JPH0416098B2 - - Google Patents

Description

[Detailed description of the invention]

(Field of Industrial Application) The present invention relates to an image forming method, and relates to a method for quickly forming a silver image having a quality suitable for use in the field of photolithography, sometimes using a stable processing liquid. It is. (Prior art) In the photoengraving process, halftone images (dotimages)
In order to achieve good continuous tone reproduction or line drawing reproduction, an image forming system is required that exhibits ultra-high contrast photographic characteristics. Conventionally, for this purpose, it has been common to use a hydroquinone developer (infectious developer) with an extremely low effective concentration of sulfite ions (usually 0.1 mol/less or less). However, in this method, since the concentration of sulfite in the developer is low, the developer is extremely unstable and cannot be stored for more than 3 days. On the other hand, in recent years in the photolithography field, there has been an increasing need for work rationalization and efficiency, and to meet this need, rapid access systems that can perform simple and quick processing using stable processing liquids have become popular. are doing. This system uses a combination of hydroquinone and 0.1 g/or more of 1-phenyl-3-pyrazolidones. However, since this system does not provide the ultra-high contrast photographic characteristics necessary to obtain good halftone dot quality, its use has been limited. By the way, polyalkylene oxides are used in this field for the purpose of improving the halftone dot quality, but when this compound is used in an amount sufficient to improve the halftone dot quality, the surface of the developed film is There was a problem that uneven development was likely to occur. (Objective of the Invention) Therefore, the object of the present invention is to provide an image forming method that can quickly obtain an ultra-high contrast image with good halftone dot quality without uneven development and using a stable processing solution. (Structure of the Invention) The above object of the present invention is to have at least one silver halide emulsion layer on a support, and to contain a compound represented by the following general formula () in the emulsion layer or other hydrophilic colloid layer. After imagewise exposure of the photographic material containing the dihydroxybenzene-based developing agent, 0.05 to 0.5 mol/contains a dihydroxybenzene-based developing agent, and 0 to 0.05 g/contains an auxiliary developing agent.
Contains 0.25 mol/or more of free sulfite ions, and 20% of 5- or 6-nitroindazole.
1. An image forming method characterized by processing with a developer containing alkali in an amount of at least mg/mg/ml and a sufficient amount to raise the pH to 10.5 or more. General formula () [In the formula, R ¹ represents a substituted or unsubstituted alkyl group having 10 or less carbon atoms, or a substituted or unsubstituted aryl group; R ² and R ³ each independently represent a hydrogen atom, a halogen atom, a carboxyl group, Sulfonic acid group, carbon number 10
It represents the following aliphatic group or aromatic group. However, at least one of R ¹ , R ² or R ³ shall contain a carboxyl group or a sulfonic acid group. ] Preferred groups among the groups represented by R ¹ are alkyl groups, alkoxy-substituted alkyl groups, alkyl groups having a carboxy group, alkyl groups having a sulfonic acid group, and primary, secondary, or tertiary amino groups having 10 or less carbon atoms. an alkyl group, a halogen-substituted alkyl group, a hydroxy-substituted alkyl group, a substituted or unsubstituted phenyl group having 10 or less carbon atoms (as a substituent, an alkyl group, an alkoxy-substituted alkyl group, a halogen-substituted alkyl group, an alkoxy group, an alkoxy-substituted alkoxy group, an alkyl group having a carboxyl group, an alkyl group having a sulfonic acid group, a carboxyl group, a sulfonic acid group, a halogen atom, a hydroxy group, a hydroxy-substituted alkyl group, etc.). Particularly preferred as R ¹ are an alkyl group having 8 or less carbon atoms, an alkoxy-substituted alkyl group, a phenyl group, a phenyl group having a carboxyl group, and a phenyl group having a sulfonic acid group. The aliphatic group or aromatic group for R ² and R ³ includes a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or Unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted carbonamide group, substituted or unsubstituted sulfamoyl group, substituted or unsubstituted sulfonamide group, substituted or unsubstituted unsubstituted alkylcarbonyl group,
