EP0326853A1 - Emulsions photographiques à l'halogénure d'argent et procédé pour les préparer - Google Patents

Emulsions photographiques à l'halogénure d'argent et procédé pour les préparer Download PDF

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Publication number
EP0326853A1
EP0326853A1 EP89100764A EP89100764A EP0326853A1 EP 0326853 A1 EP0326853 A1 EP 0326853A1 EP 89100764 A EP89100764 A EP 89100764A EP 89100764 A EP89100764 A EP 89100764A EP 0326853 A1 EP0326853 A1 EP 0326853A1
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Prior art keywords
silver
grains
silver halide
emulsion
iodide
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EP89100764A
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German (de)
English (en)
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EP0326853B1 (fr
Inventor
Shigeharu Urabe
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Priority claimed from JP785288A external-priority patent/JPH01183644A/ja
Priority claimed from JP63007853A external-priority patent/JPH07104569B2/ja
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Publication of EP0326853A1 publication Critical patent/EP0326853A1/fr
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    • 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
    • G03C1/06Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08Sensitivity-increasing substances
    • G03C1/10Organic substances
    • G03C1/12Methine and polymethine dyes
    • G03C1/14Methine and polymethine dyes with an odd number of CH groups
    • G03C1/18Methine and polymethine dyes with an odd number of CH groups with three CH groups
    • 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
    • G03C2001/0473Low molecular weight gelatine

Definitions

  • the present invention relates to light-sensitive silver halide emulsions useful in the field of photography and, in particular, those comprising silver halide grains containing a dispersion medium and silver iodide, as well as to a process for preparing the same.
  • silver iodobromide grains which are generally used in the field of photography contain silver iodide in the silver bromide crystal lattice of the grain in a soluble limit amount or less, or in an amount of iodide content of about 40 mol% or less.
  • the iodide content in the silver iodobromide emulsions has the following advantages (1) and disadvantages (2).
  • the iodide may exist mainly in the center of the crystal, may be distributed throughout the whole grains and may also exist mainly in the outer surface. The actual position of the iodide is determined by the preparation conditions, and the site (position) apparantly has an influence on the physical and chemical characteristics of the crystal.
  • silver iodide may uniformly be distributed throughout the grains formed, or alternatively, if addition of bromide is reduced or stopped in the course of the formation of the grains while addition of iodide only is continued, a silver iodide shell or silver iodide-rich silver iodobromide shell may be formed on the outer surface (shell) of the grains.
  • JP-­A-58-113927 (the term "JP-A" as used herein means an "unexamined published Japanese patent application") corresponding to U.S.
  • Patent 4,434,226 mentions a silver halide emulsion wherein tabular silver iodobromide grains having a thickness of less than 0.5 ⁇ m, a diameter of 0.6 ⁇ m or more and a mean aspect ratio of 8/1 or more account for at least 50% of the total projected area of the grains therein, in which the tabular silver iodobromide grains have first and second parallel main surface planes which face each other and a center region extending between the two main planes. The silver iodide content in the center region is lower than that in at least one region which also extends between the two main planes and which is crosswise displaced.
  • JP-A-59-99433 mentions a silver halide emulsion containing silver halide grains, in which tabular silver halide grains having an aspect ratio of 5 or more account for 10% (by number) of the silver halide grains.
  • the grains contain silver iodide in the inside site by 80 mol% of the silver amount of the total grains from the center of the grains in the major axis or minor axis direction of the grains (inside iodine-rich phase).
  • the mean iodine content in the inside iodine-rich phase is 5 times or more of the mean iodine content in the silver halide existing outside this phase, and the silver amount in the inside iodine-rich phase is 50 mol% or less of the silver amount of the whole grain.
  • JP-60-147727 mentions a silver halide photographic emulsion containing multi-layered silver halide grains having an aspect ratio of 5 or less, in which the difference in the mean iodine content between the adjacent two layers, each having a uniform iodine distribution, is 10 mol% or less, and the total silver iodide content in the multi-layered silver halide grains is 10 mol% or less.
  • the silver iodide content is varied in different sites in one grain (especially the content is varied between the inside and the outside of the grain), so as to obtain a better photographic characteristic.
  • the result indicates that the silver iodide content in the silver iodobromide phase in the shell is higher in the center part (inner part) than in the peripheral part (outer part). That is, although the grains were grown so that the iodine content in the shell could be 11 mol% (uniform silver iodide phase) in the formation of the shells over the cores, the result was not so.
  • JP-A-60-14331 mentions a silver halide photographic emulsion containing silver halide grains with a distinct layered structure, in which the grains are composed of a core part containing from 10 to 45 mol% of silver iodide and a shell part having 5 mol% or less silver iodide and have a means silver content of 7 mol% or more.
  • JP-A-61-245151 corresponding to EP 202784A mentions a silver halide emulsion containing silver halide grains having a multi-layered structure with a different silver iodide content in the respective layers, in which the silver iodide content in the outermost layer is 10 mol% or less, a silver iodide rich layer having a higher silver iodide content than the outermost layer by 6 mol% or more is provided inside the outermost layer, and a interlayer having an intermediate silver iodide content is provided between the outermost layer and the silver iodide-rich layer.
  • the silver iodide content is varied in different sites in one grain (especially the content is varied between the inside and the outside of one grain), so as to obtain a better photographic characteristic.
  • silver halide grains having a completely uniform silver iodobromide phase and the grains are those in which the above-mentiond microscopic silver iodide distribution is completely uniform.
  • the microscopic silver iodide distribution in silver iodobromide grains can be observed by a cooling type transmission electron microscope.
  • the silver halide grains where the silver iodide distribution is completely uniform, which are provided by the present invention, could not be obtained by any conventional technical means.
  • the object of the present invention is to provide a negative type silver halide emulsion which has a high sensitivity with less fog, which has improved graininess and sharpness-covering power and which is excellent in storability and pressure-resistance.
  • the object of the present invention has been met by a silver halide photographic emulsion comprising a dispersion medium and silver halide grains, in which the silver halide grains contain a silver halide phase containing 3 mol% or more silver iodide and the distribution of the silver iodide in the silver iodide-­containing silver halide phase is completely uniform.
  • tabular silver iodobromide grains having a silver iodobromide phase will be mentioned hereunder.
  • tabular silver iodobromide grains having a silver iodobromide phase with a completely uniform silver iodide distribution of the present invention will be mentioned hereunder.
  • the "completely uniform silver iodide distribution" as herein referred to means a more microscopic distribution", being different from the silver iodide distribution as heretofore been discussed for conventional silver halide grains.
  • the microscopic silver iodide distribution may be observed by the direct method with a transmission electron microscope at a low temperature, as described in J.F. Hamilton, Photographic Science and Engineering , Vol. 11, 1967, page 57 and T. Shozawa, Journal of Japan Photographic Association , Vol. 35, No. 4, 1972, page 213. Briefly, silver halide grains as taken out under a safelight so that the grains are not printed out and are set on a mesh for electron microscopic observation. The grains are observed by transmission electron microscopy under the condition that the sample is cooled with a liquid nitrogen or liquid helium so that the sample is not damaged (or printed out) by electron rays.
  • the accelerated voltage of the electron microscope to be used in the method is better to be higher so as to obtain a more sharp microscopic image.
  • the voltage is preferably 200 KV for grains having a thickness of up to 0.25 ⁇ m, and it is preferably 1000 KV for grains having a thickness larger than 0.25 ⁇ m. If the accelerated voltage becomes higher, the damage of the grains by the irradiated electron rays would become larger. Accordingly, the sample is desired to be cooled with a liquid helium rather than with a liquid nitrogen.
  • the photographing magnification is generally from 20,000 times to 40,000 times, although it may properly be varied in accordance with the grain size of the grains to be observed.
  • Fig. 1 When tabular silver iodobromide grains are photographed by transmission electron microscopy, extremely fine annual ring-like stripe patterns are observed in the portion of the silver iodobromide phase.
  • the tabular grains shown in Fig. 1 are tabular core/shell grains prepared by forming a silver iodobromide shell (silver iodide: 10 mol%) around a tabular silver bromide grain core.
  • the structure of the grains may distinctly be observed by the transmission electron microscopic photograph. That is, the core part is silver bromide and is naturally uniform, which is therefore seen as only a uniform flat image.
  • the interval between the respective stripes in the pattern is extremely fine and small or is or the order of 100 ⁇ or less and the stripes are extremely microscopically non-uniform.
  • the extremely fine stripe patterns indicates the non-uniformity of the silver iodide distribution in the grains, which may be clarified by various methods. More directly, when the tabular grains are annealed under the condition that the iodide ion may move in the silver halide crystals (for example, at 250°C for 3 hours), the stripe patterns are lost. From this fact, non-uniformity may be concluded.
  • the regular ring-like stripe patterns showing the non-uniformity of the silver iodide distribution in the tabular silver iodobromide emulsion grains as hereinbefore mentioned are also distinctly observed in the transmission electron microscopic photograph, attached to JP-A-58-­113927 and in the transmission microscopic photograph in the aforesaid King et al's study. From these facts, the conventional silver iodobromide grains prepared to have a substantially uniform silver iodide distribution had, in fact, an extremely microscopically non-uniform silver iodide distribution, as opposed to the intended object of preparing grains with uniform silver iodide distribution.
  • the tabular silver halide grains of the present invention having a "completely uniform silver iodide distribution", which have hereinbefore mentioned, can be distinctly differentiated from conventional silver halide grains by observing the transmission image of the grains with a cooling type transmission electron microscope. That is, the silver iodide-containing tabular silver halide grains of the present invention have at most two, preferably one, more preferably no, microscopic lines, which are caused by the microscopic non-uniformity of silver iodide, if any, at an interval cf 0.2 ⁇ m.
  • the lines constituting the regular ring-like stripe patterns show the microscopic non-uniformity of silver iodide occurring at a right angle to the direction of growth of the grain.
  • the lines distribute in the form of concentric circles from the center of the grain.
  • the lines constituting the regular ring-like stripe patterns which show the non-uniformity of the silver iodide, are at a right angle to the direction of the growth of the tabular grain, so that the lines are parallel to the lines is towards the center of the grain, so that the regular ring-like stripe patterns formed of the lines are distributed in the form of concentric circles around the center of the grain.
  • the boundary line caused by such rapid variation would be observed as a line which is similar to the above-mentioned lines for the regular ring-like stripe patterns by the above-mentioned observation method.
  • the line caused by the rapid variation of the silver iodide content is a single line, which therefore may be distinctly differentiated from the plural lines caused by the microscopic non-uniformity of silver iodide distribution in the grain.
  • the line derived from the rapid variation of the silver iodide content may apparently be confirmed by measurement of the silver iodide content in both sides separated by the line by the above-mentioned analytical electron microscope.
  • the lines caused by the variation of the silver iodide content is quite different from the lines caused by the microscopic non-uniformity of silver iodide distribution as herein referred to, and the former shows "macroscopic silver iodide distribution".
  • the lines showing the variation of the above-­ mentioned macroscopic silver iodide content are not observed since the silver iodide content does not rapidly vary. Accordingly, if the grain has at least 3 or more lines at an interval of 0.2 ⁇ m, these lines mean the existence of microscopic non-uniform silver iodide content in the grain formed.
  • the silver halide grains of the present invention having a completely uniform silver iodide distribution are those having at most 2, preferably one, more preferably no, lines showing the microscopic silver iodide distribution at an interval of 0.2 ⁇ m in the direction perpendicular to the lines, as the transmission image of the grain obtained by the use of a cooling-type transmission electron microscope.
  • the emulsion emulsion of the present invention contains such silver halide grains in an amount of at least 60%, preferably at least 80%, more preferably at least 90% of the total silver halide grains therein.
  • Tabular silver halide grains which have heretofore been called “tabular silver halide grains containing a uniform silver iodide” were prepared by merely adding a silver nitrate and a halide mixture having a determined composition (or having a determined iodide content) to a reactor vessel by double jet method for growth of the grains in the reactor vessel. Therefore, the microscopic silver iodide distribution in the thus prepared grains is not uniform although the macroscopic silver iodide distribution therein may surely be uniform. Accordingly, such grains are called “tabular grains having a determined halogen composition in accordance with the present invention and these are distinctly differentiated from the "completely uniform tabular grains" of the present invention.
  • nucleation of the tabular silver halide grains of the present invention is composed of two processes of nucleation of tabular grains and ripening of the resulting nuclei. Precisely, as mentioned in Japanese Patent Application No.
  • nucleation of tabular grains is accompanied by formation of other fine grains(especially octahedral grains and simplex twin plane grains), and after subsequent ripening of the resulting nuclei, other grains than tabular grain nuclei are lost so that only nuclei which are to be tabular grains may thereby be obtained.
  • the nucleation process includes two processes of generation of tabular nuclei and ripening of the resulting nuclei.
