EP0096727B1 - Emulsion photographique a base d'halogenure d'argent et son procede de preparation - Google Patents

Emulsion photographique a base d'halogenure d'argent et son procede de preparation Download PDF

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Publication number
EP0096727B1
EP0096727B1 EP19830900065 EP83900065A EP0096727B1 EP 0096727 B1 EP0096727 B1 EP 0096727B1 EP 19830900065 EP19830900065 EP 19830900065 EP 83900065 A EP83900065 A EP 83900065A EP 0096727 B1 EP0096727 B1 EP 0096727B1
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EP
European Patent Office
Prior art keywords
silver halide
emulsion
grains
crystals
silver
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Expired
Application number
EP19830900065
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German (de)
English (en)
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EP0096727A1 (fr
EP0096727A4 (fr
Inventor
Takeo Koitabashi
Toshifumi Iijima
Toshihiko Yagi
Yuji Hotta
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Konica Minolta Inc
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Konica Minolta Inc
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Publication of EP0096727A1 publication Critical patent/EP0096727A1/fr
Publication of EP0096727A4 publication Critical patent/EP0096727A4/fr
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Publication of EP0096727B1 publication Critical patent/EP0096727B1/fr
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Classifications

    • 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
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • 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
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/0357—Monodisperse emulsion
    • 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
    • G03C2200/00—Details
    • G03C2200/06—Additive

