EP0340168A2 - Emulsion photographique avec image interne - Google Patents

Emulsion photographique avec image interne Download PDF

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Publication number
EP0340168A2
EP0340168A2 EP89810292A EP89810292A EP0340168A2 EP 0340168 A2 EP0340168 A2 EP 0340168A2 EP 89810292 A EP89810292 A EP 89810292A EP 89810292 A EP89810292 A EP 89810292A EP 0340168 A2 EP0340168 A2 EP 0340168A2
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EP
European Patent Office
Prior art keywords
silver
photographic
silver halide
direct positive
emulsions
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.)
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Application number
EP89810292A
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German (de)
English (en)
Other versions
EP0340168A3 (fr
Inventor
Arnd Dr. Kriebel
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.)
Ilford Imaging Switzerland GmbH
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Ilford AG
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Filing date
Publication date
Application filed by Ilford AG filed Critical Ilford AG
Publication of EP0340168A2 publication Critical patent/EP0340168A2/fr
Publication of EP0340168A3 publication Critical patent/EP0340168A3/fr
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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
    • 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
    • G03C1/485—Direct positive emulsions
    • G03C1/48538—Direct positive emulsions non-prefogged, i.e. fogged after imagewise exposure
    • G03C1/48569—Direct positive emulsions non-prefogged, i.e. fogged after imagewise exposure characterised by the emulsion type/grain forms, e.g. tabular grain emulsions
    • G03C1/48576—Direct positive emulsions non-prefogged, i.e. fogged after imagewise exposure characterised by the emulsion type/grain forms, e.g. tabular grain emulsions core-shell grain emulsions
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/03547—Cubooctahedral grains

