JPH0473861B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to photographic developers, particularly silver halide photographs containing a novel developer which oxidatively releases photographically effective groups during the development process. It relates to photosensitive materials. (Prior art) Hydroquinone derivatives (so-called DIR-hydroquinone) have been used as compounds that release photographically effective groups in accordance with the density of the image during development. )It has been known. Examples of DIR-hydroquinone include U.S. Patent Nos. 3379529 and 3620746;
Compounds described in, for example, No. 129536 are known. DIR-hydroquinone, as known from the above-mentioned patents, is used for the purpose of obtaining so-called DIR effects such as controlling image tone, making images finer, improving image sharpness, and improving color reproduction. However, the above known
DIR-hydroquinone compounds have a low release rate and release efficiency of development-inhibiting groups from oxidants.
DIR-hydroquinone activity is insufficient. Other known examples include JP-A-56
-153342 and JP-A-56-153336, but in these cases, the compound released imagewise is an indazole derivative, and the release rate from the oxidized product is still not sufficient, and furthermore, the compound released imagewise is an indazole derivative. It is known that there are many cases in which derivatives do not exhibit sufficient development inhibiting effects. It has been found that the novel photographic developer of the present invention has unexpectedly excellent performance in overcoming the insufficient activity of DIR-hydroquinone compounds as described above. (Object of the Invention) Therefore, the first object of the present invention is to provide a silver halide photographic light-sensitive material containing a novel photographic developer. A second object of the present invention is to provide a silver halide photographic light-sensitive material containing a photographic developer that promptly releases photographically useful groups after being oxidized in a development process. A third object of the present invention is to provide a silver halide photographic material that contains a novel photographic developer and has improved image tone control, image graininess, image sharpness, and color reproduction. That's true. (Structure of the Invention) The above object of the present invention is to provide at least one
This can be achieved by having two silver halide emulsion layers and containing a compound represented by the following general formula [] in the silver halide emulsion layer or other hydrophilic colloid layer. In the formula, A and A' may be the same or different and represent a hydrogen atom which can be hydrolyzed with an alkali,
X represents an electron-withdrawing group, and PUG represents an optionally substituted mercaptotriazole residue, mercaptotetrazole residue, or 1-benzotriazole residue. Next, general formula [] will be explained in detail. The alkali-hydrolyzable groups represented by A and A' include optionally substituted acyl groups (e.g., chloroacetyl group, dichloroacetyl group, etc.), alkoxycarbonyl groups (e.g., ethoxycarbonyl group, etc.), aryloxy Examples include carbonyl groups (eg, phenoxycarbonyl groups, etc.). Further, X represents an electron-withdrawing group, and examples thereof include [Formula] [Formula] [Formula] -SO ₂ -R ⁵ or [Formula]. Here, R ¹ to R ⁷ may be the same or different and are hydrogen atoms,
Substituted or unsubstituted alkyl group (preferably one carbon number
~30, examples include methyl group, ethyl group, propyl group, allyl group, butyl group, octyl group, dodecyl group, adamantyl group, cyclohexyl group,
methoxyethyl group, hydroxyethyl group, sulfoethyl group, carboxypropyl group, etc.), substitution,
Unsubstituted aryl group (preferably has 1 to 30 carbon atoms, examples include dodecylphenyl group, tolyl group, p-methoxyphenyl group, phenyl group, p-
chlorophenyl group, m-nitrophenyl group, etc.)
