JPH0456967B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a silver halide photographic light-sensitive material, and particularly to a silver halide photographic light-sensitive material containing a compound that releases a development inhibitor during a development process. (Background Art) Hydroquinone derivatives (so-called DIR-hydroquinone), which release a development inhibitor in response to the image density during development, have been used as compounds that release photographically effective groups in response to the image density during development. )
It has been known. Examples of DIR-hydroquinone include U.S. Pat. No. 3,379,529; U.S. Pat. No. 3,620,746;
U.S. Patent No. 4377634, U.S. Patent No. 4332878, JP-A-Sho
Compounds described in, for example, No. 49-129536 are known. DIR-Hydroquinone, as known from the above patents, can control image tone, make images finer, improve image sharpness, improve color reproduction, etc.
It is used for the purpose of obtaining the so-called DIR effect. In order for DIR-hydroquinone to exhibit sufficient activity during development processing, the following points are important. First, DIR-hydroquinone either undergoes a cross-oxidation reaction with the oxidized form of the developing agent or auxiliary developing agent generated during development, or directly reduces silver halide and becomes an oxidized form at a sufficiently high rate. is necessary. Second, it is necessary that the release of photographically useful groups from the oxidized product of DIR-hydroquinone thus produced be rapid and efficient. Regarding the first point of view, in order to increase the rate at which DIR-hydroquinone is oxidized, it is necessary to
It is generally thought that this problem can be solved by lowering the oxidation potential of hydroquinone. However, if the oxidation potential is reduced, "Journal of American Chemical Society" Vol. 60, 20841
(1938), during storage, the rate of autooxidation due to oxygen in the air also increases, so from this point of view it is difficult to achieve both stability during storage. Furthermore, in order to prevent this autoxidation, the phenol moiety of hydroquinone is often protected. Such protection can be obtained when the pH of the developer is high, when the specific accelerating effect of the processing solution composition as described in JP-A-59-197037 can be ideally utilized, or when the processing time is short. It can be used effectively if it is very long. However, such protection generally requires one or more reaction steps and a number of reactions for DIR-hydroquinone to show activity, so a certain amount of time is required from the start of development to the onset of activity. In many cases, this is not desirable in order to show activity. On the other hand, with regard to the second aspect, experiments conducted by the present inventors have revealed that the hitherto known DIR-hydroquinone described in the above patent is insufficient. (Objects of the Invention) The first object of the present invention is to provide a silver halide photographic light-sensitive material containing a photographic reagent that promptly releases a development inhibitor after being oxidized in a development process. A second object of the present invention is to improve photographic performance such as image tone control, image graininess, image sharpness, storage stability, and color reproducibility by containing the above-mentioned novel photographic reagent. An object of the present invention is to provide a silver halide photographic light-sensitive material. (Structure of the Invention) The present inventors investigated various substituents of DIR-hydroquinone, and surprisingly found that
It has been found that a significant improvement in activity is achieved only when an electron-withdrawing group is introduced at the 2-position relative to the released inhibitor. In other words, only when there is a potential-withdrawing group at the 2-position with respect to the released inhibitor, the rate at which the inhibitor is released from the oxidized form of DIR-hydroquinone is 100 times higher than when there is no electron-withdrawing group. It turned out that the speed was more than several thousand times faster than before. As a result of further research, the present inventors found that DIR-hydroquinone, which has an electron-withdrawing group at the 2-position with respect to the released inhibitor, has an unexpectedly high acid resistance against oxygen in the air. It was also found that there was an increase in chemical resistance. As a result, DIR-hydroquinone, which has an electron-withdrawing group at the 2-position with respect to the released inhibitor,
It was found that sufficient stability can be obtained even when the phenol moiety is protected, if necessary, or even without protection. The present invention was completed based on these discoveries, and includes a compound represented by the following general formula [] that releases a development inhibitor imagewise after being oxidized, into a silver halide emulsion layer or other materials. This is a silver halide photographic material containing silver halide in a hydrophilic colloid layer. General formula [] In the formula, A and A' may be the same or different and each represents hydrogen or a protecting group for a phenolic hydroxyl group that can be deprotected during a photographic processing step. In this case, during the photographic processing step is during or before development, and examples of protecting groups for phenolic hydroxyl groups include acyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthiocarbonyl group, arylthiocarbonyl group, Examples include an alkylaminocarbonyl group and an arylaminocarbonyl group, and may also be a protecting group known in JP-A-59-197037. R ¹ and R ² may be the same or different, each with σp of the fit.
Represents a substituent of up to 0.3, such as hydrogen or an alkyl group (preferably one with up to 30 carbon atoms,
For example, methyl group, ethyl group, t-butyl group, t-
octyl group, sec-octyl group, n-pentadecyl group, n-octyl group, etc.), aryl group (phenyl group, naphthyl group, etc.), alkoxy group (preferably up to 30 carbon atoms, such as methoxy group,
ethoxy group, n-octyloxy group, etc.), aryloxy group (phenoxy group, naphthyloxy group, etc.), alkylthio group (preferably up to 30 carbon atoms, such as methylthio group, n-butylthio group, sec-butylthio group, n-octylthio group,
n-dodecylthio group, etc.), arylthio group (such as phenylthio group), acylamido group (preferably one having up to 30 carbon atoms, such as an acetamide group, propionamide group, benzamide group, etc.), sulfonamide group (preferably up to 30 carbon atoms) a ureido group (preferably one having up to 30 carbon atoms, such as a methylureido group ^, phenylureido group, hexylureido group); and R ² , R ¹
and A, R ² and A' may be bonded to each other to form a non-aromatic ring. Examples of those in which R ¹ and R ² combine to form a non-aromatic ring include the following.

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] Examples of compounds in which R ¹ and A or R ² and A' combine to form a non-aromatic ring include the following. (combines with phenolic oxygen)

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] In addition, these R ¹ and R ² further include a halogen atom, an alkyl group, an aryl group, an alkoxy group,
Cyano group, carboxy group, formyl group, amide group, carbamoyl group, sulfonamide group, sulfamoyl group, acyloxy group, nitro group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, amino group, imino group, nitroso group, alkenyl may be substituted with one or more arbitrary substituents such as a group, an alkynyl group, a heterocycle, an alkylthio group, an arylthio group, a ureido group, a sulfonyl group, a sulfo group, etc. Preferred R ¹ and R ² other than hydrogen atoms are as follows. When R ¹ and R ² do not form a ring, preferably an alkyl group, an alkylthio group, an alkoxy group,
It is an acylamido group or a sulfonamide group, and more preferably an alkyl group, an alkylthio group, or an alkoxy group. When R ¹ and R ² combine with each other to form a non-aromatic ring, preferably,

【formula】

【formula】

【formula】

[Formula] or

[Formula], more preferably,

[Formula] or

[Formula], most preferably

[Formula]. EGW represents an electron-withdrawing group with a Hammett's σp value exceeding 0.3. An example of EWG is
trifluoromethyl group, cyano group, formyl group,
Examples include acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, sulfonyl group, sulfamoyl group, sulfinyl group, and particularly preferred are alkoxycarbonyl group, aryloxycarbonyl group (-COOH-R ⁴ ), and carbamoyl group.

[Formula] Sulfamoyl base

[Formula] is a sulfonyl group (-SO ₂ ^-R4 ). (More preferably as EWG, −CO ₂ R ⁴ ,

