EP0438791B1 - Matériau photographique à l'halogénure d'argent sensible à la lumière - Google Patents

Matériau photographique à l'halogénure d'argent sensible à la lumière Download PDF

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Publication number
EP0438791B1
EP0438791B1 EP19900125597 EP90125597A EP0438791B1 EP 0438791 B1 EP0438791 B1 EP 0438791B1 EP 19900125597 EP19900125597 EP 19900125597 EP 90125597 A EP90125597 A EP 90125597A EP 0438791 B1 EP0438791 B1 EP 0438791B1
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Prior art keywords
silver halide
silver
tabular
sensitive material
grains
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EP19900125597
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German (de)
English (en)
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EP0438791A1 (fr
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Shigeru c/o Fuji Photo Film Co. Ltd. Shibayama
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/0051—Tabular grain emulsions

Definitions

  • the present invention relates to a silver halide photographic light-sensitive material having high sensitivity, high contrast and improved graininess and sharpness.
  • a tabular silver halide grain (to be referred to as a tabular grain hereinafter), when a surface area/volume ratio is increased to increase an adsorption amount of a sensitizing dye, its sensitivity is expected to be improved as light absorption increases.
  • a tabular grain therefore, is superior to a non-tabular grain (e.g., an octahedral grain) having the same volume in a sensitivity/graininess relationship.
  • a tabular grain since a tabular grain has only a small light scattering effect due to its geometrical shape, not only sharpness in a layer containing tabular grains but also that of its underlying layer (located farther from a light source) can be improved. According to a relationship between the shape of an emulsion grain and light scattering described in Research Disclosure No 25330 (May, 1985), the shape of an emulsion grain largely contributes to an improvement in sharpness of a silver halide photographic light-sensitive material.
  • a tabular grain having a high aspect ratio makes it difficult to prepare an emulsion in which a grain size is monodispersed Since a grain size is polydispersed consequentially, a sensitivity distribution is widened between grains to decrease the contrast.
  • a decrease in contrast leads to, e.g., an increase in silver coating amount.
  • the increase in silver amount increases a manufacturing cost, and an increase in light scattering which decreases sharpness. If a film is softened in order to compensate for the decrease in contrast, graininess is degraded, and the film is easily damaged during treatments.
  • a coupler coating amount is increased in a color photographic light-sensitive material, disappearance of graininess in the layer is lost due to a decrease in silver/coupler ratio, thereby degrading the graininess
  • a silver halide photographic light-sensitive material comprising at least one silver halide emulsion layer containing a silver halide emulsion prepared by adding at least one compound represented by the following general formula (I), (II), or (III) during a manufacturing process,
  • Compounds represented by the general formulas (I) to (III) may be polymers containing divalent groups derived from structures represented by the formulas (I) to (III) as repeating units. If possible, R, R 1 , R 2 , and L may be bonded each other to form a ring.
  • the tabular silver halide grains occupying at least 50% of the total projected area preferably consist of silver iodobromide, silver iodochloride, or silver iodochlorobromide each containing 3.0 mol% or more of silver iodide on an average, and a relative standard deviation between silver iodide contents of individual grains is preferably 30% or less.
  • a tabular grain is a grain having a plurality of parallel twinning planes and a tabular outer shape regardless of its aspect ratio. Although a grain having no twinning plane and an aspect ratio of 2 or more is included in the tabular grain, a tabular grain having twinning planes is preferred.
  • An example of the latter tabular grain is an anisotropically grown regular crystal grain as reported by A. Mignot et al. in Journal of Cryst. Growth, Vol. 23, page 207 (1974).
  • an aspect ratio means a ratio of a diameter with respect to a thickness of a silver halide grain. That is, the aspect ratio is a value obtained by dividing the diameter of each silver halide grain by its thickness.
  • the diameter is a diameter of a circle having an area equal to a projected area of a silver halide grain upon observation of the grain by an optical microscope or electron microscope. Therefore, when the aspect ratio is 3 or more, the diameter of a circle is three times or more the thickness of a grain.
  • An average aspect ratio is obtained as follows. That is, 1,000 silver halide grains of the emulsion are extracted at random to measure their aspect ratios, tabular grains are selected, until that reaches 50% of the total projected area in the order from the one with the highest aspect ratio, and an average of aspect ratios of the selected tabular grains is calculated. An average of a diameter or thickness of the tabular grains used to calculate the aspect ratio corresponds to an average grain size or average grain thickness.
  • An example of an aspect ratio measuring method is a method of photographing an image obtained by a transmission electron microscope with a replica technique to obtain a sphere-equivalent diameter and a thickness of each grain. In this case, the thickness is calculated from the length of a shadow of the replica.
  • the average aspect ratio of the tabular grains used in the present invention is 3.0 or more, preferably, 3.0 to 20.0, and most preferably, 3.0 to 8.0.
  • a ratio occupied by tabular grains in a projected area of all the silver halide grains is 50% or more, preferably, 70% or more, and more preferably, 85% or more.
  • An average grain size of the tabular grains used in the present invention is 0.2 to 10.0 pm, and preferably, 0.3 to 5.0 pm, and an average grain thickness thereof is preferably 0.5 ⁇ m or less. More preferably, the average grain size is 0.3 ⁇ m to 5.0 pm, the average grain thickness is 0.5 pm or less, the average aspect ratio is 3.0 to 8.0, and 85% or more of a total projected area of all silver halide grains of the layer are occupied by the tabular grains.
  • the tabular grains used in the present invention are described in reports by Cugnac or Chateau, Duffin, "Photographic Emulsion Chemistry” (Focal Press, New York, 1966), pp. 66 to 72, and A.P.H. Trivelli, W.F. Smith ed., "Phot. Journal” 80 (1940), p 285.
  • the tabular grains can be easily prepared by methods described in JP-A-58-113927, JP-A-58-113928, and JP-A-58-127921 ("JP-A” means published unexamined Japanese patent application).
  • the emulsions can be prepared by forming a seed crystals including 40% (by weight) or more of tabular grains in an atmosphere in which a pBr is 1.3 or less and pAg is relatively high, and simultaneously adding silver and halogen solutions to grow the seed crystals while the pBr value is maintained substantially constant. In this grain growth process, it is preferred to add the silver and halogen solutions so that no new crystal nucleus is generated.
  • the size of the tabular silver halide grain can be adjusted by controlling a temperature, selecting the type or quality of a solvent, or controlling addition rates of silver salts and halides used in grain formation.
  • a grain size distribution of the tabular grains may be either wide or narrow. In general, however, it is difficult to prepare so-called monodispersed tabular grains having a narrow grain size distribution as compared with non-tabular grains (especially an octahedral regular-crystal grain). The reason why the tabular grains cannot be monodispersed by the conventional techniques is assumed that a growth mechanism of the tabular grains is not exactly the same as that of non-tabular grains (especially an octahedral regular crystal grain).