Definitions

  • This invention relates to light-sensitive silver halide emulsion for photography and more particularly to a silver iodobromide type light-sensitive silver halide emulsion of which the sensitivity, the antifogging property and the storability have been improved, and a method for preparing the same.
  • a monodispersed emulsion is advantageous not nnly for attainment of sensitization in a silver halide emulsion but also for an effective performance of'high sensitivity with keeping a fogging property low in a step referred to as chemical sensitization which will be described in more detail below.
  • Silver halide emulsions prepared under such a condition as mentioned above comprise so called regular crystal grains which have any shape of cube, octahedron and tetradecahedron and have the face (100) and the face (111) at various proportions.
  • the present inventors prepared monodispersed emulsions comprising octahedral or tetradecahedral grains and conducted the generally known chemical sensitization thereon, however, they could merely obtain results equivalent or rather inferior indeed to those given by polydispersed emulsions generally used in the art.
  • octahedral grains have not heretofore been employed for negative type high sensitivity light-sensitive materials, although octahedral grains are assumed to have a good relationship between the anti-fogging property and the sensitivity according to Japanese Patent Publication No.
  • Such characteristics of octahedral grains can be understood from reports in Journal of Photographic Science 14; 181-184 (1966); ibid, 16: 102-113 (1968); Photographic Korrespondenz, 106: 149-160 (1970) and Journal of Japanese Photographic Society, 42; 112-121 (1979). Further, since the progress of the chemical sensitization of tetradecahedral grains is expected to be dominated by the face (111), tetradecahedral grains are considered to exhibit the same characteristic as that of octahedral grains and actually our studies have revealed that tetradecahedral grains have a property similar to that of octahedral grains.
  • the term physical ripening is defined as follows: a procedure in which grains with a large specific surface area are dissolved in a solvent to deposit or precipitate upon larger grains and thereby crystal growth are performed while reducing the number of grains. In physical ripening, it is thus a prerequisite to have grains grow by utilizing the difference in solubilities among grains having different grain sizes and therefore grain size distribution becomes generally broadened after physical ripening, so that it is considered to be not preferably as a method for preparing a monodispersed emulsion.
  • An object of the present invention is to provide a light-sensitive silver halide emulsion having a low fogging property and a high sensitivity.
  • Another object of the present invention is to provide a light-sensitive silver halide emulsion having an excellent storability.
  • Still another object of the present invention is to provide a method for preparing such a light-sensitive silver halide emulsion as described above.
  • a monodispersed silver halide emulsion having silver halide grains which have octahedral crystals or tetradecahedral crystals primarily constituted of the face (111) and comprise substantially iodobromide grains, the grains having the characteristic features that they exhibit roundness at the vertices of the crystal faces the radius of curvature of said roundness being, for octahedral crystals, 1/10 r-1/6 r with respect to the angle of the vertex, wherein r is a length of one side in a triangle supposedly formed by extending sides of one arbitrary outer surface of a crystal and, for tetradecahedral crystals, 1/10 r-1/6 r with respect to
  • the invention also relates to a manufacturing method for a silver halide emulsion characterized in that a monodispersed silver halide emulsion having monodispersed silver grain which comprise octahedral crystals or tetradecahedral crystals constituted mainly of the face (111) and which substantially comprise silver iodobromide grains is subjected, after formation of said silver halide grains, to treatment with a thioether or thiourea solvent until the radius of curvature of roundness at the vertices of the crystal faces of said silver halide grains is, for octahedral crystals, 1/10 r-1/6 r with respect to the angle of the vertex, wherein r is a length of one side in a triangle supposedly formed by extending sides of one arbitrary outer surface of the crystal, and for tetradecahedral crystals, 1/10 r-1/6 r with respect to the angle, wherein r is a length of the longest side
  • silver halide grains which are tetradecahedral crystals comprise crystals primarily constituted of the face (111), namely, comprise grains giving the external appearance of hexagon and square and grains giving the external appearance of square and triangle, 30% or more of total surface area in the grains having been occupied by the area of said face (111).
