EP0560036A2 - Photographische Silberhalogenidemulsion von hoher Empfindlichkeit und mit guter Verarbeitungsstabilität und Druckfestigkeit - Google Patents

Photographische Silberhalogenidemulsion von hoher Empfindlichkeit und mit guter Verarbeitungsstabilität und Druckfestigkeit Download PDF

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Publication number
EP0560036A2
EP0560036A2 EP93101342A EP93101342A EP0560036A2 EP 0560036 A2 EP0560036 A2 EP 0560036A2 EP 93101342 A EP93101342 A EP 93101342A EP 93101342 A EP93101342 A EP 93101342A EP 0560036 A2 EP0560036 A2 EP 0560036A2
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Prior art keywords
emulsion
grains
twin
silver halide
grain
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EP93101342A
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English (en)
French (fr)
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EP0560036B1 (de
EP0560036A3 (en
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Hideaki Konica Corporation Haraga
Kouji Konica Corporation Tashiro
Makoto Konica Corporation Nomiya
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Konica Minolta Inc
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Konica Minolta Inc
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/0051—Tabular grain emulsions
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain

Definitions

  • the present invention relates to a silver halide photographic emulsion having a high sensitivity and high color forming performance and promissing a good processing stability and good pressure resistance. More particularly it relates to a silver halide photographic emulsion that can provide a light-sensitive silver halide photographic material having a good processing stability and processing operability.
  • the silver halide grains contained in light-sensitive materials are commonly responsive to pressure, and become sharply more responsive to pressure as they are made to have a higher sensitivity. In other words, they cause phenomena of fogging by pressure and desensitization by pressure to fatally affect photographic images, when light-sensitive material films are folded or have scratches on their surfaces. In particular, improper handling during the processing in mini-labs, or photographic processing carried out therein in the state any dirt or dust in the surroundings has adhered, brings about a serious problem of fogging by pressure.
  • Japanese Patent O.P.I. Publications No. 99433/1984, No. 301937/1988, No. 149641/1988, No. 106746/1988, No. 151618/1988, No. 220238/1988 and No. 231739/1991 disclose means for improving pressure resistance. Techniques disclosed therein, however, have achieved no enough improvements, and are still unsatisfactory.
  • An object of the present invention is to provide a silver halide photographic emulsion having a high sensitivity and high color forming performance and promissing a good processing stability and good pressure resistance, in particular, a silver halide photographic emulsion that can provide a light-sensitive silver halide photographic material having a good processing stability and processing operability.
  • a silver halide photographic emulsion comprising grains having a twin plane, wherein part or all of said grains each have a start point of development at a cross point at which a line formed by a twin-plane border lying bare to the grain surface intersects an edge of the grain, or the vicinity of said cross point.
  • Fig. 1 illustrates cross points (black spots (b)) at which lines (dotted lines (a)) formed by twin-plane borders lying bare to the grain surfaces intersect edges of each grain, in octahedral twinned crystals of grains of Em-3 in Example 1.
  • the silver halide photographic emulsion according to the present invention is mainly comprised of grains having a twin plane (hereinafter “twinned grains”).
  • twinned grains are that at least 60%, preferably not less than 70%, and more preferably not less than 80%, of projected areas of the whole grains is held by twinned crystals when subjected to chemical ripening.
  • the twin plane may be either ⁇ 111 ⁇ twin plane or ⁇ 100 ⁇ twin plane, or may be formed of the both. It may preferably be ⁇ 111 ⁇ twin plane. In instances in which a grain has two or more twin planes, these twin planes should preferably be parallel to each other. Twinned grains having two parallel ⁇ 111 ⁇ twin planes (hereinafter “parallelly double-twinned grains”) are particularly preferred.
  • the parallelly double-twinned grains prefferably be in a percentage of not less than 50% based on the whole twinned grains, and most preferred for them to be in a percentage of not less than 80% based on the same.
  • the silver halide grains can be of various shapes so long as they have twin planes.
  • they should preferably be tabular grains having an aspect ratio of less than 5.0.
  • the aspect ratio is expressed as a diameter calculated as a circle corresponding to a projected area, taking the thickness of a tabular grain as a denominator.
  • the twinned grains may preferably have an aspect ratio of not more than 3.5, and most preferably from 1.0 to 2.5.
  • a parallelly double-twinned grain having an aspect ratio of about 1.0 is observed as an octahedron, or an octahedron whose tops are cut away or rounded to give a slightly deformed shape.
  • the diameter of a tabular silver halide grain is expressed as a diameter of a circle having the same projected area as that of the tabular grain when tabular silver halide grains are aligned on a flat surface in the manner that the facing two main planes of each grain is parallel to this flat surface.
  • This diameter may preferably be from 0.1 to 5.0 ⁇ m, more preferably from 0.2 to 4.0 ⁇ m, and particularly preferably from 0.3 to 3.0 ⁇ m.
  • the silver halide emulsion according to the present invention may preferably be monodisperse in its grain size distribution.
  • the emulsion may preferably have a coefficient of variation ( ⁇ ) of less than 20%, more preferably less than 18%, and most preferably less than 15%.
  • the coefficient of variation is defined as follows: The diameter can be determined by photographing the silver halide emulsion containing the tabular silver halide grains of the present invention, by the use of an electron microscope at a magnification of 10,000 to 50,000, and actually measuring the projected areas of the grains on a print thus obtained. (The measurement is made on at least 1,000 grains counted at random.)
  • the silver halide emulsion according to the present invention may have any composition, and may preferably be comprised of silver iodobromide having a silver iodide content of from 4 to 20 mol%, and particularly preferably from 5 to 15 mol%.
  • the emulsion may contain silver chloride so long as the effect of the present invention is not lost.