Substituted or unsubstituted arylcarbonyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted an alkylsulfoxy group, a substituted or unsubstituted arylsulfoxy group, a substituted or unsubstituted alkyl group, each having 10 or less carbon atoms. Among the groups represented by R ² or R ³ , preferred are a hydrogen atom, an alkyl group having 10 or less carbon atoms, an alkoxy group, an alkoxy-substituted alkyl group, an alkyl group having a carboxyl group, an alkyl group having a sulfonic acid group, An alkyl group having a primary, secondary or tertiary amino group, a halogen-substituted alkyl group, a hydroxy-substituted alkyl group, a phenyl group, a substituted phenyl group having 10 or less carbon atoms (as a substituent, an alkyl group, an alkoxy-substituted alkyl group, a halogen-substituted alkyl group) Alkyl group, alkoxy group, alkyl group having a carboxyl group, alkyl group having a sulfonic acid group, carboxyl group, sulfonic acid group, halogen atom, hydroxy group, hydroxy-substituted alkyl group, etc.), halogen atom, carboxyl group, It is a sulfonic acid group. Particularly preferred R ² and R ³ are hydrogen atoms,
an alkyl group, an alkoxy-substituted alkyl group, a phenyl group, a phenyl group having a carboxyl group, a phenyl group having a sulfonic acid group, having 8 or less carbon atoms;
It is a carboxyl group or a sulfonic acid group. Specific examples of the compound represented by the general formula () are listed below. The compound represented by the general formula () can be synthesized according to the conventional method for synthesizing mercaptoimidazoles, that is, 2,3-dihydroimidazole-2-thiones, and the method is described in, for example, US Pat. No. 2,585,388;
No. 2541924, Chemical Abstract 58 , 7921g
(1963); IIKovtunovskaya-Levshina Tr.Ukr.Inst.
Eksperim. Endo krinol. 18 , p. 345 (1961); M.
Chamben et al., Bull.Soc. 79 , p. 4922 (1957);
It is described in A.Wohl, W.Marckwald, Journal of the German Chemical Society (Ber.), 22 , p. 568 (1889). More specifically, compounds -7 to -10 are obtained by hydrolyzing the esters described in US Pat. No. 2,585,388 and US Pat.
It is described in. As other synthesis methods, the following methods can be used. For example, Compound-1 can be synthesized from para-aminobenzoic acid ester (eg, ethyl ester) by the following procedure. That is, para-aminobenzoic acid ester is treated with carbon disulfide and triethylamine to form the corresponding triethylammonium dithiocarbamate salt, and then treated with ethyl chloroformate or methyl chloroformate and then heated to form the corresponding isothiocyanate. When aminoacetaldehyde diethyl acetal is added to this isothiocyanate and then heated in the presence of acid and water, the ester is hydrolyzed at the same time as the ring is closed, yielding Compound-1. Substituted compounds of Compound-1 can also be synthesized in the same manner. Note that the isothiocyanate used here (for example, paracarboethoxyphenyl isothiocyanate) is described, for example, by SRSandler and W. Karo.
Organic Functional Group Preparations,
It can be synthesized according to the method described in Academic Press, 1968, pages 312-315. Next, the synthesis method of the compound of the present invention will be explained by giving specific synthesis examples, but compounds for which synthesis examples are not listed can also be synthesized according to the following synthesis examples. (Synthesis example) Synthesis of compound-1 (1) N-(4-carboethoxyphenyl)-N'-
Synthesis of (2,2-diethoxyethyl)thiourea: 20 g of 4-carboethoxyphenyl isothiocyanate was dissolved in 50 ml of carbon tetrachloride, and 13 g of aminoacetaldehyde ethyl acetal was added dropwise thereto over 5 minutes. The mixture was then stirred at room temperature for 1 hour. 50 ml of carbon tetrachloride was added to the reaction mixture, and the precipitated crystals were collected, washed with 50 ml of carbon tetrachloride, and then dried. Yield 27.5g, yield 80.9% (2) Synthesis of compound-1 (1-(4-carboxyphenyl)-2,3-dihydroimidazole-2-thione) ethoxyphenyl)
-N'-(2,2-diethoxyethyl)thiourea
400 ml of 30% sulfuric acid was added to 80 g and refluxed on an oil bath for 1 hour. After cooling the reaction mixture to room temperature, add 600 ml of water.