  • the nucleation step is outside the technical scope of the present invention and, therefore, in the transmission image of the finally obtained tabular grains as photographed with a cooling type transmission electron microscope, the center part of the grain indicating the nucleus thereof is outside the subject matter of the present invention.
  • a different layer may be added to the resulting nucleus and grown thereon, whereby the boundary line between the nucleus and the grown phase may apparently be observed in the transmission image of the grain and the position of the nucleus in the grain may be confirmed from the boundary line.
  • the boundary line may be confirmed more clearly.
  • composition of the tabular silver halide grains of the present invention which have a completely uniform silver iodide distribution may be any one of silver iodobromide, silver iodochloride or silver iodochlorobromide, but it is preferably silver iodobromide or silver iodochlorobromide.
  • the phase may be in the center part of the tabular grain or may be throughout the whole grain or may also be in the peripheral part of the grain.
  • the grain may have one or more silver iodide-containing phases.
  • the silver iodide-containing phase frequently forms a cyclic structure in the grain because of the mechanism of the growth thereof, but this may be in a particular site in the grain.
  • the silver iodobromide phase may be formed only in the edges of the tabular grain or only in the corner parts thereof, by utilizing the difference in the properties between the edge and corner of the tabular grain.
  • tabular silver halide grains which have silver iodide in a particular point and which do not have a cyclic structure may be formed.
  • Second Coating Layer Third Coating Layer 1 Uniform AgBrI (*) - - 2 AgBr Uniform AgBrI - 3 Uniform AgBrI AgBr - 4 " Uniform AgBrI - 5 AgBr " AgBr 6 " Non-uniform AgBrI Uniform AgBrI 7 Uniform AgBrI AgBr Uniform AgBrI 8 Non-uniform AgBrI " " 9 " Uniform AgBrI AgBrI Non-uniform AgBrI " Note (*) : "Uniform” means "complete uniform” as herein referred to.
  • silver chloride may be added to the above-mentioned procedures, whereupon the silver chloride-containing layer may be any one of the first coating layer, the second coating layer or the third coating layer.
  • the proportion of the uniform AgBrI to be in one tabular grain is preferably from 5 to 95 mol%, more preferably 30 to 95 mol%, and most preferably 50 to 95 mol%.
  • the silver iodide content in the silver iodobromide phase in the emulsion grains of the present invention is from 3 to 45 mol%, preferably from 5 to 35 mol%. If the silver iodide content is less than 3 mol%, the existence of microscopically non-uniform silver iodide, if any, in the grain would cause only a substantially negligible width of the silver iodide distribution, which therefore is not so inconvenient.
  • the conventional grains having a non-uniform silver iodide distribution can not be conveniently chemically sensitized, or that is, the sensitivity attainable by chemical sensitization is extremely low and the degree of fog of the resulting emulsion is noticeably high.
  • the conventional grains having a silver halide phase with a "determined silver iodide composition" as the outermost layer are inhibited to be chemically sensitized, which is as mentioned hereinbefore.
  • the conventional silver iodide containing grains can not fully display all of the advantages of the silver iodide content in the grains, so that an emulsion containing such grains may have high sensitivity, low fog, good graininess and high sharpness, which could not heretofore be attained by the prior art.
  • the reason why the grains having a non-uniform silver iodide distribution on the surface thereof is inhibited to be chemically sensitized while the grains having a completely uniform silver iodide distribution on the surface thereof is not is believed to be as follows:
  • the lattice constant in the surface of the grain crystal is not constantly determined in the former non-uniform silver iodide distribution-having grains so that the composition of the chemically sensitized nuclei to be formed over the surface as well as the size of the nuclei would be non-uniform. Accordingly, an optimum chemical sensitization condition could not be obtained in this case.
  • the composition and the size of the chemically sensitized nuclei can be uniform so that the grains can be optimally chemically sensitized.
  • further investigation is necessary on this aspect.
  • the silver iodide content in the inside of the grains is less than 3 mol%, the attainable sensitivity does not substantially vary, irrespective of whether the silver iodide distribution of the grains is completely uniform or non-uniform, because of the same reason as mentioned above.
  • the silver iodide content is 3 mol% or more, especially 5 mol% or more, the sensitivity of the completely uniform silver iodide distribution-having grains is apparently higher than non-uniform grains.
  • the total silver iodide content in the emulsion grains of the present invention is 2 mol% or more, and more effectively it is 4 mol% or more. Further preferably, it is 5 mol% or more.
  • the size of the completely uniform silver iodide distribution-having tabular silver halide grains of the present invention is not specifically limited, but the size is preferably 0.5 ⁇ m or more as the mean projected area-corresponding diameter, and more effectively, it is 1.0 ⁇ m or more, especially 1.5 ⁇ m or more.
  • the size distribution of the tabular silver halide grains in the emulsion of the present invention may be either monodispersed or polydispersed, but it is preferably monodispersed with respect to the shape and the grain size of the grains.
  • tabular silver halide grains having two parallel hexagonal outer surfaces where the ratio of the maximum side to the minimum side is 2 or less in one haxagonal plane account for 70% or more of the total projected area of all the grains in the silver halide emulsion of the present invention, like the emulsion mentioned in Japanese Patent Application No. 61-299155.
  • the hexagonal tabular silver halide grains are more preferably monodispersed emulsion ⁇ as herein referred to means that the fluctuation coefficient of the grain size in the emulsion is 20% or less, preferably 15% or less.
  • the tabular grains for use in the present invention are grains composed of two parallel facing main (111) planes and having a mean aspect ratio of 2 or more, preferably from 3 to 20, more preferably form 3 to 15.
  • the grain size of the grains is 0.4 ⁇ or more, preferably from 0.4 to 4 ⁇ .
  • tabular silver halide grains having a mean aspect ratio larger than 2/1 occupy 50% or more of the total projected area of the silver halide grains.
  • the "mean aspect ratio ( ⁇ )" as referred to herein may be defined by the following formula (1), when the tabular silver halide grains are oriented on a plane surface so that the two facing main planes of the thus oriented grain are horizontal to the plane surface.
  • Di means a diameter of a circle having the same area as the projected area of the i'th silver halide grain; and t i means the thickness of the grain in the direction vertical to the two facing main planes.
  • N means a number which is necessary and indispensable for giving the mean aspect ratio of the silver halide grains and, in general, the value of N mostly satisfies the following formula (2).
  • the above-mentioned formula (1) indicates that the mean aspect ratio ( ⁇ ) may be a mean value of the aspect ratio ⁇ i of the respective silver halide grains.
  • the value ( ⁇ ′) which is defined by the following formula (5) is substantially same as the value ( ⁇ ).
  • the mean aspect ratio may be defined by the formula for ⁇ ′, provided that this may fall within the range of the accuracy acceptable in measurement of the grain size.
  • the method for preparation of the silver halide grains of the present invention comprises nucleation (formation of tabular nuclei and ripening thereof) and growth of grains.
  • nucleation formation of tabular nuclei and ripening thereof
  • the nucleation may be conducted by any conventional methods.
  • an aqueous solution of water-soluble silver salt and an aqueous solution of alkali halide(s) are reacted in an aqueous solution containing a dispersion medium, while the pBr value in the reaction system is kept at 1.0 to 2.5, for nucleation.
  • Tabular silver halide grains have one or more twin planes in the inside thereof, and the twin plane formation corresponds to a so-called nucleation process.
  • the nucleation condition is determined by the frequency of formation of twin planes, which depends upon various super-saturation factors (temperature in nucleation, gelatin concentration, addition rate of the aqueous silver salt solution and aqueous alkali halide solution, Br ⁇ concentration, number of stirring rotation, iodine content in the aqueous alkali halide solution to be added, amount of silver halide solvent, pH, salt concentration, etc.). These are illustrated in Japanese Patent Application No. 61-238808.
  • the shape of the nuclei grains number of the twin planes per one grain
  • the number of grains for determining the grain size after growth of the grains
  • fine nuclei grains with uniform grain size distribution can be formed.
  • fine tabular grain nuclei are formed in nucleation and at the same time a number of other fine grains (especially octahedral grains or singlet twin plane grains) are also formed.
  • a number of other fine grains especially octahedral grains or singlet twin plane grains.
  • the grain nuclei formed in the above-mentioned nucleation are ripened.
  • an aqueous solution of water-soluble silver salt and an aqueous solution of alkali halide(s) are added to the reactor vessel so as to grow the resulting nuclei without forming any new nuclei.
  • aqueous solutions of silver salt and halide(s) are added to the reactor vessel with efficiently stirring.
  • a silver halide of a single halogen composition for example, silver bromide, silver chloride
  • the silver halide phase is quite uniform so that any microscopical non uniformity is not admitted by observation with a transmission electron microscope.
  • any non-uniform growth would not occur in principle in a single halide composition.
  • non-uniformity does not apply to the growth of pure silver bromide or pure silver chloride, irrespective of the condition of preparing the grains.
  • the non-uniform growth in the halide composition is a serious problem.
  • non-uniform distribution of silver halide can distinctly be observed by a transmission electron microscope, as already mentioned hereinbefore.
  • the grains for use in the present invention may be in the form of other various shapes than the aforesaid tabular grains.
  • the grains may have a regular crystalline form (normal crystal grains), such as cubic, octahedral, dodecahedral, tetradecahedral, tetracosahedral (tri-octahedral, tetra-hexahedral, rhomboid), or hexatetracontahedral crystals, or may also have an irregular crystalline form, such as spherical or potato-like crystals.
  • the silver halide grains for use in the present invention may be other than tabular grains, and the method for preparing non-tabular grains for use in the present invention will briefly be mentioned below.
  • the silver halide grains which may be nuclei of the silver halide grains of the present invention may be prepared by the methods described in P. Glafkides, Chimie et Phisique Photographique (published by Paul Montel, 1967), G.F. Duffin, Photographic Emulsion Chemistry (published by The Focal Press, 1966) and V.L. Zelikman et al, Making and Coating Photographic Emulsion (published by The Focal Press, 1964). Briefly, the grains may be prepared by any of an acid method, a neutrallization method, an ammonia method, etc. Also, as a method of reacting a soluble silver salt and soluble halide(s), a single jet method, a double jet method, or a combination thereof may be used.
  • a so-called reverse mixing method capable of forming silver halide grains in the presence of excessive silver ions can also be employed.
  • a so-called controlled double jet method of keeping a constant pAg in a liquid phase of forming silver halide grains can also be employed. According to the method, a silver halide emulsion containing silver halide grains having a regular crystal form and almost uniform grain sizes can be obtained.
  • Two or more kinds of silver halide emulsions separately prepared can be blended for use in the present invention.
  • the nuclei prepared In preparation of the silver halide grain nuclei for use in the present invention, it is preferred that the nuclei prepared have a uniform halogen composition.
  • a double jet method or controlled double jet method is preferably employed.
  • the pAg value in preparation of the silver halide nuclei for the present invention is preferably from 7 to 11.
  • use of silver halide solvents is preferred as the time for formation of silver halide grains may be shortened.
  • generally well known silver halide solvents such as ammonia or thioethers may be used for this purpose.
  • the nuclei may be spherical or may also be octahedral, cubic or tetradecahedral, or these may further be in a mixed system thereof.
  • the nuclei may be polydispersed or monodispersed, but they are more preferably monodispersed.
  • the "monodispersed nuclei" as herein referred to have the same meaning as mentioned above.
  • the silver halide grains may have a uniform grain size
  • a method of varying or properly controlling the adding speed of the silver nitrate or aqueous alkali halide solution in accordance with the growing speed of the silver halide grains formed for example, as described in British Patent 1,535,016 and JP-­B-48-36890 (the term "JP-B" as referred to herein means an "examined Japanese patent publication") and JP-B-52-16364, and a method of varying the concentration of the aqueous solutions to be added, for example, as described in U.S.
  • Patent 4,242,445 and JP-A-55-158124 are preferably employed, so that the grains may rapidly be grown within a range not exceeding the critical persaturation degree for the reaction system.
  • re-nucleation hardly occurs and the individual silver halide grains can be uniformly coated for growing.
  • these methods are also preferably used in the case where the coating layer, which will be mentioned hereunder, is to be introduced into the grain.
  • an aqueous silver salt solution and an aqueous halide solution are added to a reactor vessel having a dispersion medium-containing aqueous solution therein with efficient stirring.
  • fine silver halide grains having a small grain size may be added to the reactor vessel, in place of adding the aqueous silver salt solution and the aqueous halide solution thereto, and the fine grains may optionally subsequently be ripened in the reactor vessel for nucleation. This will be mentioned hereunder for the method of growing the grain nuclei.
  • the size of the fine silver halide grains to be added in the method is preferably 0.1 ⁇ m or less, more preferably 0.06 ⁇ m or less, especially preferably 0.03 ⁇ m or less.
