EP0421740B1 - Matériau photographique à l'halogénure d'argent sensible à la lumière à haute sensibilité et voile et granularité améliorés, et méthode pour sa fabrication - Google Patents

Matériau photographique à l'halogénure d'argent sensible à la lumière à haute sensibilité et voile et granularité améliorés, et méthode pour sa fabrication Download PDF

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Publication number
EP0421740B1
EP0421740B1 EP90310790A EP90310790A EP0421740B1 EP 0421740 B1 EP0421740 B1 EP 0421740B1 EP 90310790 A EP90310790 A EP 90310790A EP 90310790 A EP90310790 A EP 90310790A EP 0421740 B1 EP0421740 B1 EP 0421740B1
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Prior art keywords
grains
silver halide
process according
light
sensitive material
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German (de)
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EP0421740A1 (fr
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Toshihiko Konica Corporation Yagi
Hiroyuki Konica Corporation Hoshino
Toshiya Konica Corporation Kondou
Katsuhiko Konica Corporation Heki
Katsuhiko Konica Corporation Suzuki
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Konica Minolta Inc
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Konica Minolta Inc
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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
    • G03C1/015—Apparatus or processes for the preparation of emulsions
    • 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
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/07—Substances influencing grain growth during silver salt formation

Definitions

  • the present invention relates to a silver halide photographic light-sensitive material and a method of its production, more specifically to a light-sensitive material with high sensitivity, reduced and excellent granularity and a production method thereof.
  • Japanese Patent Publication Open to Public Inspection No. 113934/1983 discloses a method of improving color photographic light-sensitive materials wherein a tabular silver halide emulsion having a diameter/thickness ratio of a grain (aspect ratio) exceeding 8 is applied to a green or red-sensitive layer.
  • the emulsions having high aspect ratios exceeding 8 does not have satisfactory improvement in sensitivity or granularity since its latent image-forming efficiency is not necessarily high while having an excellent photoreceptive efficiency.
  • Japanese Patent Publication Open to Public Inspection (hereinafter referred to as Japanese Patent O.P.I. Publication) Nos. 14636/1986, 112142/1986 and 163451/1988 disclose monodispersed twinned tabular grains having a core-shell structure.
  • the grains having the aspect ratios of 3 to 8 show good performance but have insufficient improvement in sensitivity and granularity.
  • the object of the present invention is to provide a silver halide photographic light sensitive material (hereinafter referred to as a light-sensitive material) with high sensitivity, improved fog and excellent granularity and a production method thereof, more specifically to a light-sensitive material containing an improved core/shell type twinned silver halide grains and a production method thereof.
  • a light-sensitive material with high sensitivity, improved fog and excellent granularity and a production method thereof, more specifically to a light-sensitive material containing an improved core/shell type twinned silver halide grains and a production method thereof.
  • a silver halide photographic light-sensitive material comprising a support and provided thereon photographic component layers including at least one light-sensitive emulsion layer containing a monodispersed silver halide emulsion consisting mainly of twined halide grains, characterised in that the silver halide grains comprise: (a) a high silver iodide core; (b.) an aspect ratio of not less than 1.3 to less than 2; (c.) mainly [111] planes; and (d.) parralel twin planes of an even number in a ratio of 50% or more by number based on the total twinned grains.
  • Figs. 1 and 2 are X ray diffraction patterns at (420) of emulsions Em-1 and emulsion Em-2 prepared in Examples 2 and 4, respectively, both having two peaks corresponding to high and low silver iodide contents.
  • Fig. 3 is a schematic diagram of the twinned silver halide grain of the present invention, in which a-a', b-b' and c-c' each represent parallel twinned planes.
  • A) and (B) show twinned crystals comprising ⁇ 111 ⁇ planes alone, and
  • C) shows a twinned crystal comprising about 95% ⁇ 111 ⁇ planes and about 5% ⁇ 100 ⁇ planes.
  • a monodispersion of a silver halide emulsion is defined by that the silver halide grains falling within the range of 80 to 120% of an average grain diameter d ⁇ accounts for not less than 70%, preferably not less than 80%, more preferably not less than 90% by weight of the total silver halide grains.
