Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/08—Sensitivity-increasing substances
  • G03C1/10—Organic substances
  • G03C1/12—Methine and polymethine dyes
  • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/015—Apparatus or processes for the preparation of emulsions
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/08—Sensitivity-increasing substances
  • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/08—Sensitivity-increasing substances
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/08—Sensitivity-increasing substances
  • G03C1/10—Organic substances
  • G03C1/12—Methine and polymethine dyes
• • 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
  • G03C2001/03511—Bromide content
• • 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
  • G03C2001/03517—Chloride content
• • 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
  • G03C2001/03535—Core-shell grains

Definitions

• the present invention concerns a process for obtaining a silver halide emulsion for colour photography containing chemically and spectrally sensitised silver halide grains and having a structure with a core and a shell (referred to hereinafter as core-shell).
• the present invention also concerns the use of such silver halide emulsions in colour negative processes.
• sensitising dyes used to sensitise the emulsion spectrally for example cyanine dyes
• the present invention provides a means to eliminate the phenomenon of desensitisation generally caused by some sensitising dyes, and enables these dyes to be used without causing the undesirable effects which might have been expected. Accordingly, one object of the present invention is a process for obtaining a spectrally and chemically
• a spectral sensitising dye corresponding to the following formula is adsorbed on the said grains during the step of chemical sensitisation of these grains:
• Z 1 and Z 2 represent independently the atoms required to complete a benzoxazole radical, a naphthoxazole radical, a benzothiazole radical, a naphthothiazole radical, a
• benzimidazole radical or a naphthimidazole radical in which the aromatic cycles may be substituted by groups such as the alkyl, aryl, aralkyl, alkaryl, halogeno or cyano groups;
• R 1 and R 2 represent independently a sulphoalkyl radical, such as ß-sulphoethyl, ⁇ -1-sulphobutyl; and n is l or 2
• the emulsion of the invention makes it possible to compensate for the loss of sensitivity resulting from the desensitisation due to the dye and even to increase the sensitivity.
• substantially free mean that the outer layer of the grain contains only a small quantity of iodide, generally not more than about 0.5 % molar.
• the process of the invention for producing a chemically and spectrally sensitised silver halide photographic emulsion consists of forming a silver halide core emulsion, forming, at the periphery of this emulsion, an area which is
• the emulsion comprises a chlorohalide peripheral area or shell so that, the chloride is distributed on the periphery of the grain, and in this peripheral area the chloride content may vary abruptly or gradually, forming areas with a high or low chloride content, within the ranges previously mentioned.
• the chlorobromide shell of an emulsion according to the invention comprises from 1 to 50% molar chloride ; the shell preferably contains from 1 to 30% molar chloride and more preferably from 2 to 20% molar chloride based on total silver in the grain.
• the emulsion of the present invention comprises silver halide grains containing a core and one or more shells, the composition of the halides being different in the core and the shell or shells.
• the peripheral area containing the chloride preferably represents a thickness greater than 100 A and less than 60% of the radius of the grain.
• chloride represents from 10 to 50% of the radius of the grain.
• the silver halide grains have the crystalline structures generally used in silver halide photography. They have crystalline structures of the cubic halite type with isomorphic aligned faces.
• the core of the grains may consist of silver bromide, silver bromoiodide, silver chloroiodide or mixtures of these.
• the maximum possible quantity of iodide is the quantity which can be accepted by the cubic crystal lattice.
• up to about 40% molar iodide can be incorporated, depending on the precipitation temperature.
• the grains preferably contain less than about 15% molar iodide.
• the iodide concentrations are generally below about 20% molar.
• the distribution of the iodide may be homogeneous (for example, resulting from precipitation by a continuous jet of iodide) or discrete, the structures resulting from a sudden addition of iodide during precipitation.
• the emulsions may comprise large, medium or fine silver halide grains, predominantly delimited by crystal planes [100] or [111], and they may be regular or irregular in shape, for example cubic or octahedral.
• the emulsions prepared according to the process of the invention preferably consist of cubic, octahedral or cubooctahedral grains, comprising a bromide or bromoiodide core and an outer peripheral area with a high chloride content, as mentioned above.
• the emulsions forming the core of the grains may be
• Modifying compounds may be present during the precipitation of the grains. Such compounds may be present in the reaction vessel initially or they may be added at the same time as one or more salts, in accordance with conventional operating methods.