[Formula] or

[Formula] Yes, most preferably

[Formula] or

[Formula]) Here, R ⁴ , R ⁵ , and R ⁶ are hydrogen atoms or alkyl groups (preferably those having 1 to 30 carbon atoms, such as methyl, ethyl, n-butyl, n-octyl, isopropyl group, cyclohexyl group, tetradecyl group, etc.), aryl group (phenyl group, naphthyl group, etc.), and R ⁵ and R ⁶ may be the same or different, and are bonded to each other to form a nitrogen-containing group. It may also form a heterocycle. Also, R ⁴ , R ⁵ ,
R ⁶ may be further substituted with one or more arbitrary substituents as in the case of R ¹ and R ² . X is a group of a development inhibitor that is released after the compound of the general formula [] is oxidized in the development process and does not substantially undergo any change in activity even when it comes into contact with a developer, and specifically is -S-R ³ , a substituted or unsubstituted benzotriazole residue (e.g. 1
-benzotriazolyl group) or a substituted or unsubstituted tetrazole residue (for example, 1-tetrazolyl group). In the above, R ³ represents a substituted or unsubstituted 5-membered, 6-membered, or fused heterocyclic group, and these may be fused with a benzene nucleus or a naphthalene nucleus. A specific example of X is given below. (expressed in the form after release) 1-phenyl-5-mercaptotetrazole,
1-(4-hydroxyphenyl)-5-mercaptotetrazole, 1-(3-hydroxyphenyl)-
5-mercaptotetrazole, 1-(4-carboxyphenyl)-5-mercaptotetrazole,
1-(3-carboxyphenyl)-5-mercaptotetrazole, 1-(4-sulfophenyl)-5-
Mercaptotetrazole, 1-(4-sulfamoylphenyl)-5-mercaptotetrazole,
1-(3-hexanoylamidophenyl)-5-mercaptotetrazole, 1-{3-(3-methylureido)phenyl}-5-mercaptotetrazole, 1-(2-diethylaminoethyl)-5-mercaptotetrazole, 1-(2-dimethylaminoethyl)-5-mercaptotetrazole, 1-ethyl-5-mercaptotetrazole, 1-(2-
carboxyethyl)-5-mercaptotetrazole, 1-(2-hydroxyethyl)-5-mercaptotetrazole, 2-methylthio-5-mercapto-1,3,4-thiadiazole, 2-(2-carboxyethyl)-5- Mercapto-1,3,4
-thiadiazole, 2-(4-sulfobutyl)-5
-Mercapto-1,3,4-thiadiazole, 2
-mercapto-1,3-benzoxazole, 2
-mercapto-1,3-benzimidazole, 2
-mercapto-1,3-benzothiazole, 3-
Mercapto-4-phenyl-1,2,4-triazole, 2-mercapto-1-phenylimidazole, 2-methyl-5-mercapto-1,3,4
-thiadiazole, benzotriazole, 5-methylbenzotriazole, 5,6-dimethylbenzotriazole, 5-chlorobenzotriazole, 5-bromobenzotriazole, 5-nitrobenzotriazole, 5-carboxybenzotriazole, 4,5,6- Trichlorobenzotriazole, 4,5,6,7-tetrachlorobenzotriazole, 5-octyloxybenzotriazole, 5-acetamidobenzotriazole, 5-
(2,2,2-trichloroethoxycarbonyl)
benzotriazole, 1-phenyl-2-tetrazoline-5-thione, etc. In order to describe the content of the present invention more specifically, compounds represented by the general formula [] will be specifically shown below, but the compounds that can be used in the present invention are not limited to these specific examples. Synthesis Example 1 Synthesis of Compound-1 2-Hydroxy-
3-Methyl-5-formylbenzoic acid was synthesized.
Organic Synthesis coll.vol.
2,5-dihydroxy-3-methylbenzoic acid was synthesized according to the method described on page 759. Next, 100 g of 2,5-dihydroxy-3-methylbenzoic acid was dissolved in the ethanol from Step 3, and heated under reflux for 8 hours while blowing hydrogen chloride gas. After the reaction was completed, ethanol was distilled off to obtain 2,5-dihydroxy-3-methylbenzoic acid ethyl ester. 8.0 g of this ester was dissolved in 30 ml of ethyl acetate and stirred. Then, 12 g of anhydrous sodium sulfate and 23 g of silver oxide were added to this solution. After 30 minutes, inorganic substances were filtered off. For this filtrate, 1-phenyl-5-
A solution of 4 g of mercaptotetrazole and paratoluenesulfonic acid monohydrate dissolved in 20 ml of tetrahydrofuran was added. After reacting at room temperature for one hour, the solvent was distilled off and the main component was separated using column chromatography to obtain Compound-1. Yield 6.0g Melting point 147°C Synthesis Example 2 Synthesis of Compound-3 4g of 2,5-dihydroxy-3-methylbenzoic acid ethyl ester and 3.1g of 5,6-dimethylbenzotriazole were dissolved in acetonitrile and stirred. To this was added 4.2 g of potassium carbonate, and then 20.7 g of silver oxide was added little by little. After the reaction was completed, excess sodium hydrosulfite was added as an aqueous solution and stirred vigorously. Next, the acetonitrile was distilled off, and the mixture was extracted with ethyl acetate, followed by a conventional method to obtain Compound-3, which was recrystallized from methanol-water. Yield 2.4g Melting point 200-202℃ Synthesis Example 3 Synthesis of Compound-7 22.2g and 17.1g of n-octylhydroquinone
KOH was dissolved in water, and dimethyl sulfuric acid was added dropwise thereto. An additional 11.4g of KOH when the pH becomes acidic
was added, and dimethyl sulfate was added dropwise again. After completion of the reaction, extraction with ethyl acetate and evaporation of the solvent yielded 2,5-
Dimethoxyoctylbenzene was obtained. Next, 2,5-dimethoxyoctylbenzene 25.0
g was dissolved in dichloromethane, 27 g of aluminum chloride was added, and the mixture was stirred. The mixture was cooled to 5° C. and 12.2 g of ethyl isocyanate was slowly added dropwise. The temperature was gradually increased to room temperature, and after reacting at room temperature for 8 hours, the reaction solution was poured into ice and extracted with dichloromethane. After evaporating the solvent and separating it from the raw material using column chromatography,
2,5-dimethoxy-4-n-octylbenzoic acid ethylamide was obtained. Next, 25.8 g of this compound was dissolved in 1,2-dichloroethane, 26 g of aluminum chloride was added, and the mixture was heated under reflux for 4 hours, cooled, and poured into ice water. After separating the dichloroethane layer from the aqueous layer, the dichloromethane was distilled off. When separated by column chromatography, 2,
5-dihydroxy-4-n-octylbenzoic acid ethylamide was obtained. 14.7 g of this hydroquinone compound was dissolved in ethyl acetate and stirred. 10g anhydrous sodium sulfate and 34.5
g of silver oxide was added and reacted for 40 minutes. After filtering out inorganic substances, 9.8 g of 1-phenyl-5-mercaptotetrazole and 10.5 g of p-toluenesulfonic acid were extracted.
g of tetrahydrofuran solution. After reacting for 1 hour, the solvent was distilled off and the main product was separated by column chromatography to obtain Compound-7. Yield 7.3g Melting point 120-122℃ Synthesis Example 4 Synthesis of Compound-27 Gentisic acid ethyl ester 24.6g and 5,6-
15.5 g of dimethylbenzotriazole was dissolved in acetone. 69.0 g of silver oxide was added to this and stirred. The reaction was checked by TLC, and after the reaction was completed, inorganic substances were filtered off. The obtained compound is 2-(5,6
-dimethylbenzotriazol-1-yl)-3
-ethoxycarbonyl-p-benzoquinone. Dissolve 19.7g of this compound in acetonitrile
3.3 g of cyclopentadiene was added and reacted at room temperature. After the reaction was completed, a catalytic amount of triethylamine was added and the mixture was further stirred to precipitate compound-27 as crystals. It was recrystallized from acetonitrile.
Yield 10.1 g, melting point 221°C (decomposed) Synthesis Example 5 Synthesis of Compound-34 12.4 g of 3,6-dihydroxy-4-ethylcarbamoylbenzonorbornene was dissolved in ethyl acetate, and 12 g of anhydrous sodium sulfate and 35 g of silver oxide were added. After 30 minutes, the mixture was filtered, and an ethyl acetate solution of 0.9 g of p-toluenesulfonic acid and 9.8 g of 1-phenyl-5-mercaptotetrazole was added thereto. After reacting for 1 hour at room temperature, most of the solvent was distilled off, and n
- When hexane and a small amount of ethyl acetate were added, compound-34 precipitated as crystals. Ethyl acetate-n
- Recrystallized from hexane. Yield 36% Melting point 182-183°C Synthesis Example 6 Synthesis of compound-39 Dissolve 28.3 g of 4-bromo-3,6-dimethoxybenzonorbornene in tetrahydrofuran and -78
Cooled to ℃. To this was added dropwise 60.6 ml of a 1.7 molar solution of n-butyllithium. 3-30 minutes after completion of dripping
A solution of 32.7 g of (2,5-di-t-pentylphenoxy) propyl isocyanate in THF was slowly added dropwise to the reaction mixture at -78°C for 1 hour, and the temperature was reduced to 0°C for removal. After reacting at 0℃ for 2 hours, add ice to the reaction solution.
When THF is distilled off and extracted with ethyl acetate, 4-{3-
(2,5-di-t-pentylphenoxy)propylcarbamoyl-3,6-dimethoxybenzonorbornene was obtained. Next, 26.0 g of this compound was dissolved in dry acetonitrile and 45 g of sodium iodide was added thereto. 33 g of trimethylchlorosilane are added dropwise to this solution at room temperature. This mixture was heated under reflux for 35 hours, cooled, water was added, acetonitrile was distilled off, and the mixture was extracted with ethyl acetate. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and then briefly purified by silica gel column chromatography to obtain 4-{3-(2,5-di-t-pentylphenoxy) in which only methyl ether had been cleaved. ) Propylcarbamoyl-3,6-dihydroxybenzonorbornene was obtained. Melting point: 142℃ Next, 6.2g of this compound was dissolved in ethyl acetate,
10 g of anhydrous sodium sulfate and 8.7 g of silver oxide were added and stirred. After reacting for 30 minutes, inorganic substances were filtered off.
Next, 2.2 g of 1-phenyl-5-mercaptotetrazole and a catalytic amount of a THF solution of para-toluenesulfonic acid were added to this solution, and the mixture was reacted at room temperature for one hour.
After the reaction was completed, the solvent was distilled off and the main product was carefully separated using flash column chromatography to obtain Compound-39. Yield 3.2g, yield 37.9%,
Melting point 157-158℃. Synthesis Example 7 Synthesis of compound-45 2-(2-methylthio-1,3,4-thiadiazol-5-ylthio)-4-t-octyl-p
- 4 g of benzoquinone were dissolved in 50 ml of acetic acid-ethyl acetate 1:1 solution. Next, an excess amount of sodium p-toluenesulfinate was added to this solution, and the mixture was heated to room temperature.
Time reacted. Next, the solvent was distilled off, and the residue was purified by silica gel chromatography. Melting point: 207-209°C Synthesis Example 8 Synthesis of Compound-51 A small amount of chloroform was added to 50 g of 3,6-dimethoxybenzonorbornene, and the mixture was stirred under ice-water cooling.
To this was slowly added 65 ml of chlorosulfonic acid. After reacting at 0°C for 1 hour, the reaction solution was poured onto ice. This was extracted with diethyl ether, dried over anhydrous sodium sulfate, and then the diethyl ether was distilled off to obtain 4-chlorosulfonyl-3,6-dimethoxybenzonorbornene. Yield: 58% Next, 15 g of this compound was dissolved in acetonitrile, and 10 g of triethylamine and 11 g of n-tetradecylamine were added in this order under ice-water cooling. After reacting for 1 hour, water was added, extracted with ethyl acetate, and dried over anhydrous sodium sulfate. The oily residue after evaporation of the solvent was dissolved in 80 ml of dichloromethane, and this solution was dissolved in boron tribromide 28
g and dichloromethane (140 ml) was slowly added dropwise. After reacting for 2 hours, the reaction solution was poured into ice water and extracted with ethyl acetate. After the solvent was distilled off, n-hexane was added to the oil to crystallize it. Yield 14.3g
Obtained 4-tetradecylsulfamoyl-
8g of 3,6-dihydroxybenzonorbornene
10 g of anhydrous sodium sulfate and 10.1 g of silver oxide were dissolved in 150 ml of ethyl acetate, and after reaction for 40 minutes, inorganic substances were removed by vacuum filtration. 20ml of concentrated hydrochloric acid for the filtrate
was added and stirred vigorously. After 20 minutes, 100 ml of water was added and the mixture was separated. The ethyl acetate layer was washed with aqueous sodium bicarbonate and then dried over anhydrous sodium sulfate. After filtering off the inorganic substances, 10 g of anhydrous sodium sulfate was added again, followed by 10 g of silver oxide. After 20 minutes, inorganic substances were filtered off, the solvent was distilled off, and n-hexane was added to precipitate yellow crystals. Yield: 6.5 g 1.5 g of the obtained chloroquinone was dissolved in ethyl acetate, 0.6 g of 1-phenyl-5-mercaptotetrazole was added, and the mixture was reacted for 1 hour. Next, an excess amount of sodium hydrosulfite aqueous solution was added to this solution and stirred vigorously. After the reaction was completed, the layers were separated, the ethyl acetate layer was washed with water, the solvent was distilled off, and the resulting oil was purified by column chromatography to obtain Compound-51. Melting point: 111-114°C The compound of the general formula [] of the present invention is cross-oxidized by a redox reaction with the oxidized developing agent produced in an imagewise manner during development, releases a development inhibitor in an imagewise manner, and transforms into a colorless oxidized product. It is estimated that
The development-inhibiting substance released in an imagewise manner suppresses development in an imagewise manner, resulting in finer particles of the image, softening of the tone of the image, improvement of image sharpness, improvement of color reproduction, etc.
Showing DIR effect. As described below, the DIR compound of the present invention has extremely high activity compared to conventional DIR hydroquinone, and exhibits surprising effects even when added in small amounts. The compounds of the present invention are added in the silver halide emulsion layer, in the hydrophilic colloid layer provided above or below the emulsion layer, or in both layers to achieve the intended purpose. The amount added varies depending on the type of photographic material, but is generally preferably in the range of 1 x 10 ^-7 mol to 1 x 10 ^-1 mol per mol of silver halide. Conventional methods are applicable for addition to silver halide emulsion layers and/or other hydrophilic colloid layers. That is, a water-soluble compound may be dissolved in water or added as it is to an aqueous gelatin solution. For compounds that are insoluble or sparingly soluble in water, a method may be used in which the compound is dissolved in a water-miscible solvent and mixed with an aqueous gelatin solution, or the method described in, for example, US Pat. No. 2,322,027. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (such as acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (e.g. tributyl trimesate) etc., or boiling point approx.
Organic solvent at 30°C to 150°C, such as ethyl acetate,