  • the silver halide emulsion has inside its each grain a phase with a higher silver iodide content.
  • the phase with a higher silver iodide content may preferably have a silver iodide content of from 15 to 45 mol%, more preferably from 20 to 42 mol%, and particularly preferably from 25 to 40 mol%.
  • the silver halide grains of the present invention having inside the grain the phase with a higher silver iodide content are grains in which the phase with a higher silver iodide content is covered with a phase with a lower silver iodide content, having a lower silver iodide content than the former.
  • the phase with a silver iodide content lower than the phase with a higher silver iodide content, the former of which forms an outermost phase, may preferably have an average silver iodide content of not more than 6 mol%, and particularly preferably from 0 to 4 mol%.
  • Other silver iodide-containing phase (an intermediate phase) may also be present between the outermost phase and the phase with a higher silver iodide content.
  • the intermediate phase may have a silver iodide content of from 10 to 22 mol%, and particularly preferably from 12 to 20 mol%.
  • silver iodide content between the outermost phase and intermediate phase and between the intermediate phase and the inside phase with a higher silver iodide content there may preferably be a difference of not less than 6 mol% each, and particularly preferably a difference of not less than 10 mol% each.
  • other silver halide phases may be further present at the center of the inside phase with a higher silver iodide content, between the inside phase with a higher silver iodide content and intermediate phase and between the intermediate phase and outermost phase, respectively.
  • the outermost phase should preferably have a volume of from 4 to 70 mol%, and more preferably from 10 to 50 mol%, based on that of the whole grain.
  • the phase with a higher silver iodide content should have a volume of from 10 to 80%, preferably from 20 to 50%, and more preferably from 20 to 45%, based on that of the whole grain.
  • the intermediate phase should preferably have a volume of from 5 to 60%, and more preferably from 20 to 55%.
  • phase may each be a single phase with uniform composition, or may be a group of phases having composition stepwise changed, comprised of a plurality of phases with uniform composition.
  • any of the phases may be a continuous phase having composition continuously changed, or may be a combination of these.
  • Another embodiment of the silver halide emulsion according to the present invention can be an embodiment in which the silver iodide localized in a grain does not form a substantially uniform phase and the silver iodide content continuously changes from the core of a grain toward the shell thereof.
  • the silver iodide content at the point where the silver iodide content is maximum may preferably be from 15 to 45 mol%, and more preferably from 25 to 40 mol%.
  • the silver iodide content in the grain surface phase may preferably be not more than 6 mol%, and particularly preferably from 0 to 4 mol%. Such silver iodobromide should be used.
  • the silver halide emulsion of the present invention may preferably satisfy at least one condition of the following (1) to (4).
  • the relative standard deviation is obtained in the following way: The standard deviation of silver iodide content in the measurement of silver iodide content in, for example, at least 100 emulsion grains is divided by the average silver iodide content determined in that measurement, and the resulting value is multiplied by 100.
  • the silver halide grains used in the light-sensitive material of the present invention may be grown by any of the acid method, the neutral method and the ammonia method. It is possible to use known methods as disclosed in Japanese Patent O.P.I. Publications No. 6643/1986, No., 14630/1986, No. 112142/1986, No. 157024/1987, No. 18556/1987, No. 92942/1988, No. 151618/1988, No.1613451/1988, No. 220238/1988, No. 311244/1988 and so forth.
  • iodide can be fed using a method in which an aqueous solution of its soluble salt is added, or by adding it in the form of fine silver halide grains as exemplified by fine silver iodide or silver iodobromide grains followed by Ostwald ripening to make them grow.
  • the method in which it is fed in the form of fine silver halide grains is preferred.
  • the growth of the silver halide grains of the present invention may be made in the presence of a known silver halide solvent such as ammonia, thioether or thiourea.
  • a crystal form control agent may also be used.
  • metal ions may be added to the silver halide grains by the use of at least one selected from a cadmium salt, a zinc salt, a lead salt, a thallium salt (including complex salts thereof), an iridium salt, a rhodium salt and an iron salt so that any of these metal elements can be incorporated in grain insides and/or grain surfaces.
  • the silver halide grains may also be placed in an appropriate reducing atmosphere so that reducingly sensitizing nuclei can be imparted to the grain insides and/or grain surfaces.
  • excess soluble salts may be removed after the growth of the silver halide grains has been completed, or they may remain unremoved. In the case when the slats are removed, they can be removed by the method described in Research Disclosure No. 17643, paragraph II.
  • start point of development or “development start point”
  • start point of development or “development start point” is a point recognized as a point at which development is started, when developing and stopping are carried out and observation is made thereon. Stated specifically, it can be specified as follows:
  • light-sensitive materials comprising a support coated thereon with a photographic emulsion to be noted are processed in the following way.
  • a part of the light-sensitive materials is subjected to wedge exposure, followed by conventional photographic processing to obtain the characteristic curve. Then the remaining light-sensitive materials are exposed in the amount of exposure that corresponds to (maximum density - minimum density) ⁇ 3/4 on the characteristic curve to the amount of exposure that is 50 times that amount, and then developed using developing solutions having substantially the same composition. After the developing is started, the light-sensitive materials are immersed in a 3% acetic acid solution, and the developing is stopped.
  • Conditions for the photographic processing to specify the start points of development may be appropriately selected so as to enable easy observation of the start points of development.
  • the present invention is characterized in that part or all of the twinned grains described above each have a start point of development at a cross point at which a line formed by a twin-plane border lying bare to the grain surface intersects an edge of the grain, or the vicinity of said cross point (the cross point or the vicinity thereof is abridged to "cross area").
  • At least 70% of the total sum of development start points on a grain are present in its cross areas when the development start points of twinned grains are observed by the above exposure and developing method.