Definitions

  • the present invention relates to new photographic interior image emulsions which contain layered silver halide crystals and which can provide a latent interior image.
  • Photographic interior image emulsions containing layered silver halide crystals are known.
  • US Pat. No. 3,206,313 describes silver halide emulsions which have crystals consisting of a chemically sensitized core and a shell.
  • Such emulsions can be used to make direct positive images.
  • latent inner image centers are formed at exposed locations on the surface of the cores.
  • the shell protects these interior image centers from development by the surface developer.
  • this surface developer can attack the unexposed silver halide crystals under the known conditions - development in the presence of a nucleating agent or fogging agent or homogeneous flash exposure (second exposure) before or during development - so that an image reversal occurs. So the result is a direct positive picture.
  • Direct positive images can also be made with the emulsions described in US 4,704,349. These emulsions also contain silver halide crystals with a layered structure: a chemically sensitized core is surrounded by a shell which has first been subjected to sulfur-gold sensitization and then to treatment with iodide ions.
  • the great advantage of these emulsions is that direct positive images without the use of nucleating agents or more diffuse Post exposure can be obtained.
  • the manufacture of the emulsions involves complex optimization work, since the chemical sensitization of the core and the shell and the shell thickness must be precisely coordinated.
  • the present invention is therefore based on the object of proposing a simplified method for producing direct positive emulsions.
  • the object was achieved by starting with new interior image emulsions which contain silver halide crystals with a layered structure and which can provide a latent interior image.
  • new interior image emulsions which contain silver halide crystals with a layered structure and which can provide a latent interior image.
  • nuclei of these silver halide crystals have a cuboctahedral shape and the surface of the nuclei is completely or partially covered with silver iodide or silver bromoiodide, the chemical sensitization of the nuclei can be dispensed with. This considerably simplifies the optimization work mentioned above.
  • the present invention thus relates to photographic interior image emulsions which contain silver halide crystals with a layered structure and can provide a latent interior image, characterized in that the silver halide cores have a cubo-octahedral shape, the cubo-octahedron coated with silver iodide or silver bromoiodide and coated with a layer of silver bromide with cubic and / or octahedral boundary surfaces are surrounded.
  • the present invention further relates to processes for the preparation of direct positive emulsions using the internal image emulsions according to the invention, the direct positive emulsions thus prepared, photographic recording materials, photographic elements and film units for chromogenic development, for color diffusion transfer processes and for the silver color bleaching process which contain these direct positive emulsions, and processes for the preparation direct positive images using these recording materials.
  • the cores In the internal image emulsions with a layered structure according to the invention, the cores must have a cuboctahedral shape, i.e. have both (100) and (111) faces.
  • the size of the cubic boundary surfaces of the cores preferably makes up 15 to 95% of the total surface area of the cores, so it can vary within wide limits.
  • the cores are preferably made of silver bromide or silver chlorobromide.
  • core emulsions can be prepared by processes known per se, for example by the methods given in Frieser, Haase, Klein, Fundamentals of Photographic Processes with Silver Halides, Volume 3, pages 63 ff.
  • the nuclei have a narrow crystal size distribution, i.e. the coefficient of variation of the crystal size is less than 20%. (The coefficient of variation is defined as the 100-fold standard deviation of the crystal diameter divided by the mean crystal diameter.)
  • the core emulsion is completely or partially coated with a silver iodide or silver bromoiodide layer.
  • This coating can be achieved, for example, by conventional precipitation methods by adding iodide and silver salt solutions to the core emulsion in a defined manner.
  • the amount of iodide required for coating the cores is preferably 0.5 to 10 mol% of the core emulsion.
  • the cores coated in this way are surrounded by a shell made of silver bromide with cubic and / or octahedral boundary surfaces.
  • This shell is preferably obtained by direct precipitation of silver bromide, for example using the controlled double-jet method.
  • the thickness of the envelope must be large enough to contribute to high minimum densities and the appearance of a negative image known as rereversal To largely suppress overexposure. Furthermore, the thickness of the shell also depends on the silver halide solvent power of the surface developer to be used.
  • the thickness of the casing is preferably at least 0.04 ⁇ m.
  • the emulsion can be washed using known washing techniques such as e.g. in Research Disclosure No. 17643, Section IIA, December 1978, are freed from water-soluble salts. A washing process can also follow after the core emulsion has precipitated, if this is considered necessary.
  • the internal image emulsions according to the invention - cast on a support to form a layer - do not produce an image after exposure and development in a surface developer (curve 1, FIG. 1).
  • a direct positive image is only obtained when the shells of the silver halide crystals of these interior image emulsions are also coated with silver iodide or silver bromoiodide and are thus converted into direct positive emulsions.
  • the shells are preferably sensitized to gold or gold sulfur before this coating (curve 2, FIG. 1).
  • Direct positive photographic materials containing such emulsions provide, as described in U.S. 4,704,349, in a simple manner, i.e. Exposure and development in a surface developer, direct positive images of good quality.
  • the use of nucleating agents or fogging agents or a homogeneous second exposure in development is not necessary.
  • the interior image emulsions according to the invention can also be used to produce direct-positive images if the silver bromide shell of the silver halide crystals is only gold or gold sulfur-sensitized.
  • the conventional path must then be followed in the development of appropriate direct posive materials (fogging agents or second exposure).
  • the direct positive emulsions according to the invention contain a dispersion medium in which the silver halide crystals are dispersed.
  • the dispersion medium of the direct positive emulsion layers and other layers of the photographic elements can contain various colloids alone or in combination as a binder or dispersant.
  • Preferred binders and dispersants such as e.g. Gelatin and gelatin derivatives are e.g. in Research Disclosure 17,643, Section IX.
  • the photographic elements and film units produced with the direct positive emulsions according to the invention can be prepared using known hardening agents such as e.g. known from Research Disclosure No. 17 643, Section X, to allow processing at higher temperatures.
  • stabilizers To protect against instabilities that could change the properties of the direct positive materials, stabilizers, antifoggants, pressure-sensitive agents, latent image stabilizers and similar additives commonly used in the manufacture of photographic emulsions can be added. Such additives are known for example from Research Disclosure No. 17,643, December 1978, Section VI. Many antifoggants that are effective in emulsions can also be used in developers. Such antifoggants are described in more detail, for example, in CEK Mees, The Theory of the Photographic Process, 2nd edition, Macmillan Verlag, 1954, pages 677-680.
  • direct positive emulsions of different sensitivity according to the invention can be mixed with one another.
  • the emulsions according to the invention can also be mixed or combined with conventional negative emulsions which form a surface image to meet special requirements. The latter is particularly important for masking silver color bleaching materials.
  • a recording material according to the invention contains a direct positive emulsion layer.