After being dissolved in a lower alkyl acetate such as butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination. The compound of the general formula [] of the present invention can be emulsified and dispersed in combination with a reducing substance such as hydroquinone and its derivatives, catechol and its derivatives, aminophenol and its derivatives, ascorbic acid and its derivatives, and the like. Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as the photosensitive silver halide in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. The average grain size of the silver halide grains in the photographic emulsion (the grain size is the grain diameter in the case of spherical or approximately spherical grains, the ridge length in the case of cubic grains,
Expressed as an average based on the projected area. ) is not particularly limited, but is preferably 3μ or less. The grain size distribution can be narrow (so-called "monodisperse" emulsions) or wide. Silver halide grains in photographic emulsions may have regular crystal structures such as cubes, octahedrons, tetradecahedrons, and rhombidodecahedrons, or may have irregular crystal structures such as spherical, plate-like, etc. (irregular) It may have a crystalline form, or it may be a composite form of these crystalline forms. It may also consist of a mixture of particles of various crystalline forms. Further, an emulsion may be used in which ultratabular silver halide grains having a grain diameter of five times or more the grain thickness occupy 50% or more of the total projected area. Details are described in the specifications of JP-A-58-127921 and JP-A-58-113927. The silver halide grains may have different phases inside and on the surface. Further, the particles may be particles in which the latent image is mainly formed on the surface, or may be particles in which the latent image is mainly formed inside the particles. The photographic emulsion used in the present invention is written by P. Glafkides.
Chimie et Physique Photographique (Paul
Montel Publishing, 1967), GFDuffin
Photographic Emulsion Chemistry (The Focal
Press, 1966), VLZelikman et al.
Making and Coating Photographic Emulsion
(The Focal Press, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good. 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 of keeping pAg constant in the liquid phase in which silver halide is produced, that is,
A so-called controlled double jet method may also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained. Two or more types of silver halide emulsions formed separately may be mixed and used. During the process of silver halide grain formation or physical ripening, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or their complex salts, rhodium salts or their complex salts, iron salts or iron complex salts, metals or their complex salts, etc., coexist. You may let them. Even if silver halide emulsions are chemically image sensitive,
It doesn't have to be done. For chemical sensitization, see for example "Die Grundlagen der" edited by H. Frieser.
Photographischen Prozesse mit
Silberhalogeniden” (Akademische
Verlagsgesellschaft.1968) pages 675-734 can be used. That is, a sulfur sensitization method using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds) reduction sensitization method;
Noble metal compounds (e.g., gold complex salts, Pt, It, etc.)
A noble metal sensitization method using complex salts of metals in the periodic table group such as Pd can be used alone or in combination. 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, tetrazaindenes (especially 4-hydroxy substituted (1,3,
3a, 7) Tetraazaindenes), pentaazaindenes, etc.; Known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc., and many compounds can be added. 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. The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholins, and quaternary ammonium salts for the purpose of increasing sensitivity, increasing contrast, or accelerating development. compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like. 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. 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. 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.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of Imidazole nuclei, quinoline nuclei, etc. can be applied.
These nuclei may be substituted on carbon atoms. Merocyanine dyes or composite merocyanine dyes include nuclei with a ketomethylene structure such as pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thioxazoline-2,4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, etc. can be applied. The photographic emulsion layer of the photographic light-sensitive material prepared using the present invention contains a dye-forming coupler, that is, an aromatic primary amine developer (e.g., phenylene diamine derivative, aminophenol derivative, etc.) in the color development process. A compound capable of developing color through oxidative coupling may also be used. For example, magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, and yellow couplers include acylacetamide couplers (e.g., benzoylacetanilide, pivaloylacetanilide),
Examples of cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusible and have a hydrophobic group called a ballast group in their molecules, or are polymerized. The coupler may be either 4-equivalent or 2-equivalent to silver ions. In addition, colored couplers have the effect of color correction,
Alternatively, it may be a coupler (so-called DIR coupler or DAR coupler) that releases a development inhibitor or development accelerator during development. In addition to the DIR coupler, the coupling reaction product is colorless and may contain a colorless DIR coupling compound that releases a development inhibitor. In addition to the DIR coupler, the light-sensitive material may contain a compound that releases a development inhibitor during development. Of course, two or more types of the above-mentioned couplers and the like can be used in the same layer in order to satisfy the characteristics required of a photosensitive material, or the same compound can be added to two or more different layers. 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. As the binder or protective colloid that can be used in the emulsion layer or hydrophilic colloid layer (e.g., protective layer, intermediate layer) of the light-sensitive material 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 sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid,
polyacrylamide, polyvinylimidazole,
A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers such as polyvinylpyrazole. In addition, lime-treated gelatin, acid-treated gelatin, enzyme-treated gelatin, etc. can be used. Various other additives may be used in the silver halide photographic material of the present invention. For example, brighteners, dyes, desensitizers, coating aids, antistatic agents, plasticizers, slipping agents, matting agents, development accelerators, mordants,
UV absorbers, anti-fading agents, anti-fogging agents, etc. For more information on these additives, please refer to Research Disclosure (RESEARCH).
DISCLOSURE) No. 176, pages 22-31 (RD-17643)
(Dec., 1978) can be used. Any known method can be used to photographically process the silver halide photographic material of the present invention. A known treatment liquid can be used. 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. Depending on the purpose, either a development process that forms 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 developer used in black-and-white photographic processing can contain conventionally known developing agents.
Examples of developing agents include dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone), aminophenols (e.g. N-methyl-p-aminophenol), 1-phenyl-3-pyrazoline. Ascorbic acid, and heterocyclic compounds such as those described in US Pat. No. 4,067,872 in which a 1,2,3,4-tetrahydroquinoline ring and an indolene ring are condensed can be used alone or in combination. The developer generally contains other known preservatives,
Contains alkaline agents, PH buffering agents, anti-fogging agents, etc., and further contains solubilizing agents, color toning agents, development accelerators, surfactants, antifoaming agents, water softeners, hardening agents, viscosity imparting agents, etc. May include. 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. When forming a dye image, conventional methods can be applied. For example, negative-positive method (for example, “Journal of the
Society of Motion Picture and Television
Engineers, Vol. 61 (1953), pp. 667-701), developed in a developer containing a black and white developing agent to produce a negative silver image, followed by at least one uniform exposure or other suitable exposure. Perform fog treatment,
The color reversal method, in which a dye-positive image is obtained by subsequent color development, and the silver dye bleaching method, in which a photographic emulsion layer containing a dye is exposed and developed to create a silver image, and this is used as a bleaching catalyst to bleach the dye, etc. . Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylenediamines (e.g., 4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N-diethylaniline, 4-amino- N-ethyl-N-β
-Hydroxyethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfamide ethylaniline,
4-amino-3-methyl-N-ethyl-N-β-
methoxyethylaniline, etc.) can be used. Other Photography by LFAMason
Processing Chemistry (Focal Press, 1966)
pages 226-229, U.S. Patent No. 2193015, U.S. Patent No. 2592364
JP-A No. 48-64933, etc. may be used. Color developers may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates and phosphates, development inhibitors or antifoggants such as bromides, iodides and organic antifoggants. can. If necessary, water softeners, preservatives such as hydroxyamines, organic solvents such as benzyl alcohol and diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, competitive couplers, fogging agents such as sodium borohydride, auxiliary developers such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, polycarboxylic acid chelating agents as described in U.S. Pat. No. 4,083,723, and as described in OLS No. 2,622,950. It may also contain antioxidants and the like. After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Bleach agents include iron (), cobalt (), chromium (), and copper ().
Compounds of polyvalent metals such as, peracids, quinones, nitroso compounds, etc. are used. For example, ferricyanides, dichromates, organic complexes of iron () or cobalt (), such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-
Aminopolycarboxylic acids such as 2-propanoltetraacetic acid; complex salts of organic acids such as citric acid, tartaric acid, and malic acid; persulfates, permanganates; nitrosophenols, and the like can be used. Of these, potassium ferricyanide, sodium ferric ethylenediaminetetraacetate, and ammonium ferric ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid iron() complexes are useful in both stand-alone bleach solutions and single bath bleach-fix solutions. For bleaching or bleach-fixing solutions, U.S. Patent 3042520
No. 3241966, Special Publication No. 1972-8506, Special Publication No. 1973
- Drifting accelerator described in No. 8836, etc., JP-A-53-
In addition to the thiol compound described in No. 65732, various additives can also be added. The compound of the general formula [] of the present invention can be applied to various silver halide photographic materials. An example is given below. (1) For example, the compound of the present invention has a layer of silver chlorobromide or silver chloroiodobromide emulsion containing at least 60% silver chloride and 0 to 5% silver iodide (the emulsion must be monodispersed). (preferably), and is effective for improving (lengthening) the halftone gradation and halftone dot quality of a silver halide photosensitive material for photolithography containing polyalkylene oxides without deteriorating them. In this case, the compound of the invention preferably contains from 1×10 ^-7 mol to 1× mol per mol of silver halide.
It is used in an amount of 10 ^-1 mol, especially in the range of 1 x 10 ^-6 mol to 1 x 10 ^-2 mol. Further, to the polyalkylene oxide compound used here, either a silver halide photographic material, a developer, or both a silver halide photographic material and a developer may be added. The polyalkylene oxide compound has 2 or more carbon atoms.
a polyalkylene oxide of at least 10 units, preferably of ethylene oxide, such as ethylene oxide, propylene-1,2-oxide, butylene-1,2-oxide, etc.; and water, aliphatic alcohol, aromatic alcohol. , fatty acids, organic amines,
It includes condensates with compounds having at least one active hydrogen atom such as hexitol derivatives, block copolymers of two or more types of polyalkylene oxides, and the like. Specifically, polyalkylene oxide compounds include polyalkylene glycols, polyalkylene glycol alkyl ethers, polyalkylene glycol aryl ethers, polyalkylene glycol (alkylaryl) esters, polyalkylene glycol esters, and polyalkylene glycols. Fatty acid amides, polyalkylene glycol amines, polyalkylene glycol block copolymers, polyalkylene glycol graft polymers, and the like can be used. As for the molecular weight, those having a molecular weight of 500 to 10,000 are preferably used. Specific examples of polyalkylene oxide compounds preferably used in the present invention are as follows. Polyalkylene oxide compound example 1 HO (CH ₂ CH ₂ O) ₉ H 2 C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₅ H 3 C ₈ H ₁₇ CH=CHC ₈ H ₁₆ O (CH ₂ CH ₂ O) _15H 5 C ₁₁ H ₂₃ COO (CH ₂ CH ₂ O) ₈₀ H 6 C ₁₁ H ₂₃ CONH (CH ₂ CH ₂ O) ₁₅ H 8 C ₁₄ H ₂₉ N(CH ₂ )(CH ₂ CH ₂ O) ₂₄ H a+b+c=50 b:a+c=10:9 These polyalkylene oxide compounds may be used alone or in combination of two or more. When the above polyalkylene oxide compound is added to a silver halide photographic light-sensitive material, it is added in an amount of 5 x 10 ^-4 g to 5 g, preferably 1 x 10 ^-3 g to 1 g, per mole of silver halide. Can be added to the material. In addition, when adding the above polyalkylene oxide compound to the developer, 0.1g to 10g per developer
It can be added to the developer in an amount within the range of g. (2) The compound of the general formula [] of the present invention is also applicable to US Pat. No. 4,224,401, US Pat.
Same No. 4311781, No. 4272606, No. 4221857, Same No.
4243739, 4272614, 4269929, etc., a network of photographic light-sensitive materials having a monodispersed silver halide emulsion layer capable of forming ultra-high contrast negative images with a stable developer due to the action of a hydrazine derivative. It is effective for improving (lengthening) the gradation without deteriorating the halftone dot quality. In the above, a stable developer is one that contains at least 0.15 mol/sulfite ion as a preservative and has a pH of