  • the present inventors made extensive studies of a technique entirely different from the conventional grain size monodispersing technique to achieve the expected object and could obtain a light-sensitive material having high sensitivity and contrast and improved graininess and sharpness. That is, the contrast could be improved by adding at least one compound represented by the general formulas [I] to [III] described above during a manufacturing process of a silver halide emulsion.
  • the silver halide manufacturing process is roughly classified into, e.g., grain formation, desalting, chemical sensitization, and coating steps.
  • the grain formation step is subdivided into, e.g., nucleation, ripening, and growth. These steps are performed not in a predetermined order but in a reverse order or repeatedly.
  • the present invention contains a silver halide emulsion prepared by adding at least one compound represented by the above formulas [I] to [III] during the manufacturing process.
  • "During the manufacturing process” means that a compound can be basically added at any timing in the manufacturing process.
  • the compound is preferably added before chemical sensitization.
  • the compound is most preferably added during grain formation.
  • the compound can be added in a reaction vessel beforehand, it is preferably added at an arbitrary timing during grain formation.
  • a compound represented by general formula [I], [II] ; or [I I can be added in an aqueous solution of a water-soluble silver salt or water-soluble alkali halide to perform grain formation by using the aqueous solution.
  • a method of adding a solution of a compound represented by general formula [I], [II] ; or [III] several times during grain formation or a method of continuously adding it over a long time period during grain formation is also preferable.
  • a compound represented by general formula [I], [II], or [II is preferably added in an amount of 10- 7 to 10 -1 mol per mol of a silver halide.
  • the addition amount is more preferably 10- 6 to 10- 2 mol/mol Ag, and most preferably, 10- 5 to 1 0- 3 mol/mol Ag.
  • a conventional method of adding an additive in a photographic emulsion can be adopted to add compounds represented by general formulas [I] to [III] in a manufacturing process.
  • a water-soluble compound can be added in the form of an aqueous solution having an arbitrary concentration, and a water-insoluble compound or a compound which is hardly dissolved in water is dissolved in an arbitrary organic solvent such as alcohols, glycols, ketones, esters, and amides, which is miscible with water and does not adversely affect photographic properties, and then added as a solution.
  • R, R 1 , and R 2 are aliphatic groups, it is a saturated or unsaturated, straight-chain, branched, or cyclic aliphatic hydrocarbon group and is preferably an alkyl group having 1 to 22 carbon atoms, or an alkenyl group or an alkinyl group having 2 to 22 carbon atoms. These groups may have substituents.
  • alkyl group examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, isopropyl, and t-butyl.
  • alkenyl group examples include allyl and butenyl.
  • alkinyl group examples are propargyl and butynyl.
  • An aromatic group of R, R 1 , and R 2 includes a monocyclic or condensed ring aromatic group and preferably has 6 to 20 carbon atoms. Examples of such an aromatic group are phenyl and naphthyl. These groups may be substituted.
  • a heterocyclic group of R, R 1 , and R 2 is a 3- to 15-membered ring, preferably, a 3- to 6-membered ring having at least one element of nitrogen, oxygen, sulfur, selenium, and tellurium and at least one carbon atom.
  • the heterocyclic group are pyrrolidine, piperidine, pyridine, tetrahydrofurane, thiophene, oxazole, thiazole, imidazole, benzothiazole, benzoxazole, benzimidazole, selenazole, benzoselenazole, tellurazole, triazole, benzotriazole, tetrazole, oxadiazole, and thiadiazole.
  • R, R 1 , and R 2 are an alkyl group (e.g., methyl, ethyl, and hexyl), an alkoxy group (e.g., methoxy, ethoxy, and octyl), an aryl group (e.g., phenyl, naphthyl, and tolyl), a hydroxy group, a halogen atom (e.g., fluorine, chlorine, bromine, and iodine), an aryloxy group (e.g., phenoxy), an alkylthio group (e.g., methylthio and butylthio), an arylthio group (e.g., phenylthio), an acyl group (e.g., acetyl, propionyl, butyryl, and valeryl), a sulfonyl group (e.g., methylsulfonyl and phenylsul
  • a divalent linking group represented by L is an atom or an atom group containing at least one of C, N, S, and O.
  • L are an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, -S-, -NH-, -CO-, and -S0 2 -. These compounds can be used singly or in a combination of two or more thereof.
  • L is preferably a divalent aliphatic group or a divalent aromatic group.
  • divalent aromatic group of L are a phenylene group and a naphthylene group.
  • M is preferably a metal ion or an organic cation.
  • the metal ion are a lithium ion, a sodium ion, and a potassium ion.
  • the organic cation are an ammonium ion (e.g., ammonium, tetramethylammonium, and tetrabutylammonium), a phosphonium ion (e.g., tetraphenylphosphonium), and a guanidyl group.
  • the above polymer may be a homopolymer or a copolymer with another comonomer.
  • a most preferable compound is a compound represented by general formula [I].
  • an efficiency (to be referred to as a latent image formation efficiency hereinafter) of converting photoelectrons generated by light absorption due to emulsion grains into a silver cluster (latent image) is known to be important as one factor having an effect on the sensitivity of emulsion grains. It is known that the latent image formation efficiency is not uniform but has a distribution between grains even in one emulsion. Therefore, if the distribution of the latent image formation efficiency between grains is widened, a sensitivity distribution between the grains is widened to decrease contrast. Although various factors having an effect on the latent image formation efficiency are possible, the latent image formation efficiency may be decreased if an unnecessary electron trap is present in an emulsion grain. A silver nucleus to be introduced in a grain during the manufacturing process of an emulsion can be such an electron trap.
  • a grain having a low latent image formation efficiency has a silver nucleus as an unnecessary electron trap inside or on the surface of the grain.
  • This silver nucleus is converted into a silver sulfide nucleus upon addition of compounds represented by general formulas [I] to [III], and the latent image formation efficiency is improved to narrow its distribution, thereby increasing the contrast.
  • the tabular silver halide grains consist of silver iodobromide, silver iodochloride, or silver iodochlorobromide each having an average silver iodide content of 3.0 mol% or more, and preferably, 3.0 to 30.0 mol%.
  • a grain structure considered in terms of a halogen composition of the tabular silver halide grains used in the present invention may be a double or multiple structure or a structure in which a composition distribution is localized.
  • the grain structure is preferably a double or multiple structure.
  • the tabular grains used in the present invention contain silver iodide, wherein the relative standard deviation between silver iodide contents of the individual grains is 30% or less, and more preferably, 20% or less.
  • a silver iodide content of each grain can be measured by analyzing the composition of the grain by using, e.g., an X-ray microanalyzer.
  • the "relative standard deviation between silver iodide contents of the individual grains” is a value calculated by dividing a standard deviation between silver iodide contents measured for at least 100 emulsion grains by an average silver iodide content and multiplying the obtained value by 100.