  • the method for preparation of the fine silver halide grains for use in the method will be mentioned in detail in the item of "growth of grains" to follow.
  • the fine silver halide grains have an extremely high solubility as the grain size thereof is extremely fine. Thus, they are rapidly dissolved immediately after being added to the reactor vessel to be decomposed to the constituting silver ion and halide ion. Accordingly, they are deposited on a slight amount of the fine grains as introduced into the reactor vessel to form nuclei grains.
  • silver halide solvents may be used, if desired, which will be mentioned hereinafter.
  • the nucleation temperature is preferably 50°C or higher, more preferably 60°C or higher.
  • the fine silver halide grains may be added to the reactor vessel all at once or they may be gradually and continuously added thereto. In the latter case of continuous addition, the flow rate of the grains to be added may be constant or this may be accelerated over the course of time.
  • a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, or an iron salt or a complex salt thereof may be incorporated into the reaction system.
  • an aqueous solution of a water-soluble silver salt and an aqueous solution of alkali halide(s) are added to the reactor vessel so as to grow the resulting nuclei without forming any new nuclei.
  • aqueous solutions of silver salt and halide(s) are added to the reactor vessel with efficient stirring.
  • a silver halide of a single halogen composition for example, silver bromide, silver chloride
  • the silver halide phase is completely uniform so that any microscopical non-uniformity is not admitted by observation with a transmission electron microscope.
  • Patent 3,415,650 British Patent 1,323,464 and U.S. Patent 3,692,283 are known.
  • a hollow rotary mixer which has slits in the cylindrical wall (the inside of the mixer is filled with an aqueous colloid, and more preferably the mixer is divided into two rooms, i.e., upper and lower rooms, by a disc) is provided in a reactor vessel filled with an aqueous colloid so that the rotary shaft of the mixer may be vertical to the reactor vessel.
  • aqueous halide solution and an aqueous silver solution are fed into the mixer from the top and bottom open mouths through feeding ducts while the mixer is rapidly rotated so that the solutions are rapidly blended and reacted together (when the mixer has the separating disc, the aqueous halide solution and the aqueous silver salt solution as fed into the two rooms are diluted with the aqueous colloid as filled in each room, and these are rapidly blended and reacted near the outlet slits of the mixer), whereby the silver halide grains formed by the reaction are expelled out into the aqueous colloid in the reactor vessel because of the centrifugal force formed by rotation of the mixer and the grains are grown in the colloid in the reactor vessel.
  • the problem of the non-uniform silver iodide distribution in the grains formed can not be overcome at all by this method, and the grains formed are observed by a cooling type transmission electron microscope to have regular ring-like stripe patterns which indicate the non-uniform distribution of silver iodide in the grains.
  • JP-B-55-10545 mentions a technique of improving the local distribution of the ion concentrations so as to prevent the non-uniform growth of grains.
  • a mixer filled with an aqueous colloid is provided in the inside of a reactor vessel filled with an aqueous colloid is provided in the inside of a reactor vessel filled with an aqueous colloid, an aqueous halide solution and an aqueous silver halide solution are separately fed into the mixer through feeding ducts so that the reaction solutions are rapidly and vigorously stirred and blended by the lower stirring blades (turbine blades) as equipped in the mixer to form and grow silver halide grains.
  • JP-A-62-99751 mentions a photographic element containing silver bromide and silver iodobromide tabular grains having a mean diameter range of from 0.4 to 0.55 ⁇ m and an aspect ratio of 8 or more
  • JP-A-62-115435 mentions the same element with the same grains having a mean grain size of from 0.2 to 0.55 ⁇ m.
  • the conventional techniques which have heretofore been known and disclosed can not attain formation of tabular silver halide grains having a completely uniform silver iodide distribution.
  • the present inventors earnestly studied and at last have found that, in order to overcome the problem of the non-uniform silver iodide distribution in the growth of iodide-containing tabular silver halide grains,the silver ion and the halide ion(s) (iodide ion, bromide ion, chloride ion) for forming the grains are not added to the reactor vessel in the form of the respective aqueous solutions but, rather, fine silver halide grains having the intended halide composition are fed into the reactor vessel and the grains are grown therein to the desired tabular grains, whereby no regular ring-like stripe patterns are formed in the tabular grains thus grown and the tabular grains have a completely uniform silver iodide distribution.
  • the result could not be attained by any conventional methods, and the technique of the present invention
  • the process of the present invention of forming iodide-containing tabular silver halide grains having a completely uniform silver iodide distribution includes the following methods.
  • An emulsion containing fine silver halide grains (silver iodobromide, silver chloroiodobromide, silver iodochloride having the same silver iodide content as that in the intended tabular grains (to be finally obtained) is previously prepared, and the fine grains-­containing emulsion only is fed into the reactor vessel without feeding either an aqueous solution of a water-­soluble silver salt nor an aqueous solution of water-­soluble halide(s) thereto, and the fine grains are grown to the intended tabular grains in the reactor vessel.
  • an aqueous solution of water-soluble halide(s) and an aqueous protective colloid are fed into the mixer vessel and rapidly blended therein to form extremely fine silver halide grains therein.
  • the resulting grains are immediately and directly fed into the reactor vessel, whereupon neither an aqueous solution of a water-soluble silver salt nor an aqueous solution of water-soluble halide(s) is fed into the reactor vessel like the case of the above-mentioned method (1).
  • U.S. patent 2,246,938 mentions a method of growing coarse grains in an emulsion by blending coarse grains on which nothing has been adsorbed and fine grains on which nothing has also been adsorbed or by gradually adding a fine grains-containing emulsion to a coarse grains-­containing emulsion.
  • the same silver iodobromide emulsion is divided into two parts, ammonia is added to one part to ripen and then the other part is blended therewith or gradually added thereto. Accordingly, this method is quite different from the process of the present invention for growing silver iodide-containing tabular grains.
  • this U.S. Patent is silient on the limitation of the silver iodide content in the silver halide grains formed. The silver iodide content in the grains formed in the example is only 2.6 mol%.
  • JP-A-57-23932 mentions a method of growing silver halide grains, in which a fine grains containing emulsion as prepared in the presence of a growth inhibitor is washed with water by decantation and re-dispersed. The resulting emulsion is again re-dissolved, and the solution thus prepared is added to the emulsion containing fine grains to be grown, whereby the fine grains are grown after dissolution thereof.
  • fine grains having a smaller grain size are advantageously be obtained, but the re-dissolution of the fine grains in the reactor vessel is interfered with by the growth inhibitor.
  • JP-A-57-23932 is silent on the halogen composition of the fine grains. In the example thereof, fine grains of pure silver bromide only are illustrated. Accordingly, the invention of JP-A-­57-23932 should be said quite different from the present invention which relates to growth of silver iodide-­containing tabular grains.
  • U.S. Patent 3,317,322 and 3,206,313 mention a method of forming a core/shell grains-containing silver halide emulsion having a high internal sensitivity, in which a silver halide grain emulsion containing chemically sensitized core grains having a mean grain size of at least 0.8 pm is blended with another silver halide grain emulsion containing not chemically sensitized silver halide grains having a mean grain size of 0.4 ⁇ m or less. The resulting mixture is ripened so a to form shells over the cores.
  • the method disclosed relates to the preparation of internal latent image-forming type grains having a high internal sensitivity. In the examples of these U.S.
  • the silver iodide content for shell formation is only 2 mol% or less. Accordingly, the inventions of these U.S. Patents are quite different from the present invention which relates to surface latent image-forming type tabular grains having a high silver iodide content (3 mol% or more).
  • JP-A-58-113927 mentions (page 207) that "Silver, bromide and iodide may be introduced initially or during the growing stage of the grains in the form of fine silver halide grains as suspended in a dispersion medium. Concretely, silver bromide, silver iodide and/or silver iodobromide grains may be introduced for the purpose.” However, it is quite silent on the technique of growing tabular grains by addition of only a fine grains-­containing emulsion to a reactor vessel without feeding aqueous solutions of silver salt and halide(s) thereto.
  • JP-A-62-124500 mentions an example of growing host grains in a rector vessel from previously prepared extremely fine grains (about 0.02 ⁇ m) as put in the reactor vessel.
  • the fine grains used therein are silver bromide grains, and this reference relates to growth of normal crystalline grains. Accordingly, this is quite different from the present invention.
  • tabular grains which are to be nuclei or cores are previously put in the reactor vessel and an emulsion containing previously prepared fine grains having a small grain size is added to the reactor vessel, whereby the fine grains are dissolved by Ostwald ripening and are deposited on the nuclei or cores existing in the reactor vessel so that the nuclei or cores are grown to the intended tabular grains.
  • the halide composition of the previously prepared fine grains is to have the same silver iodide content as that in the intended tabular grains to be finally obtained, which is silver iodobromide, silver chloroiodobromide or silver iodochloride.
  • the mean diameter is preferably 0.1 ⁇ m or less, more preferably 0.06 ⁇ m or less.
  • the dissolution speed of the fine grains is an important factor, and use of silver halide solvents is preferred so as to accelerate the speed.
  • silver halide solvents to be used for this purpose there may be mentioned water-­soluble bromides, water-soluble chlorides, thiocyanates, ammonia, thioethers and thioureas.
  • thiocyanates such as those described in U.S. Patents 2,222,264,2,448,534, 3,320,069), ammonia, thioether compounds (such as those described in U.S. Patents 3,271,157, 3,574,628, 3,704,130, 4,297,439, 4,276,347), thione compounds (such as those described in JP-A-53-144319, 53-82408, 55-77737), amine compounds (such as those described in JP-A-54 100717), thiourea derivatives (such as those described in JP-A 55-2982), imidazoles (such as those described in JP-A-54-100717), substituted mercaptotetrazoles (such as those described in JP-A-57-202531), etc.
  • thiocyanates such as those described in U.S. Patents 2,222,264,2,448,534, 3,320,069
  • ammonia such as those described in U.S. Patents 3,271,157
  • the temperature of growing the tabular grains is 50°C or higher, preferably 60°C or higher, more preferably 70°C or higher.
  • the fine grains-containing emulsion may be added hereto all at a once, or alternatively, the emulsion may be divided into parts which are added one by one to the reactor vessel.
  • the fine grains-containing emulsion is fed into the reactor vessel at a constant flow rate, and more preferably, at an accelerated flow rate.
  • the accelerating degree of the addition speed is determined in accordance with the concentration of the existing colloid, the solubility of the silver halide crystals, the size of the fine silver halide grains, the stirring degree in the reactor container, the size and concentration of the crystals as existing in each reaction stage, the hydrogen ion concentration (pH) and silver ion concentration (PAg) in the aqueous solution in the reactor container, and the size and distribution of the intended crystal grains to be finally obtained.
  • the addition speed to be accelerated may be determined on the basis of the related general experimental method.
  • fine silver halide crystal grains necessary for growing the silver halide crystal grains are added to the reactor vessel, without adding silver ion and halide ion(s) (containing iodide ion) in the form of respective aqueous solutions thereto (like the known conventional means) to cause Ostwald ripening because of the high solubility of the said fine grains, whereby the core nuclei existing in the reactor vessel are grown to the intended tabular grains.
  • the reaction stage in the reaction system depends upon the speed of the dissolution of the fine grains as fed to release silver ion and halide ion(s) in the reactor vessel, but not the growing speed of the tabular grains to be finally obtained.
  • the fine grains to be added are desired to have a possibly minimum grain size.
  • silver halide grains having a smaller grain size have a higher solubility, so that these would be extremely unstable to cause Ostwald ripening by themselves. As a result, the grain size of the grains would increase.
  • T.H. James The Theory of the Photographic Process , 4th Ed. refers to a Lippman emulsion as an example of fine grains and mentions that the mean grain size of the grains is 0.05 ⁇ m. Preparation of fine grains having a grain size of 0.05 ⁇ m or less is possible, but if obtained, the grains would be unstable and would easily undergo Ostwald ripening. As a result, the grain size of the resulting grains is increase. The Ostwald ripening may be prevented to some degree by adsorbing something to the fine grains, which, however would decrease the dissolution speed and is therefore contrary to the intended object of the present invention.
  • the mixer vessel is provided extremely near to the reactor vessel so that the residence time of the reaction solutions in the mixer vessel is shortened. Accordingly, the fine grains formed in the mixer vessel may immediately be introduced into the reactor vessel, whereby the Ostwald ripening is prevented.
  • the residence time (t) of the solutions as added to the mixer vessel is represented by the following formula: in which v means the volume of the reaction chamber in the mixer vessel (ml); a is the amount of the silver nitrate solution added (ml/min); b is the amount of the halide solution added (ml/min); and c is the amount of the protective colloid solution added (ml/min).
  • (t) is 10 minutes or less, preferably 5 minutes or less, more preferably 20 seconds or less. Accordingly, the fine grains formed in the mixer vessel may directly and immediately be introduced into the reactor vessel without the grain size thereof increasing further.