ml was added and cooled on ice. Take the precipitated crystals and add water
It was washed with 200 ml, 100 ml of isopropyl alcohol, and 100 ml of hexane in this order, and dried. Yield: 48g Yield: 92.8% A light-sensitive material containing the compound of the general formula () of the present invention added to an emulsion layer or other hydrophilic colloid layer quickly develops into a good image when processed with the developer of the present invention described below. Ultra-high contrast images that can achieve halftone dot quality can be formed without developing unevenness. The preferred amount of the compound of general formula () according to the invention is in the range from 10 ^-6 to 10 ^-1 mol, especially from 10 ^-5 to 10 ^-3 mol, per mol of silver halide. The silver halide in the silver halide photosensitive material used in the present invention may have any composition, such as silver chloride, silver chlorobromide, silver iodobromide, silver iodobromochloride, etc.
It is preferable that 40 mol% consists of silver chloride, and more preferably 70 mol% or more consists of silver chloride. The content of silver iodide is 5 mol% or less, more preferably 1 mol% or less. In the present invention, the soluble silver salt and the soluble halogen salt may be reacted by any method such as a one-sided mixing method, a 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. A silver halide emulsion with nearly uniform grain size can be obtained. Although the silver halide grains in the photographic emulsions used in the present invention can have a relatively wide grain size distribution, it is preferred that they have a narrow grain size distribution, particularly in terms of weight or number of silver halide grains. It is preferable that the size of the grains accounting for 90% is within ±40% of the average grain size (such an emulsion is generally called a monodisperse emulsion). The silver halide grains used in the present invention are preferably fine grains (eg, 0.7 μm or less), particularly preferably 0.4 μm or less. Silver halide grains in photographic emulsions may have regular crystals such as cubes and octahedrons, or irregular crystals such as spheres and plates. , or may have a composite form of these crystal forms.
It may also consist of a mixture of particles of various crystalline forms. The silver halide grains may have a uniform phase inside and on the surface, or may have a simple phase. Two or more types of silver halide emulsions formed separately may be mixed and used. The silver halide emulsion used in the present invention contains cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, or iron salts or A complex salt thereof may also be present. The soluble salts are usually removed from the emulsion after precipitation or physical ripening, and the long-known Nudel water washing method, which involves gelatinizing gelatin, may be used. 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. 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 methods are known as methods for chemical sensitization of silver halide emulsions, and any of these methods can be used alone or in combination for chemical sensitization. Good too. Regarding these, see the above-mentioned book by Glafkides or Zelikman et al. or Die Grundlagen der edited by H. Frieser.
Photographischen Prozesse mit
Silberhalogeniden (Akademische
Verlagsgesellschafr, 1968). Among the noble metal sensitization methods, the gold sensitization method is a typical method and uses a gold compound, mainly a gold complex salt. There is no problem in containing complex salts of noble metals other than gold, such as platinum, palladium, and iridium. Specific examples thereof are described in US Pat. No. 2,448,060, British Patent No. 618,061, etc. As the sulfur sensitizer, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thiourea salts, 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. 3150313, and No. 3656955. As the reduction sensitizer, stannous salts, amines, formamidine sulfinic acid, silane compounds, etc. can be used, and specific examples thereof are described in the U.S. patent.
No. 2487850, No. 2518698, No. 2983609, No. 2983610,
Described in No. 2694637. The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. These sensitizing dyes may be used alone or in combination, 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. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Disclosure, Vol. 176, 17643 (1978).
Published in December 2017), page 23, Section J. Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, but other hydrophilic colloids can also be used. For example, gelatin includes lime-processed gelatin,
Acid-treated gelatin may be used, and gelatin hydrolysates and gelatin oxygen-decomposed products may also be used. In the present invention, a polyalkylene oxide compound having a molecular weight of 600 or more can be used for the purpose of further improving halftone dot quality. The polyalkylene oxide compound used in the present invention is an alkylene oxide having 2 to 4 carbon atoms, such as ethylene oxide, propylene-1,2
- oxide, such as butylene-1,2-oxide, preferably ethylene oxide.