  • the "line formed by a twin-plane border lying bare to the grain surface" can be readily recognized from its grain form in the case when the twin-plane border forms a clear ridge line on the grain surface in the case when, for example, the grain has only a single twin plane.
  • the stated line can be readily recognized when a scanning electron microscope having a high resolving power is used at a low accelerating voltage to observe the grains.
  • cross point at which a line formed by a twin-plane border lying bare to the grain surface intersects an edge of the grain, or the vicinity of said cross point is a point at which the line formed by a twin-plane border lying bare to the surface of a grain crosses an edge thereof not parallel to that line, or the vicinity of that point.
  • the vicinity of that point is the area of a circle around the aforesaid cross point (the center of the cross area), having a radius corresponding to about 1/3, and preferably 1/4, of grain thickness. A greater effect can be brought about when the area has a radius corresponding to 1/5 of grain thickness.
  • the center of the cross area forms a top.
  • resistance to the fogging by pressure as aimed in the present invention may become slightly poor compared with the case when the center of the cross area does not form a top, but is clearly superior to the case when the start point of development is present at a top including no twin-plane border.
  • edge and top of the grain are meant by portions crystalographically judged to be substantially an edge and a top.
  • a scanning electron microscope having a high resolving power is used at a low accelerating voltage like the case when the line formed by a twin-plane border lying bare to the grain surface is observed. If necessary, the observation may be made in the state the sample is cooled, whereby much better results of observation can be obtained.
  • Transmission electron microscopes can only obtain two-dimensional flat information in respect of the development start points of the tabular grains, and it is difficult for them to obtain three-dimensional information. It is also difficult for them to specify the line formed by a twin-plane border lying bare to the grain surface. Thus they can be of no use.
  • Japanese Patent O.P.I. Publications No. 305343/1988 and No. 77047/1989 discloses techniques in which development start points of tabular grains are specified at edges and tops and the vicinities thereof. In these techniques, however, substantially two-dimensional information only is obtained in respect of the development start points of tabular grains. In other words, they do not specifically state whether or not the start point of development are present at the cross point at which the line formed by a twin-plane border lying bare to the grain surface intersects an edge of the grain, or the vicinity of the cross point.
  • the present invention is a technique in which the position of the start point of development is more precisely specified, and therefore not only a greater sensitizing effect and an improvement in photographic processing stability have been achieved but also an improvement in resistance to fogging by pressure has been achieved.
  • the silver halide emulsion of the present invention may be spectrally sensitized using a spectral sensitizer. It may also be chemically sensitized.
  • the silver halide emulsion of the present invention may preferably be chemically sensitized in the presence of a spectral sensitizer. More preferably it should be chemically sensitized in the presence of two or more kinds of spectral sensitizers.
  • a silver halide solvent may preferably be present at the time when the chemical sensitization is started.
  • the silver halide emulsion of the present invention can be chemically sensitized by any known methods such as sulfur sensitization, selenium sensitization, reduction sensitization and gold sensitization, any of which may be used alone or in combination.
  • the gold sensitization is a typical method of noble metal sensitization, where a gold compound, chiefly a gold complex salt, is used.
  • a gold compound chiefly a gold complex salt
  • Preferable gold sensitizers are typified by chloroauric acid and salts thereof. It is also useful to use a thiocyanate in combination to increase gold sensitization.
  • Noble metals other than gold, as exemplified by complex salts of platinum, palladium, iridium or the like may also be used alone or in combination with gold sensitizers. Examples thereof are disclosed in U.S. Patent No. 2,448,060, British Patent No. 618,061 and so forth.
  • sulfur sensitizers various sulfur sensitizers can be used besides a sulfur compound contained in gelatin, which are exemplified by thiosulfates, thioureas, thiazoles and rhodanines. Specific examples thereof are those disclosed in U.S. Patents No. 1,574,944, No. 2,278,947, No. 2,410,689, No.2,728,668, No. 3,501,313 and No.3,656,955.
  • Organic sulfur sensitizers in particular, thiourea type sulfur sensitizers are preferable as sensitizers used when the silver halide emulsion of the present invention is chemically sensitized.
  • thiourea type sulfur sensitizers are exemplary compounds disclosed in Japanese Patent O.P.I. Publications No. 45016/1980, No. 196645/1987 and No. 114839/1989.
  • stannous salts As reduction sensitizers, stannous salts, amines, formamidinesulfinic acids, silane compounds and so forth can be used.
  • the sulfur sensitizer may be used preferably in an amount of from 1 ⁇ 10 ⁇ 7 mol to 1 ⁇ 10 ⁇ 4 mol, and more preferably from 1 ⁇ 10 ⁇ 6 mol to 5 ⁇ 10 ⁇ 5 mol, per mol of silver halide, in terms of active sulfur.
  • the gold sensitizer may be used preferably in an amount of from 1 ⁇ 10 ⁇ 7 mol to 1 ⁇ 10 ⁇ 4 mol, and more preferably from 5 ⁇ 10 ⁇ 7 mol to 5 ⁇ 10 ⁇ 5 mol, per mol of silver halide.
  • sulfur sensitization and gold sensitization are used in combination, they may preferably be used in a ratio of from 3:1 to 1:1.
  • the sulfur sensitizer and gold sensitizer may be added in the form of a mixture, or may be separately added. It is preferred for them to be separately added. In the case when they are separately added, they may be added at the same time or one of them may be added first. The present invention can be more effective when the sulfur sensitizer is added first.
  • the sulfur sensitizer is added first, it is common to use a method in which the sulfur sensitizer is added, then the gold sensitizer is added and thereafter the reaction of the sulfur sensitizer is further continued.