  • the stirring blades in the reactor chamber may be rotated at a high rotation speed. Accordingly, strong and highly efficient stirring and mixing can be effected by the process of the invention, although such could not be effected by the use of a conventional open type reactor vessel.
  • the reaction solution would be scattered because of the centrifugal force by the high speed rotation, and further the reaction solution would be foamed. Therefore, such high speed rotation is impracticable in the conventional open type reactor vessel.
  • the above-mentioned coalescence ripening may be prevented in the process of the present invention.
  • the rotation speed of the stirring blades in the process of the present invention is 1000 r.p.m. or more, preferably 2000 r.p.m. or more, especially preferably 3000 r.p.m. or more.
  • coalescence ripening may noticeably be prevented by impartation of a protective colloid to the fine silver halide grains.
  • the aqueous protective colloid is added to the mixer vessel by the following means.
  • the concentration of the protective colloid may be 1% by weight or more, preferably 2% by weight or more, and the flow rate thereof is at least 20%, preferably at least 50%, more preferably 100% or more, of the sum of the flow amounts of the aqueous silver nitrate solution and aqueous halide solution.
  • the concentration of the protective colloid is 1% by weight or more, preferably 2% by weight or more.
  • the protective colloid is incorporated into the aqueous silver nitrate solution.
  • the concentration of the protective colloid is 1% by weight or more, preferably 2% by weight or more.
  • silver gelatin When gelatin is used, silver gelatin is formed from silver ion and gelatin and this gives a silver colloid by photolysis and pyrolysis. Accordingly, the silver nitrate solution and the protective colloid it is better that be blended immediately before use.
  • the grain size of the fine grains for use in the present invention is 0.06 ⁇ m or less, preferably 0.03 ⁇ m or less, more preferably 0.01 ⁇ m or less.
  • extremely fine grains having a small grain size may directly be fed into the reactor vessel, whereupon the dissolution speed of the fine grains is high so that the growing speed of the tabular grains in the reactor vessel is advantageously high.
  • silver halide solvents are no longer indispensable, but silver halide solvents may of course be used also in the method of the present invention, if desired, for the purpose of further accelerating the growing speed or for any other purposes.
  • the description for the aforesaid Method (1) may be referred to.
  • the feeding speed of silver ion and halide ion(s) to the reactor vessel may freely be controlled. These may be fed thereto at a constant speed, or preferably the feeding speed may be accelerated.
  • the means of accelerating the feeding speed is mentioned in JP-B-48-36890 and 52-16364.
  • the description for the aforesaid Method (1) may be referred to.
  • the halogen composition of the growing grains may freely be controlled during the growing step of the grains, and for example, it is possible to maintain a constant silver iodide content, or to vary the silver iodide content at a certain point, during the step of growing the tabular grains.
  • the reaction temperature in the mixer vessel may advantageously be 60°C or lower, preferably 50°C or lower, more preferably 40°C or lower.
  • a low molecular weight gelatin a synthetic high molecular compound having a protective colloidal action on silver halide grains or other natural high molecular compounds than gelatin are preferably used as a binder, since general gelatin would easily solidify at such a low temperature.
  • Examples of high molecular compounds having a protective colloidal action on silver halide grains which can be used in the present invention include the following compounds.
  • Low molecular weight gelatins may also be used in the present invention.
  • the mean molecular weight of gelatins for use in the present invention is preferably 30,000 or less, more preferably 10,000 or less.
  • Low molecular weight gelatins which are used in the present invention can be prepared generally as mentioned below.
  • a gelatin which is generally used and which has a mean molecular weight of 100,000 is dissolved in water and gelatin-decomposing enzyme (gelatinase) is added thereto to decompose the gelatin molecules with the enzyme.
  • gelatinase gelatin-decomposing enzyme
  • the descriptions in R.J. Cox, Photographic Gelatin II (published by Academic Press, London, 1976), pages 233,251 and pages 335 to 346 may be referred to.
  • low molecular weight gelatins having a relatively narrow molecular weight distribution can advantageously be obtained since the position of the bond to be cleaved by the enzyme is determined.
  • the longer the enzyme-­decomposing time the lower the molecular weight of the decomposed gelatins.
  • a general gelatin is heated and hydrolyzed under a low pH (pH of from 1 to 3) or high pH (pH of from 10 to 12) atmosphere.
  • the concentration of the protective colloid to be added to the mixer vessel in Method (A) is 0.2% by weight or more, preferably 1% by weight or more, more preferably 2% by weight or more.
  • the concentration thereof is 0.2% by weight or more, preferably 1% by weight ore more, more preferably 2% by weight or more.
  • the concentration of the aqueous protective colloid solution in the reactor vessel in previous preparation of the fine silver halide grains is 0.2% by weight or more, preferably 1% by weight or more, more preferably 2% by weight or more.
  • the emulsion of the present invention is generally spectrally sensitized.
  • spectral sensitizing dyes for use in the present invention, there are generally methine dyes, which include, for example, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
  • methine dyes include, for example, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
  • nuclei include pyrroline nuclei, oxazoline nuclei, thiazoline nuclei, pyrrole nuclei, oxazole nuclei, thiazole nuclei, selenazole nuclei, imidazole nuclei, tetrazole nuclei and pyridine nuclei; the nuclei obtained by fusing alicyclic hydrocarbon rings to these nuclei; and the nuclei obtained by fusing aromatic hydrocarbon rings to these nuclei, such as indolenine nuclei, benzindolenine nuclei, indole nuclei, benzoxazole nuclei, naphthoxazole nuclei, benzothiazole nuclei, naphthothiazole nuclei, benzoselenazole nuclei, benzimidazole nuclei and quinoline nuclei. Each of these nuclei may be substituted on the carbon atom of the dye.
  • merocyanine dyes or complex merocyanine dyes can be applied 5-membered or 6-membered heterocyclic nuclei such as pyrazolin-5-one nuclei, thiohydantoin nuclei, 2-thiooxazolidine-2,4-dione nuclei, thiazolidine-­2,4-dione nuclei, rhodanine nuclei or thiobarbituric acid nuclei, as nuclei having a ketomethylene structure.
  • 5-membered or 6-membered heterocyclic nuclei such as pyrazolin-5-one nuclei, thiohydantoin nuclei, 2-thiooxazolidine-2,4-dione nuclei, thiazolidine-­2,4-dione nuclei, rhodanine nuclei or thiobarbituric acid nuclei, as nuclei having a ketomethylene structure.
  • the amount of the sensitizing dye to be added to the silver halide emulsion being prepared can not be indiscriminately determined, and depends upon the kind of the additives added to the emulsion or the amount of the silver halide therein. However, it may be almost the same as that to be used in the preparation of conventional emulsions by conventional methods.
  • the amount of the sensitizing dye to be added may be from 0.001 to 100 mmol, preferably from 0.01 to 10 mmol, per mol of silver halide.
  • the sensitizing dye is added to the emulsion before or after chemical ripening thereof.
  • the sensitizing dye is most preferably added to the emulsion during chemical ripening or before chemical ripening (for example during formation of the grains or during physical ripening of the grains formed).
  • the emulsion of the present invention may further contain, together with the sensitizing dye, a dye having no spectral sensitizing action by itself or a material which does not substantially absorb visible lights but shows supersensitizing action.
  • a dye having no spectral sensitizing action by itself may contain a nitrogen-containing heterocyclic group-­substituted aminostyryl compound (for example, as described in U.S. Patent 2,933,390 and 3,635,721), an aromatic organic acid/formaldehyde condensation product (for example, as described in U.S. Patent 3,743,510), a cadmium salt or an azaindene compound for the purpose.
  • the combinations described in U.S. Patents 3,615,613, 3,615,641, 3,617,295 and 3,635,721 are especially useful.
  • the silver halide emulsion of the present invention is generally chemically sensitized.
  • chemical sensitization for example, the method described in H. Frieser, Die Unen der Photographischen Sawe mit Silberhalogeniden (published by Akademische Verlagsgesellschaft, 1968), pages 675 to 734 may be employed.
  • a sulfur sensitization method using a sulfur-containing compound capable of reacting with active gelatin or silver e.g., thiosulfates, thioureas, mercapto compounds, rhodanines
  • a reduction sensitization method using a reducing substance e.g., stannous salts, amines, hydrazine derivatives, formamidinesulfinic acid, silane compounds
  • a noble metal sensitization method using a noble metal compound e.g., gold complexes, as well as complexes of metals belonging to Group VIII of the Periodic Table such as platinum, iridium or palladium
  • a noble metal compound e.g., gold complexes, as well as complexes of metals belonging to Group VIII of the Periodic Table such as platinum, iridium or palladium
  • the photographic emulsion of the present invention can contain various compounds for the purpose of preventing of photographic materials and for the purpose of stabilizing the photographic property of the materials.
  • various compounds which are known as an anti-­foggant or stabilizer can be added for the above purposes, which compounds include azoles, such as benzothiazolium salts, nitroindazoles, traizoles, benzotriazoles, benzimidazoles (especially nitro- or halogen-substituted derivatives); heterocyclic mercapto compounds, such as mercaptothiazoles, mercaptobenzothiazoles , mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-­mercaptotetrazole), mercaptopyrimidines; the heterocyclic mercapto compounds having a water-soluble group such as carboxyl group or sulfone group; thioketo compounds, such as oxazo
  • the anti-foggant or stabilizer is generally added to the emulsion after chemical sensitization thereof, and more preferably, it is added thereto in the course of chemical ripening of the emulsion or at any time selected from prior to the beginning of chemical ripening of the emulsion. Specifically, it may be added to the emulsion at any time in the course of the formation of the silver halide grains of the emulsion, for example, during the course of addition of the silver salt solution, or after addition of the solution and before beginning of chemical ripening of the emulsion, or during the course of chemical ripening of the emulsion (preferably within the time of 50% from the beginning of chemical ripening, more preferably within the time of 20% therefrom.
  • the emulsion of the present invention may be applied to any of mono-layered and multi-layered photographic materials having one or more layers in the form of any desired layer constitution.
  • the emulsion of the present invention may be applied to a silver halide multi-layer color photographic material, which has a multi-layered structure composed of laminates of binder and silver halide grains-containing layers, for the purpose of separately recording blue light, green light and red light, and the respective emulsion layers comprise two of a high sensitive layer and a low sensitive layer.
  • a silver halide multi-layer color photographic material which has a multi-layered structure composed of laminates of binder and silver halide grains-containing layers, for the purpose of separately recording blue light, green light and red light
  • the respective emulsion layers comprise two of a high sensitive layer and a low sensitive layer.
  • B means a blue-­sensitive layer
  • G means a green-sensitive layer
  • R means a red-sensitive layer
  • H means a highest sensitive layer
  • M means a middle sensitive layer
  • L means a low sensitive layer
  • S means a support.
  • Other non-light sensitive layers such as a protective layer, filter layer, interlayer, anti-halation layer or subbing layer are not mentioned.
  • CL mans an interlayer effect-imparting layer, and the others have the same meanings as mentioned above.
  • the high sensitive layer and the low sensitive layer may be arranged reversely.
  • the silver halide emulsion of the present invention may be applied to color photographic materials as mentioned above, and it may further be applied to other mono-layered or multi-layered photographic materials having one or more emulsion layers, such as X ray photographic materials, picture-taking black-and-white photographic materials, photographic materials for photomechanical process and printing photographic papers.
  • additives to be added to the silver halide emulsion of the present invention such as binder, chemical sensitizer, spectral sensitizer, stabilizer, gelatin hardening agent, surfactant, antistatic agent, polymer latex, mat agent, color coupler, ultraviolet absorbent, anti-fading agent and dye, as well as supports for the emulsion-having photographic materials, the coating method, the light-exposing method and the developing method are not specifically limited, and for example, the descriptions of Research Disclosure , Vol. 176, Item 17643 (RD 17643), ibid ., Vol. 187, Item 18716 (RD-18716) and ibid ., Vol. 225, Item 22534 (RD-22534) may be referred to.
  • Color Image Stabilizer p. 25 p. 32 9. Hardening Agent p. 26 p. 651, left column p. 28 10.
  • Antistatic Agent p. 27 ditto 14 Color Coupler p. 25 p. 649 p. 31
  • the color couplers for use in the present invention are preferably non-diffusible as having a ballast group or being polymerized.
  • 2-Equivalent couplers in which the coupling active position is substituted by a coupling-releasing group are more preferred than 4-­equivalent couplers where a hydrogen atom is in the coupling active position, because the amount of silver to be coated may be reduced.
  • couplers capable of forming a colored dye with a pertinent diffusibility, colorless couplers, DIR couples capable of releasing a development inhibitor by a coupling reaction, or couplers capable of releasing a development accelerator by a coupling reaction may also be used.