Alternatively, it is a substituted or unsubstituted aralkyl group (preferably having 1 to 30 carbon atoms, examples include benzyl group and phenethyl group). Furthermore, PUG in the formula represents a substituted or unsubstituted merptazole residue or a substituted or unsubstituted vedozoriazole residue that can exhibit photographically useful activity after being released, and its action is to inhibit development. . A specific example of PUG is 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-mercaptotetozole, 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-
mercaptetrazole, 1-(2-hydroxyethyl)-5-mercaptotetrazole, benzotriazole, 5-methylbenzotriazole,
5,6-dimethylbenzotriazole, 5-chlorobenzotriazole, 5-bromobenzotriazole, 5-nitrobenzotriazole, 5-carboxybenzotriazole, 4,5,6-trichlorobenzotriazole, 4,5,6,7- Tetrachlorobenzotriazole, 5-phenoxycarbonylbenzotriazole, 5-octyloxybenzotriazole, 5-acetamidobenzotriazole, 5-(2,2,2-trichloroethoxycarbonyl)benzotriazole, 3-mercapto-4 -phenyl-1,2,4-triazole, and the like. Particularly favorable results can be obtained when compounds having water-soluble groups such as carboxyl groups are used in black-and-white light-sensitive materials. Here, mercaptotrizole or mercaptotetrazole is bonded to the naphthalene nucleus via the sulfur atom of the mercapto group, and bonded to the naphthalene nucleus via the nitrogen atom at the 1-position of benzotriazole. Next, specific examples of the compound represented by the general formula [] are listed below, but the compounds are not limited to those shown here. The symbol () represented by the general formula can generally be synthesized by the following two methods. That is, the first is p-toluenesulfonic acid, benzenesulfonic acid, in chloroform, 1,2-dichloroethane, carbon tetrachloride,
This is a method in which a naphthoquinone derivative and a mercaptoazole or benzotriazole derivative are reacted at a temperature between room temperature and 100°C in the presence of an acid catalyst such as trifluoromethanesulfonic acid or methanesulfonic acid. Second, naphthoquinone derivatives substituted with chlorine, bromine, or iodine in an aprotic polar solvent such as acetone, tetrahydrofuran, or dimethylformamide in the presence of a base such as potassium carbonate, sodium hydrogen carbonate, or sodium hydride are useful for photography. This is a method in which compounds are reacted between -20°C and 100°C and the resulting quinone body is reduced with a reducing agent such as diethylhydroxylamine or sodium hydrosulfite. [ReferencesResearch
Disclosure 18227 (1979), Liebigs Ann.Chem
764, 131 (1972)] For the synthesis of naphthochitone derivatives used as raw materials, see, for example, U.S. Patent Nos. 2987334 and 3700453:
UK Patent No. 557750, UK Patent No. 557802: US Patent No.
No. 3043690: Specifications of No. 2616793 and No. 3009958, or Helv Chem Acta., 30 , 578
(1947); J.Org, Chem, 22 , 772 (1957) and the cited references described therein. Some specific synthesis examples of compounds are shown below, and the compounds used in the present invention can be synthesized very easily by applying these methods. Synthesis Example 1 Synthesis of Compound 2 Synthesis of 2-laurylcarbamoyl-1,4-dihydroxynaphthalene (1) Under nitrogen flow, 2-phenoxycarbonyl-
28 g of 1,4-dihydroxynaphthalene was dissolved in 150 ml of acetonitrile, 22.2 g of laurylamine was added dropwise thereto, and the mixture was refluxed for 4 hours. After the reaction is complete, cool and collect the precipitated crystals. yield
26.8g, yield 72% 3-chloro-2-laurylcarbomoyl-
Synthesis of 1,4-naphthoquinone (2) Add 7.4 g of (1) to 100 ml of chloroform and stir. Slowly add 5.7 g of sulfuryl chloride dropwise to this while maintaining the temperature at 5 to 10°C. After the reaction is completed, water is added and the mixture is separated. Take the chloroform solution,
After evaporating the solvent, it is quickly purified by column chromatography using silica gel. Yield 3.4g,
Yield 42% 2-laurylcarbamoyl-3-(1-phenyltetrazol-5-ylthio)-1,4-
Synthesis of naphthoquinone (3) (2), 4 g was dissolved in 70 ml of acetone and 5 ml was added to ice water.
Cool to ℃. Add 2.1 g of 1-phenyl-5-mercaptotetrazole to this, and add anhydrous potassium carbonate.