  • the average grain size d ⁇ is defined by the grain size di in which the product of ni x di 3 is maximized, wherein ni is the number of the grains having the size di (the significant figure is calculated down to the third decimal place and the forth digit is rounded to the nearest whole number).
  • a diameter of a twinned grain is defined by a diameter of the circle having the same area as that of the projected grain.
  • Grain size can be determined by taking an electron micrograph of the grain at a magnifying rate of 10000 to 50000 and measuring the diameters of the printed grain images or the area of the projected images of more than 1000 grains selected arbitrarily.
  • the silver halide emulsion is prepared preferably by precipitating a high iodide content phase on a monodispersed seed grain, more preferably by the method described in Japanese Patent O.P.I. Publication No. 6643/1986, in which monodispersed, twinned spherical seed grains are grown.
  • the silver halide emulsion of the invention has mainly an even number of parallel twinned planes, preferably two twinned planes.
  • the silver halide emulsion of the invention comprises a silver iodobromide having an average silver iodide content of 4 to 20 mol%, preferably 5 to 15 mol%.
  • the concentration of an aqueous solution of silver nitrate used to grow the high silver iodide content phase present in the center of a grain is not more than 1 N, preferably 0.3 to 0.8 N.
  • the twinned silver halide grains of the invention comprise mainly ⁇ 111 ⁇ planes in a ratio of not less than 60%, preferably 70 to 100%, more preferably 75 to 98% based on the whole grain.
  • the average ratio of a diameter of a circle having the same area as that of the projected major plain to a distance (thickness) between two grain surfaces parallel to the twinned planes is less than 1.3 to less than 2.0.
  • the two or more twinned planes may be or may not be parallel to each other.
  • the grains may comprise ⁇ 111 ⁇ planes, ⁇ 100 ⁇ planes or combination thereof.
  • pBr is maintained at -0.7 to 2.0, preferably -0.7 to 1.5 during at least a half of the time necessary for forming the grains.
  • the nuclear grains may be monodispersed or polydispersed. Polydispersion is defined by the monodispersion degree of not less than 25%.
  • the nuclear grains contain twinned grains in a ratio of not less than 50%, preferably not less than 70%, and more preferably not less than 90% based on the total grains.
  • Substantially monodispersed spherical grains are prepared by adding the silver salt and halide solutions to the nuclear grains in the presence of a silver halide solvent of 10 -5 to 2.0 mol per mol silver halide.
  • Substantially monodispersed grains are defined by the grains having the monodispersion degree of less than 25%.
  • Substantially spherical grains are defined by the grains which are round to such extent that ⁇ 111 ⁇ and ⁇ 100 ⁇ planes are not clearly recognizable via electron micrographic observation and have a L/l ratio of 1.0 to 2.0, preferably 1.0 to 1.5, wherein L and l represent the maximum and minimum grain diameters, respectively.
  • the spherical grains account for not less than 60%, preferably not less than 80%, and more preferably almost all of the total seed grains.
  • Examples of the silver halide solvent used in the seed grain formation are (a) organic thioethers described in US Patent Nos. 3,271,157, 3,531,289 and 3,574,628, Japanese Patent O.P.I. Publication Nos. 1019/1979 and 158917/1979 and Japanese Patent Examined Publication No. 30571/1983; (b) thiourea derivatives described in Japanese Patent O.P.I. Publication Nos. 82408/1978, 29829/1980 and 77737/1980; (c) AgX solvents having a thiocarbonyl group located between an oxygen or sulfur atom and a nitrogen atom described in Japanese Patent O.P.I. Publication Nos.
  • silver halide solvents (a) to (k) are given below.
  • K 2 SO 3 , Na 2 SO 3 (f) NH 4 SCN, KSCN (g) NH 3 (j) NaBr, NH 4 Br, KBr
  • solvents may be used in combination.
  • Preferred solvents are thioethers, thiocyanates, thioureas, ammonia and bromides, more preferably a combination of ammonia and bromide.
  • pH is 3 to 13, preferably 6 to 12, and the temperature is 30 to 70°C, preferably 35 to 50.
  • the seed grains are prepared by ripening for 30 seconds to 10 minutes using 0.4 to 1.0 mol/l ammonia and 0.03 to 0.5 mol/l potassium bromide in combination at pH of 10.8 to 11.2 and a temperature of 35 to 45°C.
  • a water-soluble silver salt may be added for adjustment of ripening during the seed grain formation.
  • the seed grains are grown by adding the silver salt and halide solutions by the double jet method with the addition speed varied gradually so that the new grains are not formed and Ostwald ripening does not occur, as described in Japanese Patent O.P.I. Publication Nos. 39027/1976, 142329/1980, 113928/1983, 48521/1979 and 49938/1983.