Polyalkylene oxide consisting of units, water,
aliphatic alcohols, aromatic alcohols, fatty acids,
It includes condensates with compounds having at least one active hydrogen atom, such as organic amines and hexitol derivatives, and block copolymers of two or more types of polyalkylene oxides. That is, as polyalkylene oxide compounds, specifically, polyalkylene glycols, polyalkylene glycol alkyl ethers, polyalkylene glycol aryl ethers, 〃 〃 (alkylaryl) ethers, polyalkylene glycol esters, polyalkylene glycol aliphatic amides, polyalkylene Glycolamines, polyalkylene glycol block copolymers, polyalkylene glycol graft polymers, and the like can be used. The molecular weight needs to be 600 or more. The number of polyalkylene oxide chains is not limited to one in the molecule, and two or more may be included. In this case, the individual polyalkylene oxide chains may consist of less than 10 alkylene oxide units, but the total number of alkylene oxide units in the molecule must be at least 10. If there is more than one polyalkylene oxide chain in the molecule, each of them may consist of different alkylene oxide units, such as ethylene oxide and propylene oxide. The polyalkylene oxide compound used in the present invention is preferably 14 or more.
Contains up to 100 alkylene oxide units. Specific examples of the polyalkylene oxide compounds used in the present invention are as follows. Polyalkylene oxide compound example-1 HO (CH ₂ CH ₂ O) ₉₀ H −2 C ₄ H ₉ O (CH ₂ CH ₂ O) ₁₅ H −3 C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₅ H − 4 C ₁₈ H ₃₇ O (CH ₂ CH ₂ O) ₁₅ H −5 C ₁₈ H ₃₇ O (CH ₂ CH ₂ O) ₄₀ H −6 C ₈ H ₁₇ CH=CHC ₈ H ₁₆ O (CH ₂ CH ₂ O ) _15H −10 C ₁₁ H ₂₃ COO (CH ₂ CH ₂ O) ₈₀ H −11 C ₁₁ H ₂₃ COO (CH ₂ CH ₂ O) ₂₄ OCC ₁₁ H ₂₃ −13 C ₁₁ H ₂₃ CONH (CH ₂ CH ₂ O) ₁₅ H −15 C ₁₄ H ₂₉ N(CH ₂ )(CH ₂ CH ₂ O) ₂₄ H −20 HO(CH ₂ CH ₂ O) _a (CH ₂ CH ₂ CH ₂ CH ₂ O) _b (CH ₂ C
H ₂ O) _c H a+c=30, b=14 -24 HO (-CH ₂ CH ₂ O-) ₃₄ H and other polyalkylene oxide compounds described in JP-A-50-156423, JP-A-52-108130 and JP-A-53-3217 can be used. can. These polyalkylene oxide compounds may be used alone or in combination of two or more. When these polyalkylene oxide compounds are added to a silver halide emulsion, they are added as an aqueous solution of an appropriate concentration or dissolved in a water-miscible low-boiling organic solution at an appropriate time before coating, preferably. , the emulsion can be added after chemical ripening. It may be added to non-photosensitive hydrophilic colloid layers, such as intermediate layers, protective layers, filter layers, etc., instead of being added to the emulsion. In the present invention, when polyalkylene oxide is used, the amount of polyalkylene oxide used can be made smaller than usual, so that the quality of halftone dots can be further improved without causing uneven development. For example, the compound of general formula () of the present invention is used in combination in an amount of 20 to 150 mg per mole of silver halide. The photosensitive material of the present invention includes a photosensitive material manufacturing process,
Various compounds can be contained for the purpose of preventing fog during storage or photographic processing or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole)
mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinthione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4
-hydroxy-substituted (1,3,3a,7)tetrazaindenes), pentaazaindenes, etc.; benzenetheosulfonic acid, benzenesulfinic acid,
Many compounds known as antifoggants or stabilizers can be added, such as benzenesulfonic acid amides and the like. The light-sensitive materials used in the present invention include, for example, water-soluble materials (for filtering or anti-irradiation purposes, such as oxonol dyes, hemioxonol dyes, merocyanine dyes, etc.), hardeners (such as chromium salts, aldehyde agents, N
-methylol compounds, dioxane derivatives, active vinyl compounds, active halogen compounds, etc.), surfactants (for example, various known nonionic, anionic, cationic, amphoteric surfactants), etc. The developer used in the present invention does not contain any auxiliary developing agent (for example, 1-phenyl-3-pyrazolidones or p-aminophenols) or
The amount of dihydroxybenzenes as the main developing agent is kept at 0.05 to 0.5 mol/(especially 0.1
~0.4 mol/), the free sulfite ion concentration is 0.25 mol/or more, and 5
- or 6-nitroindazole in an amount of 20 mg or more, and a sufficient amount of alkali to adjust the pH to 10.5 or higher (particularly 11.5 or higher).
