position, 2-mercaptobenzimidazole compounds (but must not contain a nitro group), 2-mercaptobenzimidazole compounds, -Mercaptopyrimidines, 2-mercaptobenzothiazoles, benzothiazolium compounds (for example, N-alkylbenzothiazolium halides, N-allylbenzothiazolium halides, 2-mercapto-3,4-
These include thiadiazoles. There are some antifoggants that are not effective by themselves as antifoggants, such as 6-nitrobenzimidazole, 4
-Hydroxy-1,3,3a,7-tetrazaindenes, etc. However, they can also be used in combination with advantageous antifoggants. Adding small amounts of iodide (such as potassium iodide) to the emulsion after grain formation, before chemical ripening, after chemical ripening, or before coating further enhances the effectiveness of the present invention. It is appropriate to add iodide in an amount of 10 ^-4 to ^{10 -2} mol/molAg. The photographic emulsions used in this invention may be spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes, merocyanine dyes, 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. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and these Nuclei in which aromatic hydrocarbons are fused to the nucleus, i.e., indolenine nucleus, benzindolenine nucleus,
Indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms. Merocyanine dyes or composite merocyanine dyes include a nucleus having a ketomethylene structure such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, A 5- to 6-membered heteroartic ring nucleus such as a thiobarbituric acid nucleus can be applied. Useful sensitizing dyes include, for example, German Patent No. 929080;
U.S. Patent No. 2231658, U.S. Patent No. 2493748, U.S. Patent No. 2503776,
Same No. 2519001, No. 2912329, No. 3656959, Same No.
No. 3672897, No. 3694217, British Patent No. 1242588,
This was described in Special Publication No. 14030/1973. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Typical examples of this are U.S. Pat.
No. 3397060, No. 3522052, No. 3527641, No. 3527641, No. 3522052, No. 3527641, No.
No. 3617293, No. 3628964, No. 3666480, No.
No. 3679428, No. 3703377, No. 3769301, No.
No. 3814609, No. 3837862, British Patent No. 1344281,
It is described in Special Publication No. 43-4936. 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 nitrogen-containing heterocyclic groups (e.g.,
2933390 and 3635721), aromatic organic acid formaldehyde condensates (for example, those described in US Pat. No. 3743510), cadmium salts, azaindene compounds, and the like. US patent
No. 3615613, No. 3615641, No. 3617295, No. 3635721
The combinations described in this issue are particularly useful. The light-sensitive material used in the present invention may contain a water-soluble dye as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hekioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful. Specific examples of dyes that can be used include British Patent No. 584609, British Patent No. 1177429, and Japanese Patent Application Laid-open No. 1977.
-85130, US Patent No. 49-99620, US Patent No. 49-114420, US Patent No. 2274782, US Patent No. 2533472, US Patent No. 2956879,
No. 3148187, No. 3177078, No. 3247127, No. 3177078, No. 3247127, No.
No. 3540887, No. 3575704, No. 3653905, No.
It is described in No. 3718472. The photosensitive material used in the present invention may contain an inorganic or organic hardening agent. Examples include 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.) ), activated vinyl compound (1,
3,5-Triacryloyl-hexahydro-s-
triazine, bis(vinylsulfonyl) methyl ether, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.),
Mucohalogen acids (mucochloric acid, mucophenoxychloric acid, etc.), isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin, and the like can be used alone or in combination. A specific example is the U.S. patent
No. 1870354, No. 2080019, No. 2726162, No.
No. 2870013, No. 2983611, No. 2992109, No.
No. 3047394, No. 3057723, No. 3103437, No. 3047394, No. 3057723, No. 3103437, No.
No. 3321313, No. 3325287, No. 3362827, No. 3321313, No. 3325287, No. 3362827, No.
No.3539644, No.3543292, British Patent No.676628, No.3543292, British Patent No.676628,
No. 825544, No. 1270578, German Patent No. 872153,
It is described in No. 1090427, Special Publication No. 34-7133, No. 46-1872, etc. The light-sensitive materials used in the present invention contain various known interfaces for various purposes such as coating aids, antistatic properties, improving slipperiness, emulsification and dispersion, preventing adhesion, and improving photographic properties (for example, accelerating development, increasing contrast, and sensitizing). It may also contain an activator. For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl or alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl amines or amides) , polyethylene oxide adducts of silicones), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, and non-ionic materials such as urethanes or ethers. surfactants; triterpenoid saponins, alkyl carboxylates, alkyl sulfonates, alkylbenzenesulfonates, alkylnaphthalenesulfonates,
Alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurates, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates, etc. , carboxy group, sulfo group, phosphor group,
Anionic surfactants containing acidic groups such as sulfate ester groups and phosphate ester groups; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric esters, alkyl betaines, amine imides, and amine oxides. ;
Alkylamine salts, aliphatic or aromatic quaternary
Cationic surfactants such as quaternary ammonium salts, heterocyclic quaternary ammonium salts such as viridinium, imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used. Specific examples of these surfactants are listed in the U.S. patent.
No. 2240472, No. 2831766, No. 3158484, No.
No. 3210191, No. 3294540, No. 3507660, British Patent No. 1012495, No. 1022878, No. 1179290, British Patent No.
No. 1198450, Japanese Unexamined Patent Publication No. 117414, US patent
No. 2739891, No. 2823123, No. 3068101, No.
No. 3415649, No. 3666478, No. 3756828, British Patent No. 1397218, US Patent No. 3133816, No. 3441413,
Same No. 3475174, No. 3545974, No. 3726683, Same No.
No. 3843368, Belgian Patent No. 731126, British Patent
No. 1138514, No. 1159825, No. 1374780, Tokko Akira
40-378, 40-379, 43-13822, U.S. Patent No. 2271623, 2288226, 2944900, U.S. Pat.
No. 3253919, No. 3671247, No. 3772021, No.
3589906, 3666478, 3754924, West German patent application OLS 1961638, Japanese Patent Application Laid-Open No. 50-59025, etc. The light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, alkyl (meth)acrylates, alkoxyalkyl (meth)acrylates, glycidyl (meth)acrylates, (meth)acrylamides, vinyl esters (e.g. vinyl acetate), acrylonitrile,
Olefin, styrene, etc. alone or in combination, or combinations of these with acrylic acid, methacrylic acid, α,β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. A polymer having as a monomer component can be used. For example, US Patent No. 2376005,
Same No. 2739137, No. 2853457, No. 3062674, Same No.
No. 3411911, No. 3488708, No. 3525620,
Those described in British Patent No. 3607290, British Patent No. 3635715, British Patent No. 3645740, British Patent No. 1186699, British Patent No. 1307373 can be used. Since high-contrast emulsions such as those of the present invention are suitable for reproduction of line drawings, and dimensional stability is important in such applications, it is preferable to include such polymer dispersions. Example 1 A silver bromide emulsion with an average grain size of 0.25 μm was prepared by simultaneously adding a silver nitrate aqueous solution and a potassium bromide aqueous solution for 50 minutes to an aqueous gelatin solution kept at 50° C. and maintaining pAg at 7.9 during that time. After removing the soluble salts in a conventional manner, this emulsion was chemically ripened at 60 DEG C. for 60 minutes with the addition of 43 mg of sodium thiosulfate per mole of silver bromide. This emulsion contains 120 grams of gelatin per mole of silver bromide. The internal sensitivity of this emulsion is negligibly low compared to the surface sensitivity. This silver bromide emulsion was divided into two parts, and to one side, 2×10 ^-2 mol of Compound Example 2 of the present invention was added per 1 mol of silver halide, and a hardener, 2-hydroxy-4,6-dichloro-1,3, 5-triazine sodium salt was added. To the other side, only the above-mentioned hardener was added, and each was coated on a polyethylene terephthalate film in an amount of 45 mg of silver per 100 cm ² .
After exposing these samples for 1 second under a light wedge, compounds of the present invention -1, -2, -3 and -5
20℃ using a developer with the following composition containing one of the following:
The film was developed for 3 minutes and then processed as usual. For comparison, a sample containing none of the compound examples was treated in the same manner. N-methyl-p-aminophenol hemisulfate
5 g Hydroquinone 10 g Anhydrous sodium sulfite 75 g Sodium metaborate tetrahydrate 30 g Potassium hydroxide 12 g Compound of general formula [ ] Add water shown in Table 1 1 (PH = 11.5) The obtained photographic properties are shown in Table 1 It is like that.
In Table 1, the relative sensitivity is the relative value of the reciprocal of the exposure amount that provides a density of 2.0 excluding fog, and is the value for sample 1.
It is shown as 100.