  • Grains comprising crystals primarily constituted of the face (100) and giving the external appearance of octagon and triangle are not preferable for the objects of the present invention.
  • an emulsion in which 20% or more (in terms of number of the grains) of total silver halide grains contained therein consist of silver halide grains having such a roundness as described above is preferable and also as to the degree to which the grains are subjected to treatment with a solvent for a silver halide (hereinafter referred to as "solvent treatment") in the manufacturing method, it is similarly preferable.
  • solvent treatment a solvent for a silver halide
  • the intensity of the diffracted ray for the face (220) is preferably less than 8% of that for the face (111).
  • the grain size is expressed by the diameter of the circumcircle in an electron microscopic photograph of the silver halide grain.
  • the monodispersed silver halide emulsion to be treated with the solvent is such that the silver halide grains contained therein consist essentially of octahedral or tetradecahedral silver halide crystals. Further, breadth of the grain size distribution of the silver halide grains contained in the monodispersed silver halide emulsion to be treated with a solvent is 15% or less in terms of CV and more preferably 10% or less.
  • solvent treatment may be conducted merely by adding the thioether or thiourea solvent for a silver halide (AgX) to a silver halide emulsion in which silver halide grains have been formed into the final size and shape through completion of a mixing or a mixing followed by a physical ripening procedure; and subsequently by mixing uniformly to act said solvent onto the surface of the silver halide grain. Therefore, there may be employed a procedure similar to a procedure for the conventional chemical ripening in which a solvent is used in place of a chemical sensitizer. Moreover, after formation of silver halide grains, there may be conducted desalting (including washing with water) prior to the solvent treatment. The solvent treatment is itself followed by desalting and chemical ripening.
  • AgX silver halide
  • desalting including washing with water
  • the solvents for silver halide employed in the present invention are (a) organic thioethers as described in the specifications of US-A-3271157, 3531289 and 3574628; JO-A-1019/1979 and -158917/1979; or (b) thiourea derivatives as described in JP-A-82408/1978, -77737/1980 and -2982/1980.
  • the silver halide emulsion of the present invention has a lower fogging property and a higher sensitivity as compared with an emulsion which comprises grains consisting of octahedral crystals ortetra- decahedral crystals which have been subjected to solvent treatment to be shaped into a spherical form, a confetto-like form (defined as such, when a recess at a central part of the face (111) of the grain has a depth of 0.20 I or more, wherein I represents a diameter of the circumsphere for the grain) or a potato-like form (defined as such, when an outer crystal habit of the grain is indefinite and irregular).
  • the manufacturing method for the silver halide emulsion of the present invention it is desirable that there are essentially no differences in the average grain size and in the grain size distribution of the silver halide grains contained in the emulsion between those before and after solvent treatment, respectively.
  • the effect of the method of the present invention is remarkably large as compared with the effect in case out of this range. It is inferred that this is attributable to the fact that the degree of the physical ripening becomes remarkable in case said difference is out of this range. If grain size distribution of the silver halide emulsion to be subjected to solvent treatment ranges within the value of CV described above, the physical ripening is hard to occur and thereby the effect of the present invention can be sufficiently exhibited, with a result that the difference between grain size distributions before and after solvent treatment falls approximately within the range described above.
  • the silver halide emulsion of the present invention includes, as one of the embodiments, an emulsion comprising two or more kinds of the monodispersed emulsions according to the present invention having different average grain sizes in admixture with each other.
  • an emulsion comprising two or more kinds of the monodispersed emulsions according to the present invention having different average grain sizes in admixture with each other.
  • the silver halide grains to be treated with a solvent are octahedral crystals or tetradecahedral crystals described above and an effect given by grains having these crystal habits is unexpectedly large and remarkable as compared with that given by grains having other crystal habits than said habits.
  • the manufacturing method of the present invention is characterized in that after formation of silver halide grains, the grains are treated with the specific solvent for a silver halide to a specifically determined degree, before desalting and hence it is different from a technique in which a solvent for a silver halide, for example, ammonia is present at the time of formation of silver halide grains.