  • yellow couplers for use in the present invention there are oil-protect type acylacetamide couplers as the typical examples. Specific examples thereof are described in U.S. Patents 2,407,210, 2,875,057 and 3,265,506.
  • 2-equivalent yellow couplers are preferably used, and specific examples of these yellow couplers are the oxygen atom-releasing type yellow couplers described in U.S. Patent 3,408,194, 3,447,928, 3,933,501 and 4,022,620, and the nitrogen atom-­releasing type yellow couplers described in JP-B-58-10739, U.S.
  • magenta couplers for use in the present invention there are oil-protect type indazolone or cyanoacetyl couplers, preferably pyrazoloazole couplers such as 5-pyrazolones or pyrazolotriazoles.
  • pyrazoloazole couplers such as 5-pyrazolones or pyrazolotriazoles.
  • 5-­pyrazolone couplers those substituted by an arylamino or acylamino group at the 3-position thereof are preferred from the viewpoint of the hue and coloring density of the colored dyes formed. Specific examples of these couplers are described in U.S. Patents 2,311,082, 2,343,703, 2,600,788, 2,908,573, 3,062,653, 3,152,896 and 3,936,015.
  • the nitrogen atom-releasing groups described in U.S. Patent 4,310,619and the arylthio groups described in U.S. Patent 4,351,897 are especially preferred.
  • the 5-pyrazolone magenta couplers having a ballast group described in European Patent 73,636 give high coloring density.
  • the pyrazoloazole couplers there may be mentioned the pyrazolobenzimidazoles described in U.S. Patent 3,061,432, preferably the pyraozolo[5,1-c][1,2,4]-­triazoles described in RD-24220 (June, 1984)and JP-A-60-­33552, and the pyrazolopyrazoles described in RD-24230 (June, 184) and JP-A-60-43659.
  • the imidazo[1,2-b]-­pyrazoles described in U.S. Patent 4,500,630 are preferred because of the small yellow side-absorption of the colored dye and the sufficient light-fastness thereof.
  • the pyraozolo[1,5-b][1,2,4]triazoles described in U.S. Patent 4,540,654 are especially preferred.
  • cyan couplers for use in the present invention there are oil-protect type naphthol couplers.
  • the couplers there be mentioned the naphthol couplers described in U.S. Patent 2,474,293, preferably the oxygen atom-releasing 2-equivalent naphthol couplers described in U.S. Patents 4,052,212, 4,146,396, 4,228,233 and 4,296,200.
  • Specific examples of phenol couplers which may be used in the present invention are described in U.S. Patent 2,369,929, 2,801,171, 2,772,162 and 2,895,826.
  • Cyan couplers having high fastness to humidity and temperature are preferably used in the present invention and specific examples of these cyan couplers include the phenol cyan couplers having an alkyl group of 2 or more carbon atoms at the meta-position of the phenol nucleus described in U.S. patent 3,772,002; the 2,5-diacylamino-substituted phenol cyan couplers described in U.S. patents 2,772,162, 3,758,308, 4,126,396, 4,334,011 and 4,327,173, West German Patent Application (OLS) No.
  • colored couplers are preferably used in picture-taking color negative photographic materials.
  • colored couplers to be used for this purpose there are the yellow-colored magenta couplers described in U.S. Patent 4,163,670 and JP-B-57-39413, and the magenta-colored cyan couplers described in U.S. Patents 4,004,929 and 4,138,258 and British Patent 1,146,368.
  • the dye-forming couplers and the above-mentioned particular couplers for use in the present invention may form dimers or higher polymers.
  • Typical examples of the polymerized dye-forming couplers are described in U.S. Patents 3,451,820 and 4,080,211.
  • specific examples of the polymerized magenta couplers are described in British Patent 2,102,173, U.S. Patent 4,367,282 and Japanese Patent Application Nos. 60-75041 and 60-113596.
  • So-called DIR couplers capable of releasing a development inhibitor along with coupling may also be used in the present invention.
  • DIR couplers there may be mentioned the couplers which release a heterocyclic mercapto-type development inhibitor, described in U.S. Patent 3,227,554; the couplers which release a benzotriazole derivative as a development inhibitor, described in JP-B-58-9942; the couplers which are so-­called colorless DIR couplers, described in JP-B-51-16141; the couplers which release a nitrogen-containing heterocyclic development inhibitor via methylol decomposition after release of the inhibitor-containing group, described in JP-A-52-90932; the couplers which release a development inhibitor via an intramolecular nucleating reaction after release of the inhibitor-­containing group, described in U.S.
  • Patent 4,248,962 and JP-A-57-56837 the couplers which release a development inhibitor via an electron transfer in a conjugated system after release of the inhibitor-containing group, described JP-A-56-114946, 57-154234, 57-188035, 58098728, 58-209736, 58-209737, 58-209738, 58 209739 and 58-209740; the couplers which release a diffusive development inhibitor which deactivate a developer, described in JP-A-57-151944 and 58-217932; and the couplers which release a reactive compound which forms a development inhibitor or deactivates the development inhibitor by reaction in the film during development, described in Japanese Patent Application Nos.
  • DIR couplers those which are especially preferably used in combination with the photographic materials of the present invention are developer-­deactivating type DIR couplers, such as those described in JP-A-57-151944; the timing-type DIR couplers, such as those described in U.S. Patent 4,248,962 and JP A-57-­ 154234; and the reactive type DIR couplers, such as those described in Japanese Patent Application No. 59-39653.
  • the developer-deactivating type DIR couplers described in JP-A-57-151944 and 58-217932, Japanese Patent Application Nos. 59-75474, 59-82214 and 59-90438, and the reactive type DIR couplers described in Japanese Patent Application No. 59 39653 are especially preferred.
  • the photographic materials of the present invention can contain compounds which may imagewise release a nucleating agent or a development accelerator or a precursor thereof (hereinafter referred to as "development accelerator or the like") in development.
  • development accelerator or the like a nucleating agent or a development accelerator or a precursor thereof.
  • Typical examples of such compounds are described in British Patents 2,097,140 and 2,131,188.
  • the compounds are so-called DAR couplers which release a development accelerator or the like by a coupling reaction with the oxidation product of an aromatic primary amine developing agent.
  • the development accelerator or the like to be released from such DAR couplers is preferred to have an absorbability to silver halides, and specific examples of such DAR couplers are described in JP A-59-157638 and 59-­170840.
  • DAR couplers which release an N-­acyl-substituted hydrazine compound having a monocyclic or condensed-heterocyclic absorbing group, from the coupling active position or the coupler via the sulfur atom or nitrogen atom are especially preferred, and specific examples of such couplers are described in JP-A-60-128446.
  • phthalic acid esters e.g., dibutyl phthalate, dicyclohexyl phthalate, di-2-­ethylhexyl phthalate, decyl phthalate
  • phosphoric acid or phosphonic acid esters e.g., triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl-diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phospahte, tributoxyethyl phospahte, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate), benzoic acid esters (e.g., 2-ethylhexyl benzoate, dodec
  • organic solvents having a boiling point of from about 30°C, preferably from about 50°C, to about 160°C are advantageously used, and specific examples of such organic solvents include ethyl acette, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-­ethoxyethyl acetate and dimethylformamide.
  • gelatin is preferred.
  • other gelatin derivatives such as phthalated gelatin, as well as dextran, cellulose derivatives, polyvinyl acetate, polyacrylamide and polyvinyl alcohol may also be used.
  • gelatin hardener for example, active halogen compounds (e.g., 2,4-dichloro-6-hydroxy-1,3,5-­triazine and sodium salt thereof) as well as active vinyl compounds (e.g., 1,3 bisvinylsulfonyl-2-propanol, 1,2-­bis(vinylsulfonylacetamide)ethane or vinyl polymers having a vinylsulfonyl group in the side chain) are preferred, as these may rapidly harden hydrophilic colloids such as gelatin to give a stable photographic characteristic to the thus hardened emulsion.
  • active halogen compounds e.g., 2,4-dichloro-6-hydroxy-1,3,5-­triazine and sodium salt thereof
  • active vinyl compounds e.g., 1,3 bisvinylsulfonyl-2-propanol, 1,2-­bis(vinylsulfonylacetamide)ethane or vinyl polymers having a vinylsulfonyl group in the
  • N-­carbamoylpyridinium salts e.g., 1-morpholinocarbonyl-3-­ pyridinio)methanesulfonate
  • haloeamidinium salts e.g., 1-(1-chloro-1-pyridinomethylene)phrrolidinium-2-­naphthalene-sufonate, are also preferred, as having a high hardening speed.
  • the color photographic materials containing the silver halide photographic emulsion of the present invention can be developed by conventional methods, for example, in accordance with the methods described in RD-­17643, pages 28 to 29 and RD-18716, page 651, from left-­hand column to right-hand column.
  • the color photographic materials containing the silver halide photographic emulsion of the present invention are, after being developed and bleach-fixed or fixed, generally rinsed with water or stabilized.
  • two or more rinsing tanks are generally used in a countercurrent system, so as to economize the rinsing water to be used.
  • Stabilization may be effected in place of rinsing in water, and one typical example is the multi-stage countercurrent stabilization system described in JP-A-57 8543.
  • the color developer for use in development of the photographic materials of the present invention is preferably an aqueous alkaline solution consisting essentially of an aromatic primary amine developing agent.
  • an aromatic primary amine developing agent As the color developing agent for the developer, p-­ phenylenediamine compounds are preferably used, although aminophenol compounds are useful.
  • the compounds include 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethyl-aniline, 3-methyl-­4-amino-N-ethyl-N- ⁇ -methyanesulfonamidoethyl-aniline, 3-­methyl-4-amino-N-ethyl-N- ⁇ -methoxyehtylaniline and sulfates, hydrochlorides and p-toluenesulfonates thereof. Two or more of these compounds may be used in combination, in accordance with the object thereof.
  • the color developer generally contains a pH buffer such as an alkali metal carbonates, borates or phosphates, and a development inhibitor or an antifoggant such as bromides, iodides, benzimidaozles, benzothiazoles or mercapto compounds.
  • a pH buffer such as an alkali metal carbonates, borates or phosphates
  • a development inhibitor or an antifoggant such as bromides, iodides, benzimidaozles, benzothiazoles or mercapto compounds.
  • this may further contain, if desired, various kinds of preservatives, such as hydroxylamine, diethylhydroxylamine, sulfates, hydrazines, phenylsemicarbazides, triethanolamine, catecholsulfonic acids, triethylenediamine (1,4-­diazabicyclo[2,2,2]-octanes); an organic solvent such as ethylene glycol or diethylene glycol; a development accelerator such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts or amines; a dye-forming coupler; a competing coupler; a foggant such as sodium boronhydride; an auxiliary developing agent such as 1-­phenyl-3-pyrazolidone; a tackifier; as well as various kinds of chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids or phosphonocarboxylic acids, e.g., ethylenediamine-t
  • the black-and-white developer to be used in the black-and-­white development may contain known black-and-white developing agents, for example, dihydroxybenzenes such as hydroquinone, 3-pyraozlidones such as 1-phenyl-3-­pyrazolidone or aminophenols such as N-methyl-p-amino­phenol, singly or in combination thereof.
  • the color developer and black-and-white developer generally have a pH value of from 9 to 12.
  • the amount of the replenisher to the developer is, although depending upon the color photographic materials to be processed, generally 3 liters or less per m2 of the material. By lowering the bromide ion concentration in the replenisher, the amount may be 500 ml or lower. When the amount of the replenisher to be added is lowered, it is desired to prevent the evaporation and aerial oxidation of the processing solution by reducing the contact surface area of the processing tank with air. In addition, the amount of the replenisher to be added may also be reduced by means of suppressing accumulation of bromide ion in the developer.
  • the photographic emulsion layer is generally bleached.
  • Beaching may be carried out simultaneously with fixation (bleach-fixation) or separately from the latter.
  • bleaching may be followed by bleach fixation.
  • bleach-fixation in continuous two processing tanks fixation prior to bleach-­fixation or bleach-fixation followed by bleaching may also be applied to the photographic materials of the present invention, in accordance with the object thereof.
  • the bleaching agent can be used, for example, compounds of polyvalent metals such as iron (III), cobalt (III), chromium (VI) or copper (II), as well as peracids, quinones and nitro compounds.
  • the bleaching agent include ferricyanides; bichromates; organic complexes of iron (III) or cobalt (III), for example, complexes with aminopolycarboxylic acids such as ethylenediamine-tetraacetic acid, diethylenetriamine-­pentaacetic acid, cyclohexanediamine-tetraacetic acid, methylimino-diacetic acid, 1,3-diaminopropane-tetraacetic acid or glycolether-diamine-tetraacetic acid, as well as with citric acid, tartaric acid or malic acid; persulfates; bromates; permanganates; and nitrobenzenes.
