EP0660176B1 - Farbphotographisches lichtempfindliches Silberhalogenidmaterial - Google Patents

Farbphotographisches lichtempfindliches Silberhalogenidmaterial Download PDF

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Publication number
EP0660176B1
EP0660176B1 EP94309680A EP94309680A EP0660176B1 EP 0660176 B1 EP0660176 B1 EP 0660176B1 EP 94309680 A EP94309680 A EP 94309680A EP 94309680 A EP94309680 A EP 94309680A EP 0660176 B1 EP0660176 B1 EP 0660176B1
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EP
European Patent Office
Prior art keywords
grains
silver halide
grain
emulsion
silver
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP94309680A
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English (en)
French (fr)
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EP0660176A3 (de
EP0660176A2 (de
Inventor
Sadayasu C/O Konica Corporation Ishikawa
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Konica Minolta Inc
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Konica Minolta Inc
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Publication of EP0660176A3 publication Critical patent/EP0660176A3/de
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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
    • 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
    • G03C1/015—Apparatus or processes for the preparation of emulsions
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/07—Substances influencing grain growth during silver salt formation
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
    • G03C1/16—Methine and polymethine dyes with an odd number of CH groups with one CH group
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
    • G03C1/18—Methine and polymethine dyes with an odd number of CH groups with three CH groups
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/28—Sensitivity-increasing substances together with supersensitising substances
    • G03C1/29—Sensitivity-increasing substances together with supersensitising substances the supersensitising mixture being solely composed of dyes ; Combination of dyes, even if the supersensitising effect is not explicitly disclosed
    • 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
    • G03C2001/0055—Aspect ratio of tabular grains in general; High aspect ratio; Intermediate aspect ratio; Low aspect ratio
    • 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
    • G03C2001/0058—Twinned crystal
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/015—Apparatus or processes for the preparation of emulsions
    • G03C2001/0156—Apparatus or processes for the preparation of emulsions pAg value; pBr value; pCl value; pI value
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/03535—Core-shell grains
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/0357—Monodisperse emulsion
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G03C2001/03594—Size of the grains

Definitions

  • This invention relates to a silver halide color photographic light-sensitive material useful for the photographic field and, particularly, to a silver halide color photographic light-sensitive material high in sensitivity and excellent in latent image preservability.
  • h + and e - represent a free positive hole and a free electron produced upon exposure; hv represents a photon; and Ag 2 represents a reduction-sensitization nucleus. Based on assumption as above-mentioned, it can be considered that a reduction-sensitization nucleus can prevent efficiency deterioration due to the recombination of an electron and a positive hole so as to contribute to an increase in sensitivity.
  • the following processes have been known; namely, a process in which a reduction-sensitization is applied to the surface of a silver halide grain or it is applied in the course of growing silver halide grains, or a process in which a seed crystal is reduction-sensitized in advance when making use of the seed crystal for growing up a grain.
  • JP OPI Publication Japanese Patent Publication Open to Public Inspection
  • JP OPI Publication Nos. 48-87825/1973 and 57-179835/1982.
  • JP OPI Publication Nos. 48-87825/1973 and 57-179835/1982.
  • JP OPI Publication Nos. 48-87825/1973 and 57-179835/1982.
  • JP OPI Publication Nos. 48-87825/1973 and 57-179835/1982.
  • JP OPI Publication Japanese Patent Publication Open to Public Inspection
  • a dye positive hole remaining on the surface of silver halide may destroy a latent image formed on the silver halide surface.
  • a reduction-sensitization cannot be effected, because a reduction-sensitization nucleus present inside a grain does not effectively trap a dye positive hole on the surface of the grain.
  • JP OPI Publication Nos. 2-105139/1990, 2-108038/1990, 2-125247/1990, 2-127636/1990, 2-130545/1990, 2-150837/1990, 2-168247/1990, 2-135043/1990, 4-232945/1992 and 4-32832/1992 disclose the techniques applicable particularly to a spectrally sensitized silver halide emulsion, such as that for increasing sensitivity, for improving preservability and for improving pressure resistance property.