• the modifying compounds such as the middle chalcogens (namely sulphur, selenium and tellurium), gold and the noble Group VIII metals (for example iridium), may be present during the precipitation of the halides, as described in Research Disclosure, Vol. 134, June 1975, Article 13452.
• chloride is coprecipitated with another silver halide, so as to form a mixed phase of silver chlorohalide in the outer peripheral area of the grain.
• the process of the invention consists of precipitating a bromide or bromoiodide core emulsion, and then coprecipitating a chlorobromide emulsion on the core emulsion.
• the bromide or bromoiodide core emulsion can first be shelled with a bromide emulsion which will itself be shelled by coprecipitating a
• concentrations and the number of moles precipitated as a function of time and temperature largely depend on the type of emulsion in question and on the desired results, and will consequently be determined in each case by a person skilled in the art.
• the emulsions are sized using a grain volume analyser and the determination is based on the principle of direct electrolytic reduction.
• a grain volume analyser is described by A Holland and A Feinerman in J. Applied Photo. Eng. 8., 165 (1982).
• Such an apparatus makes it possible to obtain a volume distribution of the size of the grains from which a mean distribution volume (V) can be calculated, and then an equivalent spherical diameter (ESD) and a standard
• SIGMA volume of a given grain and N being the number of grains counted.
• COV coefficient of variation
• emulsions are preferably monodisperse, that is to say they have a narrow size distribution characterised, for example, by a coefficient of variation of less than 20% and preferably less than 10%.
• the emulsions obtained according to the invention are intended for negative working black and white or colour processes.
• the colour materials generally comprise a support covered with at least two layers of silver halide emulsion with which are associated one or more dye-forming couplers. Colour reversal techniques are well known.
• sensitiser such as those indicated in Research Disclosure No 308, December 1989, paragraph III. These sensitisers comprise, for example, active gelatin, as described by T H James, The Theory of the Photographic Process, 4th Edition, Macmillan; 1977, pages 67-76, or sulphur, selenium,
• the chemical sensitisation may optionally be effected in the presence of thiocyanates, preferably at concentrations between 2 ⁇ 10 -3 and 2% molar with respect to the total silver content, as described by Damschroder in US patent 2 642 361; sulphur-containing compounds of the type described in the US patents 2 521 926 of Lowe et al, 3 021 215 of Williams et al and 4 054 457 of Bigelow.
• chemical sensitisation can be effected in the presence of compounds which modify chemical sensitisation, that is to say
• sensitisation such as the azaindenes, azapyridazines, azapyrimidines and salts of benzothiazolium, and
• sensitisers comprising one or more heterocyclic rings .
• finishing modifiers are described in the US patents 2 131 038 of Brooker et al, 3 411 914 of Dostes, 3 554 757 of Kuwabara et al, 3 565 631 of Oguchi et al and 3 901 714 of Oftedahl, in the Canadian patent 778 723 of Walworth and in Duffin. Photographic Emulsion Chemistry, Focal Press (1966), New York, pages 138-143.
• the emulsions may be sensitised by reduction - for example, with hydrogen, as described by Janusonis in US patent
• chloride or chlorobromide is sensitised using gold and/or sulphur.
• the silver halide emulsions of the present invention are also present.
• spectral sensitising dyes of the class defined above. It is considered specifically that spectral sensitising dyes can be used which have maximum absorption levels in the blue and minus blue portions, ie green and red in the visible spectrum. In addition, in specialised applications, spectral sensitising dyes which improve the spectral response beyond the visible spectrum can be used.
• One or more spectral sensitising dyes can be used. Dyes are known which have maximum sensitisation at various wavelengths in the visible spectrum and a great variety of spectral sensitivity curve forms. The choice and the relative proportions of the dyes depend on the region of the spectrum where it is desired to obtain the sensitivity and on the desired spectral sensitivity curve form. A mixture of sensitising dyes can be used with partially overlapping absorption spectra; such a mixture can give a spectral sensitivity which, at each wavelength in the overlap, is at least equal to and sometimes greater than the sum of the individual sensitivities of the individual dyes. Mixtures of the dyes specified above can also be used with other conventional sensitising dyes.
• a characteristic of the present invention is that the sensitising dye is added during the chemical sensitisation of the emulsion, as indicated in the following examples.
• the indicated silver potentials are measured by means of a saturated calomel electrode, unless otherwise indicated.