Among these, it is preferable to use dihydroxybenzenes (especially hydroquinone) alone without containing an auxiliary developing agent. This developing solution makes it possible to rapidly obtain extremely high contrast photographic properties using the light-sensitive material of the present invention, and is extremely stable since it can develop with a large amount of sulfite ions. In the above, examples of the dihydroxybenzene-based developing agent include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydrohydroquinone,
Examples of 1-phenyl-3-pyrazolidone-based developing agents include methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dimethylhydroquinone, and 1-phenyl-3-pyrazolidone.
4,4-dimethyl-1-phenyl-3-pyrazolidone, 4-hydroxymethyl-4-methyl-1-
Examples include phenyl-3-pyrazolidone, 4,4-dihydroxymethyl-1-phenyl-3-pyrazolidone, etc., and p-aminophenol, N-methyl-p-aminophenol, etc. are used as p-aminophenol developing agents. . A compound that provides free sulfite ions, such as sodium sulfite, potassium sulfite, potassium metabisulfite, and sodium bisulfite, is added to the developer as a preservative. In the case of an infectious developer, sodium formaldehyde bisulfite may be used, which provides almost no free sulfite ions in the developer. As the alkaline agent for the developer used in the present invention, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, sodium acetate, tribasic potassium phosphate, diethanolamine, triethanolamine, etc. are used. It is preferable that the developer that can be used in the present invention contains the same type of polyalkylene oxide as described above as a development inhibitor. For example, molecular weight 1000~
10000 polyethylene oxide etc. 0.1~10
It can be contained within a range of g/g/. It is preferable to add nitrilotriacetic acid, ethylenediaminetetraacetate acid, triethylenetetraamine hexaacetate acid, diethylenetetraamine pentaacetate acid, etc. as a water softener to the developer that can be used in the present invention. 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 fixer may also contain a complex of ethylenediaminetetraacetic acid and trivalent iron ions as an oxidizing agent. Processing temperature and processing time are set appropriately, but usually18
Processing temperatures of .degree. C. to 50.degree. C. are suitable, while rapid processing of 15 to 120 seconds using so-called automatic processors is preferred. The present invention will be explained in more detail with reference to Examples below. The photosensitive material of the present invention obtains characteristics of extremely high contrast that are effective in reproducing halftone images and line drawings by processing the photosensitive material containing the compound represented by the general formula () with a developer having the above-mentioned specific composition. Furthermore, the developing solution is stable, so it has the excellent advantage of being able to be used for a long period of time. Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1 A silver nitrate aqueous solution and a mixed aqueous solution of sodium chloride and potassium bromide were simultaneously added at a constant rate for 30 minutes to a gelatin aqueous solution with a pH of 4.0 kept at 50°C to obtain a 0.3μ silver chlorobromide agent (30 moles of Br). %) was prepared. This emulsion was washed with water in a conventional manner to remove soluble salts, and then chemical sensitization was performed by adding sodium thiosulfate and potassium chloroaurate. These silver chlorobromide emulsions were divided, comparative compounds and compounds of the present invention were added as shown in Table 1, and 5-[3-(4-sulfobutyl) was added as a sensitizing dye to each.
-5-chloro-2-oxazolidylidene]-1-
Hydroxyethoxyethyl-3-(2-pyridyl)
-2-thiohydantoin was added, and then 4-
Hydroxy-6-methyl-1,3,3a,7-tetrazaindene, dispersion of polyethyl acrylate, 2-hydroxy-4,6-dichloro-1,
After addition of 3,5-triazine sodium salt, 4 g/m ² of silver was deposited on the cellulose triacetate film.
I applied it as desired. After exposing these films through a sensitometric exposure wedge using a 150-line magenta contact screen, they were exposed to light using a developer solution with the following composition.
