EP0645670A1 - Emulsion d'halogénure d'argent - Google Patents

Emulsion d'halogénure d'argent Download PDF

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Publication number
EP0645670A1
EP0645670A1 EP94115393A EP94115393A EP0645670A1 EP 0645670 A1 EP0645670 A1 EP 0645670A1 EP 94115393 A EP94115393 A EP 94115393A EP 94115393 A EP94115393 A EP 94115393A EP 0645670 A1 EP0645670 A1 EP 0645670A1
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EP
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Prior art keywords
grains
silver halide
tabular
emulsion
range
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EP94115393A
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German (de)
English (en)
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EP0645670B1 (fr
Inventor
Mitsuo C/O Fuji Photo Film Co. Ltd. Saitou
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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
    • G03C1/0051—Tabular grain emulsions
    • G03C1/0053—Tabular grain emulsions with high content of silver chloride
    • 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
    • G03C1/12—Methine and polymethine dyes
    • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
    • G03C1/16—Methine and polymethine dyes with an odd number of CH groups with one CH group
    • 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
    • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
    • G03C1/346—Organic derivatives of bivalent sulfur, selenium or tellurium
    • 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
    • G03C2200/01—100 crystal face

Definitions

  • the present invention relates to a silver halide emulsion useful in photography.
  • the invention relates to a silver halide emulsion containing tabular silver halide grains that have (100) major faces.
  • Japanese Patent Provisional Publication No. 51(1976)-88017, Japanese Patent No. 64(1989)-8323 and European Patent Publication No. 0534395A1 disclose silver halide emulsions containing tabular silver halide grains that have ⁇ 100 ⁇ major faces.
  • European Patent Publication No. 0534395A1 further discloses high chloride tabular grains, which are shown in photographs of Figures 1 to 5. Referring to the Figures, twinned crystal grains are remarkably observed in the photographs. Further, the grains shown in the photographs have a relatively broad grain size distribution. The Figure 1, which represents statistically reliable number of the grains is now described in more detail.
  • the ratio of twinned crystal grains to tabular grains having an aspect ratio of not less than 2 is about 11 % based on projected areas of the grains.
  • the grain size distribution of tabular grains having a thickness of not more than 35 ⁇ m is relatively broad.
  • the grain size distribution of relatively large tabular grains is particularly broad, which affects the photographic property of the grains.
  • the relatively large grains have a distribution coefficient of more than 0.12, in which the relatively large grain comprises 70 % of the tabular silver halide grains based on projected areas of the grains.
  • the amount of tabular silver halide grains having a square projected shape is relatively small.
  • about 40 % of the tabular silver halide grains have a square projected shape that a ratio of a long side to a short side is not more than 1.4.
  • Japanese Patent Provisional Publication No. 63(1988)-271335 discloses a silver halide emulsion containing the above-described tabular grains and needle-like grains.
  • An object of the present invention is to provide a silver halide emulsion containing silver chloride, which is improved in sensitivity and image quality.
  • the present invention provides a silver halide emulsion comprising silver halide grains, which are dispersed in a dispersing medium, wherein at least 60 % of the silver halide grains based on projected areas of the grains are tabular grains having an aspect ratio of not less than 2, said tabular silver halide grains having a chloride content in the range of 20 to 99.99 mol %, ⁇ 100 ⁇ major faces, and a thickness of not more than 0.35 ⁇ m, and wherein twinned crystal grains contained in the emulsion comprise not more than 10 % of the tabular silver halide grains based on projected areas of the grains, and the tabular silver halide grains are formed from grain nuclei, which have at least one gap interface of halide composition.
  • the present inventor has prepared a new silver halide emulsion having the above-defined specific characteristics.
  • the new silver halide grains are superior to conventional tabular silver halide grains having ⁇ 100 ⁇ major faces with respect to the sensitivity and the image quality (particularly graininess).
  • Figure 1 is a micrograph (about ⁇ 6,500) showing silver halide grains of the present invention obtained in Example 1.
  • Figure 2 is a micrograph (about ⁇ 5,000) showing silver halide grains of the present invention obtained in Example 2.
  • Figures 3a (about ⁇ 18,000) and 3b (about ⁇ 13,000) are micrographs showing silver halide grains of the present invention obtained in Example 3.
  • silver halide grains contained in emulsions are evaluated about the following characteristics (1) to (9):
  • the aspect ratio means diameter per thickness.
  • the thickness means a distance between two major planes of a tabular grain.