  • the monodispersed emulsion having silver halide grains comprising octahedral crystals or tetradecahedral crystals is preferably one prepared according to the ammonia method.
  • This invention exhibits particularly large effect when it is applied to a silver halide emulsion for color development.
  • the sensitivity in an emulsion subjected to solvent treatment of the present invention reaches about five times the sensitivity given by an emulsion prepared without such solvent treatment of the present invention and further increase in fogging is scarcely observed even at such a high sensitivity.
  • Silver halide grains according to the present invention may coexist with a cadmium salt, a zinc salt, a lead salt, a thallium salt, a iridium salt or complex salts thereof, a rhodium salt or a complex salt thereof, or an ion complex salt in the course of formation of grains or treatment with the solvent.
  • Silver iodobromide grains of the present invention preferably contain silver iodide at proportion of 0.5 to 15 mole% and more preferably 10 mole% or less.
  • Silver halide grains of the present invention may be different in phases between inner portion and surface layer thereof or may comprise a uniform phase. Regardless of the distribution in composition of halogen within silver halide grains described above, reduction sensitization may be conducted at any stage before completion of grain growth and treatment with a solvent.
  • Silver halide grains according to the present invention have preferably an average grain size of 0.1-4 ⁇ m and more preferably of 0.2-2 pm.
  • the light-sensitive silver halide emulsion according to the present invention may be subjected to doping treatment using various kinds of metallic salts or metallic complex salts during formation of silver halide precipitates, during or after grain growth.
  • metallic salts and complex salts of gold, platinum, palladium, iridium, rhodium, bismuth, cadmium, copper, and combinations of these salts.
  • the method for preparing the emulsion of the present invention there may be suitably employed, as means for desalting, the Nudel rinsing, dialysis or a coagulation technique, which is commonly employed in a general emulsion manufacture.
  • chemical ripening may be conducted by use, singly or in combination, of chemical sensitizers such as noble metal sensitizers, including water-soluble gold salts, water-soluble platinum salts, water-soluble palladium salts, water-soluble rhodium salts or water-soluble iridium salts; a sulfur sensitizer; a selenium sensitizer; and reduction sensitizers including polyamine, and stannous chloride.
  • chemical sensitizers such as noble metal sensitizers, including water-soluble gold salts, water-soluble platinum salts, water-soluble palladium salts, water-soluble rhodium salts or water-soluble iridium salts
  • sulfur sensitizer a selenium sensitizer
  • reduction sensitizers including polyamine, and stannous chloride.
  • the silver halide emulsion of the present invention can optically be sensitized to a desired wave length region.
  • a spectral sensitization method for the emulsion of the present invention is not particularly critical and can be accomplished, for example, by use, singly or in combination (e.g., supersensitization) of spectral sensitizers such as cyanine dyes or merocyanine dyes including a zeromethine dye, a mono- methine dye, a dimethine dye, and a trimethine dye.
  • the monodispersed silver halide emulsion of the present invention may be put to use keeping its grain size distribution intact or may be put to use in combination with two or more monodispersed emulsions having different average grain sizes by blending these emulsions at an arbitrary stage so as to obtain a desired gradation.
  • the emulsion of the present invention may include an emulsion containing silver halide grains other than those of the present invention to such an extent that the effectiveness of the present invention is not thereby impaired.
  • the emulsion of the present invention may include generally usable various additives depending on the purposes thereof.
  • additives described above there are mentioned, for example, stabilizers and antifogging agents such as azaindenes, triazoles, tetrazoles, imidazolium salts, tetrazolium salts and polyhydroxy compounds; hardeners such as aldehyde series, aziridine series, isoxazole series, vinylsulfonic series, acryloyl series, carbodiimimde series, maleimide series, methanesulfonic ester series and triazine series; development accelerators such as benzyl alcohol and polyoxyethylene series compounds; image stabilizers such as chroman series, coumaran series, bisphenol series and phosphorous ester series; lubricants such as waxes, glycerides of higher fatty acids and higher esters of higher fatty acids.