  • the present invention can be made more effective by a method in which, after the reaction has been allowed to proceed to a certain extent using only the sulfur sensitizer, the emulsion temperature is dropped to about 40°C until the reactivity of the sulfur sensitizer is lowered, whereupon the gold sensitizer is slowly reacted.
  • the silver halide solvent such as a thiocyanate, a thioether compound, a thiazolidinethione or a four-substituted thiourea may be made present during chemical sensitization.
  • a thiocyanate, a four-substituted thiourea and a thioether compound are preferred solvents. Any of these silver halide solvents may be made present at any time during the chemical sensitization. It is particularly effective for it to be made present before the chemical sensitization is started.
  • a spectral sensitizer should be added so that spectral sensitivity to light in the desired wavelength region can be imparted to the emulsion.
  • spectral sensitizer it is possible to use various dyes including polymethine dyes including cyanine dyes, merocyanine dyes, holopolar cyanine dyes, complex cyanine dyes, complex merocyanine dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merostyryl dyes, streptocyanine dyes and pyrylium dyes. Cyanine dyes are particularly preferred.
  • Cyanine dyes preferably used are the cyanine dyes represented by Formula I, described in Japanese Patent O.P.I. Publication No. 231739/1991, from page 313, right upper column to page 318, left lower column, which are denoted by S-1 to S-71.
  • Spectral sensitization using any of these spectral sensitizers may be carried out by conventioally well known methods. More specifically, it is carried out by a method in which the spectral sensitizer is dissolved in a suitable solvent such as methanol, ethanol, propanol, fluorinated alcohol, 1-methoxyethanol, ethyl acetate, water or an aqueous acid or alkali solution having a suitable pH value to form a solution with a suitable concentration, and the solution is added to the silver halide emulsion or an aqueous hydrophobic colloid solution.
  • a suitable solvent such as methanol, ethanol, propanol, fluorinated alcohol, 1-methoxyethanol, ethyl acetate, water or an aqueous acid or alkali solution having a suitable pH value to form a solution with a suitable concentration
  • the aforesaid solution is added at any step in the course of the preparation of the silver halide emulsion.
  • it may be added at any step before the formation of the silver halide grains, during the formation thereof, after the formation thereof and during physical ripening, before chemical ripening, during chemical ripening, after the chemical ripening and before the preparation of a coating solution, or at the preparation of the coating solution, without regard to the order in which a stabilizer and an antifoggant are added.
  • the present invention can thereby be made more effective.
  • These dyes may each be used alone. Alternatively, two or more kinds of dyes may be used in combination. The latter is particularly effective.
  • the amount in which these spectral sensitizers are added may vary over a wide range as occasion calls. In usual instances, they may be used in an amount ranging from 1 ⁇ 10 ⁇ 6 mol to 1 ⁇ 10 ⁇ 2 mol, and more preferably from 5 ⁇ 10 ⁇ 6 mol to 1 ⁇ 10 ⁇ 3 mol, per mol of silver halide. This can make the present invention more effective.
  • the spectral sensitizer may be added by from 40% to 80%, preferably from 50 to% to 80%, and more preferably from 55% to 75%, based on the amount of saturated monomolecular layer adsorption.
  • the spectral sensitizers to be added may preferably be used in such a combination that gives supersensitization.
  • the combination that gives supersensitization two or more kinds may be selected from the dyes described above, to form the desired combination.
  • Compounds other than the above may also be used as supersensitizers.
  • a dye having no spectrally sensitizing action in itself, or a substance capable of absorbing substantially no visible light and showing supersensitization.
  • Such a substance may include, for example, aromatic organic acid formaldehyde condensates as exemplified by those disclosed in U.S. Patent No.
  • the silver halide emulsion of the present invention may preferably be chemically sensitized in the presence of the nitrogen-containing heterocyclic compound disclosed in Japanese Patent O.P.I. Publication No. 126526/1983.
  • the emulsion may be chemically sensitized in the presence of both the two or more kinds of spectral sensitizers and the above nitrogen-containing heterocyclic compound, whereby the present invention can be made more effective.
  • the amount of the nitrogen-containing heterocyclic compound used together with the two or more kinds of spectral sensitizers may vary over a wide range as occasion calls.
  • they may be used in an amount ranging from 5 ⁇ 10 ⁇ 7 mol to 1 ⁇ 10 ⁇ 2 mol, and more preferably from 1 ⁇ 10 ⁇ 6 mol to 1 ⁇ 10 ⁇ 3 mol, per mol of silver halide.
  • the fine-grain silver halide (fine silver halide grains) disclosed in Japanese Patent O.P.I. Publication No. 238444/1991 may preferably be added in the course of from the step of chemical ripening to the step of coating.
  • the fine-grain silver halide may preferably be added in an amount of not more than 1/100 d mol per mol of twinned grains where an average grain diameter of the twinned grains is represented by d ( ⁇ m), more preferably in an amount ranging from 1/20,000 d to 1/300 d mol per mol of mother grains, and most preferably from 1/5,000 d to 1/500 d mol per mol of mother grains.
  • the fine-grain silver halide in the present invention may be added at any steps of from the step of chemical ripening to the step right before coating. It may preferably be added at the step of chemical ripening.
  • the fine-grain silver halide may particularly preferably be added before the addition of a sulfur sensitizer or within 30 minutes after the addition of a sulfur sensitizer.
  • an antifoggant and a stabilizer may be added for the purposes of stabilizing emulsion performance and preventing fog.
  • the additives used in the present invention can be added by the dispersion method as described in RD308119, paragraph XIV.
  • the light-sensitive material of the present invention may also be provided with the auxiliary layers such as filter layers and intermediate layers as described in RD308119, paragraph VII-K.
  • the light-sensitive material used in the present invention may have various layer structures such as regular layer order, inverse layer order or unit structure as described in the above RD308119, paragraph VII-K.
