EP0462581A1 - Emulsion photographique à l'halogénure d'argent - Google Patents

Emulsion photographique à l'halogénure d'argent Download PDF

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Publication number
EP0462581A1
EP0462581A1 EP91110004A EP91110004A EP0462581A1 EP 0462581 A1 EP0462581 A1 EP 0462581A1 EP 91110004 A EP91110004 A EP 91110004A EP 91110004 A EP91110004 A EP 91110004A EP 0462581 A1 EP0462581 A1 EP 0462581A1
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EP
European Patent Office
Prior art keywords
silver halide
grains
emulsion
silver
grain
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP91110004A
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German (de)
English (en)
Inventor
Yoshiro Ito
Syoji Matsuzaka
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Konica Minolta Inc
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Konica Minolta Inc
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Publication date
Priority claimed from JP16313690A external-priority patent/JPH0452636A/ja
Priority claimed from JP16502990A external-priority patent/JPH0456840A/ja
Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Publication of EP0462581A1 publication Critical patent/EP0462581A1/fr
Withdrawn legal-status Critical Current

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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
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain

Definitions

  • the present invention relates to a silver halide emulsion for photographic use, more specifically to a silver halide emulsion which offers high sensitivity and good developability.
  • a silver iodobromide emulsion having a silver iodide content of not more than 10 mol% is well known.
  • conventional methods used to prepare such emulsions include the ammoniacal method, the neutral method, the acidic method and other methods for controlling pH and pAg conditions, and the single jet method, the double jet method and other methods for mixing the components.
  • the silver halide emulsion produced under such conditions comprises so-called normal crystal grains in the form of either a cube, octahedron or tetradecahedron, which have various ratios of the ⁇ 100 ⁇ surface and ⁇ 111 ⁇ surface on the surface thereof. Such normal crystal grains are known to contribute to sensitivity improvement.
  • silver halide grains which offer high sensitivity are silver iodobromide grains having the ⁇ 110 ⁇ surface with excellent photographic properties, disclosed in Japanese Patent O.P.I. Publication Nos. 35440/1986 and 222842/1985.
  • Japanese Patent Examined Publication No. 42737/1980 discloses a photographic emulsion containing rhombic dodecahedral silver chlorobromide grains having the ⁇ 110 ⁇ surface which is not liable to fogging.
  • Japanese Patent O.P.I. Publication No. 83531/1986 discloses silver bromide and silver iodobromide grains having the crystal structure wherein a ridge is present on the center of the ⁇ 110 ⁇ surface, showing the possibility of further improvement in the sensitivity.
  • This crystal surface is considered to be of high Miller indices, and its properties are described in Japanese Patent O.P.I. Publication No. 83531/1986.
  • This crystal plane is represented by (nnl) and exemplified by the ⁇ 331 ⁇ surface.
  • a conventional silver iodobromide emulsion comprising polydispersed twin crystal grains are known as a silver halide emulsion suitable to high speed photographic films.
  • Japanese Patent O.P.I. Publication No. 63914/1975 and German Patent Application OLS No. 2419798 state that the sensitivity is increased by adding a hydroxytetrazaindene compound after sulfur sensitization of a monodispersed emulsion comprising cubic silver halide grains having a silver bromide content exceeding 80%.
  • the same Japanese publication also states that the sensitivity decreases or the degree of increase is very low in the case of a non-cubic crystal configuration, such as octahedral grains which are substantially enclosed by ⁇ 111 ⁇ surfaces.
  • Japanese Patent O.P.I. Publication No. 106532/1983 discloses a silver halide emulsion containing silver halide grains having a hollow passage from the surface to the inside.
  • a silver halide emulsion of tabular silver halide grains comprising parallel ⁇ 111 ⁇ surfaces facing each other and having a hollow or empty space on the center thereof is disclosed in Japanese Patent O.P.I. Publication No. 311244/1988.
