EP0232101A2 - Light-sensitive silver halide color photographic material - Google Patents
Light-sensitive silver halide color photographic material Download PDFInfo
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- EP0232101A2 EP0232101A2 EP19870300640 EP87300640A EP0232101A2 EP 0232101 A2 EP0232101 A2 EP 0232101A2 EP 19870300640 EP19870300640 EP 19870300640 EP 87300640 A EP87300640 A EP 87300640A EP 0232101 A2 EP0232101 A2 EP 0232101A2
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- silver halide
- light
- sensitive silver
- photographic material
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/32—Colour coupling substances
- G03C7/3225—Combination of couplers of different kinds, e.g. yellow and magenta couplers in a same layer or in different layers of the photographic material
Definitions
- light-sensitive material has been remarkably improved, but sharpness and graininess can not necessarily be said to have been sufficiently improved.
- a print enlarged from a small format (such as 110 film and disc film) of negative,type color films coarseness in images (or graininess) and also poorness in sharpness make extremely low the level of image quality of the print. This is because the graininess and the sharpness of the negative type films have not been made equal to a high magnification print.
- the object of this invention can be achieved by a light-sensitive silver halide color photographic material having at least one light-sensitive silver halide emulsion layer containing a pyrazolotriazole type magenta coupler and a colored magenta coupler, wherein the layer containing the pyrazolotriazole type magenta coupler and the colored magenta coupler comprises 17 mole % or more of said colored magenta coupler based on the amount of all couplers in said layer.
- R 1 and R 2 may be linked to each other to form a carbon ring (for example, cyclopropyl, cyclopentyl, cyclohexyl, cyclohexenyl, etc.).
- the silver halide emulsion may be used by mixing tow or more kinds of silver halide emulsions which have been separately formed.
- These dye-forming couplers may preferably have a group having 8 or more of carbon atoms, which is called a ballast group and makes couplers non-diffusible.
- These dye-forming couplers may be either four equivalent ones wherein silver ions of 4 molecules must be reduced in order for a dye of 1 molecule to be formed, or two equivalent ones wherein silver ions of 2 molecules may only be reduced.
- cyan dye-forming couplers phenol type couplers and naphthol type couplers are generally used.
- Specific examples of usable cyan couplers include those disclosed, for example, in U.S. Patents No. 2,423,730, No. 2,474,293, No. 2,801,171, No. 2,895,826, No. 3,476,563, No. 3,737,326, No. 3,758,308 and No. 3,893,044, Japanese Unexamined Patent Publications No. 37425/1972, No. 10135/1975, No. 25228/1975, No. 112038/1975, No.117422/1975, No. 130441/1975, etc., or couplers disclosed in Japanese Unexamined Patent Publication No. 98731/1983.
- the color fog preventive agent may be contained in the emulsion layers per se, or may be contained in an intermediate layer provided between adjacent emulsion layers.
- a matte agent can be added for the purposes of decreasing the gloss of the light-sensitive material, improving the writing performance, and.preventing mutual sticking of light-sensitive materials.
- Any agents can be used as the matte agent, for example, silicon dioxide, titanium dioxide, magnesium dioxide, aluminum dioxide, barium sulfate, calcium carbonate, polymers of acrylic acid and methacrylic acid and esters thereof, polyvinyl resins,,polymers of polycarbonates and styrene and copolymers thereof.
- the matte agent may preferably have a grain size of 0.05 p to 10 p. It is added preferably in an amount of 1 to 300 mg/m 2.
- An antistatic agent aiming at preventing static charge can be added to the light-sensitive material.
- the antistatic agent may be used in an antistatic layer provided on the side of a support at which no emulsion layer is laminated, or may be used in an emulsion layer and/or a protective colloid layer other than the emulsion layers provided on the side of a support on which emulsion layers are laminated.
- Antistatic agents preferably used are the compounds disclosed in RD No. 17643, Paragraph XIII.
- a thickening agent may be used in order to improve the coating performance.
- a hardening agent which has a fast reactivity and therefore may cause gelation before coating if previously added in a coating solution, it is preferably mixed just before the coating and with use of a static mixer or the like.
- the surface active agent there is no particular limitation on the surface active agent, but there may be added, for example, natural surface active agents such as saponin; nonionic surface active agents such as alkylene oxide type, glycerol type and glycidol type; cationic surface active agents such as higher alkyl amines, quaternary ammonium salts, pyridines and other hetero cyclic rings, and phosphoniums or sulfoniums; anionic surface active agents containing an acidic group such as carboxylic acid, sulfonic acid, phosphoric acid, sulfate and phosphate; and amphoteric surface active agents such as amino acids, aminosulfonic acids, and sulfate or phosphate of amino alcohols.
- fluorine type surface active agents for example, it is also possible to use fluorine type surface active agents.
- the processing may further comprise a pre-hardening step, a neutralizing step thereof, a stop fixing step and a post-hardening step.
- a color developing agent or a precursor thereof may be contained in advance in the materials to carry out, in place of the color developing step, activator processing which carries out the developing in an activator solution.
- the activator processing can be applied in the monobath processing.
- the color developing solution generally comprises an alkaline aqueous solution containing a color developing agent.
- the color developing agent is an aromatic primary amine color developing agent, including aminophenol type and p-phenylenediamine type derivatives. These color developing agents can be used as salts of organic acid and inorganic acid, and there can be used, for example, hydrochloride, sulfate, p-toluenesulfonate, sulfite, oxalate, benzenesulfonate, etc.
- the addition amount in the light-sensitive silver halide photographic material refers to the amount per 1 m 2 unless particularly mentioned. Also, silver halide and colloidal silver are shown by calculating them in terms of silver.
- a gelatin layer same as the second layer.
- a gelatin hardener (H-l) and a surface active agent were added in addition to the above compositions.
- the processing solution used in each of the processing steps had the following formulation. Made up to 1 liter by adding water.
- [Bleaching solution] Made up to 1 liter by adding water, and adjusted to pH 6.0 using ammonia water. Made up to 1 liter by adding water, and adjusted to pH 6.0 using acetic acid.
- the amount of couplers added was indicated in terms of mole % per 1 mole of silver halide; the numerals in parentheses in the column of the amount indicate proportional percentage (%) to all the couplers in the corresponding layer; MTF indicates a relative value when Sample 1 was assumed to be 100; RMS is indicated by a 1,000 time value of the standard deviation in the density value fluctuation caused when a density point of the minimum density + 0.7 was scanned by use of a microdensitometer having an open scanning area of 250 ⁇ m 2 . Accordingly, the values indicate that, the larger the MTF is and the smaller the RMS is, the higher image quality has been achieved.
- magenta coupler comprises pyrazolotriazole type magenta coupler and the colored magenta coupler is contained in the proportion of 17 % or more of the amount of all couplers in the layer containing the same.
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- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
Description
- This invention relates to a light-sensitive silver halide photographic material, and, particularly, to.a light-sensitive silver halide color photographic material having been improved in sharpness and graininess.