  • a coating agent improvers for permeability of a treatment solution, defoaming agents and agents for controlling various physical properties of light-sensitive materials
  • a various type of surfactants such as those of anionic type, cationic type, nonionic type or amphoteric type.
  • antistatic agents diacetylcellulose, styrene perfluoroalkyllithium maleate copolymer, and an alklai salt of a reaction product between styrene maleic anhydride copolymer and p-aminobenzenesulfonic acid are effective.
  • matting agents there may be mentioned methyl polymethacrylate, polystyrene and alkali-soluble polymers.
  • colloidal silica As latexes which are added to improve the physical properties of the coated film, there may be mentioned acrylic esters and vinyl esters, and their copolymers with the other monomers having an ethylic group. As gelatin plasticizers there may be mentioned glycerin and glycol series compounds, and as thickening agents there may be mentioned styrene-sodium maleate copolymer and alkyl vinyl ether-maleate copolymer.
  • supports for the light-sensitive material manufactured by the use of the emulsion of the present invention which is prepared in the above-mentioned manner there may be mentioned, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass paper, cellulose acetate, cellulose nitrate, polyvinyl acetal, polypropylene, a polyester film, for example, polyethyleneterephthalate, and polystyrene.
  • the support is suitably selected from them depending upon the use and the purpose of the silver halide light-sensitive photographic material, respectively.
  • Supports may be provided with undercoating if desired.
  • the emulsion of the present invention may be effectively used for a variety of light-sensitive materials for general black and white photography, X-ray photography, color photography, infrared photography, microphotography, silver dye bleach process, reversal development, and the diffusion transfer process. Among uses described above, it is particularly effectively used for color photography to which color development is applied.
  • cyan, magenta and yellow couplers in a combination into the emulsion of the present invention which has previously been adjusted for red-sensitivity, green- sensitivity and blue-sensitivity.
  • yellow couplers there may be used open-chain ketomethylene series couplers known to the art, among which benzoylacetanilide series and pivaloylacetanilide series compounds are useful.
  • magenta couplers there may be used pyrazolone series compounds, indazalone series compounds and cyanoacetyl compounds and as cyan couplers, phenol series compounds, and naphthol series compounds.
  • the light-sensitive material prepared by the use of the emulsion of the present invention may be developed by a known method commonly used after exposure.
  • the black and white developer is an alkaline solution containing developing agents such as hydroxy benzenes, aminophenols, or aminobenzenes, and it may further contain alkali metal salts such as a sulfite, a carbonate, a bisulfite, a bromide and an iodide.
  • developing agents such as hydroxy benzenes, aminophenols, or aminobenzenes
  • alkali metal salts such as a sulfite, a carbonate, a bisulfite, a bromide and an iodide.
  • the light-sensitive material is for color photography, it may be developed by a color developing process which is commonly used. In a reversal process, it is firstly developed by a developer for a black and white negative and then subjected to white color exposure, or subjected to treatment in a bath containing an antifogging agent, and further developed for color development in an alkaline developing solution containing color developing agents.
  • any method may be applied.
  • the obtained emulsion was divided into six portions, to each of which, tetramethylthiourea or a thioether represented by the formula [I] was added to conduct ripening at 50°C, followed by desalting and washing with water according to the ordinary method and then pAg value was adjusted to 8.2 at 40°C.
  • These emulsions were designated as Em - 1 to Em - 6.
  • Table 1 added amounts of tetramethylthiourea and thioether [I] and results with respect to grain shapes after treatment obtained by observation through an electron microscope.
  • Em - 1 to Em - 6 in Example 1 0.45 ml of a 0.2% by weight aqueous chloroauric acid tetrahydrate solution and 1.5 ml of a 0.25% by weight aqueous sodium thiosulfate dihydrate solution based on one mole of AgX were added respectively and subjected to chemical ripening at 46°C for 110, 80, 30, 80, 30 and 30 minutes, respectively.
  • Samples described above were exposed through an optical wedge, developed at 38°C for 2 minutes by the use of the same color developing solution as in Example 1 and washed with water after bleaching and fixing to be subjected to evaluation of the sensitivity and the antifogging property.
  • Samples other than Sample Nos. 13, 16, 19, 22, 25 and 28 were, however, exposed through a glass filter Y-48 (manufactured by Toshiba Glass Co., Ltd.). Results in sensitometry are shown in Table 6.