  • Japanese Patent O.P.I. Publication Nos. 244030/1988, 264739/1988, 89949/1987, 269948/1987, 38930/1988 and 179140/1989 each disclose a silver halide emulsion comprising silver halide grains having a silver halide projection on their surface.
  • the projection occupies only a very small part of the surface area of the corresponding face.
  • the silver halide is a silver chlorobromide containing no silver iodide, or the silver halide projection is substantially silver chloride, or the silver halide projection is present in an extremely large number. For these reasons, none of these silver halide emulsions offer a satisfactory sensitivity improving effect.
  • the silver halide emulsion of the present invention comprises silver halide polyhedral crystal grains and each of crystal surfaces of each grain has an outward protrusion at the center of the surface.
  • Figures 1 and 2 are electron micrographs showing the grain structure of the silver halide grains of emulsions EM-1 and EM-3 of the present invention obtained in Examples 1 and 2, respectively.
  • Figure 3 is a schematic oblique view of a grain of EM-3.
  • a protrusion at the center of a crystal surface means that there is a wide (occupies not less than 50% of the area of the surface) protrusion in any shape near the center of the surface (any position, as long as it almost serves as the center), i.e., a non-marginal position.
  • the protrusion is often quadrangular, but its shape varies depending upon conditions of grain preparation.
  • the diameter of the protrusion expressed as the diameter of the circle converted from the area of the projection of the protrusion varies according to the diameter of the parent octahedral or tetradecahedral grain, but preference is given to 0.005 to 20 ⁇ m, more preferably 0.005 to 2.0 ⁇ m.
  • the height of the protrusion is preferably over 0.005 ⁇ m, more preferably over 0.02 ⁇ m, in the direction perpendicular to the corresponding plane of the grain.
  • every ⁇ 111 ⁇ surface of the octahedron is triangular strictly speaking, triangular with every vertex cut out, and has thereon a triangular protrusion which is almost concentric to the triangle, which is smaller than the triangle and which has almost the same shape as the triangle.
  • FIG. 2 shows the grain structure of EM-3
  • a slightly round prismatic protrusion is present on every ⁇ 100 ⁇ surface of the cube, with the root of these protrusions surrounded by a groove-like hollow.
  • Figure 3 schematically shows a magnified view of a grain of EM-3, in which symbol 1 denotes the silver halide grain, symbol 2 denotes the protrusion and symbol 3 denotes the hollow.
  • a crystal surface having particular Miller indices according to the silver ion and silver halide ion density thereon, lattice energy, surface energy and/or grain growth conditions occurs predominantly to provide a particular crystal phase for the crystal. Furthermore, when there is a grain size difference among the crystal grains, the crystal grains have different crystal habits according to surface size despite that they have the same Miller indices.
  • the eventual crystal plane is the plane that has the minimum rate of growth in the normal direction
  • the object is accomplished by delaying the growth of grains, i.e., the deposition of silver ions and halide ions, on the cubic surfaces in comparison with that on the crystal surfaces having another combination of Miller indices.
  • silver halide is additionally precipitated under such growth conditions that the growth of the cubic ⁇ 100 ⁇ surfaces are suppressed, whereby a tetrahedron which is a cubic octahedron or an octahedron with its six vertexes cut out occurs intermediately, followed by gradual reduction in the ⁇ 111 ⁇ surfaces, which in turn results in the formation of crystal grains exclusively with cubic planes, followed by thickening of cubic crystal grains with the addition of silver halide.
  • octatriacontahedral crystal grains can be derived from cubic crystal grains as the host grain. Accordingly, when precipitation of silver halide is continued under such growth conditions that the growth in the normal direction with respect to the octatriacontahedral crystal surface is slower than that on surfaces with other Miller indices, a octatriacontahedral crystal surface first appears, and eventually the host grain is totally covered by octatriacontahedral crystal surfaces.
  • the desired crystal grain can be obtained by choosing such growth conditions that the growth of the surface which provides the corresponding crystal surface is suppressed.