- Recent years, image quality of light-sensitive silver halide photographic materials (hereinafter "light-sensitive material") has been remarkably improved, but sharpness and graininess can not necessarily be said to have been sufficiently improved. In particular, in a print enlarged from a small format (such as 110 film and disc film) of negative,type color films, coarseness in images (or graininess) and also poorness in sharpness make extremely low the level of image quality of the print. This is because the graininess and the sharpness of the negative type films have not been made equal to a high magnification print.
- Conventionally, there has been known a variety of I techniques for improving the sharpness. One of them includes a techniqque for preventing light scattering, and another of them, a technique for improving the edge effect.
- The latter technique includes a method employing a so-called DIR coupler, and a method employing an unsharp mask. Of these, the method employing an unsharp mask may sometimes cause the sharpness to be lowered and the graininess to be deteriorated to give a limit in practical use. The method employing the DIR coupler has been known in great number, and useful DIR couplers include the compounds disclosed in Japanese Patent Publication No. 34933/1980, Japanese Unexamined Patent Publication No. 93344/1982, U.S. Patents No. 3,227,554, No. 3,615,506, No. 3,617,291 and No. 3,701,783, etc. However, when the edge effect is strengthened by using the DIR couplers, MTF (modulation transfer function) can be improved at a lower frequency region, but the improvement of MTF at a higher frequency region, which is necessary for achieving a high enlargement magnification, can not be expected, accompanying undesirable side effects such as the lowering of sensitivity and the lowering of density. It is possible to minimize the fall of sensitivity and density if DIR couplers such as diffusible DIR and timing DIR having the so-called long distance effectiveness are used, but MTF may be improved at a region shifted to a further lower frequency side, and there can not be so much expectation of the improvement in the sharpness at the high enlargement magnification.
- On the other hand, as the technique for preventing light scattering, it has been known to add a coloring substance, decrease the amount of silver halide, or make a film thinner. Drastic reduction of coated silver weight may decrease the number of color developing spots to cause the deterioration of graininess. It can be also considered to reduce the amount of gelatin, coupler or coupler solvent in a coating solution, but any of these measures may cause the deterioration of coating performances or the lowering of color density to have their own limits.
- Attempts have been conventionally made to suppress the light scattering and increase the sharpness by adding a coloring substance as former-mentioned, but no satisfactory result has been yielded.
- Recent years, pyrazolotriazole type couplers have attracted notices as a magenta coupler. Such couplers show not only so little secondary absorption as to be advantageous in the color reproducibility, but also so good color developing performance as to need less amount of the coupler used. Accordingly, they have been found to be very advantageous for making a film thinner and effective for improving the sharpness.
- However, it was found that the pyrazolotriazole type couplers can not be expected to have an improving effect in respect of the graininess.
- Accordingly, in the system employing the pyrazolotriazole type couplers, it has been sought after to develop a technique for improving the graininess.
- An object of this invention is to provide a light-sensitive silver halide color photographic material having been remarkably improved in not only the color reproducibility and the sharpness, but also the graininess.
- The object of this invention can be achieved by a light-sensitive silver halide color photographic material having at least one light-sensitive silver halide emulsion layer containing a pyrazolotriazole type magenta coupler and a colored magenta coupler, wherein the layer containing the pyrazolotriazole type magenta coupler and the colored magenta coupler comprises 17 mole % or more of said colored magenta coupler based on the amount of all couplers in said layer.
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- In the above Formula (I) and (II), R1 and R2 each represent an alkyl group, an aryl group or a hetero ring, and these alkyl group, aryl group and hetero ring may be linked through an oxygen atom, a nitrogen atom or an sulfur atom. The above alkyl group, aryl group and hetero ring may also be linked through a linking group selected from the following groups: Acylamino, carbamoyl, sulfonamide, sulfamoylcarbonyl, carbonyloxy, oxycarbonyl, ureido, thioureido, thioamide, sulfone and sulfonyloxy.
- The alkyl group represented by R1 or R2 includes a straight chain or branched alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, propyl, i-propyl, sec-butyl, n-butyl, t-butyl, n-octyl, t-octyl, dodecyl, octadecyl, etc.). These groups may further have a substituent (for example, a halogen atom, nitro, cyano, alkoxy, aryl, oxy, amino, acylamino, carbamoyl, sulfonamide, sulfamoyl, imide, alkylthio, arylthio, aryl, alkoxycarbonyl and acyl). Specifically, the group may include chloromethyl, bromomethyl, trichloromethyl, β-nitroethyl, 5-cyanobutyl, methoxymethyl, ethoxyethyl, phenoxyethyl, N-methylaminoethyl, dimethylaminobutyl, acetaminoethyl, benzoylamino, propyl, ethyl carbamoylethyl, methanesulfonamide ethyl, ethyl thioethyl, p-methoxyphenylthiomethyl, phenylmethyl, p-chlorophenyl- methyl, naphthylethyl, ethoxycarbonylethyl, acetylethyl, etc.
- The aryl group includes a phenyl group and a naphthyl group, and may have a substituent including the substituents for the above alkyl group.
- The hetero ring includes a 5- or 6-membered ring having at least any one of a nitrogen atom, an oxygen atom and a sulfur atom, and may be aromatic or may not be aromatic. For example, it includes pyridyl, quinolyl, pyrolyl, morpholyl, furanyl, tetrahydrofuranyl, pyrazolyl, triazolyl, tetrazolyl, thiazolyl, oxazolyl, imidazolyl, thiadiazolyl, etc. These may also have a substituent corresponding to the substituents for the alkyl group.
- R1 and R2 may be linked to each other to form a carbon ring (for example, cyclopropyl, cyclopentyl, cyclohexyl, cyclohexenyl, etc.).
- The compound wherein the alkyl group, the aryl group or the hetero ring represented by R1 or R2 is linked to each other through the linking group mentioned above or the nitrogen atom, oxygen atom or sulfur atom may include, for example, the following:
- When the hetero ring group is a pyrazolotriazole type compound, a bis type pyrazolotriazole type compound is formed, which is of course the magenta coupler included in this invention.
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- In the above formulas, Z represents a hydrogen atom or a group which is eliminable when a dye is formed through coupling with an oxidized product of an aromatic primary amine color developing agent.
- Specifically, it may include, for example, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an arylthio group, an alkylthio group, and a group of
- Examples thereof are shown below:
- Halogen atoms: Chlorine, bromine and fluorine. Alkoxy group: An ethoxy group, a benzyloxy group, a methoxyethyl carbamoylmethoxy group, a tetradecyl carbamoylmethoxy group, etc.
- Aryloxy group: A phenoxy group, a 4-methoxyphenoxy group, a 4-nitrophenoxy group, etc.
- Acyloxy group: An acetoxy group, a myristoyloxy group, a benzoyloxy group, etc.
- Arylthio group: A phenylthio group, a 2-butoxy-5-octyl- phenylthio group, a 2,5-dihexyloxyphenylthio group, etc. Alkylthio group: A methylthio group, an octylthio group, a hexadecylthio group, a benzylthio group, a 2-(diethyl- amino)ethylthio group, an ethoxycarbonylmethylthio group, an ethoxyethylthio group, a phenoxyethylthio group, etc.