  • the silver iodide content of each grain can be measured in accordance with a method described in JP-A-62-209445.
  • a light-sensitive material of the present invention preferably, at least silver halide emulsion layer, each having blue-, green-, and red-sensitivity are formed on a support, and the number and arrangement of silver halide emulsion layers and non-light-sensitive layers are not particularly limited.
  • Typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer constituted by a plurality of silver halide emulsion layers sensitive to essentially the same color but having different sensitivities on a support.
  • the light-sensitive layer is a unit light-sensitive layer having sensitivity to blue, red, or green light.
  • unit light-sensitive layers are generally arranged such that red-, green-, and blue-sensitive layers are formed in the order named from a support. In accordance with an application, however, this order may be reversed, or light-sensitive layers having the same color sensitivity may sandwich another light-sensitive layer having different color sensitivity
  • Non-light-sensitive layers such as various types of interlayers may be formed between the silver halide light-sensitive layers or as an uppermost or lowermost layer.
  • the interlayer may contain, e.g., couplers and DIR compounds described in JP-A-61-43748, JP-A-59-113438, JP-A-59-113440, JP-A-61-20037, and JP-A-61-20038 or may contain a color mixing inhibitor as in a normal application.
  • a plurality of silver halide emulsion layers constituting each unit light-sensitive layer may preferably adopt a double-layered arrangement of high- and low-sensitivity emulsion layers as described in West German Patent 1,121,470 or British Patent 923,045. Normally, these layers are preferably arranged such that the sensitivity is sequentially decreased toward a support. In addition, a non-light-sensitive layer may be formed between the silver halide emulsions.
  • the emulsion layers may be arranged such that a low-sensitivity emulsion layer is formed apart from a support and a high-sensitivity layer is formed near the support as described in, e.g., JP-A-57-112751, JP-A-62-200350, JP-A-62-206541, and JP-A-62-206543.
  • the layers may be arranged, from the farthest position from a support, in an order of low-sensitivity blue-sensitive layer (BL)/high-sensitivity blue-sensitive layer (BH)/high-sensitivity green-sensitive layer (GH)/low-sensitivity green-sensitive layer (GL)/high-sensitivity red-sensitive layer (RH)/low-sensitivity red-sensitive layer (RL), an order of BH/BUGUGH/RH/RL, or an order of BH/BUGH/GURURH.
  • BL low-sensitivity blue-sensitive layer
  • BH high-sensitivity blue-sensitive layer
  • GH high-sensitivity green-sensitive layer
  • GL low-sensitivity red-sensitive layer
  • RH low-sensitivity red-sensitive layer
  • RL low-sensitivity red-sensitive layer
  • the layers may be arranged in an order of blue-sensitive layer/GH/RH/GURL from the farthest position from a support as described in JP-B-55-34932 ("JP-B" means published examined Japanese patent application).
  • the layers may be arranged in an order of blue-sensitive layer/GURUGH/RH from the farthest position from a support as described in JP-A-56-25738 and JP-A-62-63936.
  • the layers may be arranged such that a silver halide emulsion layer having highest sensitivity is formed as an upper layer, a silver halide emulsion layer having sensitivity lower than that of the upper layer is formed as an intermediate layer, and a silver halide emulsion layer having sensitivity lower than that of the intermediate layer is formed as a lower layer, i.e., three layers having different sensitivities may be arranged such that the sensitivity is sequentially decreased toward a support.
  • emulsion layers may be arranged in a layer having the same color sensitivity in an order of medium-sensitivity emulsion layer/high-sensitivity emulsion layer/low-sensitivity emulsion layer from the farthest position from a support as described in JP-A-59-202464.
  • the layers may be arranged in an order of high-sensitivity emulsion layer/low-sensitivity emulsion layer/medium-sensitivity emulsion layer or an order of low-sensitivity emulsion layer/medium-sensitivity emulsion layer/high-sensitivity emulsion layer.
  • a donor layer (CL) exhibiting an interlayer effect which has a spectral sensitivity distribution different from that of a main light-sensitive layer such as BL, GL, or RL is preferably formed adjacent to or close to the main light-sensitive layer as described in U.S Patents 4,663,271, 4,705,744, and 4,707,436, JP-A-62-160448, and JP-A-63-89850.
  • various layer constituents and arrangements can be selectively used in accordance with an application of a light-sensitive material.
  • a preferable silver halide to be contained in a photographic emulsion layer of the photographic light-sensitive material according to the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide each containing about 30 mol% of silver iodide.
  • the silver halide is most preferably silver iodobromide or silver iodochlorobromide containing about 2 mol% to about 25 mol% of silver iodide.
  • the silver halide grains in the photographic emulsion may be grains having a regular crystal such as a cubic, octahedral, or tetradecahedral crystal, grains having an irregular crystal such as a spherical or tabular crystal, grains having a crystal defect such as a twinning plane, or grains having a composite form thereof.
  • the silver halide grains may be fine grains having a grain size of about 0.2 ⁇ m or less or large grains having a projected area diameter of up to about 10 ⁇ m and may be a polydispersed or monodispersed emulsion.
  • the silver halide photographic emulsion for use in the present invention can be prepared by using methods described in, for example, Research Disclosure (RD) No. 17643 (December, 1978), pp. 22 and 23, "I. Emulsion preparation and types” and RD No. 18716 (November, 1979), page 648; P. Glafkides, "Chimie et Physique Photographique", Paul Montel, 1967; G.F. Duffin, "Photographic Emulsion Chemistry", Focal Press, 1966; and V. L. Zelikman et al., “Making and Coating Photographic Emulsion", Focal Press, 1964.
  • tabular grains having an average aspect ratio of 3.0 or more and not using compounds represented by general formulas [I] to [III] in the manufacturing process can also be used in the present invention.
  • the tabular grains can be easily prepared by methods described in, for example, Gutoff, Photographic Science and Engineering, Vol. 14, pp. 248 to 257, (1970); and U.S. Patents 4,434,226, 4,414,310, 4,433,048, and 4,439,520, and British Patent 2,112,157.
  • a crystal structure may be uniform, may have different halogen compositions inside and outside a crystal, or may be a layered structure.
  • a silver halide having different compositions may be bonded by an epitaxial junction, or a compound other than a silver halide such as silver rhodanide or zinc oxide may be bonded.
  • a mixture of grains having various crystal shapes may also be used.
  • the silver halide emulsion is normally subjected to physical ripening, chemical ripening, and spectral sensitization before it is used.
  • Additives for use in such a process are described in Research Disclosure Nos. 17643 and 18716, and they are summarized in a table to be presented later.
  • a non-light-sensitive fine grain silver halide is preferably used.
  • the non-light-sensitive fine grain silver halide consists of silver halide fine grains which are not sensitive enough during imagewise exposure for obtaining a dye image and essentially not developed during development.
