EP0215612A2 - Emulsions photographiques à l'halogénure d'argent avec des grains à faces - Google Patents

Emulsions photographiques à l'halogénure d'argent avec des grains à faces Download PDF

Info

Publication number
EP0215612A2
EP0215612A2 EP86306797A EP86306797A EP0215612A2 EP 0215612 A2 EP0215612 A2 EP 0215612A2 EP 86306797 A EP86306797 A EP 86306797A EP 86306797 A EP86306797 A EP 86306797A EP 0215612 A2 EP0215612 A2 EP 0215612A2
Authority
EP
European Patent Office
Prior art keywords
faces
silver halide
grain
grains
silver
Prior art date
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.)
Granted
Application number
EP86306797A
Other languages
German (de)
English (en)
Other versions
EP0215612A3 (en
EP0215612B1 (fr
Inventor
Joe Edward Maskasky
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Kodak Co
Original Assignee
Eastman Kodak Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from US06/772,271 external-priority patent/US4643966A/en
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Publication of EP0215612A2 publication Critical patent/EP0215612A2/fr
Publication of EP0215612A3 publication Critical patent/EP0215612A3/en
Application granted granted Critical
Publication of EP0215612B1 publication Critical patent/EP0215612B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/0051Tabular grain emulsions
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/04Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • G03C1/047Proteins, e.g. gelatine derivatives; Hydrolysis or extraction products of proteins
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/07Substances influencing grain growth during silver salt formation
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/0051Tabular grain emulsions
    • G03C2001/0055Aspect ratio of tabular grains in general; High aspect ratio; Intermediate aspect ratio; Low aspect ratio
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/03511Bromide content
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C2200/00Details
    • G03C2200/03111 crystal face