Refers to a developer of 10.0 to 12.3. This developer can contain a large amount of preservatives, so it can be used as a normal lith developer (which can only contain a very small amount of sulfite ions).
Since it has a relatively low pH, it is less susceptible to air oxidation and is more stable than the developer (PH=12.8) of the high-contrast image forming system described in, for example, US Pat. No. 2,419,975. In this case, the compound of general formula [] of the present invention is preferably 1×10 -5 mol to 1×10 ⁻⁵ mol per mol of silver halide.
It is used in an amount of 8×10 ⁻² mol, particularly in the range of 1×10 ⁻⁴ mol to 5×10 ⁻² mol. The hydrazine derivative used above is represented by the following general formula []. General formula [] R ₁ -NHNH-G-R _2In the formula, R ₁ represents an aliphatic group or an aromatic group, and R ₂ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group ,
represents a substituted or unsubstituted alkoxy group or a substituted or unsubstituted aryloxy group,
G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group, or an N-substituted or unsubstituted imino group. In the general formula [], the aliphatic group represented by R ₁ preferably has 1 to 30 carbon atoms, particularly a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Here, the branched alkyl group may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Further, it may have a substituent such as an alkyl group, an aryl group, an alkoxy group, a sulfoxy group, a sulfonamide group, or a carbonamide group. In the general formula [], the aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group. Examples include a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrorazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, and a benzothiazole ring, among which those containing a benzene ring are preferred. Particularly preferred as R ₁ is an aryl group. The aryl group or unsaturated heterocyclic group of R ₁ may be substituted, and typical substituents include a linear, branched or cyclic alkyl group (preferably one having 1 to 20 carbon atoms), an aralkyl group (preferably a monocyclic or bicyclic alkyl group having 1 to 3 carbon atoms), an alkoxy group (preferably a carbon number of 1 to 20), a substituted amino group (preferably an alkyl group having 1 to 20 carbon atoms) an acylamino group (preferably having 2 to 30 carbon atoms), a sulfonamide group (preferably having 1 to 30 carbon atoms), and a ureido group (preferably having 1 to 30 carbon atoms). things to have), etc. In the general formula [], the alkyl group represented by R ₂ is preferably an alkyl group having 1 to 4 carbon atoms and having a substituent such as a halogen atom, a cyano group, a carboxy group, a sulfo group, an alkoxy group, or a phenyl group. may have. In the general formula [], among the groups represented by R ₂ , the optionally substituted aryl group is a monocyclic or bicyclic aryl group, and includes, for example, a benzene ring. This aryl group may be substituted with, for example, a halogen atom, an alkyl group, a cyano group, a carboxyl group, a sulfo group, or the like. Among the groups represented by R ₂ in the general formula [], the optionally substituted alkoxy group has 1 to 8 carbon atoms.
is an alkoxy group, which may be substituted with a halogen atom, an aryl group, etc. 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 , preferable ones are:
When G is a carbonyl group, it is a hydrogen atom, a methyl group, a methoxy group, an ethoxy group, or a substituted or unsubstituted phenyl group, with a hydrogen atom being particularly preferred. When G 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 is a phosphoryl group, R ₂ is preferably a methoxy group, an ethoxy group, a butoxy group, a phenoxy group, or a phenyl group, with a phenoxy group being particularly preferred. When G is a sulfoxy group, preferable R ₂ is a cyanobenzyl group, methylthiobenzyl group, etc. When G is an N-substituted or unsubstituted imino group, preferable R ₂ is a methyl group, an ethyl group, a substituted or unsubstituted imino group, etc. It is a phenyl group. R ₁ or R ₂ in the general formula [] may have a ballast group commonly used in immobile photographic additives such as couplers incorporated therein. A ballast group is a group having 8 or more carbon atoms and is relatively inert to photography, and includes, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group, etc. You can choose from. R ₁ or R ₂ in the general formula [] may have a group incorporated therein to enhance adsorption to the silver halide grain surface. Examples of such adsorption groups include groups described in US Pat. No. 4,385,108, such as a thiourea group, a heterocyclic thioamide group, a mercapto heterocyclic group, and a triazole group. G in the general formula [] is most preferably a carbonyl group. Specific examples of the compounds represented by the general group [] are shown below. However, the present invention is not limited to the following compounds. −58 n−C ₁₂ H ₂₅ −NHNHCHO The synthesis method of these compounds is disclosed in Japanese Patent Application Laid-Open No. 53-20921.
No. 53-20922, No. 53-66732, No. 53-
It is described in issues such as No. 20318. In the present invention, when a compound represented by the general formula [] is contained in a photographic light-sensitive material,
It is preferably contained in the silver halide emulsion layer, but it may be contained in other non-photosensitive hydrophilic colloid layers (eg, protective layer, intermediate layer, filter layer, antihalation layer, etc.). Specifically, when the compound used is water-soluble, it is prepared as an aqueous solution, and when it is poorly water-soluble, it is prepared as a solution of water-miscible organic solvents such as alcohols, esters, and ketones, and as a hydrophilic colloid solution. It can be added to. When added to the silver halide emulsion layer, it may be added at any time from the start of chemical ripening to before coating, but it is preferably added between after the end of chemical ripening and before coating. In particular, it is preferable to add it to a coating solution prepared for coating. The content of the compound represented by the general formula [] of the present invention depends on the grain size of the silver halide emulsion, the halogen composition, the method and degree of chemical sensitization, the relationship between the layer containing the compound and the silver halide emulsion layer, It is desirable to select the optimum amount depending on the type of antifoggant compound, etc., and testing methods for selection are well known to those skilled in the art. Usually, it is preferably used in a range of 10 ^-6 mol to 1 x 10 ^-1 mol, particularly 10 ^-5 to 4 x 10 ^-2 mol, per mol of silver halide. (3) The compound of the general formula [] of the present invention can be applied to a multilayer, multicolor photographic material having at least two different spectral sensitivities on a support, mainly for the purpose of improving graininess. Multilayer natural color photographic materials usually have at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as necessary.
The preferred layer arrangement order is from the support side to red sensitivity,
Sensitive to green, sensitive to blue, or sensitive to blue, red, and green from the support side. Further, each of the above-mentioned emulsion layers may be composed of two or more emulsion layers having different sensitivities, and a non-photosensitive layer may be present between two or more emulsion layers having the same sensitivity. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. The compounds of this invention can be used in combination with a coupler and added to the same emulsion layer as the coupler, or can be added as a separate emulsified dispersion to a photographic auxiliary layer such as an interlayer. The photographic developer of the present invention is especially effective when used in a green-sensitive emulsion layer containing a 2-equivalent magenta coupler or a red-sensitive emulsion layer containing a cyan coupler. The compound of the present invention has a content of 0.1 to 50% relative to the coupler in each light-sensitive layer, such as the yellow coupler in the blue-sensitive layer, the magenta coupler in the green-sensitive layer, or the cyan coupler in the red-sensitive layer in a color light-sensitive material. It is preferable to use mol %, preferably 0.3 to 15 mol %. Also, 1×10 ^-5 mol to 8×10 ^-2 per mol of silver halide in the layer to be added.
It is preferable to use moles, especially 1×10 ⁻⁴ mol to 5×10 ⁻² mol. Such color photographic materials also exhibit excellent photographic performance in terms of sharpness, multilayer effect, and the like. (4) The compound of the general formula [] of the present invention is a layer of silver iodobromide or silver chloroiodobromide emulsion containing 0 to 50 mol% of silver chloride and up to 15 mol% of silver iodide. It is effective for improving the photographic performance such as sharpness of black and white photographic materials, especially X-ray photographic materials, which have the following on one or both sides of the support. In this case, the amount used is 1×10 ^-6 per mole of silver halide.
Mol ~ 1 x 10 ^-1 mol, especially 1 x 10 ^-5 mol ~ 5 x
A range of 10 ^-2 moles is preferred. The compound of the general formula [] of the present invention can be applied to photographic materials for various uses such as those for electron beams, black and white for high resolution, black and white for diffusion transfer, color X-ray, and color for diffusion transfer. (Effects of the Invention) The compound of the general formula [] of the present invention has high activity, and therefore rapidly releases a development inhibitor upon oxidation.
Therefore, by adding only a small amount, you can control the tone of the image, make the image finer, improve the sharpness of the image,
It can provide DIR effects such as improved color reproduction. Furthermore, the photographic developer of the present invention is stable even in silver halide photographic light-sensitive materials and does not deteriorate storage stability, so it can be used with confidence. (Example) Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. The preparation of emulsions used in Examples 1 to 3 and the compositions of processing solutions are summarized below. Preparation of emulsion (A) A silver nitrate aqueous solution and a mixed aqueous solution of potassium iodide and potassium bromide were simultaneously added to an aqueous gelatin solution kept at 50°C using a double-jet method while keeping the pAg at 7.5 to obtain highly monodisperse silver iodobromide. An emulsion was prepared. The silver iodobromide grains obtained are cubic, with an average grain size of
It had a silver iodide content of 2 mol%. This emulsion was washed with water in a conventional manner to remove soluble salts, and then chemical sensitization was performed by adding sodium thiosulfate. Preparation of Emulsion (B) The emulsion (B) was prepared by adding and mixing the silver nitrate aqueous solution and the halogen salt aqueous solution at 60°C and in the presence of potassium hexachloroiridate () corresponding to 4 × 10 ^-7 mol per mol of silver. A monodisperse silver chlorobromide emulsion was obtained in the same manner as in A), and further washed with water and chemically sensitized in the same manner as in emulsion (A). The prepared silver chlorobromide particles were cubic, had an average particle size of 0.28 μm, and had a silver chloride content of 30 mol%. Preparation of Emulsion (C) A monodisperse silver chlorobromide emulsion was prepared by adding and mixing a silver nitrate aqueous solution and a halogen salt aqueous solution at a pAg of 7.8 simultaneously to an aqueous gelatin solution kept at 50°C using a double jet method. This emulsion was washed with precipitation in a conventional manner to remove soluble salts, and then chemically sensitized by adding sodium thiosulfate in the same manner as in emulsion (A). The silver chlorobromide grains of the emulsion thus obtained were cubic, with an average grain size of 0.30 μm and a silver bromide content of 30 mol %. Preparation of emulsion (D) The emulsion (D) was prepared by adding and mixing a silver nitrate aqueous solution and a halide aqueous solution in the presence of rhodium ammonium chloride corresponding to 5 × 10 ^-6 mol/mol silver to form silver chlorobromide grains. A monodisperse silver chlorobromide emulsion (average grain size 0.30 μm, silver bromide content 30 mol %) was prepared in the same manner as in C). After washing this emulsion with water in the same manner as in the case of emulsion (C), it was chemically sensitized by adding sodium thiosulfate and potassium chloroaurate. Developer composition (E) Hydroquinone 4.0g 4,4-dimethyl-1-phenyl-3-pyrazolidone 0.4g Anhydrous sodium sulfite 75g Sodium hydrogen carbonate 7.0g Disodium ethylenediaminetetraacetate 1.0g Potassium bromide 6.0g 5-methyl-benzo Add triazole 0.6g water and adjust the pH to 12.0 with potassium hydroxide. Developer composition (F) Hydroquinone 40.0g 4,4-dimethyl-1-phenyl-3-pyrazolidone. 4g Sodium hydroxide 13.0g Anhydrous potassium sulfite 90.0g Potassium phosphate 74.0g Disodium ethylenediaminetetraacetate 1.0g Potassium bromide 6.0g 5-methylbenzotriazole 0.6g 1-diethylamino-2,3-dihydroxypropane 17.0g Water Add 1 and adjust the pH to 11.4 with potassium hydroxide. Example 1 Emulsion (D) contains 4-hydroxy-6-methyl-1,
3,3a,7-tetrazaindene, polyethyl acrylate dispersion, polyethylene glycol (average molecular weight 1000), 1,3-bisvinylsulfonyl-2-propanol, sensitizing dye (a) and compound of general formula [] -9, and then the compound of the general formula [] of the present invention, the amount of silver coated on the cellulose triacetate film was 3.50 g/m ² and the amount of gelatin coated was 2.00 g/m ² . Coat an aqueous solution containing coating aids such as surfactants and thickeners whose main component is gelatin on the side far from the support. Coat the samples (101 to 112) at the same time so that the amount of gelatin is 1.10 g/ ^m2 . Created. Furthermore, samples (113 to 116) were prepared using exactly the same formulation except that the compound of general formula [] was replaced with comparative compounds (b) to (e). The film thus obtained was passed through a sensitometric exposure wedge, and then passed through a gray scanner negative contact screen manufactured by Dainippon Screen Co., Ltd.
After exposure using No. 2150L, development was performed at 38° C. for 30 seconds with a developer having developer composition (E), followed by fixing, washing with water, and drying. The results obtained are shown in Table 1.