℃ for 30 seconds, stopped, fixed, washed with water, and dried. (Developer composition) Potassium bromide 2.0g Potassium hydroxide 25g Potassium carbonate 35g Potassium sulfite 80g Hydroquinone 20g Triethylene glycol 30g Polyethylene glycol (molecular weight 4000) 2.0g 5-nitroindazole 0.1g Add water 1 PH12.0 Results Shown in Table 1. However, in the table, Γ relative sensitivity is the relative value of the reciprocal of the exposure amount that gives a density of 1.5, and the value of sample 1 is taken as 100. The Γ halftone quality is evaluated on a five-level scale by microscopic observation, with "5" representing the best quality and "1" representing the worst quality. "5" or "4" is practical,
"3" is inferior but barely usable, and "2" or "1" is usable. The Γ development unevenness is evaluated by observing the film with the naked eye on a five-level scale, and each numerical value is synonymous with the numerical value for evaluation of halftone dot quality.

[Table] The following is clear from Table 1. Film No. 2, which uses polyalkylene oxide alone, which is well-known as a compound for improving halftone dot quality, tends to cause uneven development and is unsuitable for the rapid processing of the present invention. Furthermore, films 3 to 6 using Comparative Compounds B and C, which have a carboxylic acid group or a sulfonic acid group but whose mother nucleus is different from that of the compound of the present invention, only cause a decrease in sensitivity and cannot achieve ultra-high contrast gamma. . On the other hand, it is said that films 7 to 10 using the compound of general formula () of the present invention can achieve high contrast and halftone dot quality comparable to commercially available lithium film and lithography through rapid processing without causing uneven development. It is clear that it shows excellent effects. Example 2 Compounds -1 and -11 of the present invention were added to the same emulsion as in Example 1 as shown in Table 2, and then coated on a cellulose triacetate film at an Ag concentration of 3.5 g/m. Developer solution A with the composition shown in the table
Developing, fixing, washing with water, and drying were carried out at 38°C using G. Furthermore, in order to compare the stability of the developer,
After aging for several days, the film was developed in the same manner. Comparison of halftone dot quality was conducted at the same sensitivity with development performed every 5 seconds.

[Table] As is clear from Table 2, it is clear that C, which is a preferred developer in the present invention, exhibits very good halftone image quality. Developer solution D contains 0.2g/1-phenyl-3-pyrazolidone as an auxiliary developing agent.
However, it is clear that the halftone dot quality is inferior to that of developer C. Further, since the developer E has a high sulfite ion concentration, the developer sensitivity decreases significantly after aging for 4 days, and a stable developer cannot be obtained. Developer F has a lower pH than Developer C, resulting in poorer halftone dot quality than Developer C and longer development time.
Furthermore, in developer G, 5-methylbenzotriazole was used instead of 5-nitroindazole, and the halftone dot quality was not as good as developer C. Therefore, it is clear from Table 2 that favorable results are sometimes obtained with developer C as a stable developer which provides good halftone image quality in a short development time.

【table】

[Table] Example 3 Compounds of the general formula () of the present invention -4, -5, -10, - under the same conditions as in Example 1 of the present invention
Experiments were conducted using 13, -16, -17, and -21. The results are shown in Table 4. As is clear from Table 4, sample No. 7 of the present invention
~24 showed good results.

【table】

Claims (1)

[Scope of Claims] 1. What has at least one silver halide emulsion layer on a support and contains a compound represented by the following general formula () in the emulsion layer or other hydrophilic colloid layer? After exposing the photographic material to light,
Dihydroxybenzene-based developing agent from 0.05 to 0.5
mol/contains auxiliary developing agent from 0 to 0.05g/
Contains 0.25 mol/or more of free sulfite ions, and 20% of 5- or 6-nitroindazole.
1. An image forming method characterized by processing with a developer containing alkali in an amount of at least mg/mg/ml and a sufficient amount to raise the pH to 10.5 or more. General formula () In the formula, R ¹ represents a substituted or unsubstituted alkyl group having 10 or less carbon atoms, or a substituted or unsubstituted aryl group; R ² and R ³ each independently represent a hydrogen atom,
halogen atom, carboxyl group, sulfonic acid group,
Represents an aliphatic group or an aromatic group having 10 or less carbon atoms. However, at least one of R ¹ , R ² or R ³ shall contain a carboxyl group or a sulfonic acid group.