Definitions

  • silver halide emulsions rarely contain more than about 15 mole percent iodide, with iodide well below 10 mole percent being most common. All silver halide grains, except rarely employed high iodide silver halide grains, hereinafter excluded from consideration except as expressly noted, exhibit cubic crystal lattice structures.
  • Silver halide favors the formation of crystallographic faces of either the cubic or octahedral form.
  • Silver chloride strongly favors the formation of cubic crystal faces.
  • Silver bromide also favors the formation of cubic crystal faces, but favors the formation of octahedral crystal faces in the presence of an excess of bromide ions.
  • Iodide ions in the crystal structure tend to increase the grain preference for crystal faces of the octahedral form.
  • FIG. 4 is a schematic illustration of a (111) crystal face, analogous to Figure 2, wherein the smaller spheres 2 represent silver ions while the larger spheres 3 designate bromine ions.
  • silver ions are shown at the surface in every available lattice position, it has been suggested that having silver ions in only every other available lattice position in the surface tier of atoms would be more compatible with surface charge neutrality.
  • the surface tier of ions could alternatively be bromide ions.
  • the tier of ions immediately below the surface silver ions consists of bromide ions.
  • Core-shell silver halide emulsions constitute the most common examples of silver halide grains of a composite structure. Core-shell emulsions are illustrated by Porter et al U.S. Patents 3,206,313 and 3,317,322, Berriman U.S. Patent 3,367,778, and Evans U.S. Patent 3,761,276, and, in tabular form, by Evans et al U.S. Patent 4,504,570.
  • Halwig U.S. Patent 3,519,426 and Oppenheimer et al disclose additions of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene to silver chloride and silver bromide emulsions, respectively.
  • novel ruffling approach of this invention and other known approaches for increasing grain surface area ratios, specifically reducing grain size or providing irregular grain shapes, are compatible and can be used in combination to produce additive increases in grain surface area ratios.
  • planar faces By reason of being ruffled these grain faces present a larger surface area than a corresponding planar grain face.
  • planar faces such as the cube 1 in Figure 1 or the octahedron 5 in Figure 3, it is apparent that the planar faces each present the minimum surface area consistent with the size of the polyhedron.
  • the silver halide grains having ruffled faces are formed starting with any conventional emulsion containing silver halide grains of a cubic crystal lattice structure presenting faces of a crystallographic form favored by the silver halide.
  • silver halide grains which are predominantly silver chloride (greater than 50 mole percent chloride, based on silver) and especially grains which are at least 90 mole percent chloride the favored crystallographic form is cubic, and the grain faces to be ruffled are therefore cubic (i.e., (100)) crystal faces.
  • pyramids with rhombic dodecahedral faces it can been seen in Figure 5 that the regular rhombic dodecahedron 7 has eight corners each formed by the intersection of three crystal faces and six corners formed by the intersection of four crystal faces.
  • a pyramid presenting rhombic dodecahedral or ⁇ 110 ⁇ crystal faces is located on a ⁇ 100 ⁇ base plane, it presents four surface faces, thus appearing in plan similarly as shown in Figure 9; but when a ⁇ 111 ⁇ base plane is presented, a pyramid with ⁇ 110 ⁇ crystal faces presents three surface faces, thus appearing in plan similarly as shown in Figure 8.
  • the (331) trisoctahedral crystal faces present a unique arrangement of surface silver and halide ions that differs from that presented by all other possible crystal faces for cubic crystal lattice structure silver halides.
  • This unique surface arrangement of ions as theoretically hypothesized is schematically illustrated by Figure 11, wherein a ⁇ 331 ⁇ trisoctahedral crystal face is shown formed by silver ions 2 and bromide ions 3. Comparing Figure 11 with Figures 2, 4, and 6, it is apparent that the surface positioning of silver and bromide ions in each figure is distinctive.
  • the (321) hexoctahedral crystal faces present a unique arrangement of surface silver and halide ions that differs from that presented by all other possible crystal faces for cubic crystal lattice structure silver halides.
  • This unique surface arrangement of ions as theoretically hypothesized is schematically illustrated by Figure 17, wherein a (321) hexoctahedral crystal face is shown formed by silver ions 2 and bromide ions 3. Comparing Figure 17 with Figures 2, 4, 6, 11, 13, and 15, it is apparent that the surface positioning of silver and bromide ions in each figure is distinctive.
  • silver halide emulsions containing any identifiable ruffled grain surface are considered within the scope of this invention, in most applications the grains having at least one identifiable ruffled face account for at least 10 percent of the total grain population and usually these grains will account for greater than 50 percent of the total grain population.
  • the silver halide emulsions can be spectrally sensitized with dyes from a variety of classes, including the polymethine dye class, which Includes the cyanines, merocyanines, complex cyanines and merocyanines (i.e., tri-, tetra-, and polynuclear cyanines and merocyanines), oxonols, hemioxonols, styryls, merostyryls, and streptocyanines.