  • the silver halide grains are preferably not fogged in advance.
  • the fine grain silver halide has a silver bromide content of 0 to 100 mol% and may contain silver chloride and/or silver iodide at need.
  • the fine grain silver halide preferably contains 0.5 to 10 mol% of silver iodide.
  • An average grain size (average value of circle-equivalent diameters of projected areas) of the fine grain silver halide is preferably 0.01 to 0.5 ⁇ m, and more preferably, 0.02 to 0.2 ⁇ m.
  • the fine grain silver halide can be prepared by the same method as for a conventional light-sensitive silver halide.
  • the surface of a silver halide grain need not be optically sensitized nor spectrally sensitized.
  • a known stabilizer such as a triazole-, azaindene-, benzothiazolium-, or mercapto-based compound or a zinc compound is preferably added.
  • a compound which can react with and fix formaldehyde described in U.S. Patent 4,411,987 or 4,435,503 is preferably added to the light-sensitive material.
  • various color couplers can be used in the light-sensitive material. Specific examples of these couplers are described in above-described Research Disclosure, No. 17643, VII-C to VII-G as patent references.
  • a yellow coupler Preferable examples of a yellow coupler are described in, e.g., U.S. Patents 3,933,501, 4,022,620, 4,326,024, 4,401,752, and 4,248,961, JP-B-58-10739, British Patents 1,425,020 and 1,476,760, U.S. Patents 3,973,968, 4,314,023, and 4,511,649, and EP 249,473A.
  • magenta coupler examples are preferably 5-pyrazolone and pyrazoloazole compounds, and more preferably, compounds described in, e.g., U.S Patents 4,310,619 and 4,351,897, EP 73,636, U.S. Patents 3,061,432 and 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552, Research Disclosure No. 24220 (June 1984), JP-A-60-43659, JP-A-61-72238, JP-A-60-35730, JP-A-55-118034, JP-A-60-185951, U.S. Patents 4,500,630, 4,540,654, and 4,556,630, and WO No. 04795/88.
  • Examples of a cyan coupler are phenol and naphthol couplers, and preferably, those described in, e.g., U.S. Patents 4,052,212, 4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,334,011, and 4,327,173, West German Patent Application (OLS) No. 3,329,729, EP 121,365A EP 249,453A, U.S. Patents 3,446,622, 4,333,999, 4,775,616, 4,451,559, 4,427,767, 4,690,889, 4,254,212, and 4,296,199, and JP-A-61-42658.
  • Typical examples of a polymerized dye-forming coupler are described in, e.g., U.S. Patents 3,451,820, 4,080,211, 4,367,282, 4,409,320, and 4,576,910, British Patent 2,102,137, and EP 341,188A.
  • a coupler capable of forming colored dyes having proper diffusibility are those described in U.S. Patent 4,366,237, British Patent 2,125,570, EP 96,570, and West German Patent Application (OLS) No. 3,234,533.
  • a colored coupler for correcting additional, undesirable absorption in a colored dye are those described in Research Disclosure No. 17643, item VII-G, U.S. Patent 4, 163, 670, JP-B-57-39413, US. Patents 4,004,929 and 4,138,258, and British Patent 1,146,368.
  • a coupler for correcting additional, undesirable absorption in a colored dye by a fluorescent dye released upon coupling described in U.S. Patent 4,774,181 and a coupler having, as a split-off group, a dye precursor group capable of forming a dye upon reaction with a developing agent described in U.S. Patent 4,777,120 are also preferable.
  • Couplers releasing a photographically useful moiety upon coupling are also preferably used in the present invention.
  • Preferable examples of a DIR coupler releasing a development inhibitor are described in the patents cited in the above-described Research Disclosure No. 17643, VII-F, JP-A-57-15194, JP-A-57-154234, JP-A-60-184248, JP-A-63-37346, JP-A-63-37350, and U.S. Patents 4,248,962 and 4,782,012
  • a coupler imagewise releasing a nucleating agent or a development accelerator upon development are those described in British Patent 2,097,140, 2,131,188, and JP-A-157638 and JP-A-59-170840.
  • Examples of a compound which can be used in the light-sensitive material of the present invention are competing couplers described in, e.g., U.S. Patent 4,130,427; poly-equivalent couplers described in, e.g., U.S.
  • Patents 4,283,472, 4,338,393, and 4,310,618 a DIR redox compound releasing coupler, a DIR coupler releasing coupler, a DIR coupler releasing redox compound, or a DIR redox releasing redox compound described in, e.g., JP-A-60-185950 and JP-A-62-24252; couplers releasing a dye which turns to a colored form after being split off described in EP 173 ; 302A and EP 313,308A; bleaching accelerator releasing couplers described in, e.g., RD. Nos.
  • legand releasing coupler described in, e.g., U.S. Patent 4,555,477; a leuco dye releasing coupler described in JP-A-63-75747; and a coupler releasing a fluorescent dye described in U.S. Patent 4,774,181.
  • the couplers for use in this invention can be introduced in the light-sensitive material by various known dispersion methods.
  • a high-boiling organic solvent for use in the oil-in-water dispersion method and having a boiling point of 175°C or more at normal pressure are phthalate esters (e.g., dibulylphthalate, dicyclohexylphthalate, di-2-ethylhex- ylphthalate, decylphthalate, bis(2,4-di-t-amylphenyl)phthalate, bis(2,4-di-t-amylphenyl)isophthalate, and bis(1,1-diethyl- propyl)phthalate), phosphate or phosphonate esters (e.g., triphenylphosphate, tricresylphosphate, 2-ethylhexyldiphe- nylphosphate, tricyclohexylphosphate, tri-2-ethylhexylphosphate, tridodecylphosphate, tributoxyethylphosphate, trichlo-
  • An organic solvent having a boiling point of about 30°C or more, and preferably, 50°C to about 160°C can be used as a co-solvent.
  • Typical examples of the co-solvent are ethyl acetate, butyl acetate, ethyl propionate, methylethylketone, cyclohexanone, 2-ethoxyethylacetate, and dimethylformamide.
  • an antiseptic agent or an antifungal agent such as phenethyl alcohol or 1,2-benzisothiazoline-3-one, n-butyl-p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, and 2-(4-thiazolyl)benzimidazole described in JP-A-63-257747, JP-A-62-272248, and JP-A-1-80941 are preferably added.
  • the present invention can be applied to various color light-sensitive materials
  • the material are a color negative film for a general purpose or a movie, a color reversal film for a slide or a television, color paper, a color positive film, and color reversal paper.
  • Examples of a support suitable for use in this invention are described, e.g., in the above-mentioned RD. No. 17643, page 28 and ibid., No. 18716, page 647, right column to page 648, left column.
  • a total film thickness of all hydrophilic colloidal layers on a side having emulsion layers is 28 pm or less, preferably, 23 ⁇ m or less, more preferably, 18 ⁇ m or less, and most preferably, 16 ⁇ m or less.