[Table] As is clear from Table 6, images with high sensitivity, high γ, and low fog are formed by the combination of the present invention. Example 2 A sulfur-sensitized silver bromide emulsion having an average grain size of 0.25 μm was prepared in the same manner as in Example 1. Before coating, a compound of the general formula [] of the present invention was added as shown in Table 2, and further 2-hydroxy-4,6-dichloro-1,3,
5-triazine sodium salt (0.4 g/100 g gelatin) was added and coated in the same manner as in Example 1. Each sample was exposed for 1 second under a light wedge, developed for 3 minutes at 20°C with a developer having the composition shown below, and then photographed as usual. N-methyl-p-aminophenol (hemisulfate) 5g Hydroquinone 10g Anhydrous sodium sulfite 75g Sodium metaborate tetrahydrate 30g Potassium hydroxide 15g Compound example-2 (1% methanol solution) 45ml Add water 1 (PH= 12) The gamma obtained is as shown in Table 2.

【table】

[Table] Reference example Instead of the compound in Table 2 represented by the general formula [], a hydrazine compound other than the present invention as shown in Table 3 is used.
γ was measured in exactly the same manner as in Example 2 except that 5.1 g/molAgBr was added. The results showed that γ did not change in the samples to which any compound was added compared to the samples to which no compounds were added (γ=5). The compound N'-phenylform hydrazide according to the invention gave a γ of over 20.

【table】

[Table] Example 3 A silver iodobromide emulsion with an average grain size of 0.25μ containing 2 mol% and 4 mol% of silver iodide, and an odor emulsion with an average grain size of 0.5μ were prepared in the same manner as the emulsion of Example 1. A silver oxide emulsion was prepared. These emulsions are designated A, B and C, respectively. Chemical ripening was carried out in the same manner as in Example 1 except that the amount of sodium thiosulfate in Emulsion C was changed to 26 mg/molAg. Emulsions A, B and C contain 120 g of gelatin per mole of silver halide and have negligible internal sensitivities compared to surface sensitivities. Compound Example 2 of the present invention was added to Emulsions A, B and C as shown in Table 4, and the emulsions were coated, exposed and developed in the same manner as Test No. 6 of Example 1, and photographic properties were measured. The results are shown in Table 4. Relative sensitivity is defined as in Example 1. Therefore, this value is not useful for comparing sensitivities between emulsions A, B and C.

Table 4 shows that even with silver iodobromide emulsions having an average grain size of 0.25μ and silver bromide emulsions having an average grain size of 0.5μ, a γ of over 20 can be obtained according to the present invention. Example 4 A silver bromide emulsion prepared as in Example 1 was added with 10
% gelatin solution was added to vary the silver halide to gelatin ratio at four levels: Emulsion a 155 g/mol AgBr b 205 c 310 d 410 2.4 g/mole of Compound Example 2 of the present invention was added to each emulsion.
With the addition of molAgBr, it was coated and exposed in the same manner as in Example 1, and developed in the same manner as in Test No. 6 of Example 1. The photographic properties obtained are as shown in Table 5. Relative sensitivity is expressed as a relative value of the reciprocal of the exposure amount that gives a density of 1.0 excluding fog.

[Table] It can be seen that when the amount of gelatin exceeds 250 g per mole of silver halide, the desired effects of the present invention cannot be obtained.

Claims (1)

[Scope of Claims] 1 Consisting of monodisperse silver halide grains of substantially surface latent image type with an average grain size not larger than 0.7 microns, and containing more than 250 g of binder per mole of silver halide After image exposure, a photographic light-sensitive material having at least one silver halide photographic emulsion containing no silver halide and containing a compound represented by the general formula [] in the photographic emulsion layer or at least one other hydrophilic colloid layer. , contains 1×10 ^-6 to 1×10 ^-1 mol of benzotriazole per developer, and 0.15
A developer containing sulfite ions of mol/more
11. A photographic image forming method characterized by developing in a range of 11.0 to 12.3. R ¹ NNHHCOR ² [] [In the formula, R ¹ represents an aryl group. R ² represents a hydrogen atom, a phenyl group, or an unsubstituted alkyl group having 1 to 3 carbon atoms. ].