  • the present invention can be preferably applied to various color light-sensitive materials as typified by color negative films for general use or motion picture, color reversal films for slide or television, color photographic papers, color positive films and color reversal papers.
  • the light-sensitive material of the present invention can be photographically processed by the conventional methods as disclosed in the above RD17643, pages 28-29, RD18716, page 615 and RD308119, paragraph XIX.
  • a silver iodobromide emulsion containing 2.0 mol% of silver iodide was prepared by double jet precipitation under conditions of 40°C, pH 8.0 and pAg 9.0, followed by washing with water to remove excess salts.
  • the resulting emulsion was comprised of grains with an average grain size of 0.27 ⁇ m and a grain size distribution [(standard deviation/average grain size) ⁇ 100] of 12.0%.
  • This emulsion was formed into an emulsion containing silver in an amount corresponding to 1,200 g in terms of silver nitrate, to give a seed emulsion A.
  • the seed emulsion A was in an amount of 4,160 g as a finished product.
  • a regular-crystal monodisperse emulsion Em-1 was prepared using the following three kinds of aqueous solutions, the following emulsion solution containing fine silver iodide grains and the seed emulsion A.
  • Aqueous solution a-1 Gelatin 231.9 g 10 vol% Methanol solution of the compound I shown below 30.0 ml 28% Ammonia water 1,056 ml Made up to 11,827 ml by adding water.
  • Aqueous solution a-2 AgNO3 1,587 g 28% Ammonia water 1,295 ml Made up to 2,669 ml by adding water.
  • Aqueous solution a-3 KBr 1,572 g Made up to 3,774 ml by adding water.
  • Emulsion solution a-4 containing fine silver iodide grains Fine-grain silver iodide emulsion 1,499.3 g 4-Hydroxy-6-methyl-1,3,3a,7-tetrazaindene 5.2 g
  • aqueous solution a-1 having the above composition, vigorously stirred at a temperature of 60°C, the emulsion A was added in an amount corresponding to 0.40 mol, and the pH and pAg were adjusted using acetic acid and an aqueous KBr solution.
  • an octahedral regular crystal monodisperse silver iodobromide emulsion with an average grain size of 1.0 ⁇ m, an average silver iodide content of 8.0 mol% and a grain size distribution of 11% was obtained.
  • Em-1 This emulsion was designated as Em-1.
  • Table 3 Addition pattern of a-2 Time (min) Rate of addition (ml/min) 0 12.2 25.6 13.0 42.6 12.9 43.9 8.4 67.5 11.0 97.3 14.8 97.7 20.6 105.0 22.3 105.4 25.4 112.3 32.1 112.6 35.1 129.4 90.3 145.7 194.2 145.7 200.5 147.4 203.9
  • Table 4 Addition pattern of a-3 Time (min) Rate of addition (ml/min) 0 10.9 25.6 11.7 42.6 11.6 43.9 7.6 97.3 13.3 97.7 18.6 105.0 20.0 105.0 36.5 112.0 56.2 112.3 60.6 121.2 106.0 121.4 91.4 132.4 263.3 132.7 141.8 147.4 230.0
  • Table 5 Addition pattern of a-4 Time (min) Rate of addition (ml/min) 0 0 43.9 0 43.9 73.6 51.7 80.6 52.5 28.5 84.3 40.4 84.9 11.6 97.7 13.0 105.0 14.1 10
  • a monodisperse spherical seed emulsion B was prepared using the following solutions A1 to D1 by the method disclosed in Japanese Patent O.P.I. Publication No. 6643/1986.
  • A1 Ossein gelatin 150 g Potassium bromide 53.1 g Potassium iodide 24 g Made up to 7.2 lit. by adding water.
  • B1 Silver nitrate 1,500 g Made up to 6 lit. by adding water.
  • C1 Potassium bromide 1,327 g 1-Phenyl-5mercaptotetrazole (dissolved using methanol) 0.3 g Made up to 3 lit. by adding water.
  • D1 Ammonia water (28%) 705 ml
  • the solution D1 was added in 20 seconds, followed by ripening for 5 minutes.
  • KBr was in a concentration of 0.071 mol/lit.
  • ammonia was in a concentration of 0.63 mol/lit.
  • the resulting seed emulsion B was observed using an electron microscope to reveal that it was a monodisperse spherical emulsion comprised of grains with an average grain size of 0.36 ⁇ m and a grain size distribution of 18%.
  • a twinned monodisperse emulsion Em-2 according to the present invention was prepared using the following seven kinds of solutions.
  • Ossein gelatin 268.2 g Distilled water 4.0 lit Polyisopropylene-polyethyleneoxy-disuccinic acid ester sodium salt 10% methanol solution 1.5 ml Seed emulsion B 0.332 mol Aqueous 28% by weight ammonia solution 528.0 ml Aqueous 56% by weight acetic acid solution 795.0 ml Methanol solution containing 0.001 mol of iodide 50.0 ml Made up to 5,930.0 ml using distilled water.
  • Aqueous 3.5N ammoniacal silver nitrate solution (Its pH was adjusted to 9.0 using ammonium nitrate)
  • Fine-grain emulsion comprised of 3% by weight of gelatin and silver iodide grains (average grain sizes: 0.05 ⁇ m) 2.39 mol
  • Fine-grain emulsion comprised of silver iodobromide grains (average grain size: 0.04 ⁇ m) containing 1 mol% of silver iodide, prepared in the same manner as the fine-grain silver iodide emulsion described for the solution D. 6.24 mol
  • the temperature was controlled to be 30°C.