  • the seed grains can be grown by another method described in the proceeding of the 1983 annual meeting of the Society of Photographic Science and Technology of Japan, p. 88, in which fine silver halide grains coexist in the emulsion for recrystallization on the nuclear grains.
  • pAg is maintained at 5 to 11, preferably 6.0 to 9.5; the temperature is 40 to 85°C, preferably 60 to 80°C; and pH is 1.5 to 5.8, preferably 1.8 to 3.0.
  • a stirring condition is an important factor.
  • the stirring apparatus disclosed in Japanese Patent O.P.I. Publication No. 160123/1988 is preferably used, in which a nozzle for adding a solution is placed near the mother liquid inlet so that the nozzle is dipped in the liquid. It is preferable that the rotating rate of the stirrer be 400 to 1200 rpm.
  • the silver halide emulsion used in the present invention may be subjected to chemical sensitization by an ordinary method and to spectral sensitization to the prescribed wavelength regions with sensitizing dyes.
  • the silver halide emulsion may contain an antifogging agent, a stabilizer and other additives.
  • Gelatin is preferably used as a binder.
  • the emulsion layers and other hydrophilic colloid layers may be hardened and contain a plasticizer and a latex.
  • the present invention is applied preferably to color photographic light-sensitive materials such as color negative films and color reversal films.
  • the emulsion layers of the color photographic light-sensitive materials contain couplers.
  • a colored coupler having a corrective effect there may be added a colored coupler having a corrective effect, a competitive coupler and a compound that releases photographically useful fragments such as a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent, a hardener, a fogging agent, an antifogging agent, a chemical sensitizer, a spectral sensitizer and a desensitizer by coupling with the oxidation product of a developing agent.
  • a development accelerator a bleaching accelerator, a developer, a silver halide solvent, a toning agent, a hardener, a fogging agent, an antifogging agent, a chemical sensitizer, a spectral sensitizer and a desensitizer by coupling with the oxidation product of a developing agent.
  • the light-sensitive material may be provided with supplementary layers such as a filter layer, an antihalation layer and an anti-irradiation layer. These layers and/or emulsion layers may contain a dye that elutes from the light-sensitive material or is bleached during development.
  • the light-sensitive material may contain a formalin scavenger, a fluorescent brightening agent, a matting agent, a lubricant, an image stabilizer, a surfactant, an anti-fogging agent, a development accelerator, a development retarder and a bleaching accelerator.
  • supports are polyethylene-laminated paper, polyethylene terephthalate film, baryta paper and cellulose triacetate film.
  • the light-sensitive material is subjected to conventional processing after exposure.
  • a monodispersed spherical seed emulsion was prepared by the method described in Japanese Patent O.P.I. Publication No. 6643/1986.
  • Solution C 1 Potassium bromide 1327 g 1-phenyl-5-mercaptotetrazole in methanol solution 0.3 g Water was added to the total quantity of 3l.
  • solution C 1 was added in 20 seconds, followed by ripening for 5 minutes, wherein the KBr and ammonia concentrations were 0.071 mol/l and 0.63 mol/l, respectively.
  • this seed emulsion contained the monodispersed spherical grains having an average grain size of 0.36 ⁇ m and a monodispersion degree of 18%.
  • An emulsion of the present invention having an average silver iodide content of 6.0% was prepared as follows: Solution A 2 Ossein gelatin 76.8 g Seed emulsion of Example 1 0.191 mol eq. Water was added to the total quantity of 4l.
  • Solution B 2-2 Silver nitrate 961.2 g Water was added to the total quantity of 5143 ml.
  • Each six nozzles for supplying the B 2 and C 2 solutions were disposed under a stirring propeller of the mixing apparatus disclosed in Japanese Patent O.P.I. Publication No. 160128/1988.
  • Solutions B 2-1 and C 2-1 were added to solution A 2 stirred at a high speed of 1000 rpm at 75°C by the double jet method with an addition rate increased gradually from 8.57 ml/min at the beginning to 24.16 ml/min at the final stage over a period of 135 minutes, during which pAg and pH were maintained at 8.0 and 2.0, respectively.
  • solutions B 2-2 and C 2-2 were added by the double jet method over a period of 73.5 minutes.
  • the initial and final addition rates of solution B 2-2 were 43.1 ml/min and 97.0 ml/min, respectively, and the initial and final addition rates of solution C 2-2 were 31.8 ml/min and 71.6 ml/min, respectively.
  • pAg and pH were maintained at 9.0 and 2.0 during the addition.
  • pH was adjusted to 6.0, and the emulsion was desalted by a conventional method.