  • the condition (2) namely the chloride content of the tabular grains is in the range of 20 to 99.99 mol %, preferably in the range of 50 to 99.9 mol %, more preferably in the range of 75 to 99.9 mol %, and most preferably in the range of 90 to 99.9 mol %.
  • the tabular grains have ⁇ 100 ⁇ major faces.
  • the major face means the largest crystal plane of a silver halide grain.
  • the condition (4) namely the thickness of the tabular grains is not more than 0.35 ⁇ m, preferably in the range of 0.05 to 0.3 ⁇ m, and more preferably in the range of 0.05 to 0.25 ⁇ m.
  • the tabular silver halide grains preferably have an average aspect ratio in the range of 2 to 25, and more preferably in the range of 4 to 20.
  • condition (1) is in the range of 0 to 10 %, preferably is in the range of 0 to 8 %, more preferably is in the range of 0 to 5 %, and most preferably is in the range of 0 to 2 %.
  • condition (6) is described below with respect to preparation of silver halide grains.
  • the photographic emulsion of the present invention preferably has at least one of the following characteristics (7) to (9):
  • condition (7) is evaluated in the following manner:
  • the condition (7) is preferably in the range of 0 to 0.11, more preferably in the range of 0 to 0.09, and most preferably in the range of 0 to 0.06.
  • the condition (7) is preferably at least 47 %, more preferably at least 50 %, further preferably at least 55 %, furthermore preferably at least 75 %, and most preferably at least 85 %.
  • the ratio of a long side to a short side is in the range of 1 to 1.4, preferably is in the range of 1 to 1.3, and most preferably in the range of 1 to 1.2.
  • a corner of the square can be rounded to some extent.
  • the ratio of the volume defected by the rounded corner to the rectangular prism volume is preferably not more than 0.2, and more preferably is not more than 0.1.
  • the rectangular prism volume means a volume of a rectangular prism, which is theoretically formed by extending edges of the grain.
  • one corner tends to be primarily rounded, as is defined in the condition (9).
  • the condition (9) is preferably at least 10 %, more preferably at least 15 %, and most preferably at least 35 %.
  • the specific rectangular tabular grains have such a rectangular projected shape that one angle is rounded compared with the other three angles.
  • one corner of the rectangular is primarily rounded.
  • the volume defected by the primarily rounded corner is preferably twice or more, more preferably 4 times or more, and most preferably 8 times or more as much as the volume defected by another corner.
  • the tabular silver halide grains preferably have an average diameter in the range of 0.2 to 10 ⁇ m, and more preferably in the range of 0.3 to 5 ⁇ m.
  • the iodide content of the tabular silver halide grains preferably is not more than 13 mol %, more preferably is not more than 6 mol %, and most preferably in the range of 0 to 3 mol %.
  • the tabular silver halide grains of the present invention are formed from grain nuclei, which have at least one gap interface of halide composition according to the condition (6).
  • the tabular grains are grown primarily along the direction of edges.
  • the primary growth is promoted by a defect in grain nuclei.
  • a defect in grain nuclei for forming a tabular grain is referred to as a spiral dislocation defect.
  • the defect is formed by at least one (preferably 1 to 3 and more preferably 1 or 2) gap interface of halide composition in the nuclei.
  • the defect is preferably formed by placing a layer of a silver halide having a low solubility (AgX2) on a layer of another silver halide (AgX1) having a high solubility. Accordingly, the gap interface of halide composition is effectively formed by a halide conversion reaction.
  • the solubility of silver halide decreases in the order of AgCl, AgBr and AgI.
  • a silver halide having a higher chloride and a lower iodide has a higher solubility.
  • a halide composition in the grain nuclei has a structure of AgX1
  • the structure can be formed by mixing simultaneously a silver (Ag+) solution with a halide (X ⁇ ) solution, and changing discontinuously a halide composition of the halide solution at the gap interface. Further, a halide solution and a silver solution can be added to a solution of a dispersing medium to form AgX1, and then another halide solution and a silver halide solution can be added to the medium to form a structure of AgX1
  • a halide solution and a silver solution can be added to the medium to form a structure of AgX1
  • a difference in chloride content or bromide content between AgX1 and AgX2, AgX1 and AgX4 or AgX4 and AgX3 is preferably in the range of 25 to 100 mol %, more preferably in the range of 50 to 100 mol %, and most preferably in the range of 75 to 100 mol %.
  • a difference in iodide content is preferably in the range of 5 to 100 mol %, more preferably in the range of 10 to 100 mol %, and most preferably in the range of 30 to 100 mol %.