  • a film swelling rate T 1/2 is preferably 30 seconds or less, and more preferably, 20 seconds or less.
  • the term "film thickness” means a film thickness measured under the controlled humidity of a relative humidity of 55% at 25°C (two days), and the film swelling rate T 1/2 can be measured in accordance with known methods in this field of art. For example, T 1/2 can be measured by using a swellometer (dilatometer) described in A.
  • T 1/2 is defined as a time required for that the film thickness reaches 1/2 of the saturated film thickness.
  • the film swelling rate T 1/2 can be adjusted by adding a film hardener to gelatin as a binder or by changing aging conditions after coating.
  • a swelling ratio is preferably 150% to 400%.
  • the swelling ratio can be calculated from the maximum swelling film thickness obtained under the conditions described above in accordance with equation : (maximum swelling film thickness - film thickness)/film thickness.
  • the color photographic light-sensitive materials of this invention can be developed by the conventional methods as described in, e.g., the above-described Research Disclosure, No. 17643, pages 28 and 29 and ibid., No. 18716, page 651, left to right columns.
  • a color developer used in developing of the light-sensitive material of the present invention is an aqueous alkaline solution mainly consisting of, preferably, an aromatic primary amine-based color developing agent.
  • an aromatic primary amine-based color developing agent although an aminophenol-based compound is effective, a p-phenylenediamine-based compound is preferably used.
  • Typical examples of the p-phenylenediamine-based compound are 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-p-methoxyethylaniline, and sulfates, hydrochlorates, and p-toluenesulfonates thereof.
  • 3-methyl-4-amino-N-ethyl-N-p-hydroxyethylaniline sulfate is most preferable.
  • These compounds can be used in a combination of two or more thereof in accordance with applications.
  • the color developer contains a pH buffer such as a carbonate, a borate or a phosphate of an alkali metal, and a development restrainer or antifoggant such as a chloride, a bromide, an iodide, a benzimidazole, a benzothiazole or a mercapto compound.
  • a pH buffer such as a carbonate, a borate or a phosphate of an alkali metal
  • a development restrainer or antifoggant such as a chloride, a bromide, an iodide, a benzimidazole, a benzothiazole or a mercapto compound.
  • the color developer may also contain a preservative such as hydroxylamine, diethylhydroxylamine, sulfite, a hydrazine such as N,N-biscarboxymethylhydrazine, a phenylsemicarbazide, triethanolamine, and a catechol sulfonic acid; an organic solvent such as ethyleneglycol and diethyleneglycol; a development accelerator such as benzylalcohol, polyethyleneglycol, a quaternary ammonium salt or an amine; a dye forming coupler; a competing coupler; an auxiliary developing agent such as 1-phenyl-3-pyrazolidone; a viscosity imparting agent; and a chelating agent such as an aminopolycarboxylic acid, an aminopolyphosphonic acid, an alkylphosphonic acid, and a phosphonocarboxylic acid.
  • a preservative such as hydroxylamine, diethylhydroxylamine, sulfite,
  • Examples of the chelating agent are ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydrox- yelhylidene-1,1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N,N-tetramethyl- enephosphonic acid and ethylenediamine-di(o-hydroxyphenylacetic acid), and salts thereof.
  • black-and-white development is performed and then color development is performed.
  • black-and-white developer well-known black-and-white developing agents, e.g., a dihydroxybenzene such as hydroquinone, a 3-pyrazolidone such as 1-phenyl-3-pyrazolidone, and an aminophenol such as N-methyl-p-aminophenol can be used singly or in a combination of two or more thereof.
  • the pH of the color and black-and-white developers is generally 9 to 12.
  • a quantity of replenisher of the developer depends on the type of a color photographic light-sensitive material to be processed, it is generally 3 liters or less per m 2 of the light-sensitive material.
  • the quantity of replenisher can be decreased to be 500 mf or less by decreasing a bromide ion concentration in a replenisher.
  • a contact area of the replenisher in a processing tank with air is preferably decreased to prevent evaporation and oxidation of the replenisher upon contact with air.
  • a contact area between a photographic processing solution and air in a processing tank can be represented by a numerical aperture to be defined below:
  • the numerical aperture is preferably 0.1 or less, and more preferably, 0.001 to 0.05.
  • Examples of a method of decreasing the numerical aperture are, in addition to a method of providing a shielding member such as a floating cover on the surface of a photographic processing solution in the processing tank, a method of using a movable cover described in JP-A-1-82033 and a slit developing method described in JP-A-63-216050.
  • the numerical aperture is preferably decreased not only in color development and black/white development steps but also in all subsequent steps such as bleaching, bleach-fixing, fixing, washing, and stabilizing steps.
  • a quantity of replenisher can be decreased by using a means for suppressing accumulation of bromide ions during developer.
  • a time required for color development is normally set between 2 to 5 minutes.
  • the processing time can be shortened by setting a high temperature and a high pH and using the color developing agent at a high concentration.
  • the photographic emulsion layer is generally subjected to bleaching after color development.
  • the bleaching may be performed either simultaneously with fixing (bleach-fixing) or independently therefrom.
  • bleach-fixing may be performed after bleaching.
  • processing may be performed in a bleach-fixing bath having two continuous tanks, fixing may be performed before bleach-fixing, or bleaching may be performed after bleach-fixing, in accordance with applications.
  • the bleaching agent are a compound of a multivalent metal such as iron (III); a peroxide; a quinone; and a nitro compound.
  • Typical examples of the bleaching agent are an organic complex salt of iron (III), e.g., a complex salt of an aminopolycarboxylic acid such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycoletherdiaminetetraacetic acid, or a complex salt of citric acid, tartaric acid, or malic acid.
  • an aminopolycarboxylic acid such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycoletherdiaminetetraacetic acid, or a complex salt of citric acid, tartaric acid, or malic acid.
  • an aminopolycarboxylatoferrate (III) complex such as ethylenediaminetetraacetatoferrate (II complex and 1,3-diaminopropanotetraacetoferrate (II complex are preferable because they can increase a processing speed and prevent an environmental contamination.
  • the aminopolycarboxylatoferrate (III) complex is effective in both the bleaching and bleach-fixing solutions.
  • the pH of the bleaching or bleach-fixing solution using the aminopolycarboxylatoferrate (III) complex is normally 4.0 to 8. In order to increase the processing speed, however, processing can be performed at a lower pH.
  • a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath, if necessary.
  • Effective examples of the bleaching accelerator are compounds having a mercapto group or a disulfide group described in, e.g., U.S.
  • Patent 3,893,858 West German Patents 1,290,812 and 2,059,989, JP-A-53-32736, JP-A-53-57831, JP-A-53-37418, JP-A-53-72623, JP-A-53-95630, JP-A-53-95631, JP-A-53-104232, JP-A-53-124424, JP-A-53-141623, JP-A-53-28426, and Research Disclosure No.