Add 1.7g and stir for 4 hours. Collect the precipitated crystals. In order to further remove inorganic substances,
Wash with 200 ml of 10% acetic acid and dry. Yield 3.5
g, yield 65% 2-laurylcarbomoyl-3-(1-phenyltetrazol-5-ylthio)-1,4-
Synthesis of dihydroxynaphthalene (compound 2) 8.7 g of sodium hydrosulfite was added to 80
Dissolve in ml of water (3) and add 5.5 g of acetonitrile solution at room temperature. Crystals will precipitate immediately, and these are collected and recrystallized from ethyl acetate. Yield 3.8 g, yield 70% Melting point 138-140°C Synthesis Example 2 Synthesis of Compound 13 Synthesis of 2-phenylsulfonyl-1,4-dihydroxynaphthalene (4) At room temperature, 15.8 g of 1,4-naphthoquinone was dissolved in acetic acid. Dissolve in 100 ml of ethyl/acetic acid = 9:1, and add 24.6 g of sodium benzenesulfinate. After stirring for 5 hours, the precipitated crystals were collected and washed with a small amount of acetone. Yield 22.5g, Yield 75
% Synthesis of 2-phenylsulfonyl-1,4-naphthoquinone (5) (4) 10 g was dissolved in 150 ml of acetone, an excess amount of manganese dioxide was added thereto, and the mixture was refluxed for 3 hours. When the inorganic substances are removed by heating and the solvent is distilled off, (6) is obtained as crystals. Yield 4.5g, yield
45% Synthesis of 2-phenylsulfonyl-3-{1-(3-carboxyphenyl)tetrazol-5-ylthio}-1,4-dihydroxynaphthalene (compound 13) (5) 3g and 1-(3-carboxyphenyl)tetrazol-5-ylthio}-1,4-dihydroxynaphthalene phenyl)-5
- 2.1 g of mercaptotetrazole in ethyl acetate
Dilute to 50ml and heat under reflux for 2.5 hours. Take the precipitated crystals. Yield 3.6g, yield 76%
mp159-197℃ (decomposition) Synthesis Example 3 Synthesis of Compound 19 Synthesis of 2-ethoxycarbonyl-1,4-dihydroxynaphthalene (6) 2-Phenoxycarbonyl-1, under nitrogen stream
28 g of 4-dihydroxynaphthalene was dissolved in ethanol, 20.4 g of sodium ethylate was added thereto, and the mixture was heated under reflux for 5 hours. After cooling, the mixture is made weakly acidic with acetic acid, and then ethanol is distilled off. After adding ethyl acetate and water and performing liquid separation and extraction, purification by silica gel column chromatography yields (6) as crystals. Yield 13g, yield 56% 2-ethoxycarbonyl-3-chloro-1,
Synthesis of 4-naphthoquinone (7) 23 g of (6) was dissolved in 300 ml of chloroform, and sulfuryl chloride 27.4
Slowly drip g. After reacting for 1.5 hours,
Add water and separate and extract. After drying the organic layer over anhydrous sodium sulfate, chloroform was distilled off under reduced pressure. When the residue is quickly purified by column chromatography using silica gel, (7) is obtained as crystals. Yield 8.8g, yield 33% 2-ethoxycarbonyl-3-(5,6-dichlorobenzotriazol-1-yl)-1,
Synthesis of 4-naphthoquinone (8) At room temperature, 5.3 g of (7) was dissolved in 100 ml of acetone, and 4.2 g of 5,6-dichlorobenzotriazole was added thereto. Add another 3 g of anhydrous potassium carbonate and stir vigorously for 5 hours. The precipitated crystals are obtained by filtration under reduced pressure. to remove inorganic matter
Wash well with 10% acetic acid, then wash with a small amount of acetone, and dry. Yield 4.3g, yield 51% 2-ethoxycarbonyl-3-(5,6-dichlorobenzotriazol-1-yl)1,4
-Synthesis of dihydroxynaphthalene (compound 19) 6.2g of sodium hydrosulfite
Dissolve in 80 ml of water and add 3 g of compound (8) in acetonyl solution. Crystals precipitate immediately. The crystals are collected and recrystallized from methanol. Yield 2.1g, yield 70% mp201-202℃ (decomposition) The novel photographic developer of the present invention is disclosed in the U.S. patent
Similar to the DIR hydroquinones described in No. 3379529, etc., it 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 converts into a colorless oxidized product. It is estimated to be. The development inhibiting substance released in an imagewise manner suppresses development in an imagewise manner, and exhibits DIR effects such as making the image finer, softening the image tone, improving image sharpness, and improving color reproduction. Such a DIR compound of the present invention is similar to the conventional DIR compound as described below.