  • the difference in the chloride or bromide content is defined above, and the difference in iodide content is preferably in the range of 0 to 5 mol %.
  • the grain nuclei preferably have a diameter of not more than 0.15 ⁇ m, and more preferably in the range of 0.01 to 0.1 ⁇ m.
  • the layer of AgX2 preferably has such a thickness that one lattice of AgX2 on the average covers the surface of AgX1.
  • the thickness of the AgX2 layer is more preferably in the range of three lattices on the average to 104 mol of the AgX1 layer.
  • the amount of the AgX4 layer is preferably in the range of 0.01 to 10 mol, and more preferably in the range of 0.1 to 3 mol based on one mole of the AgX1 layer.
  • the defect in grain nuclei is more frequently formed by increasing the difference of the gap in a halide content.
  • AgX3 can also be formed by forming AgX1 nuclei, adding an X4 ⁇ salt solution to the nuclei to form a structure of AgX1
  • the X4 ⁇ salt preferably satisfies the condition that the solubility of AgX4 is lower than that of AgX1.
  • the amount of X4 ⁇ contained in the solution is preferably in the range of 0.01 to 10 mol, and more preferably in the range of 0.03 to 3 mol based on one mole of AgX1. As the amount of AgX4 ⁇ based on the amount of AgX1 can be reduced with increasing the gap difference in the halide composition.
  • the differences in chloride content and bromide content are in the range of 25 to 100 mol %, more preferably in the range of 50 to 100 mol %, and most preferably in the range of 75 to 100 mol %.
  • AgX3 is particularly preferred.
  • the atmosphere of the dispersing medium solution is adjusted to form ⁇ 100 ⁇ faces.
  • usual conditions pCl: 0.8 to 3.0, pH 2 to 8 are under the atmosphere for forming ⁇ 100 ⁇ faces.
  • the conditions for forming the defects are adjusted to obtain the silver halide emulsion of the present invention.
  • the gap interface is uniformly formed in each of the nuclei to obtain the embodiment of the present invention.
  • a dispersing medium for forming nuclei is preferably used in the form of 0.1 to 10 wt.% solution, and more preferably 0.3 to 5 wt.% solution.
  • the solution of the dispersing medium is preferably adjusted to pH 1 to 10, and more preferably to pH 2 to 8.
  • the temperature of the solution is preferably adjusted to 10 to 80 °C, and more preferably to 30 to 60 °C. When the temperature is 30 or lower °C, the frequency of forming the defect is decreased. A certain temperature is necessary for forming the defect.
  • the excess bromide content is preferably not more than 10 ⁇ 2 mol per liter, and more preferably not more than 10 -2.5 mol per liter.
  • the excess chloride content is preferably in the range of 0.8 to 3.0 pCl, and more preferably in the range of 1.2 to 2.8 pCl.
  • the dispersing medium can be added to a silver salt solution and/or a halide salt solution to form uniform grain nuclei.
  • concentration of the dispersing medium in the silver salt or halide salt solution is preferably not less than 0.1 wt.%, more preferably in the range of 0.1 to 2 wt.%, and most preferably in the range of 0.2 to 1 wt.%.
  • the dispersing medium preferably is gelatin, which more preferably has a molecular weight in the range of 3,000 to 60,000, and most preferably in the range of 8,000 to 40,000.
  • the silver salt solution and the halide solution are preferably added through a porous addition system.
  • the system preferably has 3 to 1015 pores, and more preferably has 30 to 1015 pores.
  • the porous system is described in Japanese Patent Provisional Publications No. 3(1991)-21339 and No. 4(1992)-193336, and Japanese Patent Application No. 4(1992)-40283.
  • the frequency of forming defect is increased by decreasing the methionine content in gelatin.
  • Gelatin is preferably selected in consideration of the methionine content in the range of 1 to 60 ⁇ mol per 1 g of gelatin.
  • a ratio of twinned crystal grains can be decreased by lowering the excess halide salt concentration or the excess silver salt concentration when the grain nuclei are formed.
  • the ratio is increased by lowering the concentration of the dispersing medium or degrading stirring conditions.
  • the conditions can be experimentally determined to obtain silver halide grains of the present invention.
  • a spiral dislocation defect is formed by forming the gap interface of a halide composition and a halide conversion on the interface when the grain nuclei are formed.
  • the silver halide grains are ripened when the temperature is elevated at least 10 °C, and more preferably 20 to 70 °C.