  • Illustrative spectral sensitizing dyes are disclosed in Research Disclosure, Item 17643, cited above, Section IV.
  • the substitution of an emulsion according to the invention containing a growth modifier spectral sensitizing dye should produce a more invariant emulsion in terms of spectral properties than a corresponding emulsion containing silver halide grains lacking ruffled faces.
  • the growth modifier is capable of inhibiting fog, such as 2-mercaptoimidazole or any of the tetraazaindenes shown to be effective growth modifiers in the examples, more effective fog inhibition at lower concentrations may be expected.
  • Emulsion Example 1 illustrates the preparation of a ruffled tabular grain silver bromoiodide emulsion using as growth modifier Compound I, 5-carbethoxy-4-hydroxy-1,3,3a,7-tetraazaindene, which is known to be useful as an antifoggant and stabilizer.
  • Emulsion Example 2 was prepared as described for Example 1, except that the growth modifier was 6.0 millimole/Ag mole of Compound II, dissolved in 3mL methanol, 2mL water, and 2 drops of triethylamine. The precipitation was carried out for 37.0 min, consuming 0.015 mole Ag.
  • a thin and high aspect ratio tabular grain AgBr emulsion having major faces of octahedral form, of mean grain size 5.6 um and thickness 0.10 um containing about 20 g/Ag mole gelatin, hereinafter designated Host Grain Emulsion 2.
  • Water was added to make the total weight 50 g.
  • To the emulsion at 40°C was added 5.0 millimole/initial Ag mole of Compound III dissolved in 2mL methanol. The emulsion was then held for 15 min at 40°C. The pH was adjusted to 6.0 at 40°C.
  • the temperature was lowered to 30°C, and the pAg adjusted to 7.6 at 30°C with KBr and maintained at that level during the precipitation.
  • a 2.0M solution of AgN0 3 was introduced at a constant rate over a period of 10 min while a 2.0M solution of KBr was added as needed to hold the pAg constant.
  • a total of 0.020 mole Ag was added.
  • Example 6 illustrates the preparation of ruffled tabular grain silver bromoiodide emulsions using Compound V (Example 5) as the growth modifier.
  • Example 6A is a control showing that no ruffles are formed if the growth modifier is added following, rather than preceding, the silver halide precipitation on the host emulsion.
  • the host emulsion (0.05 mole for each experiment) and precipitation conditions were as described in Example 1, except that the growth modifier was Compound V and the addition rate of the AgN0 3 solution was half that used in Example 1, (precipitation time about 74 min, 0.015 mole Ag added).
  • the details of the three experiments are shown in Table III.
  • Figure 26A is an electron micrograph showing the fairly uniform, closely arranged ruffles which resulted.
  • the ruffles were made up of pyramidal crystal faces of the ⁇ 110 ⁇ (rhombic dodecahedral) crystallographic form.
  • Figure 26E is an electron micrograph showing the rather large ruffles which resulted.
  • the ruffles were made up of pyramidal crystal faces of the (331) trisoctahedral crystallographic form.
  • Emulsion Example 10 illustrates the preparation of a ruffled octahedral silver bromide emulsion using Compound I as a growth modifier.
  • Emulsion Example 12 illustrates the preparation of a ruffled octahedral silver bromide emulsion using Compound X as growth modifier. As the precipitation continued, the formation of trisoctahedra became evident.
  • Emulsion Example 13 illustrates the formation of octahedral silver bromide emulsions which have their surface area increased by ruffles in the form of uniform ridges.
  • Figures 30A and 30B are electron micrographs of the resulting emulsion grains produced by Examples 13A and 13B, respectively.
  • the faces are uniformly covered with ridges running in a direction perpendicular to the (110) Ag rows of the lattice. Trisoctahedral faces have begun to form. In Example 13B the ridges remain evident, while the macro habit has become (331) trisoctahedral.
  • Figures 31A and 31B are electron micrographs of the resulting emulsion grains produced by Examples 14A and 14B, respectively.
  • Figure 31A shows a pattern of growths covering the crystal faces.
  • Figure 31B illustrates the formation of ⁇ 533 ⁇ icositetrahedral grains with continued precipitation.
  • This example illustrates an increase in photographic speed which can be realized with ruffled grains according to the present invention.
  • Control Emulsion 16B was modified after precipitation and before coating by increasing the total content of Compound V to 3.75 millimole/Ag mole, which equaled its concentration in Example Emulsion 16A.
  • Example Emulsion 16A had a significantly greater blue speed relative to its 365 nm speed than did the control unruffled Control Emulsions 16B and 16C with a normal spectral sensitization or with an equal amount of sensitizing dye equal to that of the ruffled grain Example Emulsion 16A, respectively.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP19860306797 1985-09-03 1986-09-03 Emulsions photographiques à l'halogénure d'argent avec des grains à faces Expired - Lifetime EP0215612B1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US06/772,271 US4643966A (en) 1985-09-03 1985-09-03 Emulsions and photographic elements containing ruffled silver halide grains
US772271 1985-09-03
US81113385A 1985-12-19 1985-12-19
US81113285A 1985-12-19 1985-12-19
US811133 1985-12-19
US811132 1985-12-19