Compared to hydroquinone, it has extremely high activity and shows surprising effects even when added in small amounts. The photographic developer of the present invention can be equally used in light-sensitive materials to be developed in black and white as well as in light-sensitive materials for forming color images. The amount used is not particularly limited, but preferably 10 ^-6 to
1 mol/molAg, particularly preferably 10 ^-5 to
It is in the range of 10 ^-1 mol/molAg. The photographic developer of the present invention can be dispersed and introduced into the photographic layer by a known method. In this case, even if the photographic developer of the present invention is used alone,
Alternatively, two or more types may be used in combination. Further, the photographic developer of the present invention can be used in combination with a coupler and added to the same emulsion layer as the coupler, or can be made into an independent emulsified dispersion and added to a photographic auxiliary layer such as an intermediate layer. The photographic developer of the present invention has the following effects on the poor in each photosensitive 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 photosensitive material. It is preferable to use 0.1 to 50 mol%, preferably 0.3 to 15 mol%. The photographic developer of the present invention can be introduced into the silver halide emulsion layer by known methods, such as the U.S. Pat.
The method described in No. 2322027 is used. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, etc.)
dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate),
benzoic acid esters (e.g. octyl benzoate),
Alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate), trimesates (e.g. tributyl trimesate), etc., or organic solvents with a boiling point of about 30°C to 150°C, e.g. Lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β
- After being dissolved in 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 photographic developer of the present invention can be emulsified and dispersed in combination with reducing substances such as hydroquinone and its derivatives, catechol and its derivatives, aminophenol and its derivatives, and ascoribic acid and its derivatives. 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 photographic emulsion layer of the photographic light-sensitive material used in the present invention contains photosensitive silver halides such as silver bromide, silver iodobromide,
Any of silver iodochlorobromide, silver chlorobromide, and silver chloride may be used. The preferred silver halide is silver iodobromide containing up to 15 mole percent silver iodide. Particularly preferred is silver iodobromide containing from 2 mol % to 12 mol % silver iodide. 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 projected area. ) is not particularly limited, but is preferably 3μ or less. The grain size distribution can be narrow (so-called "monodisperse") or wide. Silver halide grains in photographic emulsions can be regular (cubic, octahedral, tetradecahedral, or rhombidodecahedral). It may have a crystalline form, or it may have an irregular crystalline form such as a spherical or plate-like form, or it may have a composite form of these crystal forms. It is also possible to use an emulsion in which ultratabular silver halide grains with a grain diameter of five times or more the grain thickness occupy 50% or more of the total projected area. 127921, No. 58-113927, etc. Silver halide grains may have different phases inside and on the surface.Also, silver halide grains may have different phases in their interior and surface layer.Also, they may be grains in which latent images are mainly formed on the surface. The photographic emulsion used in the present invention is described by P. Glafkides.
Chimie et Physique Photographique (Paul
Mntel, 1967), by 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. A method in which particles are formed in an excess of silver ions (so-called back-mixing method) can be used. As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called controlled double jet method can 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. In the process of silver halide grain formation or physical thermal formation, 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, gold salts or their complex salts, etc. , may coexist. Silver halide emulsions are usually chemically sensitized.
For chemical sensitization, see, for example, “Die
Grundlagen der Photographischen Prozesse
mit Silberhalogeniden” (Akademische
Verlagsgesellschaft, 1968) pages 675-734 can be used. That is, sulfur sensitization 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, Ir,
A noble metal sensitization method using complex salts of periodic group metals 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. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobezimidazoles, mercaptothiadiazoles, Aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc.; mercaptopyrimidines; mercaptotriazines; thioketo compounds, such as oxadorinthion; azaindenes, e.g. Triazaindenes, tetrazaindenes (especially 4-hydroxy substituted (1,3,3a,
7) etraazaindenes), pentaazaindenes, etc.; known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfonic acid, benzenesulfonic acid amide, etc.
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, polykylene nonionic substances such as glycolalkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, and alkyl esters of sugars. Surfactants; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates Anions containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc., sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphate esters 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 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 having a ketomethylene structure such as pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thioxazolidine-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 ion.