  • the ripening atmosphere is preferably adjusted to form ⁇ 100 ⁇ faces.
  • the ripening conditions are selected from the above-mentioned conditions for the grain nuclei formation. In the ripening, tabular grains are primarily grown and non-tabular grains are decreased. Thus the ratio of the tabular grains is increased.
  • the ripening speed can be increased by increasing pH in the range of 1 to 6 and increasing Cl ⁇ content in the range of 1 to 3 pCl.
  • solutes are added to the grains to further grow the tabular grains.
  • the solutes can be added according to an ion addition method (adding Ag+ solution and X ⁇ solution), a fine grain addition method (adding silver halide fine grains, which are previously formed) or a combination thereof.
  • the tabular grains are grown primarily along the direction of the edges under the conditions that the concentration of supersaturation is lowered so long as the tabular grains are not subjected to Ostwald ripening. Accordingly, the concentration should be precisely adjusted to a low super-saturation concentration
  • the fine grain addition method is preferably used to adjust the concentration precisely. The method is also advantageous to grow the tabular grains uniformly.
  • fine silver grains have an average particle size of not more than 0.15 ⁇ m, preferably not more than 0.1 ⁇ m, and more preferably in the range of 0.06 to 0.006 ⁇ m.
  • the fine grains are subjected to Ostwald ripening for grow the tabular grains.
  • the fine grains are continuously or discontinuously added to the emulsion.
  • the fine grains can be continuously formed by mixing AgNO3 solution and an X ⁇ salt solution in a vessel placed near a reaction vessel, and immediately and continuously added to the reaction vessel. Further, the fine grains can be formed in another vessel according to a batch method, and continuously or discontinuously added to a reaction vessel.
  • the fine grains are used in the form of an emulsion or a dry powder. The dry powder of the fine grains can be dispersed in water prior to addition.
  • the conditions in the fine grain addition method are preferably so adjusted that the fine grains are dissolved within 20 minutes, more preferably within 10 seconds to 10 minutes.
  • the time for dissolving the fine grains is increased, the grains are ripened and the grain size is increased. Accordingly, the time for dissolving the fine grains is preferably shortened.
  • the grains are gradually added to the reaction vessel.
  • the fine grains substantially do not contain multiple twinned crystal grains.
  • the multiple twinned crystal means a grain having two or more twinned plane.
  • the term "substantially do not contain (or have)" means that the ratio of the specific grains is not more than 5 % (preferably not more than 1 %, and more preferably not more than 0.1 %).
  • the halide composition of the fine grains preferably is AgCl, AgBr, AgBrI (wherein I ⁇ content preferably is not more than 10 mol %, and more preferably is not more than 5 mol %) or a mixture thereof (mixed crystals).
  • the halide compositions of the fine grains are described in Japanese Patent Application No. 4(1992)-214109.
  • dispersing mediums for a conventional silver halide emulsion are available for forming grain nuclei, grain ripening and grain growth.
  • Gelatin is preferably used as the dispersing medium.
  • the methionine content of gelatin is preferably in the range of 0 to 50 ⁇ mol, and more preferably in the range of 0 to 30 ⁇ m.
  • a synthetic polymer is available as the dispersing medium. The synthetic polymers are disclosed in Japanese Patent Publication No.
  • the concentration of the dispersing medium is preferably in the range of 10 ⁇ 1 to 10 ⁇ 6 mol per liter.
  • the concentration of the adjusting agent is preferably in the range of 10 ⁇ 1 to 106 mol per liter, and more preferably in the range of 10 ⁇ 2 to 105 mol per liter.
  • the medium and agent can be added at any stages from the nuclei formation to the grain growth.
  • a dispersing medium can be used in addition to the medium previously present in an emulsion.
  • a dispersing medium can be also be added to the emulsion after the medium previously present is removed from the emulsion.
  • the concentration of the dispersing medium, pH, the concentration of X ⁇ salt solution, the addition methods of Ag+ solution and X ⁇ solution can be adjusted by referring to the conditions for the nuclei formation, which are described above.
  • the temperature for the grain ripening and grain growth is preferably not lower than 25 °C, and more preferably in the range of 30 to 80 °C.
  • the atmosphere of the grain growth is also preferably adjusted to form ⁇ 100 ⁇ faces.
  • the atmosphere for forming ⁇ 100 ⁇ faces in the nuclei formation, the grain ripening or the grain growth are so adjusted that 60 to 100 % (preferably 80 to 100 %, and more preferably 90 to 100%) of the grain surface become ⁇ 100 ⁇ faces.