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- The colored magenta coupler according to this invention may preferably include the compound represented by the following formula:
- Formula (III):
- In the formula, Cp represents a magenta coupler residual group (provided, however, that the azo group is attached to an active site of the magenta coupler), and R3 represents an aryl group (including the group having a substituent).
- The magenta coupler residual group represented by Cp may preferably include 5-pyrazolone magenta couplers and coupler residual groups derived from pyrazolotriazole type magenta couplers, and may particularly preferably include the one represented by Formula (IV) shown below:
- Formula (IV):
- In the formula, R4 represents an aryl group; R5 represents an acylamino group, an anilino group, a ureido group or a carbamoyl group and preferably represents an anilino group; and R4 and R5 each may include the one having a substituent.
- The aryl group represented by R4 is preferably a phenyl group. The substituent for the aryl group represented by R4 may include, for example, a halogen atom (for example, fluorine, chlorine, bromine, etc.), an alkyl group (for example, methyl, ethyl, etc.), an alkoxy group (for example, methoxy, ethoxy, etc.), an aryloxy group (for example, phenyloxy, naphthyloxy, etc.), an acylamino group (for example, benzamide, a-(2,4-di-t-amylphenoxy)-butylamide, etc.), a sulfonylamino group (for example, benzenesulfonamide, n-hexadecansulfonamide, etc.), a sulfamoyl group (for example, methylsulfamoyl, phenylsulfamoyl, etc.), a carbamoyl group (for example, an n-butylcarbamoyl group, a phenyl carbamoyl group, etc.). a sulfonyl group (for example, methylsulfonyl, n-dodecylsulfonyl, benzenesulfonyl, etc.), an acyloxy group, an ester group, a carboxyl group, a sulfo group, a cyano group, a nitro group, etc.
- Specific examples of R4 are phenyl, 2,4,6-trichlorophenyl, pentachlorophenyl, pentafluorophenyl, 2,4-6-trimethylphenyl, 2-chloro-4,6-dimethylphenyl, 2,6-dichloro-4-methylphenyl, 2,4-dichloro-6-methylphenyl, 2,4-dichloro-6-methoxylphenyl, 2,6-dichloro-4-methoxylphenyl, 2,6-dichloro-4-[a-(2,4-di-t-amylphenoxy)-acetamide]phenyl, etc.
- The acylamino group represented by RS may include, for example, pivaloylamino, n-tetradecanamide, a-(3-pentadecylphenoxy)butylamide, 3-[a-(2,4-di-t-amylphenoxy)acetamido]benzamide, benzamide, 3-acetoamidobenzamide, 3-(3-n-dodecylsuccinimide)-benzamide, 3-(4-n-dodecyloxybenzenesulfonamide)bnezamide, etc.
- The anilino group represented by R5 may include, for example, anilino, 2-chloroanilino, 2,4-dichloroanilino, 2,4-dichloro-5-methoxyanilino, 4-cyanoanilino, 2-chloro-5-[α-(2,4-di-t-amylphenoxy)butylamido]anilino, 2-chloro-5-(3-octadecenylsuccinimide)anilino, 2-chloro-5-n-tetradecanamidoanilino, 2-chloro-5-[a-(3-t-butyl-4-hydroxyphenoxy)tetradecanamido]anilino, 2-chloro-5-n-hexadecansulfoamidoanilino, etc.
- The ureido group represented by R5 may include, for example, methylureido, phenylureido, 3-Ea-(2,4-di-t-amylphenoxy)butylamido]phenylureido, etc.
- The carbamoyl group represented by R5 may include, for example, n-tetradecylcarbamoyl, phenylcarbamoyl, 3-[α-(2,4-di-t-amylphenoxy)acetamide]phenylcarbamoyl, etc.
- The aryl group represented by R3 is preferably a phenyl group or a naphthyl group.
- The substituent for the aryl group represented by R1 may include, for example, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, a hydroxyl group, an acyloxy group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, etc.
- Particularly preferably substituent includes an alkyl group, a hydroxyl group, an alkoxy group and acylamino group.
- Examples of the colored magenta couplers represented by Formula (III) are shown below, but by no means limited to these.
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- The colored magenta coupler according to this invention can be synthesized following the methods as disclosed in Japanese Unexamined Patent Publications No. 123625/1974, No. 131448/1974, No. 42121/1977, No. 102723/1977, No. 52532/1979, No. 1726/1983, U.S. Patents No. 2,763,552, No. 2,801,171, No. 3,519,429, etc.
- The pyrazolotriazole type magenta coupler and the colored magenta coupler of this invention can be used in any layer or layers of the above silver halide emulsion layers, but, in general, they are used in a green-sensitive silver halide emulsion layer. When the green-sensitive silver halide emulsion layer comprises two or more emulsion layers, the couplers are required to be used in at least one of the emulsion layers, and preferably used in two or more of the emulsion layers. When the green-sensitive silver halide emulsion layer comprises two or more emulsion layers which are different in sensitivety, the couplers should preferably be used in at least the maximum sensitive layer.
- The pyrazolotriazole type magenta coupler of this invention may be used usually in the range of 1 x 10-3 mole to 1 mole, preferably 1 x 10-2 mole to 8 x 10-i r per 1 mole of silver halide the light-sensitive silver halide emulsion layer. However, from a viewpoint of the sharpness, it is preferably used in an amount of 50 mole % or more, more preferably from 60 to 80 mole %, based on the amount of all couplers in a layer to which the coupler is added.
- Also, the colored magenta coupler of this invention is required to be used in an amount of 17 mole % or more, preferably not less than 20 mole % and less than 50 mole %, more preferably not less than 30 mole % and less than 50 mole %, based on the amount of all couplers in a layer to which the coupler is added.
- The layer containing the magenta coupler and the colored magenta coupler of this invention may contain magenta couplers outside this invention. However, the magenta couplers outside this invention should be contained in an amount of less than 20 mole % based on the amount of all couplers.
- The magenta couplers that can be used together in the green-sensitive silver halide emulsion layer of this invention may include pyrazolone compounds, indazolone compounds, cyanoacetyl compounds and pyrazoloazole compounds outside this invention. In particular, pyrazolone compounds can be advantageously used.
- Specific examples of usable magenta couplers may include those disclosed in Japanese Unexamined Patent Publications No. 111631/1974, No. 29236/1981, No. 94752/1982, Japanese Patent Publication No. 27930/1973, U.S. Patents No. 2,600,788, No. 3,062,653, No. 3,408,194, No. 3,519,429, and Research Disclosure No. 12443.
- When adding the magenta coupler of this invention and the other couplers, they can be incorporated into the green-sensitive silver halide emulsion layer according to an oil protection dispersion method or a latex dispersion method. In case the couplers are alkali soluble, they may be added as an alkaline solution.