  • a silver halide color photographic light-sensitive material comprising a support bearing thereon at least one silver halide emulsion layer comprising silver halide grains, wherein the silver halide grain emulsion comprises tabular-shaped silver halide grains having a even number of twinned crystal planes parallel to the major faces thereof and an aspect ratio of less than 5, the tabular grains accounting for not less than 50% of the total projected area of the grains contained in the layer and satisfying the following requirements (A) to (C);
  • the silver halide grains contained in a silver halide emulsion of the invention are to be tabular-shaped grains.
  • Tabular-shaped grains are categorized crystallographically as a twinned crystal.
  • a twinned crystal is a silver halide crystal having not less than one twinned crystal planes in the grain thereof.
  • the classifications of the twinned crystal shapes are detailed in Klein & Moiser, Photographishe Korrespondenz, Vol. 99, p. 100 and, ibid., Vol. 100, p. 57, respectively.
  • a tabular-shaped grain has an even number of twin planes each parallel to the major face of the grain.
  • the twin planes can be observed through a transmission type electron microscope.
  • the specific observation method is as follows. First, a sample is prepared in such a manner that a silver halide photographic emulsion containing tabular-shaped grains is coated on a support so that the major face of the tabular-shaped grains are oriented in parallel with the support. The resulting sample is cut and scraped by making use of a diamond cutter into a thinned cut piece having a thickness of the order of 0.1 ⁇ m. When observing the resulting cut piece through a transmission type electron microscope, the presence of the twinned crystal planes can be confirmed.
  • the twin plane distance is the shortest distance between two or more twin planes parallel to the major face.
  • the twin plane distance is the distance between two twin planes in a grain when the grain has two twin planes, and it is the shortest distance among the distances between twin planes in a grain when the grain has four or more even-numbered twin planes.
  • a mean value of twin plane distances can be obtained in the following manner.
  • a cut piece through a transmission type electron microscope as mentioned above, not less than 1000 tabular-shaped grains having a section almost vertical to the major face are selected at random.
  • the shortest distance between two twinned crystal planes is obtained from each grain, and the mean distance between twinned crystal planes of the grains can be obtained as an arithmetic mean of the shortest distances.
  • a variation coefficient (x) of twin plane distances herein means a fluctuation of the twin plane distances of tabular-shaped grains. It is expressed in terms of a percentage obtained by dividing a standard deviation value of the twin plane distances by a mean value of the twin plane distances.
  • the mean twin plane distance is from 0.01 ⁇ m to 0.05 ⁇ m and, more preferably, from 0.013 ⁇ m to 0.03 ⁇ m.
  • the mean thickness of tabular-shaped grains useful in the emulsion of the invention can be obtained in such a manner that the thickness of each grain is obtained by observing the cut piece of a subject sample through a transmission type electron microscope in the same manner as described above and the mean thickness of the grains can be obtained by averaging out the thickness of the grains as an arithmetic mean.
  • the mean thickness of the tabular-shaped grains is from 0.05 ⁇ m to 1.5 ⁇ m and, more preferably from 0.15 ⁇ m to 1.0 ⁇ m.
  • a variation coefficient (y) of thicknesses of tabular-shaped grains herein means fluctuation of the thicknesses among the tabular-shaped grains. It is expressed in terms of a percentage obtained by dividing a standard deviation of grain thickness by a mean value of the grain thickness.
  • Tabular-shaped grains useful in the emulsion of the invention have the following relations;
  • a variation coefficient (x) of distances between the twin planes and a grain-thickness variation coefficient (y) there is a relation of 0.7 ⁇ y/x ⁇ 2.0, preferably, 0.8 ⁇ y/x ⁇ 1.6 and, most preferably, 0.9 ⁇ y/x ⁇ 1.3.
  • a tabular-shaped grain useful in the emulsion of the invention is defined as that having an aspect ratio (a grain-size/a grain thickness) of lower than 5, preferably not higher than 4.0.
  • the grain-size of a silver halide grain is indicated by a diameter equivalent to that of a circle having the same area as the projected area of the silver halide grain (i.e., a circular-equivalent diameter). It is preferably from 0.1 to 5.0 ⁇ m and, more preferably from 0.2 to 2.0 ⁇ m.