  • the ratio of the ⁇ 100 ⁇ faces can be measured, for example by a method described in T. Tani, Journal of Imaging Science, volume 29, 165 (1985).
  • the silver halide grains of the present invention can be prepared by another method.
  • the grains can be formed by (a) nuclei formation, (b) selectively growing tabular grain under a low supersaturated concentration to enlarge the size difference between the tabular grains and non-tabular grains and (c) dissolving the non-tabular grains by Ostwald ripening.
  • the grains can also be formed by (a) nuclei formation and (b) growing tabular grain under conditions of a supersaturated concentration and Ostwald ripening at a temperature elevated 10 °C or more. As is described above, the tabular grains are grown while non-tabular fine grains are dissolved.
  • the tabular grains mainly contain silver chloride.
  • Various halide compositions can be introduced into the grain structures.
  • the grains have a multiple structure, which is described in Japanese Patent Application No. 5(1993)-96250.
  • the grain structures include embodiments having a higher Br ⁇ and/or I ⁇ content on the surface of the grains, along the edges of the grains and on the major planes of the grains.
  • the high Br ⁇ content is preferably not less than 1 mol % higher than the Br ⁇ content in the other portion, more preferably of 3 to 100 mol % higher, and most preferably 5 to 70 mol % higher.
  • the high I ⁇ content is preferably not less than 1 mol % higher than the I ⁇ content in the other portion, more preferably 2 to 30 mol % higher, and most preferably 3 to 10 mol % higher.
  • the tabular grains have ⁇ 100 ⁇ major faces. On the major faces, Ag+ and X ⁇ are alternatively arranged. When a spectral sensitizing dye is adsorbed on the faces, the dye can directly be reacted with Ag+. In the silver halide grains, Ag+ forms a conductive band, and X ⁇ forms an electron charged band. Accordingly, the lowest vacant level of the dye can directly be reacted with the conductive band of Ag+. Therefore, the efficiency of the electron injection is high when the dye is excited with light. Thus, the efficiency of spectral sensitization is improved.
  • a sensitizing dye adsorbed on tabular grains having ⁇ 111 ⁇ major faces is reacted with the conductive band of Ag+ through an X ⁇ layer.
  • the surface X ⁇ layer has an excess minus charge because the chemical bond is broken on the surface.
  • the electron is injected over the barrier of the minus charge. Therefore, the efficiency of the electron injection is low.
  • the efficiency of spectral sensitization is low when tabular grains having ⁇ 111 ⁇ major faces are used.
  • the silver halide grains having ⁇ 100 ⁇ major faces of the present invention are superior to the conventional grains having ⁇ 111 ⁇ major faces.
  • the conventional tabular grains having ⁇ 111 ⁇ major faces has a tendency of inherent desensitization.
  • the formed positive hole tends to be captured by the highest occupied orbit of the dye through the X ⁇ layer.
  • the captured positive hole is combined again with the excited electron to decrease the inherent desensitization.
  • the positive hole is easily trapped with the X ⁇ layer of the ⁇ 111 ⁇ major faces.
  • Such an inherent desensitization is scarcely caused in the silver halide grains having ⁇ 100 ⁇ major faces.
  • Epitaxial grains can be formed from the obtained silver halide grains. Further, grains having dislocation lines inside the grains can be formed by using the obtains grains as grain nuclei. Further, the obtained grains can be used as substrate of other grains, which are formed by forming silver halide layer on the substrate. The halide composition of the layer is different from that of the substrate. The other various silver halide grains can be formed from the grains of the present invention.
  • a speck of chemical sensitization is usually introduced into the silver halide grains.
  • the place and number (per cm2) of the chemical sensitization specks are preferably adjusted. The adjustment is described in Japanese Patent Provisional Publications No. 64(1989)-74540, No. 1(1989)-201651, No. 2(1990)-838, No. 2(1990)-146033 and No. 3(1991)-121445 and Japanese Patent Application No. 3(1991)-73266, No. 3(1991)-140712 and No. 3(1991)-115872.
  • a shallow internal latent image emulsion can be prepared by using the tabular grains as the core.
  • a core/shell emulsion can also be prepared. These emulsions are described in Japanese Patent Provisional Publications No. 59(1984)-133542 and No. 63(1988)-151618, and U.S. Patents No. 3,206,313, No. 3,317,322, No. 3,761,276, No. 4,269,927 and No. 3,267,778.