  • the grains were found to comprise mainly ⁇ 111 ⁇ planes.
  • Em-1 The average aspect ratio of the grains having an even number of twinned planes was 1.9. This emulsion is designated as Em-1.
  • a monodispersed spherical seed emulsion having an average grain size of 0.34 ⁇ m and a monodispersion degree of 21% was prepared in the same manner as in Example 1 except that ripening time was changed from 5 minutes to 1 minute.
  • An emulsion of the present invention having an average silver iodide content of 6.0 mol% was prepared as follows: Solution A 4 Ossein gelatin 74.1 g Seed emulsion of Example 3 0.306 mol eq. Water was added to the total quantity of 4000 ml. Solution B 4-1 Silver nitrate 206.4 g Nitric acid (1.38) 5.5 ml Water was added to the total quantity of 1105 ml. Solution C 4-1 Ossein gelatin 44.2 g Potassium bromide 101 g Potassium iodide 60.8 g Water was added to the total quantity of 1105 ml. Solution B 4-2 Silver nitrate 941 g Nitric acid (1.38) 6.6 ml Water was added to the total quantity of 1582 ml.
  • Example 2 Using the same apparatus as in Example 2, an emulsion was prepared.
  • solutions B 4-1 and C 4-1 were added by the double jet method.
  • the initial and final addition rates were 12.21 ml/min and 26.03 ml/min, respectively, and the addition time was 58 minutes.
  • pAg and pH were maintained at 8.0 and 2.0, respectively, during the addition.
  • solutions B 4-2 and C 4-2 were added by the double jet method.
  • the initial and final addition rates were 19.44 ml/min and 44.0 ml/min, respectively, and the addition time was 50 minutes.
  • pAg and pH were maintained at 8.0 and 2.0, respectively during the addition.
  • pH was adjusted to 6.0, followed by desalting and washing.
  • Em-2 This emulsion is designated as Em-2.
  • Silver ioidobromide emulsion Em-3 having an average silver iodide content of 9.0% was prepared in the same manner as in Example 4 except that the volume of the high iodide content phase was increased.
  • Em-3 consisted of 100% twinned grains having a monodispersion degree of 14% and the ratio of the grains having twinned planes of an even number was 80%.
  • the grains having an even number of twinned planes had an average aspect ratio of 1.9 and consisted of 93% ⁇ 111 ⁇ planes and 7% ⁇ 100 ⁇ planes.
  • the layers having the following compositions were formed on a triacetyl cellulose film support in the order from the support to prepare comparative light-sensitive material sample No. 1.
  • each layer contained coating aid Su-2, dispersion aids Su-2 and Su-3, hardeners H-1 and H-2, stabilizer Stab-1, antifogging agents AF-1 and AF-2 and preservative DI-1.
  • Em-A is a diagrammatic representation of Em-A.
  • a monodispersed octahedral silver iodobromide emulsion having an average AgI content of 6 mol%, a high silver iodide content phase in the core, a monodispersion degree of 13% and an average grain size of 1.0 ⁇ m.
  • Em-B is a diagrammatic representation of Em-B.
  • a monodispersed octahedral silver iodobromide emulsion having an average AgI content of 9 mol%, a high silver iodide content phase in the core, a monodispersion degree of 14% and an average grain size of 1.0 ⁇ m.
  • a tabular silver iodobromide emulsion having an average AgI content of 6 mol%, a high silver iodide content phase in the core, a monodispersion degree of 21%, an average aspect ratio of 6 and an average grain size of 1.8 ⁇ m.
  • a tabular silver iodobromide emulsion having an average AgI content of 9 mol%, a high silver iodide content phase in the core, a monodispersion degree of 19%, an average aspect ratio of 5 and an average grain size of 1.6 ⁇ m.
  • the comparative light-sensitive material sample No. 2 was prepared in the same manner as in sample No. 1 except that Em-A and Em-B used in Layers 5, 9 and 13 were replaced with Em-C and Em-D as shown in Table 1.
  • inventive light-sensitive material samples No. 3 to 5 were prepared in the same manner as in comparative sample No. 1 except that the emulsions in Layers 5, 9 and 13 were replaced with Em-1, Em-2 and Em-3 of the invention each chemically sensitized with sodium thiosulfate, chloroauric acid and ammonium thiocyanate, as shown in Table 1.
  • Sample Nos. 1 to 5 were each subjected to wedge exposure with white light and then to following processing: Processes (38°C) Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Washing 3 minutes 15 seconds Fixation 6 minutes 30 seconds Stabilization 1 minute 30 seconds Drying
  • Granularity was determined by scanning an area having the density of fog + 0.3 with a microdensitometer having an opening scanning area of 250 ⁇ m2 and measuring a density variation.
  • the inventive light-sensitive materials showed remarkable improvements if fog, sensitivity and granularity in comparison with the comparative light-sensitive materials.
  • the light-sensitive materials containing the AgX grains having ⁇ 100 ⁇ planes had better performance.