  • aminopolycarboxylic acids such as ethylenediamine-tetraacetic acid, diethylenetriamine-­pentaacetic acid, cyclohexanediamine-tetraacetic acid, methylimino-diacetic acid, 1,3-diaminopropane-t
  • aminopolycarboxylic acid/iron (III) complexes such as ethylenediamine-tetraacetic acid/iron (III) complex as well as persulfates are preferred in view of the rapid processability thereof and of the prevention of the environmental pollution.
  • the aminopolycarboxylic acid/iron (III) complexes are especially useful both in a bleaching solution and in a bleach fixing solution.
  • the bleaching solution or bleach-fixing solution containing such aminopolycarboxylic acid/iron (III) complexes generally has a pH value of from 5.5 to 8, but the solution may have a lower pH value for rapid processing.
  • the bleaching solution, bleach-fixing solution and the previous bath may contain a bleaching accelerating agent, if desired.
  • a bleaching accelerating agent e.g., sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium
  • the mercapto group or disulfido group-having compounds are preferred because of the high accelerating effect thereof, and in particular, the compounds described in U.S. Patent 3,893,858, West German Patent 1,290,812 and JP-A-53-95630 are especially preferred.
  • the compounds described in U.S. Patent 4,552,834 are also added to photographic materials. When color photographic materials are bleach-fixed, the bleaching accelerating agents are especially effective.
  • thiosulfates As the fixing agent, there are mentioned thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodides. Among them, thiosulfates are generally used, and in particular, ammonium thiosulfate is most widely used.
  • sulfites, biuslfites and carbonyl bisulfite adducts are preferred.
  • the silver halide color photographic materials are of the present invention generally rinsed in water and/or stabilized, after being desilvered.
  • the amount of the water to be used in the rinsing step can be set in a broad range, in accordance with the characteristic of the photographic material being processed (for example, depending upon the raw material components, such as the coupler and so on) or the use of the material, as well as the temperature of the rinsing water, the number of the rinsing tanks (the number of the rinsing stages), the replenishment system of normal current or countercurrent and other various kinds of conditions.
  • the amount of the rinsing water to be used can be reduced noticeably, but because of the prolongation of the residence time of the water in the rinsing tank, bacteria would propagate in the tank so that the floating substances generated by the propagation of bacteria would adhere to the surface of the material as it was processed. Accordingly, the above system would often have a problem.
  • the method of reducing calcium and magneisum ions which is described in Japanese Patent Application No. 61-131632, can extremely effectively be used for overcoming this problem.
  • the pH value of the rinsing water to be used for processing the photographic materials of the present invention is from 4 to 9, preferably from 5 to 8.
  • the temperature of the rinsing water and the rinsing time can also be set variously in accordance with the characteristics of the photographic material being processed as well as the use thereof, and in general, the temperature is from 15 to 45°C and the time is from 20 seconds to 10 minutes, and preferably the temperature is from 25 to 40°C and the time is from 30 seconds to 5 minutes.
  • the photographic materials of the present invention may also be processed directly with a stabilizing solution in place of being rinsed with water.
  • any known methods for example as described in JP-A-57-8543, 58-14834 and 60-220345, can be employed.
  • the material can also be stabilized, following the rinsing step.
  • a stabilizing bath containing formaldehyde and a surfactant, which is used as a final bath for color photographic materials.
  • the stabilizing bath may also contain various chelating agents and fungicides.
  • the overflow from the rinsing and/or stabilizing solutions because of addition of replenishers thereto may be re-used in the other steps such as the previous desilvering step.
  • the silver halide photographic materials of the present invention can contain a color developing agent for the purpose of simplifying and accelerating the processing of the materials.
  • a color developing agent for incorporation of color developing agents into the photogrpahic materials, various precursors of the agents are preferably used.
  • the indoaniline compounds described in U.S. Patent 3,342, 597 the Schiff base compounds described in U.S. Patent 3,342,599 and Research Disclosrue Items 14850 and 15159
  • the aldole compounds described in Research disclosure Item 13924 the metal complexes described in U.S. Patent 3,719,492 and the urethane compounds described in JP-A-53-135628, as the precursors.
  • the silver halide color photographic materials of the present invention can contain various kinds of 1-­phenyl-3-pyrazolidones, if desired, for the purpose of accelerating the color developability thereof. Specific examples of these compounds are described in JP-A-56-­64339, 57-144547 and 58-115438.
  • the processing solutions for the photographic materials of the invention are used at 10°C to 50°C.
  • a processing temperature of from 33°C to 38°C is standard, but the temperature may be made higher so as to accelerate the processing or to shorten the processing time, or on the contrary, the temperature may be made lower so as to improve the quality of images formed and to improve the stability of the processing solutions used.
  • the cobalt intensification or hydrogen peroxide intensification described in West German Patent 2,226,770 and U.S. Patent 3,674,499 may be employed in the processing the photographic materials of the invention.
  • the silver halide emulsion of the present invention which has been explained in detail hereinabove contains tabular silver halide grains having a completely uniform silver iodide distribution.
  • a negative silver halide emulsion having excellent photographic characteristics in terms of sensitivity, gradation, graininess, sharpness, resolving power, covering power, storability, latent image stability and pressure-resistance.
  • seed crystals The thus formed tabular silver bromide grains which are to be nuclei (hereinafter referred to as "seed crystals”) were washed by the conventional flocculation method, and then adjusted to have a pH of 6.0 and a pAg of 7.5 at 40°C.
  • the mean projected area circle-corresponding diameter of the thus obtained tabular grains was 0.4 ⁇ m.
  • the resulting emulsion was cooled to 35°C and washed by the conventional flocculation method. Then such was adjusted to have a pH value of 6.5 and a pAg value of 8.6 at 40°C and stored in a cold dark place.
  • the grains formed had a mean projected area circle-­corresponding diameter of 2.2 ⁇ m and a mean thickness of 0.3 ⁇ m.
  • the total amount of the Emulsion (1-A) added was 150 g as silver nitrate, and the final flow rate of Emulsion (1-A) being added was 10 times of the initial flow rate thereof.
  • the thus prepared emulsion was washed with water in the same manner as in the case of Emulsion (1-C), and then adjusted to have a pH value of 6.5 and a pAg value of 8.6 at 40°C.
  • the tabular grains formed had a mean projected area circle-corresponding diameter of 2.2 ⁇ m and a mean grain thickness of 0.3 ⁇ m.
  • Emulsion (1-E) was prepared in the same manner as Emulsions (1-C) and (1-D), except for the following.
  • an aqueous solution containing 150 g of silver nitrate, a potassium bromide solution containing 10 mol% of potassium iodide (the potassium bromide therein being equimolecular to silver nitrate in the solution), and 250 ml of an aquoeus 3 wt.% gelatin solution were added to a strong and efficient mixer which was provided near the reactor vessel, by the triple-jet method over a period of 80 minutes, under the condition of an accelerated flow rate (the final flow rate was 10 times of the initial flow rate).
  • the reaction mixture was stirred in the mixer to give ultra-fine grains, and these were directly continuously introduced into the reactor vessel from the mixer vessel. In the procedure, the temperature of the mixer vessel was kept at 35°C.
  • the thus prepared emulsion was washed with water in the same manner as Emulsion (1-C) and then adjusted to have a pH value of 6.5 and a pAg value of 8.6 at 40°C.
  • the tabular grains formed had a mean projected area circle-corresponding diameter of 2.2 ⁇ m and a mean grain thickness of 0.3 ⁇ m.
  • Emulsion (1-F) was prepared in the same manner as Emulsions (1-C), except that the pBr value was adjusted to be 2.6 during the growth of the grains and 3,6-­dithioctane-1,8-diol was not added.
  • 80 % of the tabular grains were hexagonal tabular grains having a mean projected area circle-­corresponding diameter of 2.4 ⁇ m.
  • the fluctuation coefficient of the grains was 19 %.
  • the mean grain thickness 0.22 ⁇ m.
  • Emulsion (1-G) was prepared in the same manner as Emulsion (1-E), except that the pBr value was adjusted to be 2.6 during the growth of the grains and 3,6-­dithioctane-1,8-diol was not added.
  • 90 % of the tabular grains were hexagonal tabular grains having a mean projected area circle-­corresponding diameter of 2.3 ⁇ m. That is, the emulsion was a monodispersed tabular silver iodobromide emulsion having a fluctuation coefficient of 15 %.
  • the mean grain thickness 0.22 ⁇ m.
  • Emulsion (1-H) was prepared in the same manner as Emulsion (1-D), except that the pBr value was adjusted to be 2.6 during the growth of the grains and 3,6-­dithioctane-1,8-diol was not added. During the procedure, all of the fine grains added did not dissolve, i.e., some of the fine grains still remained after addition of the fine grains-containing emulsion was added to the reactor vessel.
  • Emulsion (1-D) and Emulsion (1-H) it is understood that a silver halide solvent is necessary so as to dissolve the/previously prepared/fine grains (1-A) having a mean grain size of 0.05 ⁇ m.
  • a silver halide solvent is necessary so as to dissolve the/previously prepared/fine grains (1-A) having a mean grain size of 0.05 ⁇ m.
  • bromide ion and 3,6-dithioctane-1,8-diol were used as the silver halide solvent.
  • silver halide solvent is not longer necessary when the seed crystals are prepared in a mixer vessel and the seed crystals prepared therein are directly introduced into the reactor vessel for growth of the intended tabular grains. This is apparent from the result of the grains of Emulsion (1-G).
  • Emulsion (1-G) was a monodiserpsed tabular grain emulsion because of the elevation of the ratio of the content of hexagonal tabular grains and of the reduction of the fluctuation coefficient of the projected area circle-corresponding diameter distribution of the grains in the emulsion. Accordingly, it is further understood with that the process of the present invention is an ideal method for growing tabular grains because of the complete uniformity of the silver iodide distribution in the tabular grains to be formed.
  • the emulsions of the present invention had an extremely higher sensitivity than the comparative emulsions.
  • the emulsion thus prepared was cooled to 35°C and washed with water by the conventional flocculation method. 60 g of gelatin was added thereto and dissolved at 40°C. Then, the emulsion was adjusted to have a pH value of 6.5 and a pAg value of 8.6.
  • the tabular silver bromide grains thus formed had a mean projected area circle-corresponding diameter of 1.4 ⁇ m and a grain thickness of 0.2 ⁇ m.
  • the emulsion was a monodispersed tabular grain emulsion having a fluctuation coefficient of 15 %.
  • Emulsion (2-A) containing silver bromide in an amount of 50 g as silver nitrate was added to 1.1 liters of water and dissolved. The resulting solution was adjusted to have a temperature of 75°C and a pBr value of 1.4 Afterwards, 1 g of 3,6-dithioctane-1,8-diol was added thereto, and immediately 100 g of silver nitrate and a potassium bromide solution containing 6.3 g of potassium bromide and 9.8 g of potassium iodide were added thereto under the condition of an equimolecular constant flow rate, over a period of 50 minutes.
  • the tabular silver iodobromide grains thus obtained were composed of silver bromide in the center part and 10 M% silver iodide-­containing silver iodobromide in the outer peripheral part.
  • the mean projected area circle-corresponding grain diameter was 2.3 ⁇ m and the mean grain thickness was 0.26 ⁇ m.
  • Emulsion (2-C) was prepared in the same manner as Emulsion (2-B), except for the following.
  • fine grain emulsion (1-A) was added thereto in an amount of 100 g as silver nitrate, at a constant flow rate over a period of 50 minutes.
  • the tabular grains thus formed had a mean projected area circle-corresponding diameter of 2.5 ⁇ m and a mean grain thickness of 0.23 ⁇ m.
  • Emulsion (2-D) was prepared in the same manner as Emulsion (2-B) and (2-C), except for the following.
  • 100 g of silver nitrate and a potassium bromide solution containing 6.3 g of potassium bromide and 9.8 g of potassium iodide were added to a strong and efficient mixer vessel which was provided near the reactor vessel, at an equimolecular constant flow rate.
  • 300 ml of a 2 wt.% gelatin solution was blended with the aqueous halide solution.
  • the ultra-fine grains formed in the mixer were directly continuously introduced into the reactor vessel from the mixer vessel. In the procedure, the temperature in the mixer vessel was kept at 40°C.
  • the tabular grains thus formed had a mean projected aea circle corresponding diameter of 2.4 ⁇ m and a mean grain thickness of 0.24 ⁇ m.
  • Emulsion (2-E) was prepared in the same manner as Emulsion (2-D), except that the pBr value was adjusted to be 2.6 during the growth of th grains and 3,6-dithioctane-­1,8-diol was not added.
  • 86 % of the tabular grains were hexagonal tabular grains having a mean projected area circle-corresponding diameter of 2.1 ⁇ m. That is, the emulsion was a monodispersed tabular silver iodobromide emulsion having a fluctuation coefficient of 17 %.