- From the viewpoints of color reproducibility, sharpness and graininess, it is preferable to use a DIR
- Typical DIR compound usable in this invention includes DIR couplers wherein a group capable of forming a compound showing a development-restraining action when eliminated from an active site of a coupler is introduced into the active site, which are disclosed, for example, in British Patent No. 935,454, U.S. Patents No. 3,227,554, No. 4,095,984, No. 4,149,886, Japanese Unexamined Patent Publication No. 151944/1982, etc. The above DIR couplers have a property that, when coupled with an oxidized product in a color developing agent, a mother nuclei of the coupler forms a dye and, on the other hand, release a development restrainer. In this invention, there may be also included the compounds that can release a development restrainer but form no dye when coupled with an oxidized product in a color developing agent, as disclosed in U.S. Patents No. 3,652,345, No. 3,928,041, No. 3,958,993, No. 3,961,959 and No. 4,052,213, Japanese Unexamined Patent Publications No. 110529/1978, No. 13333/1979, No. 161237/1980, etc.
- Also included in this invention are the so-called timing DIR compounds wherein, when reacted with an oxidized product in a color developing agent, a mother nuclei forms a dye or a colorless compound and, on the other hand, an eliminated timing group releases a development restrainer by an intramolecular neucleophilic substitution reaction or elimination reaction, as disclosed in Japanese Unexamined Patent Publications No. 145135/1979, No. 114946/1981 and No. 154234/1982.
- Also included in this invention are the timing DIR compounds wherein, when reacted with an oxidized product in a color developing agent, the timing group as mentioned above has been bonded to a coupler mother nuclei capable of forming a perfectly diffusible dye.
- Typical examples of the DIR compounds are shown below, but this invention is by no means limited by these examples.
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- The DIR compounds that can be used in combination in this invention is preferably added to a light-sensitive silver halide emulsion layer.
- Two or more kinds of the DIR compounds may be contained in the same layer, or, alternatively, DIR compounds of the same kind may be contained in different two or more layers.
- In general, these DIR compounds may be used preferably in an amount of 2 x 10-4 to 1 x 10-1, more preferably 1 x 10-3 to 2 x 10-2, per 1 mole of silver in an emulsion layer.
- For the purpose of improving image quality, which is an object of this invention, preferably used is the so-called timing DIR compound, or the so-called diffusible DIR compound wherein the released restraining group is greatly migratory.
- In a silver halide emulsion used in this invention, there may be used any of silver halides including silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide and silver chloride which are used in ordinary silver halide emulsions, but they preferably include silver bromide, silver iodobromide and silver chloroiodobromide.
- Silver halide grains used in the silver halide emulsions may be obtained by any of an acidic method, a neutral method and an ammoniacal method. The grains may be allowed to grow at one time, or grow after seed grains have been formed. The manner to prepare the seed grains and the manner to grow them may be same or different.
- The silver halide emulsion may be obtained by simultaneously mixing halide ions and silver ions, or by preparing an aqueous solution in which either one of them is present and then mixing in it the other of them. Alternatively, taking into account the critical growth rate of silver halide crystals, it may be formed by successively simultaneously adding halide ions and silver ions while controlling pH and pAg in a mixing vessel. By such procedures, there can be obtained silver halide grains having regular crystal form and substantially uniform grain size. Halogen formulation in a grain may be varied by employing a conversion method in an arbitrary step during formation of AgX.
- During the growth of silver halide grains, known silver halide solvent such as ammonia, thioether and thiourea can be made present.
- In the course of formation and/or growth of the silver halide grains, metal ions may be added to the grains by use of at least one selected from a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt (including a complex salt), a rhodium salt (including a complex salt), and an iron salt (including a complex salt) to incorporate any of these metal elements into the inside of the grains and/or the surface of the grains, and also a reduction sensitizing nuclei can be imparted to the inside of the grains and/or the surface of the grains by placing the grains in a suitable reductive atmosphere.
- The silver halide emulsion may be either one from which unnecessary soluble salts have been removed after completion of the growth of silver halide grains, or one from which they remain unremoved. When the salts are removed, they can be removed according to the method disclosed in Research Disclosure (hereinafter simply "RD") No. 17643, Paragraph II.
- The silver halide grains may be any of those having uniform distribution of silver halide formulation in a grain, or core/shell grains having different silver halide formulation between the inside portion and the surface layer of a grain.
- The silver halide grains may be grains such that a latent image is formed chiefly on the surface, or grains such that a latent image is formed chiefly in the inside of a grain.
- The silver halide grains may be any of those having a regular crystal form such as a cube, an octahedron and a tetradecahedron, or those having an irregular crystal form such as a sphere and a plate. In these grains, there can be used those having any ratio of { 100} face to { 111) face. Also, they may have a composite form of these crystal forms, or comprise a mix of grains having various crystal forms.
- As for the size of the silver halide grains, there can be used those having a grain size of 0.05 to 30 u, preferably 0.1 to 20 u.
- The silver halide emulsion that can be used may have any grain size distribution. An emulsion having a wide grain size distribution (herein called a "polydispersed emulsion") may be used, or an emulsion having a narrow grain size distribution (herein called a."monodispersed emulsion". The monodispersed emulsion herein mentioned refers to an emulsion having a value of 0.20 or less when the standard deviation of grain size distribution is divided by the average grain size. Here, the grain size refers to the diameter of a grain in the case of a spherical silver halide, and, in the case of a grain having a shape other than the spherical shape, it refers to the diameter calculated by converting a projected image of the grain into a round image having the same area.) may be used alone or as a mixture of several kinds. Also, the polydispersed emulsion and the monodispersed emulsion may by used by mixing them.
- The silver halide emulsion may be used by mixing tow or more kinds of silver halide emulsions which have been separately formed.
- The silver halide emulsion can be chemically sensitized according to conventional methods. Namely, a sulfur sensitization method, a selenium sensitization method, a reduction sensitization method and a noble metal sensitization method using noble metal compounds such as gold and so forth can be used alone or in combination.
- The silver halide emulsion can be optically sensitized to a desired wavelength region by using a dye known as a sensitizing dye in the field of photography. The sensitizing dye may be used alone, or may be used in combination of two or more of the dye. Together with the sensitizing dye, a dye having itself no action of spectral sensitization, or a supersensitizing agent which is a compound substantially absorbing no visible light and capable of strengthening the sensitizing action of the sensitizing dye, may be contained in the emulsion.
- As the sensitizing dye, there may be used cyanine dyes, merocyanine dyes, composite cyanine dyes, composite merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, sterile dyes and hemioxanol dyes.
- Particularly useful dyes are cyanine dyes, merocyanine dyes and composite merocyanine dyes.
- To the silver halide emulsion, a compound known as an antifoggant or a stabilizer in the field of photography can be added during chemical ripening, after completion of chemical ripening and/or before coating of a silver halide emulsion after completion of chemical ripening, for the purpose of preventing a light-sensitive material from being fogged during manufacturing steps, during preservation or during photographic processing, or for the purpose of keeping stable the photographic performances.
- As a binder (or a protective colloid) for the silver halide emulsion, it is advantageous to use gelatin, but it is also possible to use hydrophilic colloids such as gelatin derivatives, a graft polymer of gelatin with other macromolecules, other proteins, sugar derivatives, cellulose derivatives and synthetic hydrophilic high molecular substances such as homopolymer or copolymer.