Publications (3)

Publication Number Publication Date
EP0215612A2 true EP0215612A2 (fr) 1987-03-25
EP0215612A3 EP0215612A3 (en) 1988-11-30
EP0215612B1 EP0215612B1 (fr) 1993-02-24

Family

ID=27419684

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19860306797 Expired - Lifetime EP0215612B1 (fr) 1985-09-03 1986-09-03 Emulsions photographiques à l'halogénure d'argent avec des grains à faces

Country Status (4)

Country Link
EP (1) EP0215612B1 (fr)
JP (1) JPH0812390B2 (fr)
CA (1) CA1280312C (fr)
DE (1) DE3687808T2 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0244718A2 (fr) * 1986-05-08 1987-11-11 Minnesota Mining And Manufacturing Company Emulsion à l'halogénure d'argent sensible à la lumière et éléments radiographiques avec une qualité d'image améliorée et des taches résiduelles en quantité réduite
EP0367248A1 (fr) * 1988-10-31 1990-05-09 Konica Corporation Grains cristallins à l'halogénure d'argent et matériau à l'halogénure d'argent sensible à la lumière

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2767493B2 (ja) * 1990-11-14 1998-06-18 富士写真フイルム株式会社 ハロゲン化銀乳剤

Citations (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1696830A (en) 1926-05-20 1928-12-25 Ig Farbenindustrie Ag Light-sensitive silver halide emulsions and process of making the same
GB504283A (en) 1937-10-21 1939-04-21 Kodak Ltd Improvements in or relating to light-sensitive or image-bearing layers
GB760775A (en) 1953-07-16 1956-11-07 Kodak Ltd Increasing the speed of photographic emulsions
US3140179A (en) 1959-10-22 1964-07-07 Eastman Kodak Co Photographic element having increased speed and contrast
US3206313A (en) 1961-05-15 1965-09-14 Eastman Kodak Co Chemically sensitized emulsions having low surface sensitivity and high internal sensitivity
US3317322A (en) 1965-08-27 1967-05-02 Eastman Kodak Co Photographic emulsions having high internal sensitivity
US3367778A (en) 1965-04-15 1968-02-06 Eastman Kodak Co Silver salt direct positive emulsion
US3519426A (en) 1966-12-27 1970-07-07 Eastman Kodak Co Preparation of silver halide emulsions having high covering power
US3761276A (en) 1971-03-10 1973-09-25 Eastman Kodak Co Photographic element containing monodispersed unfogged silver halide grains chemically sensitized internally and externally
US3804629A (en) 1971-09-03 1974-04-16 Agfa Gevaert Ag Process for the production of a stain-resistant photographic silver halide emulsion
US3817756A (en) 1971-05-11 1974-06-18 Agfa Gevaert Nv Manufacture of photographic silver halide materials
US3989527A (en) 1975-01-08 1976-11-02 Eastman Kodak Company Silver halide photographic element containing blended grains
US4183756A (en) 1978-05-03 1980-01-15 Eastman Kodak Company Pre-precipitation spectral sensitizing dye addition process
US4225666A (en) 1979-02-02 1980-09-30 Eastman Kodak Company Silver halide precipitation and methine dye spectral sensitization process and products thereof
US4349622A (en) 1979-06-01 1982-09-14 Konishiroku Photo Industry Co., Ltd. Photographic silver halide emulsion comprising epitaxial composite silver halide crystals, silver iodobromide emulsion and process for preparing the same
JPS5854333A (ja) 1981-09-28 1983-03-31 Fuji Photo Film Co Ltd ハロゲン化銀乳剤
US4386156A (en) 1981-11-12 1983-05-31 Eastman Kodak Company Silver bromide emulsions of narrow grain size distribution and processes for their preparation
US4387154A (en) 1980-09-08 1983-06-07 Eastman Kodak Company Receivers with nonplanar support elements
US4399215A (en) 1981-11-12 1983-08-16 Eastman Kodak Company Double-jet precipitation processes and products thereof
US4400463A (en) 1981-11-12 1983-08-23 Eastman Kodak Company Silver chloride emulsions of modified crystal habit and processes for their preparation
US4414304A (en) 1981-11-12 1983-11-08 Eastman Kodak Company Forehardened high aspect ratio silver halide photographic elements and processes for their use
US4414306A (en) 1981-11-12 1983-11-08 Eastman Kodak Company Silver chlorobromide emulsions and processes for their preparation
US4414310A (en) 1981-11-12 1983-11-08 Eastman Kodak Company Process for the preparation of high aspect ratio silver bromoiodide emulsions
US4425425A (en) 1981-11-12 1984-01-10 Eastman Kodak Company Radiographic elements exhibiting reduced crossover
US4433048A (en) 1981-11-12 1984-02-21 Eastman Kodak Company Radiation-sensitive silver bromoiodide emulsions, photographic elements, and processes for their use
US4434226A (en) 1981-11-12 1984-02-28 Eastman Kodak Company High aspect ratio silver bromoiodide emulsions and processes for their preparation
US4435501A (en) 1981-11-12 1984-03-06 Eastman Kodak Company Controlled site epitaxial sensitization
US4439520A (en) 1981-11-12 1984-03-27 Eastman Kodak Company Sensitized high aspect ratio silver halide emulsions and photographic elements
US4463087A (en) 1982-12-20 1984-07-31 Eastman Kodak Company Controlled site epitaxial sensitization of limited iodide silver halide emulsions
US4478929A (en) 1982-09-30 1984-10-23 Eastman Kodak Company Dye image transfer film unit with tabular silver halide
US4504570A (en) 1982-09-30 1985-03-12 Eastman Kodak Company Direct reversal emulsions and photographic elements useful in image transfer film units