It may also be a colored coupler that has a color correction effect, or a coupler that releases a development inhibitor or development accelerator during development (so-called DIR coupler or DAR coupler). In addition to the DIR coupler, the purified product of the coupling reaction 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-derived couples (such as 2,3-dihydroxydioxane), active vinyl compounds (such as 1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol), active halogen compounds (such as 2 , 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-fog agents, etc. For more information on these additives, please refer to Research Disclosure (RESEARCH).
DISCLOSURE) No. 176, pages 22-31 (RD-17643)
(Dec., 1978) etc. 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 may contain conventionally known developing agents. Examples of developing agents include dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-phenyl-3-pyrozolidone), 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, alkaline agents, PH buffering agents, antifoggants, etc.
In addition, solubilizing agents, color toning agents, development accelerators, surfactants, antifoaming agents, water softeners, hardening agents,
It may also contain a viscosity-imparting agent. 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 (e.g. “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 silver dye bleaching, 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 phenylene diamines (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-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 hydroxylamine, 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, US Pat. No. 4,083,723
It may also contain a polycarboxylic acid chelating agent described in No. 1, an antioxidant described in West German Publication (CLS) No. 2622950, and the like. After color development, the photographic agent 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, ferricyanide, dichromate, organic complex salts of iron () or cobalt (), aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid, or citric acid, Organic complex salts such as tartaric acid and malic acid; persulfates, permanganates; and nitrosophenols can be used. Of these, potassium ferricyanide, sodium ferric ethylenediaminetetraacetate, and ammonium ferric ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid iron() complex salts are useful in both stand-alone bleach solutions and single bath bleach-fix solutions. Bleach or bleach-fix solution has US Patent 3042520
No. 3241966, Special Publication No. 1977-8506, Special Publication No. 1973
- Bleaching accelerator described in No. 8836 etc., JP-A-5-
In addition to the thiol compound described in No. 65732, various additives can also be added. The photographic developer of the present invention can be used in various silver halide photographic light-sensitive materials, and is useful for both black and white, color, etc., and is also useful for general black and white, black and white for printing, and X-ray. It can be applied to silver halide photographic materials for various purposes such as electron beam, high resolution black and white, diffusion transfer black and white, general color, color X-ray, and diffusion transfer color. Since the photographic developer of the present invention is highly active, it is oxidized and rapidly releases a development inhibitor. Therefore, just by adding a small amount, you can control the tone of the image.
It can provide DIR effects such as making images finer, improving image sharpness, and improving 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. Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. Example 1 Preparation of sample 1: 1 kg of silver iodobromide emulsion prepared by a conventional method (silver amount: 0.6 mol, iodine: 8 mol %)
was spectrally sensitized using sensitizing dye I3 x 10 ^-4 mol/silver 1 mol and sensitizing dye I 3 x 10 ^-4 mol/silver 1 mol. 560 g of emulsion B obtained by dissolving 100 g of coupler A, 100 ml of tolyl cresyl phosphate, and 200 ml of ethyl acetate, and emulsifying and dispersing the mixture in 1 kg of 10% gelatin aqueous solution using 4 g of sodium nonylbenzenesulfonate was added to the above spectrally sensitized iodine. Add to 1 kg of silver bromide emulsion and stir, add 2-hydroxy-4,6-dichloro-1,3,5-triazine sodium salt as a hardening agent.
1.4g was added as an aqueous solution. The coating solution thus prepared was coated on a cellulose triacetate film support so that the amount of coated silver was 1.5 g/m ² . On top of this, add 2-hydroxy-4,6-dichloro- to 1 kg of 10% gelatin solution.
2 g of 1,3,5-triazine sodium salt was added and applied as a protective layer to a dry film thickness of 1.5 microns. Preparation of samples 2 to 6: In the case of emulsification of sample 1, compounds 2, 3, 6, (a) + (b) or (c) are also added to the oil.