- Photographic emulsion layers and other hydrophilic colloid layers of the light-sensitive material in which the silver halide emulsion of this invention is used can be hardened by using one or more kinds of hardening agents that can crosslink binder (or protective colloid) molecules to enhance the film strength. The hardening agents can be added in such an amount that a light-sensitive material can be hardened to the extent that no hardening agent is required to be added in a processing solution. It, however, is also possible'to add the hardening agent in the processing solution.
- For example, there can be used, alone or in combination, aldehydes (such as formaldehyde, glyoxal and glutaraldehyde), N-methylol compounds (such as dimethylol urea and methyloldimethylhydantoin), dioxane derivatives (such as 2,3-dihydroxydioxane), active vinyl compounds (such as 1,3,5-triacryloyl-hexahydro-s-triazine and l,3-vinylsulfonyl-2-propanol), active halogen compounds (such as 2,4-dichloro-6-hydroxy-s-triazine), mucohalogeno-acids (such as mucochloric acid and mucophenoxychloric acid), etc.
- A plasticizer can be added to the silver halide emulsion layers and/or other hydrophilic colloid layers of the light-sensitive material for the purpose of enhancing flexibility. Preferable plasticizer includes the compounds disclosed in RD No. 17643, Paragraph XII-A.
- For the purpose of improving dimensional stability and the like, a dispersion (latex) of a water insoluble or hardly soluble synthetic polymer can be contained in the photographic emulsion layers and other hydrophilic colloid layers.
- For example, there can be used, alone or in combination, alkyl acrylate or methacrylate, alkoxyalkyl acrylate or methacrylate, glycidyl acrylate or methacrylate, acrylamide or methacrylamide, vinyl esters (such as vinyl acetate), acrylonitrile, olefin, styrene, etc.; or polymers containing monomer components comprising a combination of these with acrylic acid, methacrylic acid, α,β-unsaturated dicarboxylic acid, hydroxyalkyl acrylate or methacrylate, sulfoalkyl acrylate or methacrylate, styrene sulfonic acid, etc.
- In a color development processing, a dye-forming coupler capable of forming a dye through a coupling reaction with an oxidized product of an aromatic primary amine developing agent (for example, p-phenylenediamine derivative, aminophenol derivative, etc.) is used in the emulsion layers of the light-sensitive material. In a usual case, the dye forming coupler is selected in the manner that there can be formed a dye capable of absorbing light-sensitive spectral light in an emulsion layer with respect to the respective emulsion layers, and thus a yellow dye-forming coupler is used in a blue-sensitive emulsion layer; a magenta dye-forming coupler, in a green-sensitive emulsion layer; and a cyan dye-forming coupler, in a red-sensitive emulsion layer. However, the light-sensitive silver halide color photographic material may be prepared by using the couplers in the manner different from the above combination, depending on the purpose.
- These dye-forming couplers may preferably have a group having 8 or more of carbon atoms, which is called a ballast group and makes couplers non-diffusible. These dye-forming couplers may be either four equivalent ones wherein silver ions of 4 molecules must be reduced in order for a dye of 1 molecule to be formed, or two equivalent ones wherein silver ions of 2 molecules may only be reduced. The dye-forming couplers may contain a compound that can release a photographically useful fragment such as a development accelerator, a bleach accelerator, a developer, a silver halide solvent, a toning agent, a hardening agent, a fogging agent, an antifoggant, a chemical sensitizer, a spectral sensitizer and a desensitizer, through coupling with an oxidized product of a developing agent.
- A colorless coupler (also called a competing coupler) which performs a coupling reaction with an oxidized product of an aromatic primary amine developing agent, but does not form any dye. There can be also used in combination with the dye-forming couplers.
- As the yellow dye-forming coupler, known acylacetoanilido type couplers can be preferably used. Among them, advantageous are benzoyl acetoanilide type compounds and pivaloyl acetoanilide type compounds. Specific examples of usable yellow couplers include those disclosed, for example, in U.S. Patents No. 2,875,057, No. 3,265,506, No. 3,408,194, No. 3,551,155, No. 3,582,322, No. 3,725,072 and No. 3,891,445; German Patent No. 1,547,868, German Patent Application Publications No. 2,219,917, No. 2,261,361 and No. 2,414,006, British Patent No. 1,425,020; Japanese Patent Publication No. 10783/1976; Japanese Unexamined Patent Publications No. 26133/1972, No. 73147/1973, No. 6341/1975, No. 87650/1975, No. 123342/1975, No. 130442/1975, No. 21827/1976, No. 102636/1976, No. 82424/1977, No. 115219/1977 and No. 95346/1983; etc.
- As the cyan dye-forming couplers, phenol type couplers and naphthol type couplers are generally used. Specific examples of usable cyan couplers include those disclosed, for example, in U.S. Patents No. 2,423,730, No. 2,474,293, No. 2,801,171, No. 2,895,826, No. 3,476,563, No. 3,737,326, No. 3,758,308 and No. 3,893,044, Japanese Unexamined Patent Publications No. 37425/1972, No. 10135/1975, No. 25228/1975, No. 112038/1975, No.117422/1975, No. 130441/1975, etc., or couplers disclosed in Japanese Unexamined Patent Publication No. 98731/1983.
- Among the dye-forming couplers, colored couplers, DIR couplers, DIR compounds, image stabilizers, color fog preventive agents, ultraviolet absorbents, brightening agents, etc. which are not required to be absorbed on the surface of silver halide crystals, hydrophobic compounds can be dispersed by use of various methods including a solid dispersion method, a latex dispersion method, an oil-in-water emulsification dispersion method, etc., which can be appropriately selected depending on the chemical structure or the like of the hydrophobic compounds such as couplers. As the oil-in-water emulsification dispersion method, conventionally known method for dispersing hydrophobic additives such as couplers can be applied. Usually, the method may be carried out by dissolving the couplers or the like in a high boiling organic solvent having a boiling point of 1500 C or more optionally together with a low boiling and/or water soluble organic solvent, and carrying out emulsification dispersion in a hydrophilic binder such as an aqueous gelatin solution by use of a surface active agent and by use of a dispersing means such as a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic device, followed by adding the dispersion to an intended hydrophilic colloid layer solution. There may be inserted a step of removing the dispersing solution or, at the same time of the dispersion, the low boiling organic solvent.
- The high boiling solvent to be used may include organic solvents having a boiling point of 150°C or more such as phenol derivatives, alkyl phthalates, phosphates, citrates, benzoates, alkyl amides, aliphatic acid esters and trimesic acid esters which do not react with an oxidized product of a developing agent.
- Together with the high boiling solvent, or in place thereof, a low boiling or water soluble organic solvent can be used. The organic solvent which has a low boiling point and is substantially insoluble in water may include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane, benzene, etc.
- When the dye-forming couplers, colored couplers, DIR couplers, DIR compounds, image stabilizers, color fog preventive agents, ultraviolet absorbents, brightening agents, etc. have an acid radical such as carboxylic acid and sulfonic acid, they can be introduced in a hydrophilic colloid as an alkaline aqueous solution.