  • Aqueous 56% by weight acetic acid solution To the solution A maintained at 70°C in a reaction vessel, the solutions B, C and D were added by double jet precipitation over a period of 133 minutes, and thereafter the solution E was subsequently added alone at a constant rate over a period of 12 minutes to make the seed grains grow into 1.2 ⁇ m grains.
  • the solutions B and C were added by accelerated flow rate precipitation, so accelerated with respect to time as to be in accordance with the critical growth rate, at an appropriate rate of addition so that no minute grains other than the growing seed grains were produced and no emulsion became polydisperse as a result of Ostwald ripening.
  • the solution D i.e., the fine-grain silver iodide emulsion was fed while its feed rate ratio (molar ratio) to the aqueous ammoniacal silver nitrate solution was changed with respect to grain size (time of addition) as shown in Table 6.
  • a core/shell silver halide emulsion having a multiple structure was thus prepared.
  • the pAg and pH in the course of the growth of grains were controlled as also shown in Table 6.
  • the pAg and pH were measured by a conventional method, using a silver sulfide electrode and a glass electrode.
  • the emulsion grains thus obtained were observed using an electron microscope to reveal that they were comprised of edge-round octahedral twinned monodisperse grains deformed extendedly in the direction of twin planes, which were comprised of the twinned grains by 100% and in which their twin-plane percentage of grains having two or more parallel twin planes was 65%, grain size distribution was 14%, average grain size was 1.2 ⁇ m and average aspect ratio was 1.3.
  • a monodisperse spherical seed emulsion C was prepared in the following way.
  • C Ossein gelatin 32.2 g Potassium bromide 840 g Made up to 1.6 lit. by adding water.
  • the pH was adjusted to 6.0, followed by desalting according to a conventional method to give a seed emulsion.
  • This seed emulsion was observed using an electron microscope to reveal that it was a spherical emulsion comprised of grains with an average grain size of 0.318 ⁇ m, having two twin planes parallel to each other.
  • An octahedral twinned-crystal monodisperse emulsion Em-3 according to the present invention was prepared using the following seven kinds of solutions.
  • Ossein gelatin 268.2 g Distilled water 4.0 lit Polyisopropylene-polyethyleneoxy-disuccinic acid ester sodium salt 10% methanol solution 1.5 ml Seed emulsion C 0.286 mol Aqueous 28% by weight ammonia solution 528.0 ml Aqueous 56% by weight acetic acid solution 795.0 ml Methanol solution containing 0.001 mol of iodide 50.0 ml Made up to 5,930.0 ml using distilled water.
  • Aqueous 3.5N ammoniacal silver nitrate solution (Its pH was adjusted to 9.0 using ammonium nitrate)
  • Fine-grain emulsion comprised of 3% by weight of gelatin and silver iodide grains (average grain sizes: 0.05 ⁇ m) 2.39 mol
  • Fine-grain emulsion comprised of silver iodobromide grains (average grain size: 0.04 ⁇ m) containing 1 mol% of silver iodide, prepared in the same manner as the fine-grain silver iodide emulsion described for the solution D. 6.24 mol
  • the temperature was controlled to be 30°C.
  • Aqueous 56% by weight acetic acid solution To the solution A maintained at 70°C in a reaction vessel, the solutions B, C and D were added by double jet precipitation over a period of 163 minutes, and thereafter the solution E was subsequently added alone at a constant rate over a period of 12 minutes to make the seed grains grow into 1.0 ⁇ m grains.
  • the solutions B and C were added by accelerated flow rate precipitation, so accelerated with respect to time as to be in accordance with the critical growth rate, at an appropriate rate of addition so that no minute grains other than the growing seed grains were produced and no emulsion became polydisperse as a result of Ostwald ripening.
  • the solution D i.e., the fine-grain silver iodide emulsion was fed while its feed rate ratio (molar ratio) to the aqueous ammoniacal silver nitrate solution was changed with respect to grain size (time of addition) as shown in Table 7.
  • a core/shell silver halide emulsion having a multiple structure was thus prepared.
  • the pAg and pH in the course of the growth of grains were controlled as also shown in Table 7.
  • the pAg and pH were measured by a conventional method, using a silver sulfide electrode and a glass electrode.
  • the emulsion grains thus obtained were observed using an electron microscope to reveal that they were comprised of slightly deformed octahedral twinned monodisperse grains, which were comprised of the twinned grains by 100% and in which their twin-plane percentage of grains having two or more parallel twin planes was 85%, grain size distribution was 10% and average grain size was 1.0 ⁇ m.
  • Example 1 The emulsions Em-1 to Em-3 obtained in Example 1 was subjected to the following chemical ripening to give emulsions 1-A to 1-D.
  • a portion of the emulsion Em-1 was heated to 50°C and dissolved, which was then subjected to ripening with addition of 1.0 ⁇ 10 ⁇ 5 mol of sodium thiosulfate pentahydrate, 3.6 ⁇ 10 ⁇ 6 mol of chloroauric acid and 5.0 ⁇ 10 ⁇ 4 mol of ammonium thiocyanate.
  • the chloroauric acid and ammonium thiocyanate were used in the form of a mixed solution, which was added simultaneously with the sodium thiosulfate pentahydrate.
  • spectral sensitizers A, B and C were added in amounts of 1.3 ⁇ 10 ⁇ 4 mol, 1.6 ⁇ 10 ⁇ 5 mol and 1.3 ⁇ 10 ⁇ 4 mol, respectively, per mol of silver halide, for their adsorption for 15 minutes, followed by addition of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene as a stabilizer and then cooling to set to gel.
  • An emulsion 1-A was thus obtained.