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Claims (25)

  1. Un matériau photosensible photographique à l'halogénure d'argent comprenant :
    - un support sur lequel se trouvent des couches de composant photographique comprenant :
    - au moins une couche d'émulsion photosensible contenant une émulsion monodispersée d'halogénure d'argent consistant principalement en grains d'halogénure d'argent maclés,
    caractérisé en ce que les gains d'halogénure d'argent comprennent :
    a. un noyau à forte teneur en iodure d'argent ;
    b. un rapport des dimensions compris entre pas moins de 1,3 et moins de 2 ;
    c. principalement des plans [111] ; et
    d. des plans de macle parallèles en nombres pairs en proportion de 50 % ou davantage, en nombre par rapport au nombre de grains maclés totaux.
  2. Le matériau photosensible selon la revendication 1, caractérisé en ce que les grains maclés consistent en plans [111] et [110].
  3. Le matériau photosensible selon la revendication 2, caractérisé en ce que 60 % ou davantage des grains maclés consistent en plans [111].
  4. Le matériau photosensible selon la revendication 3, caractérisé en ce que 70 à 100 % des grains maclés consistent en plans [111].
  5. Le matériau photosensible selon la revendication 4, caractérisé en ce que 75 % à 98 % des grains maclés consistent en plans [111].
  6. Le matériau photosensible selon la revendication 1, caractérisé en ce que l'émulsion d'halogénure d'argent a un degré de monodispersion de 20 %, voire moins, à condition que le degré de monodispersion soit défini par l'équation suivante: Degré de monodispersion = (déviation standard de la taille de grain/taille de grain moyenne) x 100
    Figure imgb0054
  7. Le matériau photosensible selon la revendication 6, caractérisé en ce que le degré de monodispersion est de 15 % ou moins.
  8. Le matériau photosensible selon la revendication 1, caractérisé en ce que l'émulsion d'halogénure d'argent comprend des grains de bromoiodure d'argent présentant une teneur moyenne en halogénure d'argent de 4 à 20 moles %.
  9. Le matériau photosensible selon la revendication 8, caractérisé en ce que la teneur moyenne en halogénure d'argent est de 5 à 15 moles %.
  10. Le matériau photosensible selon la revendication 3, caractérisé en ce que les grains d'halogénure d'argent maclés ont deux plans maclés.
  11. Un procédé de préparation d'un matériau photosensible selon la revendication 1, caractérisé en ce que l'on prépare les grains d'halogénure d'argent par les trois étapes suivantes :
    - Etape 1 : formation de grains nucléaires ayant une teneur en iodure d'argent de 0 à 5 moles % en ajoutant une solution de sel d'argent hydrosoluble et une solution d'halogénure hydrosoluble à une solution colloïdale aqueuse de protection tout en maintenant le pBr de la liqueur mère de -0,7 à 2,0 pendant au moins la première moitié du temps nécessaire à la formation des grains nucléaires ;
    - Etape 2: formation de grains d'ensemencement monodispersés de cristaux sphériques maclés par maturation des grains nucléaires en présence d'un solvant de l'halogénure d'argent à 10-5 à 2,0 moles par mole d'halogénure d'argent ; et