  • a monodispersed octahedral series emulsion which was prepared in the same manner as in Comparative emulsion Em - 1 in Example 1, and followed by desalting and washing with water without treatment with a solvent was divided into two portions. 0.45 ml of a 0.2% by weight aqueous chloroauric acid tetrahydrate solution and 1.5 ml of a 0.25% by weight aqueous sodium thiosulfate dihydrate solution based on one mole of AgX each were added to both two portions and tetramethylthiourea and thiourea [I] were added in an amount of 5 mg and 150 mg to each portions, respectively and the resultant emulsions were subjected to chemical ripening at 46°C.
  • Example 1 the additives were added in the same manner as in Example 1, followed by coating and drying. These samples are designated as Sample Nos. 31 and 32. After completion of heat treatment of Sample Nos. 31 and 32 together with Sample Nos. 1, 3, and 7 at 55°C under a relative humidity (R.H.) of 80% for 72 hours, the same developing treatment and sensitometry as in Example 1 were conducted to compare with samples prepared without heat treatment. The results where shown in Table 8.
  • an emulsion having the same value of latitude as in the thus obtained emulsion was prepared according to the following method.
  • Em - 8: Em - 9 7: 3 in terms of the ratio between weights of silver halide in Em - 8 and Em - 9, additives were added in the same manner as described in Example 1, and the mixture was coated to obtain Sample No. 34.
  • an emulsion prepared by blending monodispersed emulsions according to the present invention was superior to a polydispersed emulsion treated with a solvent, in the antifogging property and the sensitivity.
  • a monodispersed tetradecahedral series emulsion (giving appearances of hexagon and square) which comprises silver iodobromide containing 2 mole% of silver iodide and has an average grain size of 0.70 ⁇ m was prepared.
  • This emulsion was divided and to each emulsion tetramethylthiourea or thioether [1] was added and the resultant emulsions were subjected to ripening at 50°C for 60 minutes and adjusted to pAg 8.2 at 40°C after desalting and washing with water.
  • These emulsions were designated as Em - 10 to Em - 14.
  • Added amounts of tetramethylthiourea and thioether [1] and results of observation on grain shapes after treatment obtained through an electron microscope are shown in Table 10.
  • Em - 10 to 14 there were conducted chemical ripening, addition of additives, coating and drying in the same manner as in Example 1 except that two time amount of sodium thiosulfate were added and chemical ripening was conducted for a period of time as shown in Table 11 to prepare Sample Nos. 35 to 44. With respect to samples thus obtained development treatment and sensitometry were conducted in the same manner as in Example 1. There are shown particulars of samples in Table 11 and results obtained by sensitometry in Table 12.
  • an emulsion having silver halide grains consisting of tetradecahedral crystals according to the present invention exhibits a remarkably higher sensitivity as compared with an emulsion having tetradecahedral crystal grains which have not been subjected to solvent treatment, though a slight change in grain shapes was observed, and further is able to reach a higher level of sensitivity and gives a mild increase in fogging generated by chemical ripening as compared with Em -12 and Em - 14 in which crystals are formed into spherical shapes by solvent treatment with increased amount of solvent, and thereby the degree of progress for fogging was decreased.
  • an emulsion having cubic crystals exhibit a lower sensitivity as compared with the emulsion according to the present invention and further accelerates fogging which is liable to be induced during chemical sensitization.
  • a monodisperse emulsion having tetradecahedral crystals which comprises silver iodobromide containing 2 mole% of silver iodide and has an average grain size of 0.8 11m was prepared.
  • This emulsion was divided and to each of emulsions ammonium rhodanide, tetramethylthiourea or thioether was added; then the emulsions thus obtained were subjected to solvent treatment at 50°C for 60 minutes, followed by adjustment of the pAg value to 8.2.
  • the emulsions thus obtained are designated as Em -19 to Em - 22. Added amounts of solvents and results of observation on grain shapes after treatment obtained through an electron microscope are shown in Table 16.
  • an octahedral series emulsion having an average grain size of 0.65 pm was prepared.
  • This emulsion was divided into three portions and to each of the divided emulsions tetramethylthiourea was added in an amount shown in Table 19 and the emulsions thus obtained were subjected to ripening followed by adjustment of pAg to 8.2 at 40°C after desalting and washing with water according to an ordinary method. These emulsions were designated Em - 23 to 25. The results of observation on grain shapes of these emulsions through an electron microscope are shown in Table 19.