Samples 2 to 6 were prepared in the same manner as sample 1 except for adding
was created. Each of Samples 1 to 6 was subjected to stepwise insulating color exposure and developed at 38° C. in the following processing steps. 1 Color development...3 minutes 15 seconds2 Bleaching...6 minutes 30 seconds3 Washing with water...3 minutes 15 seconds4 Fixing...6 minutes 30 seconds5 Washing with water...3 minutes 15 seconds4 Stability... 3 minutes 15 seconds The composition of the processing 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-hydroxyethyl)amino]-2-methyl- Aniline sulfate
Add 4.5g water 1 Bleach solution Ammonium bromide 160.0g Aqueous ammonia (28%) 25.0ml Ethylenediamine-tetraacetic acid sodium iron salt
130g Glacial acetic acid 14ml Add water 1 Fixer Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70% aqueous solution) 175.0ml Sodium bisulfite 4.6g Add water 1 Stabilizer Formalin (40% aqueous solution) 8.0ml Table 1 shows the characteristic values (relative sensitivity, gradation γ) obtained by measuring the density of Samples 1 to 6 which developed color by adding water using green light. [Table] Samples 2 to 4 containing the compound of the present invention from the table above
is additive-free (sample 1) or comparative compound (a) +
The decrease in sensitivity is smaller than that of Sample 5, in which compound (b) is added, and the softening effect is extremely large even with a small amount of addition compared to Sample 6, in which indazole-separating comparative compound (c) is added. It can be seen that the substance is released quickly. Example 2 As a sample, a multilayer color photosensitive material consisting of each layer having the composition shown below was prepared on a cellulose triacetate film support. Note that the additives marked with * are the same as those described in Example 1. 1st layer; antihalation layer; gelatin layer containing black colloidal silver; 2nd layer; intermediate layer; 3rd gelatin layer containing an emulsified dispersion of 2,5-di-t-octylhydroquinone; first red-sensitive emulsion layer; Silver emulsion (silver iodide 5 mol%)
...Silver coating amount 1.6g/ ^m2 Sensitizing dye
...4.5×10 ^-4 mol sensitizing dye per 1 mol silver
...1.5×10 ^-4 mol coupler EX-2 for 1 mol of silver
...0.04 mol coupler EX-4 per 1 mol of silver
...0.003 mol per mol of silver 4th layer: 2nd red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 10 mol%)
... Silver coating amount 1.4 g/m ² Sensitizing dye ... 3 x 10 ^-4 mol sensitizing dye per 1 mol silver ... 1 x 10 ^-4 mol coupler EX-2 per 1 mol silver
...0.002 mol coupler EX-3 per 1 mol silver
...0.02 mol coupler EX-4 per 1 mol of silver
...0.0016 mol of compound 2 per mol of silver ...0.002 mol per mol of silver 5th layer; Intermediate layer 6th layer same as the 2nd layer; 1st green-sensitive emulsion layer Silver iodobromide emulsion (i.e. silver oxide 4 mol%)
...Silver coating amount 1.2g/m ² sensitizing dye ^*
...5 x 10 ^-4 moles of sensitizing dye per mole of silver ^*
...2×10 ^-4 mol coupler EX-5 per 1 mol of silver
...0.05 mol coupler EX-6 per 1 mol of silver
...0.008 mol per mol of silver 7th layer; 1st green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 8 mol %)
... Silver coating amount: 1.3 g/m ² Sensitizing dye ... 3 x 10 ^-4 mol sensitizing dye per 1 mol silver
...1.2×10 ^-4 mol coupler EX-1 per mol of silver
...0.003 mol coupler EX-7 per 1 mol of silver
...0.0003 mol per mol of silver 8th layer; yellow filter layer 2,5 mol of yellow colloidal silver in gelatin aqueous solution
- gelatin layer 9th layer containing an emulsified dispersion of di-t-octylhydroquinone; first blue-sensitive emulsion layer silver iodobromide emulsion (silver iodide 6 mol%)
...Silver coating amount 0.7g/m ² Coupler EX-8
...0.25 mol coupler EX-9 per 1 mol of silver
...0.015 mol per mol of silver 10th layer; 2nd blue-sensitive emulsion layer silver iodobromide (silver iodide 6 mol %)
...Silver coating amount 0.6g/m ² Coupler EX-8
...0.06 mol per mol of silver 11th layer; first protective layer silver iodobromide (silver iodide 1 mol%, average grain size 0.07μ)
... Silver coating amount 0.5 g/m ² Gelatin layer containing an emulsified dispersion of ultraviolet absorber UV-1 12th layer: 2nd protective layer Molymethyl methanoacrylate particles (diameter
Apply a gelatin layer containing 1.5μ). In addition to the above composition, each layer contains a gelatin hardening agent H.