- As a dispersion auxiliary used when the hydrophobic compounds are dissolved in the solvent comprising the low boiling solvent alone or the combination with the high boiling solvent and dispersed in water using a mechanical means or ultrasonic wave, there can be used anionic surface active agents, nonionic surface active agents, cationic surface active agent and amphoteric surface active agents.
- A color fog preventive agent can be used in order to prevent color turbidity from being caused by the migration of an oxidized product or an electron migrator of a developing agent between emulsion layers (between the same color sensitive layers and/or different color sensitive layers) of the light-sensitive material, or prevent the deterioration of sharpness or prevent overly conspicuous graininess.
- The color fog preventive agent may be contained in the emulsion layers per se, or may be contained in an intermediate layer provided between adjacent emulsion layers.
- An image stabilizing agent for preventing the deterioration of dye images can be used in the light-sensitive material. Preferably usable compound includes the compounds disclosed in RD No. 17643, Paragraph VII-J.
- Hydrophilic colloid layers such as protective layers and intermediate layers of a light-sensitive material may contain an ultraviolet absorbent in order to prevent the fog due to static discharge caused by charging of the light-sensitive material by friction or the like, and to prevent the deterioration of images due to ultraviolet rays.
- A formalin scavenger can be used in the light-sensitive material in order to prevent the deterioration of magenta dye-forming coupler, etc. due to formalin during preservation of light-sensitive materials.
- When a dyestuff, an ultraviolet absorbent and so forth are contained in the hydrophilic colloid layers of the light-sensitive material, they may be mordanted by using a mordant such as a cationic polymer.
- Compounds such as a development accelerator and a development restrainer that may change the developing properties, or a bleach accelerator can be added to the silver halide emulsion layers and/or other hydrophilic colloid layers of the light-sensitive material. The compound preferably usable as the development accelerator includes the compounds disclosed in RD No. 17643, Paragraphs XXI-B to -D, and the development restrainer includes the compounds disclosed in RD No. 17643, Paragraph XXI-E. For the purpose of development acceleration or for other purposes, a black and white development accelerator and/or a precursor thereof may also be used.
- For the purposes of increasing sensitivity, increasing contrast, and accelerating development, the emulsion layers of the light-sensitive photographic material may contain polyalkylene oxides or derivatives such as ethers, esters or amines thereof, thioether compounds, thiomorpholines, quaternary ammonium compounds, urethane derivatives, urea derivatives, imidazole derivatives, etc.
- In the light-sensitive material, a brightening agent can be used for the purpose of increasing whiteness of a white ground and also making not conspicuous the coloring of the white ground portion. Compounds preferably usable as the brightening agent are disclosed in RD No. 17643, Paragraph V.
- The light-sensitive material can be provided with an auxiliary layer such as a filter layer, an anti-halation layer and an ant-irradiation layer. These layers and/or the emulsion layers may contain a dye that may be flowed out of the light-sensitive material, or bleached, during the development processing. Such a dye may include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, etc.
- To the silver halide emulsion layers and/or other hydrophilic colloid layers of the light-sensitive material, a matte agent can be added for the purposes of decreasing the gloss of the light-sensitive material, improving the writing performance, and.preventing mutual sticking of light-sensitive materials. Any agents can be used as the matte agent, for example, silicon dioxide, titanium dioxide, magnesium dioxide, aluminum dioxide, barium sulfate, calcium carbonate, polymers of acrylic acid and methacrylic acid and esters thereof, polyvinyl resins,,polymers of polycarbonates and styrene and copolymers thereof. The matte agent may preferably have a grain size of 0.05 p to 10 p. It is added preferably in an amount of 1 to 300 mg/m2.
- A lubricant can be added to the light-sensitive material in order to decrease sliding friction.
- An antistatic agent aiming at preventing static charge can be added to the light-sensitive material. The antistatic agent may be used in an antistatic layer provided on the side of a support at which no emulsion layer is laminated, or may be used in an emulsion layer and/or a protective colloid layer other than the emulsion layers provided on the side of a support on which emulsion layers are laminated. Antistatic agents preferably used are the compounds disclosed in RD No. 17643, Paragraph XIII.
- In the photographic emulsion layers and/or other hydrophilic colloid layers, a variety of surface active agents can be used for the purpose of improving coating performance, preventing static charge, improving slidability, emulsification dispersion, preventing adhesion, or improving photographic performances (such as development acceleration, hardening and sensitization).
- The support used in the light-sensitive material of this invention may include flexible reflective supports made of paper or synthetic paper laminated with a-olefin polymers (for example, polyethylene, polypropylene, an ethylene/butene copolymer, etc.); films comprising semisynthetic or synthetic high molecular compounds such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate and polyamide; flexible supports comprising these films provided with a reflection layer; glass; metals; ceramics; etc.
- The light-sensitive material may be applied, as occasion calls, directly on the surface of the support having been subjected to corona discharging, ultraviolet irradiation, flame treatment and so forth, or through interposition of at least one subbing layer for improving adhesion, antistatic performance, dimensional stability, abrasion resistance, hardness, anti-halation performance, friction characteristics and/or other characteristics of the surface of the support.
- In the coating of the light-sensitive material, a thickening agent may be used in order to improve the coating performance. Also, in the case of, for example, a hardening agent, which has a fast reactivity and therefore may cause gelation before coating if previously added in a coating solution, it is preferably mixed just before the coating and with use of a static mixer or the like.
- Particularly useful coating method may include extrusion coating and curtain coating by which two or more layers can be simultaneously coated, but packet coating is also useful for a certain purpose. Coating rate can be arbitrarily selected.
- There is no particular limitation on the surface active agent, but there may be added, for example, natural surface active agents such as saponin; nonionic surface active agents such as alkylene oxide type, glycerol type and glycidol type; cationic surface active agents such as higher alkyl amines, quaternary ammonium salts, pyridines and other hetero cyclic rings, and phosphoniums or sulfoniums; anionic surface active agents containing an acidic group such as carboxylic acid, sulfonic acid, phosphoric acid, sulfate and phosphate; and amphoteric surface active agents such as amino acids, aminosulfonic acids, and sulfate or phosphate of amino alcohols. For the same purpose, it is also possible to use fluorine type surface active agents.
- To obtain color images by using the light-sensitive material of this invention, color photographic processing is carried out after exposure. The color processing is carried out according to steps comprising a color developing step, a bleaching step, a fixing step, a water washing step, and optionally a stabilizing step. The processing step using a bleaching solution and the processing step using a fixing solution can be replaced by a bleach-fixing step using a combined bleaching and fixing solution. It is also possible to carry out a monobath processing which employs a combined developing and bleaching and fixing solution that can carry out color developing, bleaching and fixing in one bath.
- In combination with these processing steps, the processing may further comprise a pre-hardening step, a neutralizing step thereof, a stop fixing step and a post-hardening step. In these processings, a color developing agent or a precursor thereof may be contained in advance in the materials to carry out, in place of the color developing step, activator processing which carries out the developing in an activator solution. Also, the activator processing can be applied in the monobath processing.