[Table] In Table 1, the halftone dot quality is visually evaluated in five stages, with "5" representing the best quality and "1" representing the poorest quality. Only "5" and "4" are practically usable as halftone dot originals for plate making. The halftone gradation is the difference between the logarithmic value of the exposure amount that gives a blackened area of 5% and 95% of the halftone dot, respectively, and the larger the difference, the softer the halftone gradation. As is clear from Table 1, by using the compound represented by the general formula [] of the present invention,
Better halftone dot quality and softer halftone gradation can be obtained than when compounds other than those of the present invention are used. Example 2 Emulsion A contains 4-hydroxy-6-methyl-1,
3,3a,7-tetrazaindene, polyethylene acrylate dispersion, polyethylene glycol (average molecular weight 1000), 1,3-bisvinylsulfonyl-2-propanol, sensitizing dye (a) or (i')
After adding the compound of the general formula [] and potassium iodide, and then adding the compound of the general formula [] of the present invention, the amount of coated silver was 3.50 g/m ² and the amount of gelatin coated was 2.00 on the cellulose triacetate film. g/ ^m2
Furthermore, an aqueous solution containing coating aids such as surfactants and thickeners containing gelatin as the main component was simultaneously coated on the side far from the support so that the amount of gelatin was 1.10 g/m ² . (201-208) were produced. The film thus obtained was passed through a sensitometric exposure wedge, and then passed through a gray scanner negative contact screen manufactured by Dainippon Screen Co., Ltd.
After exposure using No.2150L, developer composition (E) or
It was developed with developer (F) at 38°C for 30 seconds, fixed, washed with water, and dried. The obtained results are shown in Tables 2-1 and 2-2. Sensitizing dye (a): the same compound as described in Example 1