  • the silver halide emulsion of the present invention can be mixed with one or more other emulsions.
  • the mixing ratio of the emulsion of the invention to other emulsions can be appropriately arranged within the range of 1.0 to 0.01.
  • additives which are used from grain formation to emulsion coating.
  • the additives include silver halide solvents, doping agents for silver halide grains (e.g., metal compounds of the group VIII or other metals, chalcogen compounds and SCN compounds), dispersing agents, antifogging agents, spectral sensitizing dyes (e.g., blue, green, red, infrared, panchromatic or orthochromatic sensitizers), supersensitizers, chemical sensitizers (e.g., sulfur sensitizers, selenium sensitizers, tellurium sensitizers, gold or other noble metals such as metals of the group VIII sensitizers, phosphor compounds, rhodan compounds or reduction sensitizers), fogging agents, emulsion precipitating agents, surface active agents, hardening agents, dyes, color image forming agents, additives for color photography, soluble silver salt, latent image stabilizer, developing agents (e.g.,
  • the silver halide grains and emulsion of the present invention are available in various conventional photographic materials.
  • the photographic materials include black and white photographic materials (e.g., X-ray sensitive materials, light-sensitive materials for printing, photographic papers, negative films, microfilms, direct positive light-sensitive materials, ultrafine-grain dry light-sensitive materials (for LSI photomask, shadow mask or liquid crystal mask) and color photographic materials (e.g., negative films, color photographic papers, reversal films, direct positive color light-sensitive materials, silver dye bleaching photographic materials).
  • the silver halide emulsion is also available in diffusion transfer light-sensitive materials (e.g., color dye diffusion transfer element, silver salt diffusion transfer element), thermal developable (black and white or color) light-sensitive materials, high density digital recording light-sensitive materials and holography light-sensitive materials.
  • diffusion transfer light-sensitive materials e.g., color dye diffusion transfer element, silver salt diffusion transfer element
  • thermal developable (black and white or color) light-sensitive materials e.g., high density digital recording light-sensitive materials and holography light-sensitive materials.
  • the coating amount of silver is preferably not less than 0.01 g/m2.
  • the structure of the photographic material e.g., the layered structure, the molar ratio of silver to coloring agents, the silver amounts in the layers
  • the conditions for light exposure and development e.g., the layered structure, the molar ratio of silver to coloring agents, the silver amounts in the layers
  • the photographic materials are also described in Japanese Patent Provisional Publications No. 58(1983)-113926, No. 58(1983)-113927, No. 58(1983)-113926, No. 59(1984)-90841, No. 58(1983)-111936, No. 62(1987)-99751, No. 60(1985)-143331, No. 60(1985)-143332, No. 61(1986)-14630, No. 62(1987)-6251, No. 63(1988)-220238, No. 63(1988)-151618, No. 63(1988)-281149, No. 59(1984)-133542, No. 59(1984)-45438, No. 62(1987)-269958, No.
  • the silver halide emulsion of the present invention is advantageously used in photographic materials disclosed in Japanese Patent Provisional Publications No. 62(1987)-269958, No. 62(1987)-266538, No. 63(1988)-220238, No. 63(1988)-305343, No. 59(1984)-142539, No. 62(1987)-253159, No. 1(1989)-131541, No. 1(1989)-297649, No. 2(1990)-42, No. 1(1989)-158429, No. 3(1991)-226730, No. 4(1992)-151649, Japanese Patent Application No. 4(1992)-179961 and European Patent Publication No. 0508398A1.
  • grain nuclei were formed.
  • the structure of the nuclei is AgCl
  • the difference in chloride content or bromide content between AgX1 and AgX4 or AgX4 and AgX3 was 100 %.
  • a precipitating agent was added to the emulsion, the emulsion was cooled to 30 °C. The emulsion was precipitated, and washed with water. After a gelatin solution was added to the emulsion, the resulting emulsion was adjusted to pH 6.2 and pCl 3.0 at 38 °C. A part of the emulsion was sampled, and a replica of the grains of the emulsion was prepared. The replica was observed by a transparent electron microscope (TEM). The micrograph (about ⁇ 6,500) of silver halide grains is shown in Figure 1. The characteristics of the grains are described below.
  • the average aspect ratio of tabular grains having an aspect ratio of not less than 2 is 3.4.
  • the average diameter of tabular grains having an aspect ratio of not less than 2 is 1.0 ⁇ m.
  • grain nuclei were formed.