  • a grain-size can be obtained, for example, in the following manner.
  • a subject grain is magnified 10,000 to 70,000 times through an electron microscope and then photographed.
  • the resulting diameter of the grain coming out on a print or the projected area of the grain is practically measured, provided that the number of the grains subject to the measurement is to be not less than 1,000 at random.
  • An average grain-size r is herein defined as a grain-size ri when maximizing a product ni ⁇ ri 3 in which ni represents a frequency of grains having a grain-size ri, provided that a significant figure is three columns and the figure in the lowest column is rounded.
  • a silver halide emulsion of the invention preferably comprises a monodisperse type silver halide emulsion.
  • the weight of silver halide having a grain-size within the scope of ⁇ 20% of an average grain-size r is to be, preferably, not less than 60% of the weight of the whole silver halide grain, more preferably, not less than 70% and, particularly, not less than 80%.
  • the distance between twin planes may be controlled by suitably selecting the following various factors, which may give an influence on the supersaturated state in the nucleation stage, including for example a gelatin concentration, a gelatin type, a temperature, an iodide ion concentration, a pBr, a pH, an ion-supply rate, an rpm for stirring and a combination thereof.
  • various factors which may give an influence on the supersaturated state in the nucleation stage, including for example a gelatin concentration, a gelatin type, a temperature, an iodide ion concentration, a pBr, a pH, an ion-supply rate, an rpm for stirring and a combination thereof.
  • the higher supersaturation in the nucleation stage the smaller becomes the distance between twin planes.
  • Silver halide grains useful in the emulsion of the invention are internally reduction-sensitized, thus, an internal portion of the grain is subjected to reduction sensitization.
  • the word internal portion herein means an inner portion of 90% or less and preferably 70% or less of the grain, based on the volume.
  • silver halide grains useful in the emulsion of the invention are subjected to reduction sensitization before 90% (preferably, 70%) of the ultimate grain volume of the grain is reached.
  • the above-mentioned reduction-sensitization is carried out by adding a reducing agent to a silver halide emulsion or a mixed solution during the growth of the grains. Or, it is carried out by ripening or grain-growing a silver halide emulsion or a mixed solution for growing grains under the conditions of a low pAg of not higher than pAg 7 or a high pH of not lower than pH 7. A process carried out by making combination use of the above-mentioned methods is preferred.
  • Preferable reducing agents include, for example, thiourea dioxide, ascorbic acid and the derivatives thereof, and stannous salt.
  • Other suitable reducing agents include, for example, a borane compound, a hydrazine derivative, formamidine sulfinic acid, a silane compound, an amine and a polyamine, and a sulfite. They may be added preferably in an amount of from 10 -2 to 10 -8 mols per mol of silver halide used therein.
  • a silver salt may be added.
  • a water-soluble silver salt is preferred.
  • silver nitrate is preferred.
  • a high pH ripening treatment may be carried out, for example, by adding an alkaline compound to a silver halide emulsion or a mixed solution for growing grains.
  • the alkaline compounds applicable thereto include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and ammonia.
  • alkaline compounds other than ammonia may preferably be used, because the ammonia effect may be deteriorated.
  • the process of adding a silver salt or an alkaline compound for making a reduction-sensitization may be rush added or may also be added by taking a given time. In the latter instance, it may be added at a certain flow rate or may also be added by varying acceleratedly the flow rate thereof. It is also allowed to add a necessary amount divided into several parts for the addition.
  • the silver salts or an alkaline compound for a reduction-sensitization may be made present in the reaction chamber, or they are mixed in a soluble halide solution and then they may be added together with the halide. Besides the above, they may further be added, separately from the soluble silver salt and soluble halide.
  • a process of growing grains from seed grains is preferably used.
  • an aqueous solution containing protective colloid and seed grains are made present in a reaction chamber in advance and silver ions, halogen ions or silver halide fine grains are supplied thereto, so that the seed grains are grown up to final grains.
  • the seed grains may be prepared by a single-jet process or a controlled double-jet process, which have been well-known in the art.