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  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Claims (8)

1. Emulsion monodispersée à base d'halogénure d'argent comportant des grains d'halogénure d'argent, ayant des cristaux octaèdriques ou tétradécaèdriques constitués principalement de la face (111) et comprenant substantiellement des grains d'iodobromure d'argent, caractérisée en ce que lesdits grains sont arrondis aux sommets des faces de cristaux, le rayon de courbure des parties arrondies étant pour les cristaux octaèdriques de 1/10 r-1/6 r par rapport à l'angle de pointe, r étant une longueur d'un côté dans un triangle que l'on suppose formé en prolongeant les côtés d'une surface extérieure arbitraire d'un cristal et, pour les cristaux tétradécaèdriques de 1/10 r-1/6 r par rapport à l'angle, r étant une longueur du plus grand côté dans un polygone ayant la plus grande aire choisi parmi des polygones que l'on suppose être formés en prolongeant les côtés de chaque surface extérieure dans les cristaux.
2. Emulsion à base d'halogénure d'argent selon la revendication 1, dans laquelle 20% du nombre total de grains d'halogénure d'argent contenus dans ladite émulsion d'halogénure d'argent ont une partie arrondie présentant ledit rayon de courbure aux sommets de la face des cristaux.
3. Emulsion à base d'halogénure d'argent selon la revendication 1, dans laquelle la granulométrie des grains d'halogénure d'argent contenus dans ladite émulsion d'halogénure d'argent présente une largeur de 13% ou moins exprimée en termes du coefficient de variation.
4. Emulsion à base d'halogénure d'argent selon la revendication 1, dans laquelle l'halogénure d'argent comprend de l'iodobromure d'argent contenant 10 moles% ou moins d'iodure d'argent.
5. Procédé de fabrication d'une émulsion à base d'halogénure d'argent, caractérisé en ce qu'une émulsion monodispersée à base d'halogénure d'argent présentant des grains d'halogénure d'argent monodispersés, lesquels comprennent des cristaux octaèdriques ou des cristaux tétradécaèdriques constitués principalement de la face (111) et qui comprennent substantiellement des grains d'iodobromure d'argent, est soumise, après formation desdites grains d'halogénure d'argent, à un traitement avec un solvant de thioéther ou de thiourée jusqu'à ce que le rayon de courbure des parties arrondies aux sommets des faces des cristaux desdits grains d'halogénure d'argent soit pour les cristaux octaèdriques de 1/10 r­1I 6 r par rapport à l'angle de pointe, r étant une longueur d'un côté dans un triangle que l'on suppose formé en prolongeant les côtés d'une surface extérieure arbitraire du cristal, et pour les cristaux tétradécaèdriques de 1/10 r-1/6 r par rapport à l'angle, r étant une longueur du plus grand côté dans un polygone ayant l'aire la plus grande, choisi parmi des polygones que l'on suppose être formés en prolongeant les côtés de chaque surface extérieure dans les cristaux; procédé suivi d'une désalination et d'un mûrissement chimique.
6. Procédé de fabrication selon la revendication 5, dans lequel l'émulsion à base d'halogénure d'argent devant être traité avec un solvant est une émulsion préparée par le procédé ammoniacal.
7. Procédé de fabrication selon la revendication 5, dans lequel l'halogénure d'argent devant être traité avec un solvant est un iodobromure d'argent contenant 10 moles% ou moins d'iodure d'argent.
8. Procédé de fabrication selon la revendication 5, dans lequel la granulométrie des grains d'halogénure d'argent devant être traité avec un solvant présente une largeur de 10% ou moins exprimée en termes du coefficient de variation.
EP19830900065 1981-12-21 1982-12-21 Emulsion photographique a base d'halogenure d'argent et son procede de preparation Expired EP0096727B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP20759781A JPS58107530A (ja) 1981-12-21 1981-12-21 ハロゲン化銀乳剤およびその製造方法
JP207597/81 1981-12-21