【table】

[Table] The values of halftone gradation shown in Tables 2-1 and 2-2 are as described in Example 1, the blackened area of halftone dots 5
It is the difference between the logarithm of the exposure that gives % and 95%,
The larger the difference, the softer the halftone gradation. As is clear from Tables 2-1 and 2-2,
By using the compound represented by the general formula [ ] of the present invention, a softer halftone gradation can be obtained than when it is not used. Comparing Example 1 and Example 2, it was found that the tone softening effect of the compound of the present invention was remarkable in both cases, although the degree of softening effect was observed depending on the emulsion composition, nucleating agent, and type of processing liquid. It turns out that it is. Example 3 Samples (301 to 310) were added to emulsion (B) or (C) in the same manner as described in Example 1 (using sensitizing dye (a) and compound-9 of general formula []). Created. After exposing this in the same manner as in Example 1, 38
It was developed at ℃ for 30 seconds, fixed, washed with water, and dried. The results obtained are shown in Table 3. As described in Example 1, the halftone gradation values shown in Table 3 are the differences in the logarithmic values of the exposure doses that give 5% and 95% blackened areas of the halftone dots. As is clear from Table 3, by using the compound represented by the general formula [] of the present invention,
It was found that even if the halogen composition of the silver chlorobromide emulsion was different, the effect of softening the halftone tone was remarkable.

[Table] Example 4 In order to evaluate the effectiveness of the compound of the present invention, a multilayer color photosensitive material 401 was prepared, consisting of each layer having the following composition on transparent triacetylcellulose provided with an undercoat layer. The amount of emulsion coated was expressed as the amount of silver coated. (Sample 401) (1) Emulsion layer Negative silver iodobromide emulsion Silver iodide 5 mol% Average grain size 0.6 μ...1.6 g/m ² Coupler C-1...0.9 g/m ² Compound of the present invention (-39) ...0.09g/m ² tricresyl phosphate
Gelatin layer ( ² ) containing ...0.6 g/m2 Protective layer Gelatin ...2.5 g/ ^m2 Sodium 2,4-dichloro-6-hydroxy-s-triazine ...0.13 g/ ^m2 (Sample 402~ 405) Sample 402 and
and created 403. In addition, samples 404 and 404 were treated in the same manner as sample 401 except that the comparative compounds (b) and (c) were substituted in equimolar amounts in place of the compound of the present invention (-39) in sample 401.
405 was created. These samples were subjected to imagewise exposure for sensitometry, with one kept under forced aging conditions (45°C 80% for 3 days) (B condition) and one without (A condition), and subjected to the next color development process. I did it. The density of the obtained developed sample was measured using a red filter. The photographic performance obtained is summarized in Table 4. The development used here was carried out at 38°C as described below. 1 Color development...3 minutes 15 seconds 2 Bleaching...6 minutes 30 seconds 3 Washing...3 minutes 15 seconds 4 Fixing...6 minutes 30 seconds 5 Washing...3 minutes 15 seconds 6 Stability... 3 minutes 15 seconds The composition of the treatment liquid used in each step is as follows. Color developer Sodium nitrilotriacetate 1.0g Sodium sulfite 4.0g Sodium carbonate 30.0g Potassium bromide 1.4g Hydroxyamine sulfate 2.4g 4-(N-ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate Add 4.5g water 1 Bleach solution Ammonium bromide 160.0g Aqueous ammonia (28%) 25.0cc Ethylenediamine-tetraacetic acid sodium iron salt
130.0g Glacial acetic acid 14.0cc Add water 1 Fixing solution Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175.0cc Sodium bisulfite 4.6g Add water 1 Stabilizing solution Formalin 8.0cc Add water In addition 1