-1 and a surfactant were added. The sample prepared as described above was designated as sample 7. The compounds used to prepare the samples are shown below. Samples 8, 9, and 10: Samples 8, 9, and 10 were prepared by removing Compound 2 from Sample 7 and adding the same amounts of Compounds 7, 17, and Comparative Compound (c) instead. Sample 11: Produced in the same manner as Sample 7 except that Compound 2 was removed from Sample 7. After exposing the sample thus obtained, it was developed in the same manner as in Example 1, and graininess and sharpness were evaluated using the RMS (Root Mean Square) method and
Table 2 shows the results of evaluation using the MTF method. In addition,
Graininess determination using the RMS method and sharpness determination using the MTF method are well known among those involved, and each is based on “Photographic Science and Engineering.”
Vol19, No.4 (1975) P.235-238 and TH
“The Theory of Photographic” by Jamas
Process" 4th Edition, published by Macmillan. [Table]
From the results in Table 2, samples 7, 8, and 9 to which the compound of the present invention was added had extremely good graininess and image sharpness compared to sample 11 to which no additive was added and sample 10 to which comparative compound (c) was added. I understand that there is something. Example 3 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 in a conventional manner. Further, gelatin contained in this emulsion was 45% by weight based on silver halide. This emulsion contains 5-
[3-(δsulfobutyl)-5-chloro-2-oxazolidylidene ethylidene]-1-hydroxyethoxyethyl-3-(2-pyridyl)-2-thiohydantoin potassium salt (spectral sensitizer), dodecylbenzene Sodium sulfonate (surfactant),
After adding the polymer latex described in Preparation Example Formulation 3 of U.S. Pat. No. 3,525,620, 2-hydroxy-
4,6-dichloro-1,3,5-triazine sodium salt (hardening agent) was added in an amount of 2.6% by weight based on the total dry gelatin (that is, based on the total dry gelatin including the non-photosensitive upper layer described below). and further,
A methanol solution of the compound shown in Table 3 was added to prepare a coating solution for a photosensitive silver halide emulsion layer. 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 and applied for the non-photosensitive upper layer. I made a liquid. Next, the photosensitive silver halide emulsion layer coating solution and the non-photosensitive upper layer coating solution were coated onto a polyethylene 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. These samples were exposed to white tungsten light for 8 seconds through a step wedge with a step height of 0.1. Further, halftone dot images were formed using 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, and white tungsten light was exposed to the screen for 10 seconds through a step wedge with a step height of 0.1. The above exposed sample was heated at 38℃ using the following developer.
Develop for 20 seconds, fix by normal method,
Washed with water and dried. Developer composition Ethylenediaminetetraacetic acid disodium salt 1g Sodium sulfite 67g Hydroquinone 23g 1-phenyl-3-pyrazolidone 0.4g Potassium hydroxide 11g Sodium carbonate (monohydrate) 11g Potassium bromide 3.0g Add water 1 PH = 10.65 Relative Table 3 shows the results of evaluation regarding sensitivity and γ. [Table] As is clear from Table 3, the sample using the compound of the present invention was compared to sample 16 using comparative compound c.
It can be seen that samples Nos. 13 to 15 have a large effect of softening the gradation, that is, the development inhibitor is quickly released. Example 4 In samples 2 and 3 of Example 1, compounds 22 and 3 of the present invention were replaced with compounds 22 and 3, respectively.
Samples 17 and 18 were prepared by adding 23. These samples 17 and 18 were evaluated in the same manner as in Example 1, and the results shown in Table 4 were obtained. From the results in Table 4, it can be seen that compounds 22 and 23 also have an extremely large tone softening effect. 【table】

Claims (1)

[Scope of Claims] 1. Having at least one silver halide emulsion layer on a support, and containing a compound represented by the following general formula [] in the silver halide emulsion layer or other hydrophilic colloid layer. A silver halide photographic material characterized by: (In the formula, A and A' represent a hydrogen atom or a group that can be hydrolyzed with an alkali, X represents an electron-withdrawing group, and PUG is an optionally substituted mercaptotriazole residue, mercaptotetrazole residue, or 1-benzo (represents a triazole residue)