  • the recording materials can also have more than just a direct positive emulsion layer, as well as top layers, adhesive layers and intermediate layers, as are present in conventional photographic recording materials.
  • a direct positive emulsion layer instead of mixing emulsions with one another, as described above, the same effect can often also be achieved by applying the emulsions in the form of separate layers.
  • the use of separate emulsion layers to achieve advantageous exposure latitude is known, for example, from Zelikman and Levi, Making and Coating Photographic Emulsions, Focal Press, 1964, pages 234-238 and GB-B-923 045.
  • a wide variety of conventional substrates can be used in the production of the direct positive recording materials according to the invention. They include substrates made of polymeric films, wood fibers, e.g. Paper, metal foils, glass supports and supports made of ceramic materials, optionally equipped with one or more adhesive layers, in order to improve the adhesive and antistatic properties, the dimensional properties, anti-halation properties and / or other properties of the support surface.
  • Such supports are known, for example, from Research Disclosure No. 17643, December 1978, Section XVII.
  • the direct positive recording materials according to the invention can be exposed by conventional methods as described, for example, in Research Disclosure No. 17643, Section XVIII. According to the invention Achievable advantages come into play in particular when an imagewise exposure to electromagnetic radiation takes place in the region of the spectrum in which the spectral sensitizing agents present have absorption maxima. If the photographic recording materials are intended to record in the blue, green, red or infrared range, then a spectral sensitizer which absorbs in the blue, green, red or infrared range of the spectrum is present. In the case of black-and-white recording materials, it has proven to be advantageous if the recording materials are sensitized orthochromatically or panchromatically in order to shift the sensitivity range into the visible spectrum.
  • the radiation used for exposure can be either non-coherent (random phase) or coherent (in phase, generated by laser).
  • the recording materials can also be exposed imagewise at normal, elevated or reduced temperatures and / or pressures with light sources of various intensities. This can be done continuously or intermittently.
  • the exposure times can range from minutes to microseconds, depending on the intensity, and can be determined by customary known sensitometric methods, as described, for example, by TH James in The Theory of the Photographic Process, 4th edition, Macmillan Verlag, 1977, Chapter 4 6, 17, 18 and 23.
  • the light-sensitive silver halide of the recording materials can be developed into visible images in a conventional manner after exposure by contacting the silver halide with an aqueous alkaline medium which contains a developer compound.
  • the developers used to develop the silver halide are surface developers.
  • the term "surface developer” encompasses those developers who expose latent surface image centers on a silver halide grain, but do not expose substantially latent interior image centers in an emulsion providing latent interior images, under the conditions generally required to develop a surface sensitive silver halide emulsion be turned.
  • the conventional silver halide developer compounds or reducing agents can be used generally in the surface developer, but the developer bath or developer composition is generally substantially free of a silver halide solvent, e.g., water-soluble thiocyanates, water-soluble thioethers, thiosulfates and ammonia, which break up or dissolve the silver halide grain exposure of the interior.
  • a silver halide solvent e.g., water-soluble thiocyanates, water-soluble thioethers, thiosulfates and ammonia, which break up or dissolve the silver halide grain exposure of the interior.
  • halide ions are desirable in the
  • Typical silver halide developer compounds that can be used in the developers are e.g. Hydroquinones, pyrocatechols, aminophenols, 3-pyrazolidones, ascorbic acid and its derivatives, reductones, phenylenediamines or combinations thereof.
  • the developer compounds can be incorporated into the recording materials themselves, whereby they are brought into contact with the silver halide after the imagewise exposure. In certain cases, however, they are preferably used in a developer solution or developer bath.
  • the direct positive material to be developed contains only gold or gold sulfur-sensitized direct positive emulsions according to the invention, the development such as e.g. shown in US 4,395,478 in the presence of an fogger or with simultaneous homogeneous flash exposure.
  • Development is preferably carried out at elevated temperatures e.g. between 30 and 60 ° C.
  • Photographic recording materials as well as elements and film units which contain the direct positive emulsions according to the invention can be used in a known manner to produce color images selective destruction or formation of dyes are used, for example for imaging by chromogenic development or by the silver color bleaching process. These methods are described in TH James, The Theory of the Photographic Process, 1977, pages 335 to 372.
  • the direct positive emulsions according to the invention can also be used for photographic diffusion transfer processes, as described, for example, in Research Disclosure No. 15, 162, November 1976.
  • the direct positive emulsions according to the invention are notable for the simplicity of preparation, the high sensitivity and universal applicability. They show no tendency to rereversal, i.e. the formation of a negative image when overexposed and have good stability during storage.
  • Example 1 Direct positive emulsion with cubic habit
  • crystals contain an inner AgBr 1-x J x layer of cuboctahedral shape. They have an interior sensitivity, but no surface sensitivity.
  • the emulsion is desalted and redispersed as in step 1.
  • This emulsion, cast onto a layer support, delivers on exposure through a step wedge and development (1 minute at 39 ° C.) in a surface developer of the composition: Ethylenediaminetetraacetic acid, sodium salt 2nd G Potassium sulfite 37 G Sodium sulfite 15 G Phenidone Z 3rd G Hydroquinone 15 G Potassium metaborate 11 G Boric acid 7.7 G Ascorbic acid 12 G Potassium bromide 2nd G Benzotriazole 0.9 G Ethyl cellol solve 57 G Water up 1000 ml a direct positive image of good sensitivity, with 96.5% of the silver halide being developed at locations of maximum density and 8.5% of silver halide at locations of minimum density.
  • a core emulsion with an iodide-coated surface, as described in Example 1, is used per mole of silver halide a) 2 moles b) 1 mole c) 0.5 mol Silver bromide with a cubic habit according to the instructions given in Example 1 was noticed.
  • the minimum density can be reduced by spectral sensitization (example 4).
  • Example 3 Direct positive emulsion with cuboctahedral habit
  • the emulsions of Example 2 are mixed with 4.8 mg of the green sensitizer of the formula per 1 g of Ag spectrally sensitized.
  • the emulsions are poured onto a polyester support at 1.2 Ag / m2 and, as usual, exposed to green light through a step wedge, as developed in Example 1 and measured sensitometrically.
  • Table 2 shows the green sensitivities E (green), as well as D-max and D-min for these three emulsions (D-max and D-min in percent of the developable silver).
  • Table 2 D-max D-min rel. log.
  • Example 5 Comparative example with cubic or octahedral silver bromide core emulsion
  • Two silver bromide emulsions are produced: D) with cubic crystals with an edge length of 0.6 ⁇ m E) with octahedral crystals, equal in volume to the cubic crystals.
  • Example 2 For both emulsions, as described in Example 1, the surface is first coated with iodide and then a silver bromide shell is struck. If the emulsions are processed according to Example 1, a negative image is obtained. Even after chemical surface sensitization and iodide coating, there is no direct positive image, but only a negative image with a high fog.
  • the size ratio of (111) to (100) boundary surfaces of the core emulsion can be changed in a simple manner by varying the point in time at which the pAg value is increased from 6.5 to 9.0.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
EP19890810292 1988-04-27 1989-04-18 Emulsion photographique avec image interne Withdrawn EP0340168A3 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH1567/88 1988-04-27
CH156788 1988-04-27