【table】

From Table 4, sample 401 using the compound of the present invention
-403, it is clear that there is almost no change in photographic performance before and after forced deterioration compared to samples using conventional compounds. Example 5 A multilayer color photosensitive material (501) was prepared on a transparent triacetyl cellulose film support, each layer having the composition shown below. 1st layer: Anti-halation layer Gelatin layer containing black colloidal silver ……0.15g/m ² Ultraviolet absorber U-1 ……0.08g/m ² Same U-2 ……0.12g/m ² 2nd layer: Medium Interlayer 2,5-di-t-pentadecylhydroquinone
……0.18g/m ² Gelatin layer containing coupler C-1 ……0.11g/m ² 3rd layer: 1st red-sensitive emulsion layer Silver iodobromide Silver iodide 4 mol% Average grain size 0.4μ ……1.2 g/ ^m2 Sensitizing dye... 1.4×10 ^-4 mol per 1 mol of silver Same... 0.4 x 10 ^-4 mol per 1 mol of silver Same... 5.6 x 10 ^-4 per 1 mol of silver Mol Same... 4.0×10 ^-4 mol per mole of silver Coupler C-2...0.45g/m ² Coupler C-3...0.035g/m ² Coupler C-4...0.025g/ ^m2 Gelatin layer 4th layer containing: 2nd red-sensitive emulsion layer Silver iodobromide emulsion Silver iodide 8 mol% Average grain size 0.8μ...1.0g/ ^m2 Sensitizing dye...5.2×10 per mole of silver ^-5 mol Same... 1.5 x 10 ^-5 mol for 1 mol of silver Same... 2.1 x 10 ^-4 mol for 1 mol of silver Same... 1.5 x 10 ^-5 mol for 1 mol of silver Coupler C -2 ...0.050g/ ^m2 Coupler C-5 ...0.070g/ ^m2 Coupler C-3 ...0.035g/ ^m2 Gelatin layer 5th layer: Intermediate layer 2,5-G-t- Gelatin layer containing pentadecylhydroquinone...0.08g/ ^m2 Sixth layer: First green-sensitive emulsion layer Silver iodobromide Silver iodide 4 mol% Average grain size 0.4μ 0.80g/ ^m2 Sensitizing dye...Silver 4.0×10 ^-4 mol per mol Same...3.0×10 ^-5 mol per mol of silver Sensitizing dye...1.0×10 ^-4 mol per mol of silver Coupler C-6...0.45 Gelatin layer containing g/m ² coupler C-7......0.13 g/m ² coupler C-8...0.02 g/m ² coupler C-4...0.04 g/ ^m 2 Seventh layer: second green-sensitive emulsion Layered silver iodobromide silver iodide 8 mol% Average grain size 0.8μ...0.85g/ ^m2 Sensitizing dye...2.7×10 ^-4 mol per mol of silver Same...1.8 per mol of silver ×10 ^-5 mol Same... 7.5 x 10 ^-5 mol per mole of silver Coupler C-6...0.095 g/m ² Coupler C-7... 0.015 g/m ² Eighth layer of gelatin layer: Yellow filter layer Yellow colloidal silver ……0.08g/m ² Gelatin layer containing 2,5-di-t-pentadecylhydroquinone ……0.090g/m ² 9th layer: First blue-sensitive emulsion layer Silver iodobromide emulsion Silver iodide 5 mol% Average grain size 0.3 μ...0.37 g/m ² Sensitizing dye...4.4 x 10 ^-4 mol per mol of silver Coupler C-9...0.71 g/m ² Coupler C-4 ...0.07 g/m ² 10th layer: 2nd blue-sensitive emulsion layer Silver iodobromide emulsion Silver iodide 7 mol % Average grain size 0.9 μ ... 0.55 g/m ² Sensitizing dye ... per mole of silver 3.0×10 ^-4 mol Coupler C-9 ……0.23g/m ² Gelatin layer 11th layer: 1st protective layer Ultraviolet absorber U-1 ……0.14g/m ² Same U-2 ……0.22 Gelatin layer containing g/m ² 12th layer: 2nd protective layer Silver iodobromide emulsion Silver iodide 2 mol % Average grain size 0.07μ ...0.25 g/m ² Polymethacrylate particles (diameter 1.5μ) ...0.10 gelatin layer containing g/m ² In addition to the above composition, each layer contains a gelatin hardening agent H-
1 and a surfactant were applied. Structure of compounds used in examples H-1 _CH2 =CH- _SO2 - _CH2 -CONH( _CH2 ) _2NHCO
−CH ₂ −SO ₂ −CH=CH (Sample 502) Sample 502 was prepared in the same manner as Sample 501 except that 0.008 g/m ² of the compound (-39) of the present invention was applied instead of coupler C-4 in the sixth layer of Sample 501. These samples were exposed to light for sensitometry and subjected to the same color development process as in Example 4. The density of the developed sample was measured using a green filter to obtain photographic data. Further, after exposure through a filter whose density changes stepwise, the color development process was performed, and graininess was measured using a green filter.
Graininess was measured using the conventional RMS method. A 48μ aperture was used for the measurement. These results are shown in Table 5.

[Table] From Table 5, sample 502 using the compound of the present invention
Sample 501 using conventional DIR coupler for comparison
It can be seen that although the sensitivity and gamma are almost the same, the graininess expressed by the RMS value is better. Example 6 Preparation of photosensitive silver halide A silver iodobromide emulsion (iodity content: 2 mol %) with an average grain size of 1.3 μm was prepared from silver nitrate, potassium bromide, and potassium iodide by the usual ammonia method. ,
Gold using chloroauric acid and sodium thiosulfate
Chemical sensitization is performed using a sulfur sensitization method, washing is performed using a conventional precipitation method, and 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene is added as a stabilizer to produce a photosensitive iodine. A silver bromide emulsion was obtained. Preparation of Samples 601 to 619 An emulsion layer obtained by adding the compound represented by the general formula [ ] of the present invention or comparative compounds (b) and (c) to the photosensitive silver halide emulsion prepared by the above method, and an aqueous gelatin solution. Samples coated uniformly and sequentially on both sides of a polyester base coated with a protective layer.
601-619 were prepared. The amount of silver coated at this time was the same on each side, and the total amount of silver coated on both sides was 8.0 g/m ² .
The amount of gelatin applied in the protective layer was 2.6g/ ^m2 .
The coating amount of gelatin in the emulsion layer was 5.2 g/m ² . Both sides of these samples were sandwiched between fluorescent intensifying screens containing calcium tungstate, and an aluminum rectangular wave chart was placed in close contact with them as a subject.
After exposure to X-rays to a density of 1.0, development was carried out at 35° C. for 25 seconds using the following processing method, followed by fixation, washing with water, and drying, and the CTF was measured using a microphotometer. The results obtained are shown in Table 6. (Developer formulation) Potassium hydroxide 29.14g Glacial acetic acid 10.96g Potassium sulfite 44.20g Sodium bicarbonate 7.50g Boric acid 1.00g Diethylene glycol 28.96g Ethylenediaminetetraacetic acid 1.67g 5-methylbenzotriazole 0.06g 5-nitroindazole 0.25g Hydroquinone 30.00g 1-phenyl-3-pyrazolidone 1.50g glutaraldehyde 4.93g Sodium metabisulfite 12.60g Add water to complete 1. As is clear from Table 6, the photographic material to which the compound of the present invention was added had a larger CTF value and improved sharpness compared to the comparative sample to which the compound was not added. In addition, the effect was compared with comparative compounds (b) and (c).
, the utility of the compounds of the present invention is clear.

【table】

[Table] Example 7 A silver halide emulsion consisting of 80 mol% silver chloride, 19.5 mol% silver bromide, and 0.5 mol% silver iodide was prepared by gold sensitization and sulfur sensitization using a conventional method. . Further, gelatin contained in this emulsion was 45% by weight based on silver halide. This emulsion contains 3-
Carboxymethyl-5-[2-(3-ethyl-thiazolinylidene)ethylidene] rhodanine (spectral sensitizer), 4-hydroxy-1,3,3a,7-tetrazaindene (stabilizer), 50% ethylene oxide group After adding polyoxyethylene nonyl phenyl ether containing polyoxyethylene nonyl phenyl ether, the polymer latex described in Preparation Example Formulation 3 of U.S. Pat. No. 3,525,620,
1,2-bis(vinylsulfonylacetamide)
Ethane (hardener) was added at a concentration of 2.6 wt% based on the total dry gelatin (i.e., based on the total dry gelatin including the non-photosensitive upper layer described below), and the compounds of the present invention were added as shown in Table 1. A coating solution for a photosensitive silver halide emulsion layer was prepared by adding the indicated compound as a methanol solution. At the same time, sodium dodecylbenzenesulfonate (surfactant) and polymethyl methacrylate latex (matting agent) with an average particle size of 3.0 to 4.0 μm were added to the 5% gelatin solution to form a non-photosensitive upper layer coating solution. I made it. Next, the photosensitive silver halide emulsion layer coating solution and the non-photosensitive upper layer coating solution were coated onto a polyester terephthalate support by a two-layer simultaneous coating method. The amount of coated silver was 3.0 g/m ² , and the dry film thickness of the non-photosensitive upper layer was 1.0 μm. In this way sample 701
~Created 708. Halftone dot images were formed on these samples by the following method. That is, a commercially available negative gray contact screen (150 lines/inch) was brought into close contact with the sample, exposed to white tungsten light for 10 seconds through a step wedge with a step difference of 0.1, and each sample was then exposed to white tungsten light for 10 seconds using the following developer. The film was developed at 27° C. for 100 seconds, fixed, washed with water, and dried in a conventional manner. Developer composition Sodium carbonate (monohydrate) 50g Formaldehyde-hydrogen sulfite adduct 45g Potassium bromide 2g Hydroquinone 18g Sodium sulfite 2g 5-nitroindazole 3mg Add water 1 The comparative compounds in Table 7 are as follows: was used. (Comparative compound a) 1-phenyl-5-mercaptotetrazole (comparative compound b) 5-methylbenzotriazole (comparative compound c) 2-methylthio-5-mercapto-1,3,4
-Thiadiazole Table 7 shows the results of evaluating the halftone dot quality and halftone gradation. Halftone dot quality is visually evaluated in four stages, with "A" being the best quality, "B" being quality that is practical, and "C" being quality below the practical limit.
"D" represents the worst quality. The halftone gradation is the difference in the logarithmic value of the exposure amount that gives the blackened area of the halftone dots of 5% and 95%, and the larger the difference, the softer the halftone gradation is.