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4011083A (en) * 1974-12-10 1977-03-08 Eastman Kodak Company Surface sensitive silver halide emulsion containing a silver complexing azaindene to reduce desensitization of optical sensitizing dye incorporated therein

Patent Citations (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1696830A (en) 1926-05-20 1928-12-25 Ig Farbenindustrie Ag Light-sensitive silver halide emulsions and process of making the same
GB504283A (en) 1937-10-21 1939-04-21 Kodak Ltd Improvements in or relating to light-sensitive or image-bearing layers
GB760775A (en) 1953-07-16 1956-11-07 Kodak Ltd Increasing the speed of photographic emulsions
US3140179A (en) 1959-10-22 1964-07-07 Eastman Kodak Co Photographic element having increased speed and contrast
US3206313A (en) 1961-05-15 1965-09-14 Eastman Kodak Co Chemically sensitized emulsions having low surface sensitivity and high internal sensitivity
US3367778A (en) 1965-04-15 1968-02-06 Eastman Kodak Co Silver salt direct positive emulsion
US3317322A (en) 1965-08-27 1967-05-02 Eastman Kodak Co Photographic emulsions having high internal sensitivity
US3519426A (en) 1966-12-27 1970-07-07 Eastman Kodak Co Preparation of silver halide emulsions having high covering power
US3761276A (en) 1971-03-10 1973-09-25 Eastman Kodak Co Photographic element containing monodispersed unfogged silver halide grains chemically sensitized internally and externally
US3817756A (en) 1971-05-11 1974-06-18 Agfa Gevaert Nv Manufacture of photographic silver halide materials
US3804629A (en) 1971-09-03 1974-04-16 Agfa Gevaert Ag Process for the production of a stain-resistant photographic silver halide emulsion
US3989527A (en) 1975-01-08 1976-11-02 Eastman Kodak Company Silver halide photographic element containing blended grains
US4183756A (en) 1978-05-03 1980-01-15 Eastman Kodak Company Pre-precipitation spectral sensitizing dye addition process
US4225666A (en) 1979-02-02 1980-09-30 Eastman Kodak Company Silver halide precipitation and methine dye spectral sensitization process and products thereof
US4349622A (en) 1979-06-01 1982-09-14 Konishiroku Photo Industry Co., Ltd. Photographic silver halide emulsion comprising epitaxial composite silver halide crystals, silver iodobromide emulsion and process for preparing the same
US4387154A (en) 1980-09-08 1983-06-07 Eastman Kodak Company Receivers with nonplanar support elements
JPS5854333A (ja) 1981-09-28 1983-03-31 Fuji Photo Film Co Ltd ハロゲン化銀乳剤
US4425425A (en) 1981-11-12 1984-01-10 Eastman Kodak Company Radiographic elements exhibiting reduced crossover
US4433048A (en) 1981-11-12 1984-02-21 Eastman Kodak Company Radiation-sensitive silver bromoiodide emulsions, photographic elements, and processes for their use
US4400463A (en) 1981-11-12 1983-08-23 Eastman Kodak Company Silver chloride emulsions of modified crystal habit and processes for their preparation
US4414304A (en) 1981-11-12 1983-11-08 Eastman Kodak Company Forehardened high aspect ratio silver halide photographic elements and processes for their use
US4414306A (en) 1981-11-12 1983-11-08 Eastman Kodak Company Silver chlorobromide emulsions and processes for their preparation
US4414310A (en) 1981-11-12 1983-11-08 Eastman Kodak Company Process for the preparation of high aspect ratio silver bromoiodide 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
US4399215A (en) 1981-11-12 1983-08-16 Eastman Kodak Company Double-jet precipitation processes and products thereof
US4434226A (en) 1981-11-12 1984-02-28 Eastman Kodak Company High aspect ratio silver bromoiodide emulsions and processes for their preparation
US4435501A (en) 1981-11-12 1984-03-06 Eastman Kodak Company Controlled site epitaxial sensitization
US4439520A (en) 1981-11-12 1984-03-27 Eastman Kodak Company Sensitized high aspect ratio silver halide emulsions and photographic elements
US4478929A (en) 1982-09-30 1984-10-23 Eastman Kodak Company Dye image transfer film unit with tabular silver halide
US4504570A (en) 1982-09-30 1985-03-12 Eastman Kodak Company Direct reversal emulsions and photographic elements useful in image transfer film units
US4463087A (en) 1982-12-20 1984-07-31 Eastman Kodak Company Controlled site epitaxial sensitization of limited iodide silver halide emulsions