  • a portion of the emulsion Em-1 was heated to 50°C and dissolved, to which the spectral sensitizers A, B and C were added in amounts of 1.3 ⁇ 10 ⁇ 4 mol, 1.6 ⁇ 10 ⁇ 5 mol and 1.3 ⁇ 10 ⁇ 4 mol, respectively, per mol of silver halide, for their adsorption for 15 minutes, followed by addition of 1.0 ⁇ 10 ⁇ 5 mol of sodium thiosulfate pentahydrate, 3.6 ⁇ 10 ⁇ 6 mol of chloroauric acid and 5.0 ⁇ 10 ⁇ 4 mol of ammonium thiocyanate to carry out ripening.
  • the chloroauric acid and ammonium thiocyanate were used in the form of a mixed solution, which was added simultaneously with the sodium thiosulfate pentahydrate. After ripening for 100 minutes, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added as a stabilizer, followed by cooling to set to gel. An emulsion 1-B was thus obtained.
  • a portion of the emulsion Em-1 was heated to 50°C and dissolved, to which, 10 minutes before the addition of spectral sensitizers, ammonium thiocyanate was first added in an amount of 4 ⁇ 10 ⁇ 4 mol per mol of silver halide. Then, the procedure as in the preparation of the emulsion 1-B was repeated, except that 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added as the nitrogen-containing heterocyclic compound in an amount of 1 ⁇ 10 ⁇ 4 mol per mol of silver halide at the same time with the addition of the spectral sensitizers. An emulsion 1-C was thus prepared.
  • a portion of the emulsion Em-1 was heated to 50°C and dissolved, to which, 10 minutes before the addition of spectral sensitizers, ammonium thiocyanate was first added in an amount of 4 ⁇ 10 ⁇ 4 mol per mol of silver halide. Then, the procedure as in the preparation of the emulsion 1-B was repeated, except that silver iodide grains comprised of a mixture of ⁇ -AgI and ⁇ -AgI with an average grain size of 0.06 ⁇ m were added as the fine silver iodide grains in an amount of 3 ⁇ 10 ⁇ 4 mol per mol of silver halide at the same time with the addition of the spectral sensitizers. An emulsion 1-D was thus prepared.
  • the emulsions 1-A to 3-D thus obtained were coated on subbed triacetyl cellulose film supports under the following coating formulation, followed by drying to give samples 101 to 112.
  • the amount of each compound added in the light-sensitive silver halide photographic materials is indicated as gram number per 1 m2.
  • the amount of silver halide is in terms of silver weight.
  • First layer Emulsion 2.0 Cyan coupler C-2 0.15 High-boiling solvent Oil-1 0.15 Gelatin 1.5
  • Second layer Protective layer Gelatin 1.0
  • coating aid Su-1 In addition to the foregoing compositions, coating aid Su-1, dispersion aid Su-2 and hardening agent H-1 were added.
  • the coated samples 101 to 112 were each subjected to wedge exposure using red light, and thereafter processed according to the following processing steps.
  • the characteristic curve was obtained, and maximum density relative sensitivity (a reciprocal of the amount of exposure that gives a density of fog + 0.1 is indicated as a relative value) and minimum amount of exposure that is necessary for obtaining a maximum density were determined.
  • Processing solutions used in the respective processing steps had the following composition.
  • Color developing solution 4-Amino-3-methyl-N-ethyl-N-( ⁇ -hydroxyethyl)aniline sulfate 4.75 g
  • Anhydrous sodium sulfite 4.25 g Hydroxylamine 1/2 sulfate 2.0 g
  • Anhydrous potassium carbonate 37.5
  • Sodium bromide 1.3 g
  • Trisodium nitrilotriacetate (monohydrate) 2.5 g Potassium hydroxide 1.0 g Made up to 1 liter by adding water and adjusted to pH 10.0 using sodium hydroxide.
  • - Bleaching solution Ferric ammonium ethylenediaminetetraacetate 100.0 g Diammonium ethylenediaminetetraacetate 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 ml Made up to 1 liter by adding water, and adjusted to pH 6.0 using ammonium water.
  • Fixing solution Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Made up to 1 liter by adding water, and adjusted to pH 6.0 using acetic acid.
  • Stabilizing solution - Formalin (aqueous 37% solution) 1.5 ml KONIDAX (trade name; available from KONICA CORPORATION) 7.5 ml Made up to 1 liter by adding water.
  • the coated samples 101 to 112 were each exposed in the minimum amount of exposure, previously determined, that is necessary for obtaining a maximum density, and the developing and stopping were carried out according to the following processing steps.
  • Table 8 shows the relative sensitivity, maximum density, extent of fogging by pressure (pressure mark), and development start points in cross areas of each sample.
  • Table 8 Sample No. Emulsion used *1 Relative sensi-tivity Maximum density *2 Pressure mark Percentage of development start point in cross area (%) Remarks 101 1-A 100 0.55 0.26 0 X 102 1-B 105 0.58 0.29 0 X 103 1-C 100 0.57 0.33 0 X 104 1-D 95 0.55 0.31 0 X 105 2-A 105 0.58 0.27 42 X 106 2-B 105 0.55 0.29 54 X 107 2-C 115 0.62 0.23 65 Y 108 2-D 110 0.60 0.20 76 Y 109 3-A 110 0.63 0.21 67 Y 110 3-B 125 0.66 0.18 80 Y 111 3-C 130 0.66 0.19 86 Y 112 3-D 125 0.68 0.16 83 Y X: Comparative Example Y: Present Invention *1 Sensitivity is indicated as a relative
  • the emulsions of the present invention have made it possible to achieve the performances that the light-sensitive materials have a high sensitivity and good color forming performance and cause less fogging by pressure.
  • Samples 201 to 209 were produced using each of the emulsions obtained in Example 2, as a high-speed red sensitive emulsion for the fifth layer in a multi-layer light-sensitive photographic material comprising a triacetyl cellulose film support and, successively provided thereon from the support side, layers having the composition shown below.