  • 17129 July, 1978; a thiazolidine derivative described in JP-A-50-140129; thiourea derivatives described in JP-B-45-8506, JP-A-52-20832, JP-A-53-32735, and U.S.
  • a compound having a mercapto group or a disulfide group is preferable since it has a large accelerating effect.
  • Patent 3,893,858, West German Patent 1,290,812, and JP-A-53-95630 are preferable.
  • a compound described in U.S. Patent 4,552,834 is also preferable.
  • These bleaching accelerators may be added in the light-sensitive material. These bleaching accelerators are effective especially in bleach-fixing of a color light-sensitive material for picture taking with camera.
  • a bleaching solution and a bleach-fixing solution preferably contain an organic acid in order to prevent a bleach stain.
  • organic acid are compounds having an acid dissociation constant (pKa) of 2 to 5, e.g., acetic acid and propionic acid.
  • Examples of the fixing agent used in the fixing solution or bleach-fixing solution are a thiosulfate a thiocyanate, a thioether-based compound, a thiourea, and a large amount of an iodide.
  • a thiosulfate especially, ammonium thiosulfate can be used in a widest range of applications.
  • a thiosulfate can be preferably used together with a thiocyanate, a thioether-based compound, and a thiourea.
  • a sulfite, a bisulfite, a carbonyl bisulfite adduct, or a sulfinic acid compound described in EP 294,769A is preferable.
  • various types of aminopolycarboxylic acids or organic phosphonic acids are preferably added.
  • a total time of a desilvering step is preferably short as long as no desilvering failure occurs. The total time is preferably one to three minutes, and more preferably, one to two minutes.
  • the processing temperature is 25°C to 50°C, and preferably, 35°C to 45°C. Within a preferable temperature range, a desilvering rate is increased, and generation of stains after the processing can be effectively prevented.
  • the degree of stirring is preferably maximized.
  • a method of increasing the degree of stirring are a method of pelting a jet stream of a processing solution against an emulsion surface of a light-sensitive material described in JP-A-62-183460, a method of enhancing a stirring effect by using a rotary means described in JP-A-62-183461, a method of moving a light-sensitive material while a wiper blade provided in a processing solution is brought into contact with an emulsion surface to produce a turbulent flow on the emulsion surface, thereby enhancing a stirring effect, and a method of increasing a circulating flow amount of a processing solution as a whole.
  • Such methods for improving stirring are effective in any of a bleaching solution, a bleach-fixing solution, and a fixing solution.
  • An improvement in stirring is assumed to increase a supply rate of a bleaching agent or a fixing agent into an emulsion film, thereby increasing a desilvering rate.
  • the above methods for improving stirring are more effective when a bleaching accelerator is used. As a result, an accelerating effect can be conspicuously enhanced, or a fixing interrupting effect caused by a bleaching accelerator can be eliminated.
  • An automatic developing machine for developing a light-sensitive material of the present invention preferably has light-sensitive material conveyor means described in JP-A-60-191257, JP-A-60-191258, and JP-A-60-191259.
  • such conveyor means can conspicuously reduce an amount of a processing solution carried from a pre-bath to a post-bath, thereby effectively preventing degradation in performance of the processing solution. This effect particularly reduces a processing time or a quantity of a processing solution replenisher in each step.
  • the photographic light-sensitive material of the present invention is normally subjected to washing and/or stabilizing steps after desilvering.
  • An amount of water used in the washing step can be arbitrarily determined over a broad range in accordance with the properties (e.g., a property determined by use of a coupler) of the light-sensitive material, the application of the material, the temperature of the water, the number of water tanks (the number of stages), a replenishing mode representing a counter or forward current, and other conditions.
  • the relationship between the amount of water and the number of water tanks in a multi-stage counter-current mode can be obtained by a method described in Journal of the Society of Motion Picture and Television Engineers, Vol. 64, pp. 248 - 253 (May, 1955).
  • the amount of water used for washing can be greatly decreased. Since washing water stays in the tanks for a long period of time, however, bacteria multiply and floating substances generated may be undesirably attached to the light-sensitive material.
  • a method of decreasing calcium and magnesium ions can be effectively utilized, as described in JP-A-62-288838.
  • a germicide such as an isothiazolone compound and thiabendazole described in JP-A-57-8542, a chlorine-based germicide such as chlorinated sodium isocyanurate, and germicides such as benzotriazole described in Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents” (1986), Sankyo Shuppan, Eiseigijutsu-kai ed., “Sterilization, Antibacterial, and Antifungal Techniques for Microorganisms” (1982), Industrial Technique Society, and Nippon Bokin Bobabi Gakkai ed., “Dictionary of Antibacterial and Antifungal Agents” (1986).
  • the pH of the water for washing the photographic light-sensitive material of the present invention is 4 to 9, and preferably 5 to 8.
  • the water temperature and the washing time can vary in accordance with the properties and applications of the light-sensitive material. Normally however, the washing time is 20 seconds to 10 minutes at a temperature of 15°C to 45°C, and preferably, 30 seconds to 5 minutes at 25°C to 40°C.
  • the light-sensitive material of the present invention can be processed directly by a stabilizer in place of washing. All known methods described in JP-A-57-8543, JP-A-58-14834, and JP-A-60-220345 can be used in such stabilizing processing.
  • Stabilizing is sometimes performed subsequently to washing.
  • An example is a stabilizing bath containing dye stabilizer and a surfactant to be used as a final bath of a color light-sensitive material for picture taking with camera.
  • the dye stabilizer are an aldehyde such as formalin and glutaraldehyde, an N-methylol compound, hexamethylenetetramine, and an aldehyde sulfite adduct.
  • Various chelating agents or antifungal agents can be added in this stabilizing bath.
  • An overflow solution produced upon washing and/or replenishment of the stabilizer can be reused in another step such as a desilvering step.
  • water is preferably added to correct a concentration.
  • the silver halide photographic light-sensitive material of the present invention may contain a color developing agent in order to simplify processing and increase a processing speed
  • a color developing agent for this purpose, various types of precursors of color developing agents are preferably used.
  • the precursor are an indoaniline-based compound described in U.S. Patent 3,342,597, Schiff base compounds described in U.S. Patent 3,342,599, Research Disclosure Nos. 14,850 and 15,159, an aldol compound described in Research Disclosure No. 13,924, a metal salt complex described in U.S. Patent 3,719,492, and an urethane-based compound described in JP-A-53-135628.
  • the silver halide photographic light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary.
  • Typical examples of the compound are described in JP-A-56-64339, JP-A-57-144547, and JP-A-58-115438.
  • Each processing solution for the light-sensitive material of the present invention is used at a temperature of 10°C to 50°C. Although a normal processing temperature is 33°C to 38°C, processing may be accelerated at a higher temperature to shorten a processing time, or image quality or stability of a processing solution may be improved at a lower temperature.