  • the structure of the nuclei is AgCl
  • the difference in chloride content or bromide content between AgX1 and AgX4 or AgX4 and AgX3 was 100 %.
  • a precipitating agent was added to the emulsion, the emulsion was cooled to 30 °C. The emulsion was precipitated, and washed with water. After a gelatin solution was added to the emulsion, the resulting emulsion was adjusted to pH 6.2 and pCl 3.0 at 38 °C. A part of the emulsion was sampled, and a replica of the grains of the emulsion was prepared. The replica was observed by a transparent electron microscope (TEM). The micrograph (about ⁇ 5,000) of silver halide grains is shown in Figure 2. The characteristics of the grains are described below.
  • TEM transparent electron microscope
  • the average aspect ratio of tabular grains having an aspect ratio of not less than 2 is 4.5.
  • the average diameter of tabular grains having an aspect ratio of not less than 2 is 1.0 ⁇ m.
  • Example 2 After the grain formation in Example 2, the emulsion was heated to 72 °C. The emulsion was further ripened for 10 minutes. A precipitating agent was added to the emulsion, and the emulsion was cooled to 30 °C. The emulsion was precipitated, and washed with water. After a gelatin solution was added to the emulsion, the resulting emulsion was adjusted to pH 6.2 and pCl 3.0 at 38 °C. A part of the emulsion was sampled, and a replica of the grains of the emulsion was prepared. The replica was observed by a transparent electron microscope (TEM). As a result, about 38 % (based on the projected area) of the tabular grains having an aspect ratio of not less than 2 have the specific structures shown in Figures 3a and 3b.
  • TEM transparent electron microscope
  • Silver halide grains are formed in the same manner as in Example 11B of European Patent Publication No. 0534395A1.
  • a precipitating agent was added to the emulsion, and the emulsion was cooled to 30 °C.
  • the emulsion was precipitated, and washed with water.
  • After a gelatin solution was added to the emulsion the resulting emulsion was adjusted to pH 6.2 and pCl 3.0 at 38 °C.
  • a part of the emulsion was sampled, and a replica of the grains of the emulsion was prepared. The replica was observed by a transparent electron microscope (TEM).
  • TEM transparent electron microscope
  • the average aspect ratio of tabular grains having an aspect ratio of not less than 2 is 10.0.
  • the average diameter of tabular grains having an aspect ratio of not less than 2 is 1.3 ⁇ m.
  • the following spectral sensitizing dye was adsorbed on the silver halide grains.
  • the amount of the dye was 65 % of the saturated amount.
  • a sodium chloride solution was added to the emulsions to adjust pCl of 2.0.
  • hypo (2 ⁇ 10 ⁇ 5 mol per 1 mol of silver) and chloroauric acid (10 ⁇ 5 mol per 1 mol of silver) were added to the emulsions.
  • antifogging agent (10 ⁇ 3 mol per 1 mol of silver) was added to the emulsions.
  • the emulsions were cooled to 40 °C.
  • a viscous agent and a coating aid were added to the emulsions.
  • Each of the emulsions and a protective layer was coated on a triacetyl cellulose film base. The film was dried to obtain samples.
  • the coated samples were exposed to light though minus blue filter (transmitting light of 520 nm or more) for 10 ⁇ 2 minute.
  • the samples were developed, and immersed in a development stopping solution and then in a fixing solution.
  • the samples were then washed with water and dried.
  • the photographic quality was evaluated as sensitivity per granularity. The quality is improved by increasing the value of the sensitivity or decreasing the value of the granularity.
  • Example 1 the evaluated value of Example 1 is 115, the value of Example 2 is 118, the value of Example 3 was 121, and the value of the Comparison Example 1 was 100. Thus, the superior quality of the present invention was confirmed.
  • gelatin solution containing 25 g of deionized alkaline treated bone gelatin having methionine content of about 30 ⁇ mol/g, pH: 4.3
  • Ag-41 solution containing 20 g of silver nitrate in 100 ml
  • X-41 solution containing 16.9 g of sodium chloride and 0.8 g of the above-mentioned gelatin in 100 ml
  • grain nuclei were formed.
  • the structure of the nuclei is AgCl
  • the difference in chloride content or bromide content between AgX1 and AgX4 was 50 %.
  • TEM transparent electron microscope
  • the average aspect ratio of tabular grains having an aspect ratio of not less than 2 is 5.5.
  • the average diameter of tabular grains having an aspect ratio of not less than 2 is 1.2 ⁇ m.
  • Example 4 was 125.