  • the mean grain thickness was 0.23 ⁇ m.
  • the core is made of a pure silver bromide containing no silver iodide. Accordingly, any stripe patterns which would indicate the existence of non-uniform silver iodide are not observed in the core.
  • the outer shell of the grains is made of a silver iodobromide phase containing 10 % of silver iodide.
  • the core/shell ratio in the grains is 1/2.
  • Sensitizing Dye (I) mentioned below 250 mg/mol(Ag) of Sensitizing Dye (I) mentioned below was added to each of Emulsions (2-B) to (2-E) having a pH of 6.5 and a pAg of 8.6, at 60°C. 10 minutes after the addition, sodium thiosulfate (5.1 x 10 ⁇ 6 mol/mol Ag), potassium chloroaurate (4.5 x 10 ⁇ 6 mol/mol Ag) and potassium thiocyanate (5.1 x 10 ⁇ 4 mol/mol Ag) were added thereto for optimum chemical sensitization. After chemical sensitization, 100 g of each of Emulsions (2-B) to (2-E) (containing 0.08 mol of Ag) was melted at 40°C and the following compounds (1) to (3) were added thereto in order with stirring to give a coating composition.
  • the thus prepared emulsion-coating composition and surface protective layer-coating composition were coated on a cellulose triacetate film support by the co-extrusion method, the volume ratio of the coated layers being 103/45.
  • the amount of silver coated was 3.1 g/m2.
  • This samples thus prepared were wedgewise exposed with a light source (200 lux) having a color temperature of 2854°K for 1/10 second and then developed with Developer (D-2) mentioned below at 20°C for 7 minutes. They were then fixed with Fixer (F-1), rinsed with water and dried.
  • the emulsions of the present invention had an extremely higher sensitivity than the comparative emulsion.
  • a silver nitrate solution was added thereto so that the pBr value was adjusted to be 2.0.
  • 75 g of a silver nitrate and potassium bromide solution containing 39.4 g of potassium bromide and 18.3 g of potassium iodide were added thereto, under the condition of an equimolecularly accelerated flow rate (the final flow rate was 10 times of the initial flow rate).
  • the pBr value was adjusted to be 2.5, and then 75 g of silver nitrate and the same molar amount of potassium bromide were added to the emulsion under the condition of an equimolecularly accelerated flow rate (the final flow rate was 10 times of the initial flow rate), over a period of 20 minutes.
  • the emulsion was cooled to 35°C and washed with water by the conventional flocculation method.
  • 60 g of gelatin was added thereto and dissolved at 40°C, and the resulting emulsion was adjusted to have a pH of 6.5 and a pAg of 8.6.
  • the thus prepared tabular grains had a core/shell structure (cor/shell ration of 1/1), in which the core was silver iodobromide having 25 mol% of silver iodide content and the shell was pure silver bromide.
  • the tabular grains had a mean projected area circle-­corresponding diameter of 2.0 ⁇ m and a mean grain thickness of 0.28 ⁇ m.
  • Tabular silver iodobromide grain nuclei containing 25 mol% of silver iodide were formed as in the case of the preparation of Emulsion (3-B), and 40 ml of an aqueous 30 % potassium bromide solution and 0.8 g of 3,6-dithioctane­1,8-diol were added thereto.
  • fine grain emulsion (3-A) as dissolved was added thereto by a pump, in an amount of 75 g as silver nitrate under the condition of an accelerated flow rate (the final flow rate was 10 times of the initial flow rate).
  • the pBr value of the resulting emulsion was adjusted to be 2.6, and 75 g of silver nitrate and the same molar amount of potassium bromide were added thereto under the condition of an accelerated flow rate (the final flow rate was 2 times of the initial flow rate).
  • the emulsion was washed with water and re-dispersed, as in the case of the preparation of Emulsion (3-B).
  • the thus prepared tabular grains were also core/shell grains, in which the core was silver iodobromide containing 25 mol% of silver iodide and the shell was silver bromide.
  • the projected area circle-­corresponding diameter of the grains was 2.6 ⁇ m and the grain thickness thereof was 0.22 ⁇ m.
  • Each of emulsions (3-B), (3-C) and (3-D) was optimally sensitized with sodium thiosulfate (5.5 x 10 ⁇ 6 mol/mol Ag), chloroauric acid (4.0 x 10 ⁇ 6 mol/mol Ag) and potassium thiocyanate (3.0 x 10 ⁇ 4 mol/mol Ag) at 60°C, and 250 mg/mol (Ag) of the following Sensitizing Dye II was added thereto.
  • Emulsion (3-B), (3-C) or (3-D) obtained in Example 3 was optimally chemically sensitized with sodium thiocyanate (4.5 x 10 ⁇ 6 mol/mol Ag), chloroauric acid (3.0 x 10 ⁇ 6 mol/mol Ag) and potassium thiocyanate (2.5 x 10 ⁇ 4 mol/mol Ag) at 60°C, and then the compounds mentioned below were added thereto.
  • the thus prepared coating composition was coated on a subbing layer-coated triacetyl cellulose film support.
  • the thus prepared samples were sensitometrically exposed and then processed by the following color development procedure.
  • the development procedure comprised the following steps, which were conducted at 38°C. 1. Color Development 2 min 45 sec 2. Bleaching 6 min 30 sec 3. Rinsing in water 3 min 15 sec 4. Fixation 6 min 30 sec 5. Rinsing in Water 3 min 15 sec 6. Stabilization 3 min 15 sec
  • the processing solution used in the respective steps had the following compositions.
  • Color Developer Nitrilotriacetic Acid Sodium Salt 1.0 g Sodium Sulfite 4.0 g Sodium Carbonate 30.0 g Potassium Bromide 1.4 g Hydroxylamine Sulfate 2.4 g 4-(N-ethyl-N- ⁇ -hydroxyethylamino)-2-methylaniline Sulfate 4.5 g Water to make 1 liter
  • Bleaching Solution Ammonium Bromide 160.0 g Aqueous Ammonia (28 wt.%) 25.0 ml Ethylenediamine-tetraacetic Acid Sodium Salt 130 g Glacial Acetic Acid 14 ml Water to make 1 liter Stabilizer: Formaldehyde 8.0 ml Water to make 1 liter
  • Emulsions (3-C) and (3-D) of the present invention had a higher sensitivity than comparative Emulsion (3-B).
  • Emulsion (1-E) obtained in Example 1 was optimally chemically sensitized by the conventional manner, using sodium thiosulfate (5.5 x 10 ⁇ 6 mol/mol Ag) potassium chloroaurate (4.5 x 10 ⁇ 6 mol/mol Ag) and potassium thiocyanate (4.5 x 10 ⁇ 4 mol/mol Ag) .
  • the resulting emulsion was used as the emulsion for the fourth layer of the Sample No. 104 in Example 1 of JP-A-62-215271 to prepare a photographic material sample. This was processed in the manner described in Example 1 of JP-A-62-215271. As a result, the sample was proved to have a good photographic property.
  • the emulsion was used as a core emulsion, and a shell (second coat layer or outer layer) of silver bromide was formed over the core.
  • the molar ratio of first coat layer/second coat layer was 1/1.
  • the thus obtained emulsion grains were monodispersed core/shell octahedral grains having a mean projected area circle-­ corresponding diameter of 2.2 ⁇ m and a core silver iodide content of 25 mol%.
  • Necleation was effected in the same manner as in preparation of Emulsion (6-A) to obtain silver iodobromide grain nuclei having a grain size of 0.3 ⁇ m. Subsequently, fine grains-containing Emulsion (3-A) (silver iodide content: 25 mol%) was added thereto in an amount of 1.2 molS as silver, with a pump over a period of 100 minutes. The first coat layer (inner layer) was formed on the nuclei. Afterwards, the emulsion was cooled and washed with water, and this was adjusted to have the same pH and pAg values as those of Emulsion (6-A).
  • the emulsion grains were used as core grains, and 800 ml of silver nitrate solution (1.5 M of AgNO3) and 800 ml of potassium bromide solution (1.5 M of KBr) were simultaneously added thereto over a period of 80 minutes in the reactor vessel by the double jet method so as to form a silver bromide shell (second coat layer or outer layer) over the core grains.
  • the ratio of first coat layer/second coat layer was 1/1.
  • the thus prepared grains were monodispersed core/shell octahedral grains having a mean projected area circle-corresponding diameter of 2.2 ⁇ m and a silver iodide core of 25 mol%.
  • Necleation was effected in the same manner as in preparation of Emulsion (6-A), and 800 ml of 1.5 M silver nitrate, 800 ml of a halide solution containing 0.375 M potassium iodide and 1.13 M potassium bromide and 500 ml of an aqueous 2 wt.% gelatin solution were added to a strong and efficient mixer as provided near the reactor vessel, by the triple jet method over a period of 100 minutes, whereupon the temperature in the mixer was kept at 30C. The ultra fine grains formed in the mixer were directly continuously introduced into the reactor vessel kept at 75°C. Thus, the first coat layer was formed on the nuclei in the reactor vessel.
  • first coat layer/second coat layer was 1/1.
  • the thus obtained grains were monodispersed octahedral core/shell grains having a mean projected area circle-corresponding diameter of 2.2 ⁇ m.
  • Each of emulsions (6-A), (6-B) and (6-C) was optimally chemically sensitized with sodium thiosulfate (4.0 x 10 ⁇ 6 mol/mol Ag), potassium chloroaurate (3.0 x 10 ⁇ 6 mol/mol Ag) and potassium thiocyanate (3.0 x 10 ⁇ 4 mol/mol Ag), and the compounds mentioned below were added thereto.
  • the resulting coating composition was coated on a subbing layer-coated triacetyl cellulose film support.
  • the development procedure comprised the following steps all of which were conducted at 38°. 1. Color Development 2 min 45 sec 2. Bleaching 6 min 30 sec 3. Rinsing in Water 3 min 15 sec 4. Fixation 6 min 30 sec 5. Rinsing in Water 3 min 15 sec 6. Stabilization 3 min 15 sec
  • Emulsions (6-B) and (6-C) of the present invention are extremely excellent because of the high sensitivity and low fog.
  • the samples were subjected to pressure test (bending test where the emulsion-coated films are bent).
  • pressure test bending test where the emulsion-coated films are bent.
  • Emulsion (6-A) showed extreme pressure desensitization
  • Emulsions (6-B) and (6-C) showed almost no pressure desensitization. From the test, therefore, it is noted that the pressure-resistance of the emulsions of the present invention was noticeably improved.
  • the grains were used as cores, and 400 ml of a 1.5 M aqueous silver nitrate solution and 400 ml of an aqueous halide solution containing 0.15 M potassium iodide and 1.35 M potassium bromide were simultaneously added thereto by the double jet method, whereby a silver iodobromide shell with 10 mol% of silver iodide content was formed over the core.
  • the resulting emulsion was cooled to 35°C and washed with water by the conventional flocculation method.
  • 85 g of gelatin was added and the emulsion was adjusted to have a pH of 6.2 and a pAg of 8.8.
  • the thus prepared grains were monodispersed octahedral core/shell grains having a mean projected area circle-corresponding diameter of 2.2 ⁇ m, in which the shell contained 10 mol% of silver iodide.
  • Emulsion of the Invention (Emulsion of the Invention):
  • Cores having a mean projected area circle-­corresponding diameter of 1.7 ⁇ m were prepared as in the case of Emulsion (7-A). 20 ml of 30 % potassium bromide was added thereto. The fine grains-containing Emulsion (1-A) of Example 1 (containing 10 mol% of silver iodide) was added in an amount of 0.6 mol as silver, with a pump, at a constant flow rate over a period of 50 minutes. Thus, core/shell grains were prepared a in the case of Emulsion (7-A). These were monodispersed octahedral core/shell grains having a mean projected area circle corresponding diameter of 2.2 ⁇ m, in which the shell contained 10 mol% of silver iodide.
  • Emulsion of the Invention (Emulsion of the Invention):
  • Silver bromide cores having a mean projected area circle-corresponding diameter of 1.7 ⁇ m were prepared as in the case of Emulsion (7-A).
  • 400 ml of an aqueous 1.5 M silver nitrate solution, 400 ml of an aqueous halide solution containing 0.15 M potassium iodide and 1.35 M potassium bromide and 200 ml of an aqueous 1 wt.% gelatin solution were simultaneously added to a strong and efficient mixer provided near the reactor vessel, by the triple jet method over a period of 50 minutes, whereupon the temperature in the mixer was kept at 35°C.
  • the ultra-­fine grains thus prepared in the mixer were directly continuously introduced into the reactor vessel kept at 75°C.
  • the thus prepared grains were monodispersed octahedral core/shell (1/1) grains having a mean projected area circle-corresponding diameter of 2.2 ⁇ m, in which the core was silver bromide and the shell was silver iodobromide having 10 mol% of silver iodide.