  • the silver halide photographic light-sensitive material of the present invention can also be applied to light-sensitive materials for heat development described in, e.g., U.S. Patent 4,500,626, JP-A-60-133449, JP-A-59-218433, JP-A-61-238056, and EP 210,660A2.
  • aqueous solution containing 145 g of silver nitrate was prepared. Equimolar amounts of the aqueous solution and an aqueous solution mixture of potassium bromide and potassium iodide were added to the seed emulsion at a predetermined temperature and a predetermined pAg while an addition rate was maintained constant, thereby preparing a tabular core emulsion.
  • An aspect ratio was adjusted by selecting the pAg upon core/shell preparation.
  • an aspect ratio was adjusted by selecting the pAg upon core and shell preparation.
  • Measurement results of the emulsions Em-A to Em-F are summarized in Table 1-1
  • a grain volume an average sphere-equivalent diameter of each of the emulsions Em-A to Em-F was 1.2 pm.
  • Each of the emulsions Em-A to Em-F was an emulsion in which 85% or more of a projected area of all grains were occupied by tabular grains having a plurality of parallel twinning planes.
  • an average silver iodide content of each of the emulsions Em-A to Em-F was 7.6 mol% in fomulation.
  • a compound 1-2 or a compound 1-16 was added in amounts shown in Table 1-2 immediately before starting of shell formation to perform grain formation, thereby preparing emulsions Em-1 to Em-28.
  • the compound 1-16 was added in an amount shown in Table 1-2 immediately before starting of grain formation of a core emulsion to perform grain formation, thereby preparing an emulsion Em-29.
  • the compound 1-16 was added in an amount shown in Table 1-2 10 minutes before starting of chemical sensitization to prepare an emulsion Em-30.
  • Each of the emulsions Em-1 to Em-30 was optimally subjected to gold-plus-sulfur sensitization by using sodium thiosulfate and chloroauric acid.
  • the following dyes were added to the emulsions Em-1 to Em-30 immediately before coating, thereby performing spectral sensitization.
  • Emulsion and protective layers were coated in the following amounts on supports made of triacetylcellulose film having undercoating layers.
  • compositions of processing solutions used in the above steps were as follows.
  • a light source was adjusted at a color temperature of 4,800°K by using a filter, and a yellow filter (SC-52 (tradename): available from Fuji Photo Film Co. Ltd.) was used.
  • each emulsion of the present invention using the compound 1-2 or 1-16 has lower fog and higher sensitivity and gamma, i.e., has improved contrast, than those of the emulsions other than the present invention not using the compounds.
  • the emulsions Em-19 and Em-26 having narrow silver iodide content distributions between grains have slightly higher sensitivities and gammas than those of the emulsions Em-4 and Em-11 having close aspect ratios, respectively.
  • the emulsions Em-20 to Em-25, Em-27, and Em-28 having narrow silver iodide content distributions have an effect which conspicuously improves gamma as compared with the emulsions Em-5 to Em-10 and Em-12 to Em-15 having wide silver iodide content distributions.
  • the gamma improving effect can be obtained in case of an addition of compounds represented by general formulas [I] to [III] during the grain formation process.
  • a sample as a multilayered color light-sensitive material constituted by layers having the following compositions was formed on an undercoated cellulose triacetate film support.
  • compositions of light-sensitive layers are provided.
  • the coating amounts of a silver halide and colloidal silver are represented in units of g/m 2 of silver, those of a coupler, an additive, and gelatin are represented in units of g/m 2 , and that of a sensitizing dye is represented by the number of mols per mol of the silver halide in the same layer. Note that formulas of compounds represented by characters are listed in Table B to be presented later.
  • B-1 (0.20 g/m 2 in total), 1,2-benzisothiazolin-3-one (about 200 ppm on the average with respect to gelatin), n-butyl-p-hydroxybenzoate (about 1,000 ppm on the average with respect to gelatin), and 2-phenoxyethanol (about 10,000 ppm on the average with respect to gelatin) were added to the layers.
  • Example 1 The emulsion prepared in Example 1 was used as the silver iodobromide emulsion I of the layer 8.
  • the sensitizing dyes were added to the emulsion immediately before coating A correspondence between numbers of the formed samples and emulsions contained in the layer 8 of the samples is shown in Table 2-1.
  • each sample was subjected to white wedge exposure for 1/100 second in accordance with a conventional method and developed as follows.
  • compositions of processing solutions used in the above steps were as follows.
  • Sensitometry measurement was performed for the developed samples to obtain characteristic curves with respect to green light.
  • M.T.F. Modulation Transfer Function
  • the light-sensitive material of the present invention produces low fog and has high gamma, i.e., has a great contrast improving effect.
  • the compound is added to the silver halide emulsion during formation of silver halide grains.
  • a plurality of layers having the following compositions were coated on an undercoated support made of triacetylcellulose film to prepare a sample as a multi-layered color light-sensitive material.
  • compositions of light-sensitive layers are provided.
  • Emulsions listed in Table 3-1 to be presented later were used in light-sensitive emulsion layers.
  • Formulas of compounds represented by characters are listed in Table C to be presented later.
  • Numerals corresponding to the respective components indicate coating amounts in units of g/m 2 .
  • a coating amount of the silver halide is represented in a silver converted score.
  • a coating amount of the sensitizing dye is represented in units of mols per mol of the silver halide in the same layer.
  • a gelatin hardener H-1 or a surfactant were added to each layer.
  • the emulsion prepared in Example 1 was used as the silver iodobromide emulsion G of the layer 12.
  • the sensitizing dyes were added to the emulsions at the end of chemical sensitization.
  • a correspondence between the numbers of the formed samples and the emulsions contained in the layer 12 of the samples is shown in Table 3-2.
  • the light-sensitive material of the present invention is excellent in sharpness and has a high gamma value, i.e., has high contrast.
  • the light-sensitive material of the present invention produces low fog.
  • each sample of the present invention was excellent in sharpness and had a great effect of increasing the gamma, i.e., improving the contrast.
  • a quantity of replenisher is represented in per meter of a 35-mm wide sample.
  • compositions of the processing solutions will be described below.
  • Washing solution common for mother solution and replenisher solutions
  • Tap water was supplied to a mixed-bed column filled with an H type strongly acidic cation exchange resin (Amberlite IR-120B: available from Rohm & Haas Co.) and an OH type strongly basic anion exchange resin (Amberlite IR-400) to set calcium and magnesium ion concentrations to be 3 mg/f or less. Subsequently, 20 mg/f of dichlorinated sodium isocyanurate and 1.5 g/l of sodium sulfate were added. The pH of the solution fell within the range of 6.5 to 7.5
  • Stabilizing solution common for mother solution and replenisher (g)
  • each sample of the present invention was excellent in sharpness and had a great effect of increasing the gamma, i.e., of improving the contrast.