Non-Patent Citations (17)

* Cited by examiner, † Cited by third party
Title
"Research Disclosure", KENNETH MASON PUBLICATIONS, LTD.
A. P. H. TRIVELLI; S. E. SHEPPARD: "The Silver Bromide Grain of Photographic Emulsions", 1921
B.M. SPINELL; C.F. OSTER: "The Encyclopedia of Microscopy and Microtechnique", 1973, article "Photographic Materials", pages: 427 - 434
BERRY: "Surface Structure and Reactivity of AgBr Dodecahedra", PHOTOGRAPHIC SCIENCE AND ENGINEERING, vol. 19, no. 3, May 1975 (1975-05-01), pages 171 - 172
BERRY; SKILLMAN: "Surface Structures and Epitaxial Growth on AgBr Microcrystals", JOURNAL OF APPLIED PHYSICS, vol. 35, no. 7, July 1964 (1964-07-01), pages 2165 - 2169
F. C. PHILLIPS: "An Introduction to Crystallography", 1971, JOHN WILEY & SONS
HIRATA ET AL.: "Crystal Habit of Photographic Emulsion Grains", J. PHOTO SOC. OF JAPAN, vol. 36, 1973, pages 359 - 363
JAMES: "The Theory of the Photographic Process", 1977, pages: 98
KLEIN ET AL.: "Formation of Twins of AgBr and AgCl Crystals in Photographic Emulsions", PHOTOGRAPHISCHE KORRESPONDENZ, vol. 99, no. 7, 1963, pages 99 - 102
MIGNOT, RESEARCH DISCLOSURE, vol. 232, August 1983 (1983-08-01)
OPPENHEIMER ET AL.: "Particle Growth and Suspension", 1973, ACADEMIC PRESS, article "Role of Cationic Surfactants in Recrystallization of Aqueous Silver Bromide Dispersions", pages: 159 - 178
RESEARCH DISCLOSURE, vol. 176, December 1978 (1978-12-01)
RESEARCH DISCLOSURE, vol. 184, August 1979 (1979-08-01)
W. REINDERS: "Studies of Photohalide Crystals", KOLLOID-ZEITSCHRIFT, vol. 9, 1911, pages 10 - 14
W. REINDERS: "Study of Photohalides III Absorption of Dyes, Proteins and'Other Organic Compounds in Crystalline Silver Chloride", ZEITSCHRIFT FUR PHYSIKALISCHE CHEMIE, vol. 77, 1911, pages 677 - 699
WYRSCH, INTERNATIONAL CONGRESS OF PHOTOGRAPHIC SCIENCE, vol. 11-13, 1978, pages 122
ZBINDEN: "Infrared Spectroscopy of HiRh Polymers", 1964, ACADEMIC PRESS, pages: 215