  • the amount of each compound added is indicated as gram number per 1 m2 unless particularly noted.
  • the amounts of silver halide and colloidal silver are in terms of silver weight.
  • Those of spectral sensitizers are each indicated as molar number per mol of silver.
  • Second layer Intermediate layer Compound SC-1 0.15 High-boiling solvent Oil-2 0.17 Gelatin 1.27
  • Third layer Low-speed red-sensitive emulsion layer Silver iodobromide emulsion (average grain size: 0.38 ⁇ m; silver iodide content: 8.0 mol%) 0.50 Silver iodobromide emulsion (average grain size: 0.27 ⁇ m; silver iodide content: 2.0 mol%) 0.21 Spectral sensitizer SD-1 2.8 ⁇ 10 ⁇ 4 Spectral sensitizer SD-2 1.9 ⁇ 10 ⁇ 4 Spectral sensitizer SD-3 1.9 ⁇ 10 ⁇ 5 Spectral sensitizer SD-4 1.0 ⁇ 10 ⁇ 4 Cyan coupler C-1 0.48 Cyan coupler C-2 0.14 Colored cyan coupler CC-1 0.021 DIR compound D-1 0.020 High-boiling
  • Components A:B:C is 50:46:4 (molar ratio)
  • Samples 202 to 209 were produced by replacing as shown in Table 9 the fifth-layer red-sensitive emulsion 1-B in the sample 201 with other emulsions used in Example 2.
  • the samples 201 to 209 thus obtained were each subjected to wedge exposure using white light, and thereafter processed according to the following processing steps in which three kinds of color developing solutions containing developing agents in different concentrations were used.
  • the characteristic curve was obtained, and logarithmic values of the amounts of exposure that correspond to a minimum density + 0.2 and a minimum density + 0.7 in red densities, i.e., log E (0.2) and log E (0.7), respectively, were determined.
  • the slope ⁇ of the characteristic curve was defined as shown below and the values thereof were calculated.
  • the ⁇ values of the samples processed using developing solutions I, II and III were determined as ⁇ I, ⁇ II and ⁇ III, respectively, and values of ⁇ I/ ⁇ II and ⁇ III/ ⁇ II were calculated. Results obtained are shown in Table 9.
  • Processing solutions used in the respective processing steps had the following composition.
  • Color developing solution I 4-Amino-3-methyl-N-ethyl-N-( ⁇ -hydroxyethyl)aniline sulfate 3.56 g
  • Anhydrous sodium sulfite 4.25 g Hydroxylamine 1/2 sulfate 2.0 g
  • Anhydrous potassium carbonate 37.5
  • Sodium bromide 1.3 g
  • Trisodium nitrilotriacetate (monohydrate) 2.5 g Potassium hydroxide 1.0 g Made up to 1 liter by adding water (pH: 10.1).
  • - Bleaching solution Ferric ammonium ethylenediaminetetraacetate 100.0 g Diammonium ethylenediaminetetraacetate 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 ml Made up to 1 liter by adding water, and adjusted to pH 6.0 using ammonium water.
  • Fixing solution Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Made up to 1 liter by adding water, and adjusted to pH 6.0 using acetic acid.
  • Stabilizing solution - Formalin (aqueous 37% solution) 1.5 ml KONIDAX (trade name; available from KONICA CORPORATION) 7.5 ml Made up to 1 liter by adding water.
  • dye images were formed by carrying out processing under the same conditions as in Processing A except that the color developing solution I was replaced with color developing solutions II and III shown below.
  • Color developing solution II 4-Amino-3-methyl-N-ethyl-N-( ⁇ -hydroxyethyl)aniline sulfate 4.75 g
  • Anhydrous sodium sulfite 4.25 g Hydroxylamine 1/2 sulfate 2.0 g
  • Sodium bromide 1.3 g Trisodium nitrilotriacetate (monohydrate) 2.5 g Potassium hydroxide 1.0 g Made up to 1 liter by adding water (pH: 10.1).
  • the samples making use of the emulsions of the present invention are characterized by causing a small change in the slope of the characteristic curve even with a change in concentration of the developing agent and hence giving a constant print quality.
  • the present invention can provide a silver halide photographic emulsion having a high sensitivity and high color forming performance and promissing a good processing stability and good pressure resistance.
  • it can provide a light-sensitive silver halide photographic material having a good processing stability and processing operability.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP19930101342 1992-02-01 1993-01-29 Photographische Silberhalogenidemulsion von hoher Empfindlichkeit und mit guter Verarbeitungsstabilität und Druckfestigkeit Expired - Lifetime EP0560036B1 (de)

Applications Claiming Priority (3)

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JP4620892 1992-02-01
JP46208/92 1992-02-01
JP04620892A JP3174839B2 (ja) 1992-02-01 1992-02-01 高感度で処理安定性・圧力耐性の優れたハロゲン化銀写真乳剤

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EP0560036A3 EP0560036A3 (en) 1995-01-11
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2206974A (en) * 1987-06-05 1989-01-18 Fuji Photo Film Co Ltd Silver halide photographic emulsions
EP0443475A2 (de) * 1990-02-19 1991-08-28 Konica Corporation Photographisches Silberhalogenidmaterial

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2206974A (en) * 1987-06-05 1989-01-18 Fuji Photo Film Co Ltd Silver halide photographic emulsions
EP0443475A2 (de) * 1990-02-19 1991-08-28 Konica Corporation Photographisches Silberhalogenidmaterial

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JP3174839B2 (ja) 2001-06-11
EP0560036A3 (en) 1995-01-11
DE69325195D1 (de) 1999-07-15
JPH05216147A (ja) 1993-08-27
DE69325195T2 (de) 1999-10-14

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