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EP0340168A2 true EP0340168A2 (fr) 1989-11-02
EP0340168A3 EP0340168A3 (fr) 1990-09-19

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0432834A1 (fr) * 1989-12-13 1991-06-19 Eastman Kodak Company Emulsions, éléments et procédés photographiques au bromo-iodure d'argent
US5168035A (en) * 1990-12-27 1992-12-01 Eastman Kodak Company Process for making a pressure fog-resistant photographic element

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0180549A2 (fr) * 1984-11-02 1986-05-07 Ilford Ag Procédé de préparation d'émulsions photographiques positives directes
US4713318A (en) * 1984-01-12 1987-12-15 Fuji Photo Film Co., Ltd. Core/shell silver halide photographic emulsion and method for production thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4713318A (en) * 1984-01-12 1987-12-15 Fuji Photo Film Co., Ltd. Core/shell silver halide photographic emulsion and method for production thereof
EP0180549A2 (fr) * 1984-11-02 1986-05-07 Ilford Ag Procédé de préparation d'émulsions photographiques positives directes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 105, no. 24, 15 December 1986 Columbus, Ohio, USA Takada, Sh. et al.: "Silver halide photographic emulsion" ref. no. 216634U *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0432834A1 (fr) * 1989-12-13 1991-06-19 Eastman Kodak Company Emulsions, éléments et procédés photographiques au bromo-iodure d'argent
US5168035A (en) * 1990-12-27 1992-12-01 Eastman Kodak Company Process for making a pressure fog-resistant photographic element
US5298384A (en) * 1990-12-27 1994-03-29 Eastman Kodak Company Pressure fog-resistant photographic element

Also Published As

Publication number Publication date
JPH02160230A (ja) 1990-06-20
EP0340168A3 (fr) 1990-09-19

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