• the final emulsion consists of octahedral grains having an equivalent spherical diameter of 1.135 micrometres and a total iodide content of 3% molar.
• This emulsion is sensitised chemically and spectrally at a point determined as being the optimum position.
• the chemical sensitisation is carried out for 20 minutes at 70°C using:
• Dye B has the formula :
• An octahedral emulsion with a core and shell of sensitised bromide is obtained, having an equivalent spherical diameter (used as the mean dimension of the grains) of 1.135 ⁇ m, and a volume coefficient of variation of 7.1%.
• the total iodide content corresponds to 3% molar and the iodide content of the core corresponds to 9% molar.
• This bromide-shell emulsion (emulsion El) is used as a control.
• the hold period is followed by a final growth segment.
• the final growth segment is precipitated over a period of 39 minutes, during which 2.0 M/l of AgNO 3 , 1.70 M/l of. NaBr and 0.30 M/l of NaCl are introduced by double-jet
• the emulsion is then washed by a conventional flocculation process.
• the final emulsion consists of octahedral grains having an equivalent spherical diameter of 1.107 ⁇ m and a total iodide content of 3% molar.
• This emulsion is sensitised chemically and spectrally at a point determined as being the optimum position.
• the chemical sensitisation is carried out for 20 minutes at 70°C using:
• the emulsion obtained (E2) is a core and shell cubo-octahedral emulsion containing 15% molar chloride in the shell in which silver chloride and silver bromide have been coprecipitated, having an equivalent spherical diameter of 1.107 ⁇ m and a volume coefficient of variation of 6.2%.
• population of AgBr microcrystals is effected by introducing 0.035 moles of AgNO 3 and NaBr by double-jet precipitation over a period of 70 seconds, using 0.5 M/l of reagents. An excess of bromide is maintained so as to obtain a pAg of 9.10 at a temperature of 60°C.
• This emulsion is sensitised chemically and spectrally at a point determined as being the optimum position.
• the chemical sensitisation is effected for 20 minutes at 70°C using: 250 mg of sodium thiocyanate per mole of Ag
• a sensitised octahedral emulsion is obtained with an equivalent spherical diameter (used as the mean grain dimension) of 1.05 ⁇ m and a volume coefficient of variation of 6.8%.
• This bromide emulsion (Emulsion E3) is used as a reference.
• This hold period of inactivity is followed by a period of initial growth lasting 41.2 minutes, during which 2.0 M/l of AgNO 3 and 2.0 M/l of NaBr are introduced, by accelerated double-jet precipitation, so as to produce a mixed phase of AgBr while maintaining the temperature and pAg at the same values as before.
• a total of 3.50 moles of silver halides are precipitated in this initial growth stage.
• This initial growth stage is followed by a shift pAg to a value of 7.11 using a solution of 2.0 M/l of AgNO 3
• This shift pAg is followed by a final growth segment.
• This emulsion is sensitised chemically and spectrally at a point determined as being the optimum position.
• the chemical sensitisation is effected for 20 minutes at 70°C using:
• a mixture of 172.5 mg of sensitising dye (formula A) per mole of Ag and 49.8 mg of sensitising dye (formula B) per mole of Ag is added for green sensitisation, during the chemical sensitisation stage.
• the emulsion obtained is a cubo-octahedral emulsion having an equivalent spherical diameter (used as the mean grain dimension) of 1.00 ⁇ m, and a volume coefficient of
• Embodiment E4 This bromide emulsion (Emulsion E4) is used as a reference.
• the pAg is adjusted to a value of 7.11 using a solution of 2.0 M/l of AgNO 3
• This shift pAg is followed by a final growth segment.
• 2.0 M/l of NaBr, 1.7 M/l of NaBr and 0.3 M/l of NaCl are introduced by accelerated double-jet precipitation, while maintaining the temperature and the pAg at the same values as before.
• a total of 6.6 moles of silver halides are precipitated during this second growth stage.
• the emulsion is then washed by a conventional flocculation process.
• the final emulsion consists of octahedral grains with an equivalent spherical diameter of 1.03 micrometres and a total chloride content of 9% molar.
• This emulsion is sensitised chemically and spectrally at a point determined as being the optimum position.