    - Etape 3 : croissance des grains d'ensemencement en ajoutant une solution de sel d'argent hydrosoluble et une solution d'halogénure hydrosoluble, ou la même chose en présence de grains fins d'halogénure d'argent.
  12. Le procédé selon la revendication 11, caractérisé en ce que le pH de la liqueur mère est maintenu entre 1,5 à 5,8 pendant la formation de toute fraction d'au moins 30 % en volume de grains d'halogénure d'argent.
  13. Le procédé selon la revendication 11, caractérisé en ce que le pBr à l'étape 1 est maintenu entre -0,7 et 1,5.
  14. Le procédé selon la revendication 11, caractérisé en ce que le rapport des grains nucléaires maclés contenus dans les grains nucléaires totaux est de 50 % ou davantage.
  15. Le procédé selon la revendication 14, caractérisé en ce que le rapport est de 70 % ou davantage.
  16. Le procédé selon la revendication 15, caractérisé en ce que le rapport est de 90 % ou davantage.
  17. Le procédé selon la revendication 11, caractérisé en ce que la proportion de grains d'ensemencement sphériques contenus dans les grains d'ensemencement totaux est de 60 % ou d'avantage.
  18. Le procédé selon la revendication 17, caractérisé en ce que le rapport est de 80 % ou davantage.
  19. Le procédé selon la revendication 14, caractérisé en ce que le solvant de l'halogénure d'argent est au moins un solvant choisi parmi un thioéther organique, un dérivé de thio-urée, un dérivé comportant un groupe thiocarbonyle entre un atome d'oxygène ou un atome de soufre et un atome d'azote, un dérivé d'imidazole, un sel sulfidique, un dérivé de thiocyanate, l'ammoniac, un dérivé d'éthylènediamine substitué par un hydroxyalkyle, un dérivé de mercaptotétrazole substitué, un bromure hydrosoluble et un dérivé de benzoimidazole.
  20. Le procédé selon la revendication 19, caractérisé en ce que le solvant de l'halogénure d'argent est au moins un solvant choisi parmi un thioéther organique, un dérivé de thiocyanate. l'ammoniac et un bromure hydrosoluble.
  21. Le procédé selon la revendication 20, caractérisé en ce que le solvant de l'halogénure d'argent est une combinaison d'ammoniac et de bromure hydrosoluble.
  22. Le procédé selon la revendication 11, caractérisé en ce que le pH et la température au cours des étapes 2 et 3 sont respectivement de 3 à 13 et de 30 à 70°C.
  23. Le procédé selon la revendication 22, caractérisé en ce que le pH et la température au cours des étapes 2 et 3 sont respectivement de 6 à 12 et de 30 à 70°C.
  24. Le procédé selon la revendication 11, caractérisé en ce que le pAg, la température et le pH au cours de l'étape 3 sont respectivement de 5 à 11, de 40 à 85°C et de 1,8 à 3,0.
  25. Le procédé selon la revendication 24, caractérisé en ce que le pAg, la température et le pH sont respectivement de 6,0 à 9,5, 60 à 80°C et de 1,8 à 3,0.
EP90310790A 1989-10-03 1990-10-02 Matériau photographique à l'halogénure d'argent sensible à la lumière à haute sensibilité et voile et granularité améliorés, et méthode pour sa fabrication Expired - Lifetime EP0421740B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP25930989A JPH03120528A (ja) 1989-10-03 1989-10-03 高感度でカブリ、粒状性の改良されたハロゲン化銀乳剤及びその製造方法
JP259309/89 1989-10-03