- The color developing solution generally comprises an alkaline aqueous solution containing a color developing agent. The color developing agent is an aromatic primary amine color developing agent, including aminophenol type and p-phenylenediamine type derivatives. These color developing agents can be used as salts of organic acid and inorganic acid, and there can be used, for example, hydrochloride, sulfate, p-toluenesulfonate, sulfite, oxalate, benzenesulfonate, etc.
- These compounds may be used generally in concentration of about 0.1 to 30 g per 1 liter of a color developing solution, preferably in concentration of about 1 to 15 g per 1 liter of a color developing solution. The amount less than 0.1 g may result in insufficient color development density.
- The above color developing agent may be used alone or in combination of two or more kinds of them. Further, the above color developing agent may be incorporated into the color photographic material per se. In such a case, the light-sensitive silver halide color photographic material can be also processed by using an alkaline solution (an activator) in place of the color developing solution, and can be bleach-fixed immediately after the processing by the alkaline solution.
- Specific examples of this invention will be described below, but working embodiments of this invention are by no means limited to these.
- In all of Examples shown below, the addition amount in the light-sensitive silver halide photographic material refers to the amount per 1 m2 unless particularly mentioned. Also, silver halide and colloidal silver are shown by calculating them in terms of silver.
- On a support made of triacetyl cellulose film, the respective layers as shown below were formed successively from the side of the support to produce a multi-layer color photographic element, Sample-1.
- Sample 1 (Comparative Example):
- First layer: Antihalation layer (HC-1)
A gelatin layer containing black colloidal silver. - Second layer: Intermediate layer (I.L.)
A gelatin layer containing an emulsified dispersion of 2,5-di-t-octylhydroquinone. - Third layer: Low sensitivity red-sensitive silver halide emulsion layer (RL-1)
- Comprising AgBrI containing 8 mole % of AgI; an average grain size (r̅) of 0.30 um.
- Monodispersed emulsion (Emulsion I) ... Coated silver weight: 1.5 g/m2 .
- Sensitizing dye I ... 6 x 10-5 mole per 1 mole of silver.
- Sensitizing dye II ...1.0 x 10-5 mole per 1 mole of silver.
- Cyan coupler (C-l) ... 0.06 mole per 1 mole of silver.
- Colored cyan coupler (CC-1) ... 0.003 mole per 1 mole of silver.
- DIR compound (D-12) ... 0.0015 mole per 1 mole of silver.
- DIR compound (D-15) ... 0.004 mole per 1 mole of silver.
- Fourth layer: High sensitivity red-sensitive silver halide emulsion layer (RH-1)
- Comprising AgBrI containing 7.0 mole % of AgI; an average grain size (r̅) of 0.65 µm.
- Monodispersed emulsion (Emulsion II) ... Coated silver weight: 1.3 g/m 2.
- Sensitizing dye I ... 3 x 10-5 mole per 1 mole of silver.
- Sensitizing dye II ...1.0 x 10-5 mole per 1 mole of silver.
- Cyan coupler (C-l) ... 0.02 mole per 1 mole of silver.
- Colored cyan coupler (CC-1) ... 0.0015 mole per 1 mole of silver.
- DIR compound (D-15) ... 0.001 mole per 1 mole of silver.
- Fifth layer: Intermediate layer (I.L.)
- A gelatin layer, same as the second layer.
- Sixth layer: Low sensitivity green-sensitive silver halide emulsion layer (GL-1)
- Emulsion I ... Coated silver weight: 1.3 g/m2 .
- Sensitizing dye III ... 2.5 x 10-5 mole per 1 mole of silver.
- Sensitizing dye IV ...1.2 x 10-5 mole per 1 mole of silver.
- Magenta coupler (M-1) ... 0.9 mole per 1 mole of silver.
- Colored magenta coupler (CM-1) ... 0.017 mole per 1 mole of silver.
- DIR compound (D-12) ... 0.0010 mole per 1 mole of silver.
- DIR compound (D-17) ... 0.0030 mole per 1 mole of silver.
- Seventh layer: High sensitivity green-sensitive silver halide emulsion layer (GH-1)
- Emulsion II ... Coated silver weight: 1.1 g/m2 .
- Sensitizing dye III ... 1.5 x 10-5 mole per 1 mole of silver.
- Sensitizing dye IV ...1.0 x 10-5 mole per 1 mole of silver.
- Magenta coupler (M-l) ... 0.020 mole per 1 mole of silver.
- Colored magenta coupler (CM-1) ... 0.004 mole per 1 mole of silver.
- DIR compound (D-12) ... 0.0010 mole per 1 mole of silver.
- Eighth layer: Yellow filter layer (YC-1)
- A gelatin layer containing an emulsified dispersion comprising yellow colloidal silver and 2,5-di-t-octylhydroquinone.
- Ninth layer: Low sensitivity blue-sensitive silver halide emulsion layer (BL-1)
- Comprising AgBrI containing 6 mole % of AgI; an average grain size of 0.38 um.
- Monodispersed emulsion (Emulsion III) ... Coated silver weight: 0.9 g/m2 .
- Sensitizing dye V ... 1.3 x 10-5 mole per 1 mole of silver.
- Yellow coupler (Y-l) ... 0.29 mole per 1 mole of silver.
- DIR compound (D-3) ... 0.01 mole per 1 mole of silver.
- Tenth layer: High sensitivity blue-sensitive emulsion layer (BH-1)
- Comprising AgBrI containing 10 mole % of AgI; an average grain size (r) of 0.8 µm.
- Monodispersed emulsion (Emulsion IV) ... Coated silver weight: 0.5 g/m 2.
- Sensitizing dye V ... 1.0 x 10-5 mole per 1 mole of silver.
- Yellow coupler (Y-l) ... 0.08 mole per 1 mole of silver.
- DIR compound (D-3) ... 0.002 mole per 1 mole of silver.
- Eleventh layer: First protective layer (Pro-1)
A gelatin layer comprising silver iodobromide (AgI: 1 mole %; average grain size: 0.07 um), having a coated silver weight of 0.5 g/m2, and containing ultraviolet absorbents UV-1 and UV-2. - Twelfth layer: Second protective layer (Pro-2)
A gelatin layer containing polymethyl methacrylate particles (diameter: 1.5 µm) and formalin scavenger (HS-1). - To each of the layers, a gelatin hardener (H-l) and a surface active agent were added in addition to the above compositions.
- The compounds contained in the respective layers of Sample 1 are as follows:
- Sensitizing dye I:
- Anhydro
- 5,5'-dichloro-9-ethyl-3,3'-di-(3-sulfopropyl)-thiacarbocyanine hydroxide
- Sensitizing dye II:
- Anhydro
- 9-ethyl-3,3'-di-(3-sulfopropyl)-4,5,4',5'-dibenzo- thiacarbocyanine-hydroxide
- Sensitizing dye III:
- Anhydro
- 5,5'-diphenyl-9-ethyl-3,3'-di-(3-sulfopropyl)-oxacarbocyanine hydroxide
- Sensitizing dye IV:
- Anhydro 9-ethyl-3,3'-di-(3-sulfopropyl)-5,6,5',6'-dibenzooxacarbocyanine hydroxide
- Sensitizing dye V:
- Anhydro
- 3,3'-di-(3-sulfopropyl)-4,5-benzo-5'-methoxy- thiacyanine
- Subsequently, Samples 2 to 12 wherein the magenta coupler and the colored magenta coupler were varied as shown in Table 1 were produced.