  • a preferred mode of the embodiment of the present invention is a silver halide emulsion containing octahedral or tetradecahedral crystal grains of silver halide having a protrusion on the center of at least one, preferably all, of the ⁇ 111 ⁇ surfaces, or cubic or tetradecahedral crystal grains of silver halide having a protrusion on the center of at least one, preferably all, of the ⁇ 100 ⁇ surfaces.
  • the growth of the silver halide grains having various crystal phases described above is affected by a large number of factors such as silver halide composition, ion density on the crystal surfaces, temperature, lattice or surface energy, adsorbents and silver halide solvent. Another factor is a growth modifier which retards the deposition of silver halide on the crystal surfaces.
  • a large number of compounds are already known to work as growth modifiers.
  • the compounds which work well as growth modifiers for photographic silver halide are surface-adsorptive photographic dyes such as cyanine dyes and stabilizers and antifogging agents such as azaindene and imidazole, disclosed in the above-mentioned Japanese patent publications, Japanese Patent Application No. 159280/1987 and other publications.
  • the silver halide grains having a protrusion on the center of at least one crystal plane, contained in the silver halide emulsion of the present invention may be prepared by any of the acidic method, neutral method and ammoniacal method. These grains may be grown continuously or grown with stepwise formation of seed grains. The method of preparing the seed grain and the method of its growth may be identical or not.
  • the silver halide composition of the silver halide emulsion of the present invention is not subject to limitation, but it is preferable that the silver halide be substantially silver bromide or silver iodobromide.
  • the emulsion of the present invention preferably contains iodine.
  • iodine ions may be added in an ion solution such as a potassium iodide solution during grain growth, and may be added as grains with a solubility product smaller than that of the growing silver halide grains.
  • This iodine is preferably supplied as silver halide grains with a solubility product equivalent to, or lower than that of the growing grains.
  • a preferred mode of the growth of the silver halide grains of the present invention is that the silver halide grains are grown in the presence of fine grains of silver halide with a solubility product equivalent to, or lower than that of the silver halide grains of the present invention (hereinafter referred to as AgX grains 2 like AgX grains 1) during at least a given period of the grain growth process.
  • “Equivalent or lower solubility product” means that the solubility product of AgX grains 2 is equivalent to, or lower than, that of AgX grains 1. In the present specification, the solubility product is used in the common sense in chemistry.
  • AgX grains 1 are grown in the presence of AgX grains 2, which have a solubility product equivalent to, or lower than, that of AgX grains 1, during at least a given period of the process of growth of AgX grains 1.
  • AgX grains 2 can be used to allow AgX grains 1 to grow before completion of the supply of grain growth elements for AgX grains 1, such as a halogen ion solution and a silver ion solution.
  • the average grain size of AgX grains 2 is usually smaller than that of AgX grains 1, but the former is greater than the latter in some cases. Also, AgX grains 2 are usually substantially non-sensitive to light.
  • the average grain size of AgX grains 2 is preferably 0.001 to 0.7 ⁇ m, more preferably 0.01 to 0.3 ⁇ m, and ideally 0.01 to 0.1 ⁇ m.
  • AgX grains 2 it is preferable to add AgX grains 2 to the suspension system in which AgX grains 1 are prepared (hereinafter referred to as the mother liquid) at latest until completion of the growth of AgX grains 1.
  • AgX grains 2 may be added to the mother liquid before the seed grains are added, or added to the mother liquid containing seed grains before adding grain growth elements, or added during addition of grain growth elements, or added in separate stages of the addition period.
  • Addition of AgX grains 2 and grain growth elements may be simultaneous, continuous or intermittent.
  • AgX grains 2 and grain growth elements are preferably added to the mother liquid by a multi-jet method such as the double jet method at a rate suitable to grain growth while controlling the pH, pAg, temperature and other factors.
  • AgX grains 2 and silver halide seed grains may be prepared in the mother liquid, or added to the mother liquid after it is prepared outside the mother liquid.
  • the solution of water-soluble silver salt used to prepare AgX grains 2 is preferably an ammoniacal solution of silver salt.