EP19940115393 1993-09-29 1994-09-29 Emulsion d'halogénure d'argent Expired - Lifetime EP0645670B1 (fr)

Applications Claiming Priority (3)

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JP264059/93 1993-09-29
JP26405993 1993-09-29
JP26405993A JPH07146522A (ja) 1993-09-29 1993-09-29 ハロゲン化銀乳剤

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EP0645670B1 EP0645670B1 (fr) 1999-12-01

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0737887A2 (fr) * 1995-04-14 1996-10-16 Fuji Photo Film Co., Ltd. Emulsion à l'halogénure d'argent
EP0809135A1 (fr) * 1996-05-21 1997-11-26 Agfa-Gevaert N.V. Procédé de préparation d'une émulsion photographique à grains tabulaires riches en chlorure
EP0843207A1 (fr) * 1996-11-15 1998-05-20 Agfa-Gevaert N.V. Procédé de préparation d'une émulsion photographique améliorée à grains tabulaires riches en chlorure
US5888718A (en) * 1997-11-25 1999-03-30 Eastman Kodak Company Modified peptizer for preparing high chloride (100) tabular grain emulsions
US5905022A (en) * 1997-11-24 1999-05-18 Eastman Kodak Company Chloride bromide and iodide nucleation of high chloride (100) tabular grain emulsion
US5908740A (en) * 1997-11-21 1999-06-01 Eastman Kodak Company Process for preparing high chloride (100) tabular grain emulsions
US6887430B1 (en) 1996-01-26 2005-05-03 Kyoto Dai-Ichi Kagaku Co., Ltd. Apparatus for immune analysis

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4063951A (en) * 1974-12-19 1977-12-20 Ciba-Geigy Ag Manufacture of tabular habit silver halide crystals for photographic emulsions
US4386156A (en) * 1981-11-12 1983-05-31 Eastman Kodak Company Silver bromide emulsions of narrow grain size distribution and processes for their preparation
EP0534395A1 (fr) * 1991-09-24 1993-03-31 Eastman Kodak Company Emulsions à haute teneur en chlorure et à haute tabularité de stabilité exceptionnelle

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4063951A (en) * 1974-12-19 1977-12-20 Ciba-Geigy Ag Manufacture of tabular habit silver halide crystals for photographic emulsions
US4386156A (en) * 1981-11-12 1983-05-31 Eastman Kodak Company Silver bromide emulsions of narrow grain size distribution and processes for their preparation
EP0534395A1 (fr) * 1991-09-24 1993-03-31 Eastman Kodak Company Emulsions à haute teneur en chlorure et à haute tabularité de stabilité exceptionnelle

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0737887A2 (fr) * 1995-04-14 1996-10-16 Fuji Photo Film Co., Ltd. Emulsion à l'halogénure d'argent
EP0737887A3 (fr) * 1995-04-14 1996-10-30 Fuji Photo Film Co., Ltd. Emulsion à l'halogénure d'argent
US5807665A (en) * 1995-04-14 1998-09-15 Fuji Photo Film Co., Ltd. Silver halide emulsion
US6887430B1 (en) 1996-01-26 2005-05-03 Kyoto Dai-Ichi Kagaku Co., Ltd. Apparatus for immune analysis
EP0809135A1 (fr) * 1996-05-21 1997-11-26 Agfa-Gevaert N.V. Procédé de préparation d'une émulsion photographique à grains tabulaires riches en chlorure
EP0843207A1 (fr) * 1996-11-15 1998-05-20 Agfa-Gevaert N.V. Procédé de préparation d'une émulsion photographique améliorée à grains tabulaires riches en chlorure
US5885763A (en) * 1996-11-15 1999-03-23 Agfa-Gevaert, N.V. Method for the preparation of an improved photographic tabular emulsion rich in chloride
US5908740A (en) * 1997-11-21 1999-06-01 Eastman Kodak Company Process for preparing high chloride (100) tabular grain emulsions
US5905022A (en) * 1997-11-24 1999-05-18 Eastman Kodak Company Chloride bromide and iodide nucleation of high chloride (100) tabular grain emulsion
US5888718A (en) * 1997-11-25 1999-03-30 Eastman Kodak Company Modified peptizer for preparing high chloride (100) tabular grain emulsions

Also Published As

Publication number Publication date
JPH07146522A (ja) 1995-06-06
EP0645670B1 (fr) 1999-12-01
DE69421878D1 (de) 2000-01-05
DE69421878T2 (de) 2000-04-20

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