  • Emulsions (7-A), (7-B) and (7-C) were optimally chemically sensitized with sodium thiosulfate (7.2 x 10 ⁇ 6 mol/mol Ag), potassium chloroaurate (5.6 x 10 ⁇ 6 mol/mol Ag) and potassium thiocyanate (5.5 x 10 ⁇ 4 mol/mol Ag).
  • photographic samples were prepared in the same manner as in Example 6. These samples were sensitometrically processed, and the photographic properties of the respective samples obtained are shown in Table 6 below.
  • Example of the Invention 7-C 350 0.15
  • Emulsions (7-B) and (7-C) of the present invention ahd an extremely higher sensitivity than the comparative Emulsion (7-A).
  • 150 cc of a 2.0 M silver nitrate solution and 150 cc of an aqueous halide solution containing 1.8 M potassium bromide and 0.2 M potassium iodide were added to 1.3 liters of a 0.8 wt% gelatin (P-1) solution containing 0.08 M potassium iodide, with stirring by the double jet method, whereupon the gelatin solution was kept at 30°C. After the addition, such as elevated up to 70°C and 30 g of gelatin (P-1) was added thereto. Afterwards, this was ripened for 30 minutes.
  • seed crystal tabular silver bromide grains which are to be nuclei
  • an aqueous solution containing 150 g of silver nitrate, a potassium bromide solution containing 10 mol% of potassium iodide (the potassium bromide therein being equimolecular to silver nitrate in the solution), and 500 ml of an aqueous 3 wt% gelatin solution were added to the mixer which was provided near the reactor vessel, by the triple-jet method over a period of 55 minutes, under the condition of an accelerated flow rate (the final flow rate was 10 times of the initial flow rate).
  • the residence time of the solutions added in the mixer vessel was 10 seconds.
  • the rotation number of the stirring blades in the mixer vessel was 3000 room temperature.
  • the thus formed fine silver iodobromide grains were observed with a direct transmission electron microscope at a magnification of 20,000 times. As a result, the mean grain size was 0.03 ⁇ m.
  • the temperature of the mixer vessel was kept at 35°C, and the fine grains formed in the mixer were continuously introduced into the reactor vessel.
  • Emulsion (8-C) was tried to be prepared in the same manner as emulsion (8-B), except that the temperature in the mixer vessel was changed to 15°C. However, when the temperature in the mixer vessel was adjusted to be 15°C, the gelatin solution gelled in the mixer vessel so that fine grains were not formed therein. In order to obtain fine grains having a small grain size, It is said necessary to lower the temperature in the mixer vessel. However, when the gelatin (P-1) was used as the protective colloid, it was found that formation of fine grains was impossible at such a low temperature.
  • the low molecular weight gelatin (P-2) was used as the protective colloid, in place of the gelatin (P-1). In this case using the gelatin (P-2), no gelation occurred even at 15°C and formation of fine grains was possible.
  • Emulsion (E) to (N) were prepared under the same condition (temperature of mixer vessel: 15°C), using each of the protective colloid synthetic polymers (P-3) to (P-12).
  • the fine grains having a smaller grain size may more rapidly dissolve.
  • the grain size of the fine grains in Emulsion (8-B) is 0.03 ⁇ m so that the dissolution of the grains in the reactor vessel is slow and the fine grains still remained in the reactor vessel. Further, the grain size of the finally obtained tabular grains was also small. In order to obtain fine grains having a smaller grain size, it is considered most effective to lower the temperature in formation of the fine grains.
  • the gelatin (P-1) was used, this gelled at a low temperature of 15°C so that formation of fine grains was impossible at such a low temperature.
EP19890100764 1988-01-18 1989-01-18 Emulsions photographiques à l'halogénure d'argent et procédé pour les préparer Expired - Lifetime EP0326853B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP7853/88 1988-01-18
JP785288A JPH01183644A (ja) 1988-01-18 1988-01-18 ハロゲン化銀写真乳剤
JP63007853A JPH07104569B2 (ja) 1988-01-18 1988-01-18 ハロゲン化銀写真乳剤
JP7852/88 1988-01-18

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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0362699A2 (fr) * 1988-10-03 1990-04-11 Eastman Kodak Company Emulsions à grains tabulaires à haut indice de forme présentant une répartition granulométrique plus étroite
EP0368275A1 (fr) * 1988-11-08 1990-05-16 Fuji Photo Film Co., Ltd. Emulsion photographique à l'halogénure d'argent et matériau
EP0416881A2 (fr) * 1989-09-06 1991-03-13 Konica Corporation Produit photographique couleur à l'halogénure d'argent sensible à la lumière
EP0443475A2 (fr) * 1990-02-19 1991-08-28 Konica Corporation Matériau photographique à halogénure d'argent
EP0451859A1 (fr) * 1990-04-12 1991-10-16 Fuji Photo Film Co., Ltd. Matériau photographique couleur à l'halogénure d'argent sensible à la lumière
EP0480294A1 (fr) * 1990-10-03 1992-04-15 Konica Corporation Emulsion photographique à l'halogénure d'argent et matériau photographique couleur à l'halogénure d'argent sensible à la lumière incorporant celle-ci
EP0509519A2 (fr) * 1991-04-18 1992-10-21 Fuji Photo Film Co., Ltd. Matériau à halogénure d'argent pour photographie en couleurs
EP0517434A1 (fr) * 1991-06-06 1992-12-09 Konica Corporation Procédé et fabrication des émulsions à l'halogénure d'argent et matériau photographique à l'halogénure d'argent sensible à la lumière
EP0531052A1 (fr) * 1991-09-06 1993-03-10 Konica Corporation Emulsion photographique à l'halogénure d'argent
EP0543319A1 (fr) * 1991-11-20 1993-05-26 Konica Corporation Matériau photographique couleur à l'halogénure d'argent sensible à la lumière
EP0549986A1 (fr) * 1991-12-27 1993-07-07 Konica Corporation Matériau photographique couleur à l'halogénure d'argent sensible à la lumière fournissant une reproduction de couleurs excéllente
US5262294A (en) * 1990-02-19 1993-11-16 Konica Corporation Silver halide photographic light sensitive material
US5320938A (en) * 1992-01-27 1994-06-14 Eastman Kodak Company High chloride tabular grain emulsions and processes for their preparation
EP0608464A1 (fr) * 1993-01-28 1994-08-03 Eastman Kodak Company Eléments photographiques multicouleur avec forme de courbe caractéristique améliorée
EP0378236B1 (fr) * 1989-01-13 1996-04-10 Fuji Photo Film Co., Ltd. Matériau photographique couleur à l'halogénure d'argent sensible à la lumière
EP0374852B1 (fr) * 1988-12-19 1998-03-25 Fuji Photo Film Co., Ltd. Procédé pour former des grains à l'halogénure d'argent
EP1022613A2 (fr) * 1999-01-25 2000-07-26 Eastman Kodak Company Composés donneurs d'électrons fragmentables en combinaison avec des émulsions à grains tabulaires riches en bromure d'argent

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FR2108386A5 (en) * 1970-09-24 1972-05-19 Fuji Photo Film Co Ltd Silver halide emulsion - pref iodobromide by mixing silver and halid solns in presence of preformed emulsion

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FR2108386A5 (en) * 1970-09-24 1972-05-19 Fuji Photo Film Co Ltd Silver halide emulsion - pref iodobromide by mixing silver and halid solns in presence of preformed emulsion

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Title
JOURNAL FÜR SIGNALAUFZEICHNUNGSMATERIALEN, vol. 14, no. 5, 1986, pages 377-379, Berlin, DD; WANG SU-E et al.: "Untersuchung der Herstellung, Strukturen und Eigenschaften von tafelförmigen Silberhalogenidkristallen - Die Verteilung von Iodidionen in verschiedenen Strukturen von tafelförmigen Silberhalogenidkristallen und ihre Ionenleitfähigkeitseigenschaften" *

Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0362699A2 (fr) * 1988-10-03 1990-04-11 Eastman Kodak Company Emulsions à grains tabulaires à haut indice de forme présentant une répartition granulométrique plus étroite
EP0362699A3 (fr) * 1988-10-03 1991-03-13 Eastman Kodak Company Emulsions à grains tabulaires à haut indice de forme présentant une répartition granulométrique plus étroite
EP0368275A1 (fr) * 1988-11-08 1990-05-16 Fuji Photo Film Co., Ltd. Emulsion photographique à l'halogénure d'argent et matériau
USH1285H (en) 1988-11-08 1994-02-01 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion and material
EP0374852B1 (fr) * 1988-12-19 1998-03-25 Fuji Photo Film Co., Ltd. Procédé pour former des grains à l'halogénure d'argent
EP0378236B1 (fr) * 1989-01-13 1996-04-10 Fuji Photo Film Co., Ltd. Matériau photographique couleur à l'halogénure d'argent sensible à la lumière
EP0416881A2 (fr) * 1989-09-06 1991-03-13 Konica Corporation Produit photographique couleur à l'halogénure d'argent sensible à la lumière
EP0416881A3 (en) * 1989-09-06 1991-07-17 Konica Corporation A silver halide light-sensitive colour photographic material
US5262294A (en) * 1990-02-19 1993-11-16 Konica Corporation Silver halide photographic light sensitive material
EP0443475A3 (en) * 1990-02-19 1992-05-20 Konica Corporation Silver-halide photographic light-sensitive material
EP0443475A2 (fr) * 1990-02-19 1991-08-28 Konica Corporation Matériau photographique à halogénure d'argent
US5534399A (en) * 1990-04-12 1996-07-09 Fuji Photo Film Co., Ltd. Silver halide color photographic photosensitive material
EP0451859A1 (fr) * 1990-04-12 1991-10-16 Fuji Photo Film Co., Ltd. Matériau photographique couleur à l'halogénure d'argent sensible à la lumière
US5273871A (en) * 1990-10-03 1993-12-28 Konica Corporation Silver halide photographic emulsion and silver halide color photographic light-sensitive material incorporating it
EP0480294A1 (fr) * 1990-10-03 1992-04-15 Konica Corporation Emulsion photographique à l'halogénure d'argent et matériau photographique couleur à l'halogénure d'argent sensible à la lumière incorporant celle-ci
EP0509519A3 (en) * 1991-04-18 1993-02-17 Fuji Photo Film Co., Ltd. Silver halide color photographic material
EP0509519A2 (fr) * 1991-04-18 1992-10-21 Fuji Photo Film Co., Ltd. Matériau à halogénure d'argent pour photographie en couleurs
US5432051A (en) * 1991-04-18 1995-07-11 Fuji Photo Film Co., Ltd. Silver halide color photographic material
EP0517434A1 (fr) * 1991-06-06 1992-12-09 Konica Corporation Procédé et fabrication des émulsions à l'halogénure d'argent et matériau photographique à l'halogénure d'argent sensible à la lumière
US5318887A (en) * 1991-06-06 1994-06-07 Konica Corporation Method for production of silver halide emulsion, and silver halide photographic light-sensitive material
EP0531052A1 (fr) * 1991-09-06 1993-03-10 Konica Corporation Emulsion photographique à l'halogénure d'argent
US5420002A (en) * 1991-11-20 1995-05-30 Konica Corporation Silver halide color photographic light sensitive material
EP0543319A1 (fr) * 1991-11-20 1993-05-26 Konica Corporation Matériau photographique couleur à l'halogénure d'argent sensible à la lumière
EP0549986A1 (fr) * 1991-12-27 1993-07-07 Konica Corporation Matériau photographique couleur à l'halogénure d'argent sensible à la lumière fournissant une reproduction de couleurs excéllente
US5332657A (en) * 1991-12-27 1994-07-26 Konica Corporation Silver halide color photographic light-sensitive material offering excellent color reproduction
US5320938A (en) * 1992-01-27 1994-06-14 Eastman Kodak Company High chloride tabular grain emulsions and processes for their preparation
US5360703A (en) * 1993-01-28 1994-11-01 Eastman Kodak Company Multicolor photographic elements exhibiting an enhanced characteristic curve shape
EP0608464A1 (fr) * 1993-01-28 1994-08-03 Eastman Kodak Company Eléments photographiques multicouleur avec forme de courbe caractéristique améliorée
EP1022613A2 (fr) * 1999-01-25 2000-07-26 Eastman Kodak Company Composés donneurs d'électrons fragmentables en combinaison avec des émulsions à grains tabulaires riches en bromure d'argent
EP1022613A3 (fr) * 1999-01-25 2002-08-28 Eastman Kodak Company Composés donneurs d'électrons fragmentables en combinaison avec des émulsions à grains tabulaires riches en bromure d'argent
US6518008B1 (en) 1999-01-25 2003-02-11 Eastman Kodak Company Fragmentable electron donor compounds in combination with high bromide tabular grain emulsions

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DE68914303T2 (de) 1994-11-10
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