  • AgX grains 1 are of silver iodobromide
  • silver bromide or a silver chlorobromide having a bromine content higher than that of the growing silver chlorobromide grains is preferred when AgX grains 1 are of silver chlorobromide.
  • AgX grains 2 are preferably of silver iodide.
  • AgX grains 1 are of silver iodobromide or silver chloroiodobromide, it is preferable that the iodine for grain growth be supplied as AgX grains 2, but some of it may be supplied in an aqueous solution of silver halide, as long as it does not interfere with the effect of the present invention.
  • a known silver halide solvent such as ammonia, thioether or thiourea, may be present during the growth of silver halide grains.
  • cadmium, zinc, lead, thallium, iridium, rhodium and iron may be contained inside and/or on the grains by adding ions of these metal elements using at least one kind selected from the group comprising cadmium salt, zinc salt, lead salt, thallium salt, iridium salt, rhodium salt, iron salt and complex salt thereof.
  • the silver halide grains may be provided with a reduction sensitization nucleus therein and/or thereon by keeping them under appropriate reductive conditions.
  • the silver halide emulsion of the present invention may have the undesirable soluble salts removed therefrom after completion of their growth or may remain containing them. Removal of these salts can be achieved in accordance with the method described in Research Disclosure (hereinafter referred to as RD) No. 17643, Paragraph II.
  • the average grain size of the silver halide grains of the present invention is preferably 0.05 to 30 ⁇ m, more preferably 0.1 to 3.0 ⁇ m.
  • the silver halide emulsion of the present invention may take any form, including a polydispersed emulsion with a broad grain size distribution and a monodispersed emulsion with a narrow grain size distribution.
  • the silver halide emulsion of the present invention may comprise a single emulsion or a mixture of two or more emulsions.
  • the grain size ri which gives a maximum value for the product of ni and ri3 (ni x ri3) wherein ni is the number of grains having a grain size of ri with an average of r is defined (significant up to three digits, rounded off at the last digit).
  • the grain diameter ri is defined as the diameter of the silver halide grain when it is spherical or the diameter converted from a circle with the same area from the projected image of the silver halide grain when it is not spherical.
  • Grain size can be obtained by measuring the diameter of the grain or the area of the projected circle on an electron micrograph taken at x 10000 to 50000 (the number of subject grains should be not less than 1000 randomly).
  • a highly monodispersed emulsion preferred for the present invention has a distribution width of not more than 20%, more preferably not more than 15%, defined by the following equation.
  • the average grain size and standard deviation are calculated from ri defined above.
  • a monodispersed emulsion can be prepared by adding a solution of water-soluble silver salt and a solution of water-soluble halide by the double jet method while controlling the pAg and pH. This method is applicable to the present invention.
  • the addition rate can be determined with reference to Japanese Patent O.P.I. Publication Nos. 48521/1979 and 49938/1983.
  • the silver halide emulsion of the present invention preferably maintains uniformity with respect to grain shape.
  • Uniformity with respect to grain shape means that at least crystal habit and grain size are uniform among the subject grains when their shape is observed by scanning electron micrography at a magnification of exceeding x 10000.
  • a low accelerated voltage below 2 kV.
  • not less than 70%, more preferably not less than 80%, and still more preferably not less than 90% of the grains in the emulsion keep uniformity with respect to the shape described above.
  • the silver halide emulsion of the present invention preferably keeps uniformity with respect to the silver iodide content among the silver halide grains.
  • the silver iodide content of each silver halide grain in the emulsion of the present invention and the average silver iodide content of the silver halide grains can be calculated by the EPMA method of electron probe microanalyzer method.
  • a sample is prepared by thoroughly dispersing emulsion grains apart from each other and making elemental analysis of very small portions of the sample using X-ray excited by electron beam irradiation.
  • This method permits determination of the halogen composition of each grain by determining the intensities of the silver and iodine characteristic X-rays from each grain.
  • the apparatus used for this measurement does not need special specifications.