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0244718A2 (fr) * 1986-05-08 1987-11-11 Minnesota Mining And Manufacturing Company Emulsion à l'halogénure d'argent sensible à la lumière et éléments radiographiques avec une qualité d'image améliorée et des taches résiduelles en quantité réduite
EP0244718B1 (fr) * 1986-05-08 1993-01-27 Minnesota Mining And Manufacturing Company Emulsion à l'halogénure d'argent sensible à la lumière et éléments radiographiques avec une qualité d'image améliorée et des taches résiduelles en quantité réduite
EP0367248A1 (fr) * 1988-10-31 1990-05-09 Konica Corporation Grains cristallins à l'halogénure d'argent et matériau à l'halogénure d'argent sensible à la lumière

Also Published As

Publication number Publication date
CA1280312C (fr) 1991-02-19
EP0215612A3 (en) 1988-11-30
DE3687808T2 (de) 1993-09-02
EP0215612B1 (fr) 1993-02-24
DE3687808D1 (de) 1993-04-01
JPH0812390B2 (ja) 1996-02-07
JPS62124552A (ja) 1987-06-05

Similar Documents

Publication Publication Date Title
US4643966A (en) Emulsions and photographic elements containing ruffled silver halide grains
US4937180A (en) Photographic emulsions containing internally modified silver halide grains
JP2670847B2 (ja) ハロゲン化銀写真乳剤およびその製造方法
GB2132372A (en) Controlled site epitaxial sensitization of limited iodine silver halide emulsions
GB2110404A (en) Radiation-sensitive photographic emulsion and process for its preparation
JP3025585B2 (ja) ハロゲン化銀乳剤
JP3597536B2 (ja) 感度の高い写真乳剤
US4724200A (en) Emulsions and photographic elements containing silver halide grains having icositetrahedral crystal faces
EP0215612B1 (fr) Emulsions photographiques à l'halogénure d'argent avec des grains à faces
EP0213964B1 (fr) Emulsions photographiques à l'halogénure d'argent avec des grains à faces
US4680256A (en) Emulsions and photographic elements containing silver halide grains having trisoctahedra crystal faces
US4680254A (en) Emulsions and photographic elements containing silver halide grains having hexoctamedral crystal faces
JP2559264B2 (ja) ハロゲン化銀乳剤及びその製造方法
US4680255A (en) Emulsions and photographic elements containing silver halide grains having tetrahexahedral crystal faces
EP0541104A1 (fr) Emulsion photographique à l'halogénure d'argent et matériau photographique sensible à la lumière contenant celle-ci
US5399477A (en) Silver halide photographic elements
JP2794247B2 (ja) ハロゲン化銀乳剤
EP0233396B1 (fr) Emulsions photographiques à l'halogénure d'argent avec des grains à faces
EP0213963B1 (fr) Emulsions photographiques à l'halogénure d'argent avec des grains à faces
EP0234090B1 (fr) Emulsions photographiques à l'halogénure d'argent avec des grains à faces
US5420005A (en) Silver halide emulsion
US5558982A (en) High chloride (100) tabular grain emulsions with modified edge structures
US5932408A (en) Silver halide emulsion
EP0613044B1 (fr) Matériau photographique contenant des grains à l'halogénure d'argent dopés au complexe cyano hexacoordiné
EP0645671A1 (fr) Emulsion photographique à l'halogénure d'argent

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): BE DE FR GB

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): BE DE FR GB

17P Request for examination filed

Effective date: 19890508

17Q First examination report despatched

Effective date: 19900723

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE FR GB

REF Corresponds to:

Ref document number: 3687808

Country of ref document: DE

Date of ref document: 19930401

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19950908

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19950926

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19951004

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19960930

Ref country code: BE

Effective date: 19960930

BERE Be: lapsed

Owner name: EASTMAN KODAK CY (A NEW JERSEY CORP.)

Effective date: 19960930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19970603

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19980806

Year of fee payment: 13

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990903

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19990903