-
-
-
-
- Results obtained are shown in Table 1.
- In Table 1, the amount of couplers added was indicated in terms of mole % per 1 mole of silver halide; the numerals in parentheses in the column of the amount indicate proportional percentage (%) to all the couplers in the corresponding layer; MTF indicates a relative value when Sample 1 was assumed to be 100; RMS is indicated by a 1,000 time value of the standard deviation in the density value fluctuation caused when a density point of the minimum density + 0.7 was scanned by use of a microdensitometer having an open scanning area of 250 µm2. Accordingly, the values indicate that, the larger the MTF is and the smaller the RMS is, the higher image quality has been achieved.
- As will be apparent from Table 1, both the sharpness and the graininess are remarkably improved in the samples in which the magenta coupler comprises pyrazolotriazole type magenta coupler and the colored magenta coupler is contained in the proportion of 17 % or more of the amount of all couplers in the layer containing the same.
-
Claims (20)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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JP1460586 | 1986-01-25 | ||
JP14605/86 | 1986-01-25 |
Publications (3)
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EP0232101A2 true EP0232101A2 (en) | 1987-08-12 |
EP0232101A3 EP0232101A3 (en) | 1989-01-25 |
EP0232101B1 EP0232101B1 (en) | 1994-03-23 |
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ID=11865832
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Application Number | Title | Priority Date | Filing Date |
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EP19870300640 Expired - Lifetime EP0232101B1 (en) | 1986-01-25 | 1987-01-26 | Light-sensitive silver halide color photographic material |
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EP (1) | EP0232101B1 (en) |
JP (1) | JPS62253170A (en) |
DE (1) | DE3789394D1 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0350022A2 (en) * | 1988-07-07 | 1990-01-10 | Konica Corporation | Silver halide color photographic light-sensitive material |
EP0646842A1 (en) * | 1993-09-30 | 1995-04-05 | Eastman Kodak Company | Photographic element containing an azopyrazolone masking coupler exhibiting improved keeping |
EP0651289A1 (en) * | 1993-09-30 | 1995-05-03 | Eastman Kodak Company | Photographic element containing an azopyrazolone masking coupler exhibiting reduced fogging |
US5482821A (en) * | 1993-09-30 | 1996-01-09 | Eastman Kodak Company | Photographic element containing an azopyrazolone masking coupler exhibiting improved keeping |
US5591569A (en) * | 1993-09-30 | 1997-01-07 | Eastman Kodak Company | Photographic element containing an azopyrazolone masking coupler exhibiting improved keeping |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH03160441A (en) * | 1989-11-20 | 1991-07-10 | Konica Corp | Silver halide color photographic sensitive material |
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DE2643965A1 (en) * | 1975-09-30 | 1977-04-07 | Fuji Photo Film Co Ltd | Subtractive colour photographic material - contg. coloured coupler of aryl arylamino arylazo pyrazolone type to give satisfactory masking |
EP0087930A1 (en) * | 1982-02-25 | 1983-09-07 | Konica Corporation | Light-sensitive silver halide color photographic material |
JPS6097353A (en) * | 1983-11-01 | 1985-05-31 | Fuji Photo Film Co Ltd | Color photographic sensitive silver halide material |
EP0152296A2 (en) * | 1984-02-10 | 1985-08-21 | Konica Corporation | Silver halide color photographic light-sensitive material |
EP0174873A2 (en) * | 1984-09-14 | 1986-03-19 | Konica Corporation | Silver halide color photo-sensitive material |
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JPS58113935A (en) * | 1981-12-26 | 1983-07-07 | Konishiroku Photo Ind Co Ltd | Silver halide color photosensitive material |
JPS59177551A (en) * | 1983-03-28 | 1984-10-08 | Konishiroku Photo Ind Co Ltd | Silver halide color photosensitive material |
JPS60262158A (en) * | 1984-06-08 | 1985-12-25 | Fuji Photo Film Co Ltd | Silver halide color photographic sensitive material |
-
1987
- 1987-01-26 DE DE87300640T patent/DE3789394D1/en not_active Expired - Lifetime
- 1987-01-26 JP JP1556087A patent/JPS62253170A/en active Pending
- 1987-01-26 EP EP19870300640 patent/EP0232101B1/en not_active Expired - Lifetime
Patent Citations (5)
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DE2643965A1 (en) * | 1975-09-30 | 1977-04-07 | Fuji Photo Film Co Ltd | Subtractive colour photographic material - contg. coloured coupler of aryl arylamino arylazo pyrazolone type to give satisfactory masking |
EP0087930A1 (en) * | 1982-02-25 | 1983-09-07 | Konica Corporation | Light-sensitive silver halide color photographic material |
JPS6097353A (en) * | 1983-11-01 | 1985-05-31 | Fuji Photo Film Co Ltd | Color photographic sensitive silver halide material |
EP0152296A2 (en) * | 1984-02-10 | 1985-08-21 | Konica Corporation | Silver halide color photographic light-sensitive material |
EP0174873A2 (en) * | 1984-09-14 | 1986-03-19 | Konica Corporation | Silver halide color photo-sensitive material |
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0350022A2 (en) * | 1988-07-07 | 1990-01-10 | Konica Corporation | Silver halide color photographic light-sensitive material |
EP0350022A3 (en) * | 1988-07-07 | 1990-09-26 | Konica Corporation | Silver halide color photographic light-sensitive material |
EP0646842A1 (en) * | 1993-09-30 | 1995-04-05 | Eastman Kodak Company | Photographic element containing an azopyrazolone masking coupler exhibiting improved keeping |
EP0651289A1 (en) * | 1993-09-30 | 1995-05-03 | Eastman Kodak Company | Photographic element containing an azopyrazolone masking coupler exhibiting reduced fogging |
US5482821A (en) * | 1993-09-30 | 1996-01-09 | Eastman Kodak Company | Photographic element containing an azopyrazolone masking coupler exhibiting improved keeping |
US5591569A (en) * | 1993-09-30 | 1997-01-07 | Eastman Kodak Company | Photographic element containing an azopyrazolone masking coupler exhibiting improved keeping |
US5641613A (en) * | 1993-09-30 | 1997-06-24 | Eastman Kodak Company | Photographic element containing an azopyrazolone masking coupler exhibiting improved keeping |
Also Published As
Publication number | Publication date |
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EP0232101B1 (en) | 1994-03-23 |
JPS62253170A (en) | 1987-11-04 |
EP0232101A3 (en) | 1989-01-25 |
DE3789394D1 (en) | 1994-04-28 |
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