  • the X-ray microanalyzer model JXA-8621, produced by JEOL Ltd. was used to determine the silver iodide content of the emulsion. Measurements were made while cooling the sample to avoid damage by the electron beam.
  • the relative standard deviation for the silver iodide content of each grain is obtained by multiplying by a factor of 100 the quotient of the standard deviation for the silver iodide content by the average silver iodide content obtained in the measurement on at least 50 emulsion grains.
  • the emulsion of the present invention preferably has a relative standard deviation of not more than 20% with respect to the silver iodide content of each silver iodobromide grain.
  • the emulsion of the present invention preferably has more uniformity of iodine content among the grains.
  • the relative standard deviation for the iodine content distribution among the grains determined by the EPMA method is preferably not more than 20%, more preferably not more than 15%, and still more preferably not more than 10%.
  • the silver halide grains of the present invention can be formed under various sets of conditions as described above, but a preferred mode of embodiment, e.g., octahedral or tetradecahedral crystal grains of silver halide having a protrusion on the center of the ⁇ 111 ⁇ surface, or cubic or tetradecahedral crystal grains of silver halide having a protrusion on the center of the ⁇ 100 ⁇ surface, can be prepared by the method described below.
  • a suspension of fine silver halide seed grains is prepared by an ordinary method.
  • a solution of water-soluble silver halt and a solution of water-soluble bromide are added in the presence of a nitrogen-containing compound and fine grains of silver iodide or silver iodobromide, and a low iodine silver halide phase with a silver iodide content of not more than 10 mol% is grown on the seed grains.
  • cubic, octahedral or tetradecahedral grains can be prepared optionally. Accordingly, a pAg of 7.6 to 9 yields octahedral grains, and a pAg below 7.6 yields cubic grains.
  • Tetradecahedral grains can be formed by setting the pAg at a critical level around 7.6. The grain formation temperature is preferably above 50°C.
  • a solution of water-soluble silver salt and a solution of water-soluble halide are added to form a high iodine phase having a silver iodide content higher by not less than 10 mol%, preferably not less than 15 mol%, than that the surface silver iodide content of each grain outside the low iodine phase in each grain, followed by growth thereon of an outer low iodine phase having an iodine content lower by 1 to 10 mol% than the surface iodine content of the high iodine phase, whereby an emulsion containing octahedral or tetradecahedral silver halide grains of the present invention, which has a protrusion on the ⁇ 111 ⁇ surface, is obtained.
  • the volume ratio of the low iodine phase to the high iodine phase is preferably not less than 30%
  • a solution of water-soluble silver salt and a solution of water-soluble halide are added to form a high iodine phase having a silver iodide content higher by not less than 10 mol%, preferably not less than 15 mol%, than the surface silver iodide content of each grain outside the low iodine phase of each grain, followed by growth thereon of an outer low iodine phase having an iodine content lower by 15 to 35 mol% than the surface iodine content of the high iodine phase, whereby a silver halide emulsion of the present invention, which comprises grains having a protrusion on the center of the ⁇ 100 ⁇ surface, is obtained.
  • the volume ratio of the high iodine phase to the low iodine phase is preferably not less than 50%, and the volume ratio of the outer low iodine phase to the high iodine phase is preferably not more than 30%.
  • the pAg during grain growth is preferably below 9.
  • the silver halide emulsion of the present invention may be chemically sensitized by the conventional method.
  • the silver halide emulsion of the present invention may be optically sensitized in the desired wavelength band using a sensitizing dye known in the photographic industry.
  • the sensitizing dye may be used singly or in combination of two or more kinds.
  • the silver halide emulsion may contain an antifogging agent, stabilizer and other additives. It is advantageous to use gelatin as the binder for the emulsion.
  • the emulsion layer and other hydrophilic colloidal layers of the light-sensitive material may be hardened, and may contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly water-soluble synthetic polymer.
  • the silver halide emulsion of the present invention can serve well for the formation of a color photographic light-sensitive material, and when it is used in the emulsion layer, it is used in the presence of a coloring coupler.