Publications (3)

Publication Number Publication Date
EP0096727A1 EP0096727A1 (fr) 1983-12-28
EP0096727A4 EP0096727A4 (fr) 1984-08-10
EP0096727B1 true EP0096727B1 (fr) 1986-11-26

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Family Applications (1)

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EP19830900065 Expired EP0096727B1 (fr) 1981-12-21 1982-12-21 Emulsion photographique a base d'halogenure d'argent et son procede de preparation

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Country Link
EP (1) EP0096727B1 (fr)
JP (1) JPS58107530A (fr)
DE (1) DE3274499D1 (fr)
WO (1) WO1983002338A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0562476A1 (fr) 1992-03-19 1993-09-29 Fuji Photo Film Co., Ltd. Emulsion photographique à l'halogénure d'argent et matériau photographique sensible à la lumière
EP0563708A1 (fr) 1992-03-19 1993-10-06 Fuji Photo Film Co., Ltd. Emulsion photographique à l'halogénure d'argent et metériau sensible à la lumière l'utilisant
EP0777153A1 (fr) 1995-11-30 1997-06-04 Fuji Photo Film Co., Ltd. Produit photographique couleur à l'halogénure d'argent sensible à la lumière

Families Citing this family (9)

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Publication number Priority date Publication date Assignee Title
JPH0785165B2 (ja) * 1985-12-26 1995-09-13 コニカ株式会社 ハロゲン化銀写真乳剤の製造方法
JPH0644136B2 (ja) * 1986-03-25 1994-06-08 コニカ株式会社 増感色素を併用する（１１０）面ハロゲン化銀写真感光材料
JPS63281150A (ja) * 1987-05-13 1988-11-17 Konica Corp カブリの発生が抑えられたハロゲン化銀写真感光材料
DE3887935T2 (de) * 1987-08-07 1994-09-08 Fuji Photo Film Co Ltd Verfahren zum Herstellen eines photographischen Silberhalogenidmaterials.
US5244782A (en) * 1987-08-07 1993-09-14 Fuji Photo Film Co. Ltd. Process for producing silver halide photographic emulsion
JPH0643569A (ja) * 1992-03-16 1994-02-18 Konica Corp ハロゲン化銀粒子、該粒子を含むハロゲン化銀写真乳剤およびハロゲン化銀写真乳剤の製造方法
US5298385A (en) * 1992-06-15 1994-03-29 Eastman Kodak Company High chloride folded tabular grain emulsions
JPH06102613A (ja) * 1992-09-22 1994-04-15 Konica Corp ハロゲン化銀写真感光材料
JPH07146521A (ja) * 1993-09-29 1995-06-06 Konica Corp ハロゲン化銀写真乳剤、その製造方法、ハロゲン化銀写真感光材料及び医療用ハロゲン化銀写真感光材料の処理方法

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Publication number Priority date Publication date Assignee Title
FR2114030A5 (fr) * 1970-11-13 1972-06-30 Kodak Pathe
JPS5851254B2 (ja) * 1973-04-24 1983-11-15 富士写真フイルム株式会社 ケンチヨニゾウカンサレタシヤシンヨウハロゲンカギンニユウザイ
JPS599890B2 (ja) * 1974-11-26 1984-03-06 富士写真フイルム株式会社 微粒子ハロゲン化銀写真乳剤の増感方法
GB1520976A (en) * 1976-06-10 1978-08-09 Ciba Geigy Ag Photographic emulsions
JPS6046417B2 (ja) * 1979-03-13 1985-10-16 三菱製紙株式会社 分光増感されたハロゲン化銀写真乳剤
JPS6046418B2 (ja) * 1979-03-22 1985-10-16 三菱製紙株式会社 色増感されたハロゲン化銀写真乳剤
JPS57182730A (en) * 1981-05-06 1982-11-10 Konishiroku Photo Ind Co Ltd Photosensitive silver halide emulsion

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0562476A1 (fr) 1992-03-19 1993-09-29 Fuji Photo Film Co., Ltd. Emulsion photographique à l'halogénure d'argent et matériau photographique sensible à la lumière
EP0563708A1 (fr) 1992-03-19 1993-10-06 Fuji Photo Film Co., Ltd. Emulsion photographique à l'halogénure d'argent et metériau sensible à la lumière l'utilisant
EP0777153A1 (fr) 1995-11-30 1997-06-04 Fuji Photo Film Co., Ltd. Produit photographique couleur à l'halogénure d'argent sensible à la lumière

Also Published As

Publication number Publication date
DE3274499D1 (en) 1987-01-15
JPH0466011B2 (fr) 1992-10-21
JPS58107530A (ja) 1983-06-27
EP0096727A1 (fr) 1983-12-28
WO1983002338A1 (fr) 1983-07-07
EP0096727A4 (fr) 1984-08-10

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