  • Stabilizing solution common to mother solution and replenisher (g)
  • Em-1 ⁇ 30 thus produced, just prior to coating, theredy spectral senitizing Em-1 ⁇ 30:

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Claims (9)

1. Matériau photographique photosensible à l'halogénure d'argent comprenant au moins une couche d'émulsion d'halogénure d'argent contenant une émulsion d'halogénure d'argent préparée en ajoutant au cours d'un processus de fabrication, au moins un composé acide thiosulfonique représenté par la formule générale ci-dessous (1), (II) ou (III),
dans lequel au moins 50% de la surface projetée totale de tous les grains d'halogénure d'argent de ladite couche d'émulsion sont occupés par des grains tabulaires d'halogénure d'argent constitués d'iodobromure d'argent, d'iodochlorure d'argent ou d'iodochlorobromure d'argent, contenant chacun en moyenne pas moins de 3,0% molaires d'iodure d'argent, un indice de forme desdits grains tabulaires d'halogénure d'argent occupant au moins 50% de la surface projetée totale vaut 3,0 ou davantage, et un écart type relatif entre les teneurs en iodure d'argent des grains individuels n'est pas supérieur à 30%:
Figure imgb0162
Figure imgb0163
Figure imgb0164
dans lesquelles R, R1 et R2 peuvent être identiques ou différents et représentent indépendamment un groupe aliphatique, un groupe aromatique ou un groupe hétérocyclique, M représente un cation, L représente un groupe de liaison bivalent et m représente 0 ou 1, des composés représentés par les formules générales (I) à (III) pouvant être des polymères contenant comme motifs récurrents des groupes bivalents dérivés de structures représentées par les formules générales (I) à (III), et R, R1, R2 et L pouvant être liés l'un à l'autre pour former un cycle, si possible.
2. Matériau photographique photosensible à l'halogénure d'argent selon la revendication 1, caractérisé en ce qu'un indice de forme desdits grains tabulaires d'halogénure d'argent vaut 3,0 à 20, et une épaisseur moyenne desdits grains tabulaires d'halogénure d'argent vaut 0,5 µm ou moins.
3. Matériau photographique photosensible à l'halogénure d'argent selon la revendication 1, caractérisé en ce qu'un indice de forme desdits grains tabulaires d'halogénure vaut 3,0 à 8,0, et une épaisseur moyenne desdits grains tabulaires d'halogénure d'argent vaut 0,5 µm ou moins.
4. Matériau photographique photosensible à l'halogénure d'argent selon la revendication 1, caractérisé en ce qu'au moins 85% de ladite surface projetée totale sont occupés par lesdits grains tabulaires d'halogénure d'argent, un indice de forme desdits grains tabulaires d'halogénure vaut 3,0 à 8,0, et une épaisseur moyenne desdits grains tabulaires d'halogénure vaut 0,5 µm ou moins.
5. Matériau photographique photosensible à l'halogénure d'argent selon la revendication 1, caractérisé en ce qu'au moins un composé représenté par la formule générale (1), (II) ou (III) est ajouté au cours de la formation des grains.
6. Matériau photographique photosensible à l'halogénure d'argent selon la revendication 1, caractérisé en ce qu'au moins un composé représenté par la formule générale (1), (II) ou (III) est ajouté au cours de la formation des grains, en quantité de 10-5 mole à 10-3 mole par mole d'halogénure d'argent.
7. Matériau photographique photosensible à l'halogénure d'argent selon la revendication 1, caractérisé en ce qu'un composé représenté par la formule générale (I) est ajouté au cours de la formation des grains en quantité de 10-5 mole à 10-3 mole par mole d'halogénure d'argent.
8. Matériau photographique photosensible à l'halogénure d'argent selon la revendication 1, caractérisé en ce qu'un composé représenté par la formule générale (I) est ajouté au cours de la formation des grains en quantité de 10-5 mole à 10-3 mole par mole d'halogénure d'argent, et ledit grain tabulaire d'halogénure d'argent présente une structure double ou multiple.
9. Matériau photographique photosensible à l'halogénure d'argent selon la revendication 1, caractérisé en ce qu'un composé représenté par la formule générale (I) est ajouté au cours de la formation des grains en quantité de 10-5 mole à 10-3 mole par mole d'halogénure d'argent, ledit grain tabulaire d'halogénure d'argent présente une structure double ou multiple, et l'écart type relatif entre les teneurs en iodure d'argent dans les grains tabulaires individuels vaut 20% ou moins.
EP19900125597 1989-12-26 1990-12-27 Matériau photographique à l'halogénure d'argent sensible à la lumière Expired - Lifetime EP0438791B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP1337684A JP2896465B2 (ja) 1989-12-26 1989-12-26 ハロゲン化銀写真感光材料
JP337684/89 1989-12-26

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EP0438791A1 EP0438791A1 (fr) 1991-07-31
EP0438791B1 true EP0438791B1 (fr) 1996-03-20

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JP2805407B2 (ja) * 1991-10-18 1998-09-30 富士写真フイルム株式会社 ハロゲン化銀感光材料
EP0613042B1 (fr) * 1993-02-25 2005-08-17 Fuji Photo Film Co., Ltd. Procédé pour la préparation d'émulsion de cristaux d'ensemencement
DE69615036T2 (de) 1996-11-13 2002-04-18 Eastman Kodak Co Verfahren zur Herstellung einer Silberhalogenidemulsion

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JPS5827486A (ja) * 1981-08-10 1983-02-18 Sony Corp 映像信号再生装置
JPS60254032A (ja) * 1983-12-29 1985-12-14 Fuji Photo Film Co Ltd 感光性ハロゲン化銀乳剤
JPH0766157B2 (ja) * 1986-02-03 1995-07-19 富士写真フイルム株式会社 感光性ハロゲン化銀乳剤
JPS63280243A (ja) * 1987-05-13 1988-11-17 Fuji Photo Film Co Ltd ハロゲン化銀写真乳剤
JP2664153B2 (ja) * 1987-06-05 1997-10-15 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料およびその現像処理方法
JPH01102453A (ja) * 1987-10-15 1989-04-20 Fuji Photo Film Co Ltd ハロゲン化銀乳剤およびハロゲン化銀カラー写真感光材料
JP2519794B2 (ja) * 1989-01-25 1996-07-31 富士写真フイルム株式会社 ハロゲン化銀カラ―写真感光材料
JPH03172836A (ja) * 1989-12-01 1991-07-26 Fuji Photo Film Co Ltd ハロゲン化銀乳剤及びこれを用いるハロゲン化銀写真感光材料

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DE69026062T2 (de) 1996-10-17
JPH03196137A (ja) 1991-08-27
JP2896465B2 (ja) 1999-05-31
DE69026062D1 (de) 1996-04-25
EP0438791A1 (fr) 1991-07-31

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