  • a colored coupler having a color correction effect it is possible to use a colored coupler having a color correction effect, a competing coupler and a compound which releases a photographically useful fragment such as a development accelerator, bleaching accelerator, developer, silver halide solvent, toning agent, hardener, fogging agent, antifogging agent, chemical sensitizer, spectral sensitizer and desensitizer by coupling with the oxidation product of a developing agent.
  • auxiliary layers such as a filter layer, anti-halation layer and anti-irradiation layer may be formed in the light-sensitive material.
  • These layers and/or the emulsion layers may contain a dye which oozes out or is bleached from the light-sensitive material during development.
  • the light sensitive-material may contain a formalin scavenger, a fluorescent whitening agent, a matting agent, a lubricant, an image stabilizer, a surfactant, an antifogging agent, a development accelerator, a development retarder and a bleaching accelerator.
  • any material can be used as the support for the light-sensitive material, such as polyethylene-laminated paper, a polyethylene terephthalate film, baryta paper and cellulose triacetate.
  • a dye image can be obtained using the light-sensitive material of the present invention by exposure followed by an ordinary color photographic process.
  • aqueous solution containing 5% by weight ossein gelatin was added to a vessel. While stirring at 40°C, a 3.5 N aqueous solution of 1 mol of silver nitrate and a 3.5 N aqueous solution of 1 mol of potassium iodide were added at constant rate over a period of 30 minutes.
  • the pAg was kept at 13.5 by the ordinary method of pAg control during the addition.
  • the resulting silver iodide was a mixture of ⁇ -AgI and ⁇ -AgI having an average grain size of 0.06 ⁇ m.
  • emulsion AI-1 This emulsion is hereinafter referred to as emulsion AI-1.
  • the mixture was desalted and washed by conventional methods and dispersed in an aqueous solution containing gelatin.
  • this emulsion is a highly monodispersed emulsion with a coefficient of variance of grain size distribution of 11.2%, comprising octahedral grains having a protrusion on the ⁇ 111 ⁇ surface which account for 92% of all silver halide grains, with an average grain size of 0.46 ⁇ m.
  • Table 4 shows the grain structure of silver halide grains contained in this emulsion.
  • Figure 1 is an electron micrograph of a silver halide grain contained in this emulsion of the present invention.
  • a comparative emulsion EM-2 was prepared in accordance with the methods described in Japanese Patent O.P.I. Publication Nos. 246740/1986, 275741/1986 and 286845/1986, which comprises octahedral grains having the same halogen composition, grain size distribution and average grain size as those of the aforementioned emulsion EM-1 and having no protrusion on the ⁇ 111 ⁇ surface in-the final configuration.
  • the emulsions EM-1 and EM-2 thus prepared were subjected to optimum gold-sulfur sensitization and then spectrally sensitized in the green band by adding 350 mg of the following sensitizing dye I and 240 mg of the sensitizing dye II per mol AgX. Then, TAI and 1-phenyl-5-mercaptotetrazole were added to stabilize the emulsions.
  • AgX represents silver halide.
  • magenta coupler M-1 at 5 x 10 ⁇ 3 mol per mol AgX
  • magenta coupler M-2 at 6.2 x 10 ⁇ 3 mol per mol AgX
  • the following colored magenta coupler CM-1 at 4.0 x 10 ⁇ 3 mol per mol AgX
  • sample Nos. 101 and 102 were each subjected to exposure through an optical wedge via a yellow filter, after which they were processed with the following processing solutions in the following processing procedures I and II and subjected to sensitivity determination.
  • Processing procedure I 35°C
  • Development 15 seconds Fixation 25 seconds Washing 25 seconds Drying 15 seconds
  • Processing procedure II 35°C
  • Development 25 seconds Fixation 25 seconds Washing 25 seconds Drying 15 seconds
  • the processing solutions used in the processing procedures had the following compositions.