• the chemical sensitisation is effected for 20 minutes at 70°C using:
• a mixture of 182.5 mg of sensitising dye (formula A) per mole of Ag and of 52.5 mg of sensitising dye (formula B) per mole of Ag is added for green sensitisation, and then 40 mg of acetamidophenylmercaptotetrazole per mole of Ag is added.
• the emulsion obtained (E5) is an octahedral core/shell emulsion containing 9% molar chloride in the part of the shell where the silver chloride and silver bromide have been coprecipitated; this emulsion has an ESD of 1.03 ⁇ m and a volume coefficient of variation of 6.9%.
• the (reference) bromide emulsion precipitated as described in Example 4 is sensitised chemically and spectrally at a point determined as being the optimum position.
• the chemical sensitisation is effected over a period of 20 minutes at 70°C, using:
• the emulsion obtained (E6) is a cubo-octahedral core/shell emulsion containing 15% molar chloride in the shell, in which silver chloride and silver bromide have been
• Dye C has the formula:
• Example 5 is sensitised chemically and spectrally at a point determined as being the optimum position.
• the chemical sensitisation is effected over a period of 20 minutes at 70°C, using:
• the emulsion obtained (E12) is a cubo-octahedral core/shell emulsion containing 15% molar chloride in the shell, in which silver chloride and silver bromide have been
• EXAMPLE 8 (Control) The (reference) bromide emulsion precipitated as described in Example 4 is sensitised chemically and spectrally at a point determined as being the optimum position. The chemical sensitisation is effected over a period of 20 minutes at 70°C, using:
• sensitising dye (formula D) per mole of Ag is added according to the method during the chemical
• the emulsion obtained (E13) is a cubo-octahedral core/shell emulsion containing 15% molar chloride in the shell, in which the silver chloride and silver bromide have been coprecipitated, and having an equivalent spherical diameter of 1.00 ⁇ m and a volume coefficient of variation of 7.3%.
• Dye D has the formula:
• Example ll is sensitised chemically and spectrally at a point determined as being the optimum position.
• the chemical sensitisation is effected over a period of 20 minutes at 70°C, using: 35 mg of sodium thiocyanate per mole of Ag
• sensitising dye D per mole of Ag is added according to the method during the chemical sensitisation, for green sensitisation, and then 40 mg of
• the emulsion obtained (E9) is a cubo-octahedral core/shell emulsion containing 15% molar chloride in the shell, in which the silver chloride and silver bromide have been coprecipitated, and having an equivalent spherical diameter of 1.03 ⁇ m and a volume coefficient of variation of 6.9%.
• EXAMPLE 10 (Control)
• the (reference) bromide emulsion precipitated as described in Example 4 is sensitised chemically and spectrally at a point determined as being the optimum position.
• the chemical sensitisation is effected over a period of 20 minutes at 70°C, using:
• the emulsion obtained (E10) is a cubo-octahedral core/shell emulsion containing 15% molar chloride in the shell, in which the silver chloride and silver bromide have been coprecipitated, and having an equivalent spherical diameter of 1.00 ⁇ m and a volume coefficient of variation of 7.3%.
• Dye E has the formula:
• Example 5 is sensitised chemically and spectrally at a point determined as being the optimum position.
• the chemical sensitisation is effected over a period of 20 minutes at 70°C, using: 35 mg of sodium thiocyanate per mole of Ag
• the emulsion obtained (E11) is a cubo-octahedral core/shell emulsion containing 15% molar chloride in the shell, in which the silver chloride and silver bromide have been coprecipitated, and having an equivalent spherical diameter of 1.03 ⁇ m and a volume coefficient of variation of 6.9%.
• Compound F has the formula:
• Example 4 (control) 125 2.47 56.1
• Example 5 (invention) 133 2.37 47.7
• Example 9 E9 (invention) 110 2.11 49.2
• Example 10 E10 (control) 100 2.61 55

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• Spectroscopy & Molecular Physics (AREA)
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• Colloid Chemistry (AREA)

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Citations (5)

• 1993
  • 1993-12-23 FR FR9315771A patent/FR2714494B1/fr not_active Expired - Fee Related
• 1994
  • 1994-12-13 WO PCT/EP1994/004129 patent/WO1995017701A1/en not_active Application Discontinuation
  • 1994-12-13 JP JP7517146A patent/JPH08508112A/ja active Pending
  • 1994-12-13 EP EP95904460A patent/EP0686273A1/en not_active Withdrawn

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