[Table] As is clear from Table 7, the compound of the present invention is extremely effective in softening the halftone gradation without deteriorating the halftone quality. That is,
When the comparative example compounds (a), (b), and (c) are used to soften the halftone gradation by 0.1 or more compared to the case without additives, the halftone quality becomes rank "D", but when the compounds of the present invention are used, When used, the halftone gradation was greatly softened to 0.1 to 0.2 compared to the case without additives, and the halftone dot quality was good with an "A" rank. Example 8 Samples 701, 702, and 703 of Example 7 were exposed and developed in the same manner as in Example 7. However, development is at 27℃.
Three treatments were conducted for 90 seconds, 100 seconds, and 110 seconds. Table 8 shows the results of evaluating the halftone dot quality in five stages. "5" is the best quality, "1" is the worst quality, and "5" to "3.5" is the practical range.

[Table] From Table 8, the halftone dot quality of the sample of the present invention is better than that of the sample without additives at both 5% and 95% halftone dots, and the development time is shorter than the standard development time (100 seconds). It can be seen that the halftone dot quality is good even with long development times, and the development latitude is wide. Example 9 Samples 701, 702 and 703 of Example 7 on a black background
A document with a white line of 50μ width (A) and a white background
A manuscript (B) containing a black line with a line width of 50 μm was exposed to white tungsten light for 10 seconds using a plate-making camera, and then each sample was developed in the same manner as in Example 1. The results are shown in Table 9.

Table 9 shows that the use of the compound of the present invention provides good line width reproducibility for fine lines. This result shows that in an actual plate-making process, the exposure latitude is wide when a document containing a mixture of Mincho characters and Gothic characters is used. Example 10 A hardener 2-hydroxy-4,6-dichloro- was added to a silver halide emulsion consisting of 95 mol% silver chloride, 5 mol% silver bromide and containing 1 x 10 ^-4 mol/mol silver of rhodium. 1x 1,3,5-triazine sodium salt and polyoxyethylene nonyl phenyl ether containing 30 ethylene oxide groups.
10 ^-4 mol/mole of silver was added, and the compounds of the present invention shown in Table 10 were added as a methanol solution as shown in Table 10 to give a silver content of 4.5 g/m ² on a polyethylene terephthalate film. It was applied like this. The film sample prepared in this manner was exposed using a P-607 printer manufactured by Dainippon Screen Co., Ltd. using a manuscript having the structure shown in Fig. 1, and then developed for 20 seconds at 38°C using the following developer. It was fixed, washed with water, and dried by the usual method. Developer composition Potassium bromide 2.0g Potassium hydroxide 20g Potassium carbonate 35g Potassium sulfite 80g Hydroquinone 20g Triethylene glycol 30g Polyethylene glycol 2.0g (Molecular weight 4000) 5-Nitroindazole 0.1g Add water 1 (PH 11.7) Check the results. It is shown in Table 5.

[Table] Here, cutout character image quality 5 in Table 10 means appropriate exposure such that the halftone dot area becomes 50% on the photosensitive material for return using the original as shown in Figure 1. This refers to the image quality at which characters with a width of 30 μm are reproduced, which is a very good quality. On the other hand, cutout character image quality 1 refers to an image quality that can only reproduce characters with a width of 150 μm or more when given the same appropriate exposure, and is poor cutout character quality, with a sensory evaluation of 4 to 2 between 5 and 1. A rank was established. A value of 2 or higher is a practical level. As is clear from Table 10, the compounds of the present invention are
Shows good cutout quality. Here, the cutout characters are the ink marks in the areas where the ink is on the paper in a halftone dot pattern (halftone areas) and the areas where the ink is on the entire surface of the paper (referred to as solid areas). Refers to parts of characters, symbols, etc. that are not included. To be more specific about how to make cut-out characters in the photolithography process, as shown in Figure 1, a transparent or translucent pasting base 3 is used.
(Usually, polyethylene reterephthalate with a thickness of several + μm is used) is pasted with a developed film (halftone dot original) 4 on which halftone dots have been formed, and similarly, so-called line drawings such as letters and symbols are attached to the pasting base 1. A developed film (line drawing original) 2 on which a positive image has been formed is superimposed to form an original, and the emulsion side of the photosensitive material 5 for return is brought into close contact with the halftone image area, and exposed and developed. This is to form blank areas of line drawings in the halftone image. An important point in this process is that the halftone dot image and the line drawing must be subjected to negative/positive image conversion according to their halftone dot area and line width, respectively. For example, a halftone image having a black area of 50% must be accurately converted to a white area of 50%, and a line drawing having a black line width of 50 μm must be accurately converted to a white line width of 50 μm. However, as is clear from FIG. 1, the halftone image is exposed by directly contacting the emulsion surface of the photosensitive material for return, whereas the line image is formed using the halftone dot original 4 (usually having a thickness of about 110 μm). and pasting base 3 (number) for the halftone original
The photosensitive material for return is exposed to light through a film (100 μm thick) in the middle. In other words, the line image is several 100μ
A blurred exposure is applied to the light-sensitive material for return through a transparent or semi-transparent spacer of m. For this reason, if a normal exposure amount (an exposure amount that faithfully converts the halftone dot area from negative to positive) is applied, the white line width of the line image will become narrower due to the effect of blurring exposure. On the other hand, if the exposure amount is reduced in order to reduce the influence of blurred exposure and to faithfully convert the line width of a line image from negative to positive, the halftone dot area becomes thin due to insufficient exposure. Due to these developments, the quality of cut characters tends to deteriorate. Example 11 The following experiment was conducted to compare the release rate and release efficiency of photographically useful groups from oxidants with known compounds for the compounds used in the present invention. Experimental method; 2× for each of samples (a) to (f)
100 ml of a 10 ^-3 mol/methanol solution was prepared.
Next, 4 ml of these solutions were quickly added to a mixture of 20 ml of Britton-Robinson buffer and 16 ml of methanol for reaction. Heterocyclic compound PMT released over time by high performance liquid chromatography ^*
The reaction rate was determined from a separately prepared calibration curve. Under these experimental conditions, the initial stage of the reaction can be regarded as almost a pseudo-first-order reaction, and the pseudo-first-order reaction rate constant k' and half-life τ were calculated and the results are shown in Table 11.

[Table] As can be seen from Table 11, the compounds used in the present invention are compared with those known so far.
It was revealed that the release rate from the oxidant was increased by 10 ² to ^{10 3} times, and the release efficiency was also significantly improved.

[Brief explanation of the drawing]

Figure 1 shows how to make cut-out characters in the photolithography process. 1 is a transparent support, 2 is a developed film (line drawing original), 3 is a transparent or translucent adhesive base, and 4 is a developed film. Processed film (halftone original), 5 represents photosensitive material for return.

Claims (1)

[Scope of Claims] 1. A silver halide emulsion layer having at least one silver halide emulsion layer on a support, and containing a compound represented by the following general formula [] in the emulsion layer or other hydrophilic colloid layer. A silver halide photographic material characterized by: General formula [] In the formula, A and A' represent a hydrogen atom or a protecting group for a phenolic hydroxyl group that can be deprotected during a photographic processing step. R ¹ and R ² may be the same or different, and each represents a hydrogen atom or a group having a σp value of 0.3 or less, and R ¹ and
R ² , R ¹ and A, and R ² and A' may be bonded to each other to form a non-aromatic ring. EGW represents an electron-withdrawing group having a Hammett's σp value greater than 0.3. X is a group of a development inhibitor that is released from the compound of general formula [] in the development process and whose activity is not substantially changed by the developer, and is -S-R ³ (where R ³ represents a nitrogen-containing heterocycle), a substituted or unsubstituted benzotriazole residue, or a substituted or unsubstituted tetrazole residue.