  • Disodium ethylenediaminetetraacetate 5.0 g Tartaric acid 3.0 g Ammonium thiosulfate 130.9 g Anhydrous sodium sulfite 7.3 g Boric acid 7.0 g Acetic acid (90 wt%) 5.5 g Sodium acetate trihydrate 25.8 g Aluminum sulfate octadecahydrate 14.6 g Sulfuric acid (50 wt%) 6.77 g
  • a seed emulsion having an average grain size of 0.27 ⁇ m and an average AgI content of 2 mol% in an amount equivalent to 0.208 mol was added, and acetic acid and an aqueous solution of KBr were added to obtain the desired pH and pAg levels.
  • Solutions a-2, a-3 and a-4 were added by the triple jet method at the flow rates shown in Tables 6, 7 and 8, respectively.
  • the mixture was desalted and washed by ordinary methods and dispersed in an aqueous solution containing gelatin.
  • this emulsion is a highly monodispersed emulsion having a coefficient of variance of grain size distribution of 11.2%, comprising nearly cubic grains having a protrusion on the ⁇ 100 ⁇ surface with an average grain size of 0.68 ⁇ m, which account for 92% of all silver halide grains.
  • Table 9 shows the grain structure of silver halide grains contained in this emulsion.
  • Figure 2 is an electron micrograph of a silver halide grain contained in this emulsion EM-3 of the present invention.
  • a comparative emulsion EM-4 was prepared in accordance with the method described in Japanese Patent O.P.I. Publication 246740/1986, 275741/1986 and 286845/1986, which comprises cubic grains having the same halogen composition, grain size distribution and average grain size as those of the aforementioned emulsion EM-3 and having no protrusion on the ⁇ 100 ⁇ surface in the final configuration.
  • the emulsions EM-3 and EM-4 thus prepared were subjected to optimum gold-sulfur sensitization and then spectrally sensitized in the green band by adding 166 mg of sensitizing dye I and 110 mg of sensitizing dye II per mol AgX. Then, TAI and 1-phenyl-5-mercaptotetrazole were added to stabilize the emulsions.
  • AgX represents silver halide.
  • magenta coupler M-1 at 5 x 10 ⁇ 3 mol per mol AgX, magenta coupler M-2 at 6.2 x 10 ⁇ 3 mol and the following colored magenta coupler CM-1 at 4.0 x 10 ⁇ 3 mol were dissolved in di-t-nonyl phthalate, and this solution was emulsified and dispersed in an aqueous solution containing gelatin. The resulting dispersion was added to each emulsion, followed by the addition of ordinary photographic additives such as an extender and a hardener to yield a coating solution. This coating solution was coated and dried on a subbed film base by a conventional method to yield sample Nos. 103 and 104.

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  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP91110004A 1990-06-21 1991-06-19 Emulsion photographique à l'halogénure d'argent Withdrawn EP0462581A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP163136/90 1990-06-21
JP16313690A JPH0452636A (ja) 1990-06-21 1990-06-21 高感度で現像性が良好なハロゲン化銀乳剤
JP16502990A JPH0456840A (ja) 1990-06-22 1990-06-22 高感度で現像性が良好なハロゲン化銀乳剤
JP165029/90 1990-06-22

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5541053A (en) * 1993-10-20 1996-07-30 Eastman Kodak Company Process for the preparation of silver halide photographic emulsions containing grains having (100) faces with cavities and photographic emulsions so prepared

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0199290A2 (fr) * 1985-04-17 1986-10-29 Fuji Photo Film Co., Ltd. Emulsion photographique à l'halogénure d'argent et matériau photographique la contenant

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0199290A2 (fr) * 1985-04-17 1986-10-29 Fuji Photo Film Co., Ltd. Emulsion photographique à l'halogénure d'argent et matériau photographique la contenant

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5541053A (en) * 1993-10-20 1996-07-30 Eastman Kodak Company Process for the preparation of silver halide photographic emulsions containing grains having (100) faces with cavities and photographic emulsions so prepared

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