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EP0421740A1 EP0421740A1 (fr) 1991-04-10
EP0421740B1 true EP0421740B1 (fr) 1997-08-06

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EP90310790A Expired - Lifetime EP0421740B1 (fr) 1989-10-03 1990-10-02 Matériau photographique à l'halogénure d'argent sensible à la lumière à haute sensibilité et voile et granularité améliorés, et méthode pour sa fabrication

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EP (1) EP0421740B1 (fr)
JP (1) JPH03120528A (fr)
CA (1) CA2026732A1 (fr)

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US5310644A (en) * 1991-09-17 1994-05-10 Eastman Kodak Company Process for preparing a photographic emulsion using excess halide during nucleation
DE69227016T2 (de) * 1991-12-30 1999-02-18 Eastman Kodak Co Kratz-resistentes dickes T-Korn
US5246827A (en) * 1992-05-08 1993-09-21 Eastman Kodak Company Preparation of photosensitive silver halide materials with a combination of organic ripening agents
JPH06118584A (ja) * 1992-10-06 1994-04-28 Konica Corp ハロゲン化銀カラー写真感光材料
DE4233714A1 (de) * 1992-10-07 1994-04-14 Agfa Gevaert Ag Verfahren zur Herstellung von Silberhalogenidemulsionen
US5750327A (en) * 1996-06-20 1998-05-12 Eastman Kodak Company Mixed ripeners for silver halide emulsion formation

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JPH06114630A (ja) * 1992-10-02 1994-04-26 Hitachi Cable Ltd 皮剥法

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GB1469480A (en) * 1974-08-07 1977-04-06 Ciba Geigy Ag Photographic emulsion
JPS616643A (ja) * 1984-06-20 1986-01-13 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真乳剤の製造方法
JPS6114630A (ja) * 1984-06-29 1986-01-22 Konishiroku Photo Ind Co Ltd ハロゲン化銀乳剤の製造方法
US4797354A (en) * 1986-03-06 1989-01-10 Fuji Photo Film Co., Ltd. Silver halide emulsions comprising hexagonal monodisperse tabular silver halide grains
JPH0727180B2 (ja) * 1986-12-26 1995-03-29 富士写真フイルム株式会社 感光性ハロゲン化銀乳剤及びそれを用いたカラ−感光材料

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JPH06114630A (ja) * 1992-10-02 1994-04-26 Hitachi Cable Ltd 皮剥法

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EP0421740A1 (fr) 1991-04-10
JPH03120528A (ja) 1991-05-22
CA2026732A1 (fr) 1991-04-04

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