  • Any halogen composition of the seed grains may be used therein, including any one of silver bromide, silver iodide, silver chloride, silver iodobromide, silver chloroiodide, silver chlorobromide and silver chloroiodobromide. Among them, silver bromide and silver iodobromide are preferred. In the case of silver iodobromide, the average silver iodide content thereof is preferably within the range of from 1 mol% to 20 mol%.
  • a value of x is preferably as small as possible.
  • silver halide grains are preferably grown from seed grains having narrow distance(s) between twin planes.
  • the pBr of a reaction mother liquor is maintained at 2.5 or less (more preferably, from 1.0 to 2.0) at the nucleation stage in the course of forming seed grains to decrease the distance between twin planes of the seed grains. It is further preferable that the resulting nucleus grains are subjected to ripening to dissolve grains other than those having an even number of twin planes.
  • the ripening is carried out at 30°C (preferably, from 18 to 26°C) and in the presence of a silver halide solvent such as ammonia, thioether, or thiocyanate.
  • a silver halide solvent such as ammonia, thioether, or thiocyanate.
  • the amount thereof may be 0.10 mol/l or more, preferably from 0.2 to 2.0 mol/l.
  • x is preferably 20% or less, more preferably 15% or less.
  • ripening treatment at a low pAg is carried out by adding silver nitrate thereto, that is to say, the ripening treatment is preferably carried out by adding silver nitrate in the course between the point of time immediately before desalting the seed grain emulsion and the time after completing the desalting treatment thereof. It is particularly preferable to add silver nitrate after desalting and then ripening the seed grains.
  • the ripening temperature is preferably kept not lower than 40°C, more preferably from 50°C to 80°C.
  • the ripening time is preferably taken for not shorter than 30 minutes, more preferably from 50 to 150 minutes.
  • An oxidizing agent may be applied to a silver halide emulsion of the invention.
  • the oxidizing agent applicable thereto includes, for example, the following ones:
  • Hydrogen peroxide (in an aqueous solution) and the adducts thereof such as H 2 O 2 , NaBO 2 -H 2 O 2 -3H 2 O, Na 4 P 2 O 7 -2H 2 O 2 and 2Na 2 SO 4 -H 2 O 2 -2H 2 O; peroxy acid salt such as K 2 S 2 O 3 , K 2 C 2 O 3 , K 4 P 2 O 3 and K2[Ti(O 2 )C 2 O 4 ]-3H 2 O; peracetic acid; ozone; iodine; bromine; and a thiosulfonic acid derivative.
  • the above-mentioned oxidizing agent may be added preferably in an amount of from 10 -2 to 10 -5 mols per mol of a reducing agent used therein, provided, however, that such an adding amount thereof as mentioned above may be varied, according to the kind of reducing agent used, the conditions of reduction-sensitization, addition time of an oxidizing agent and the condition of adding the oxidizing agent.
  • the oxidizing agent may be added optimally at a time during the course of preparing a silver halide emulsion. It is also allowed to add it in advance of adding a reducing agent.
  • reducible substances as mentioned above are those capable of reducing the above-mentioned oxidizing agent, and the reducible substances include, for example, a sulfinic acid, a di- and trihydroxybenzene, a chroman, a hydrazine and hydrazide, a p-phenylenediamine, an aldehyde, an aminophenol, an endiol, an oxime, a reducible sugar, a phenidone, a sulfite and an ascorbic acid derivative.
  • These reducible substances may be added preferably in an amount of from 10 -3 to 10 3 mols per mol of an oxidizing agent used.
  • a silver halide grain useful in the emulsion of the invention comprises substantially silver iodobromide. However, it is allowed to contain silver chloride therein, provided that the effects of the invention shall not be deteriorated thereby.
  • the silver halide grains useful in the emulsion of the invention have a silver iodobromide phase comprising not less than 5 mol% of silver iodide inside the grain. It is more preferable that the silver halide grain has a silver iodobromide phase comprising silver iodide in a proportion of from 10 mol% to 40 mol%.
  • Silver halide grains useful in the emulsion of the invention are preferably the so-called core/shell type grains comprising silver iodide localized inside the grain.
  • a silver halide grain useful in the emulsion of the invention is preferably comprised of silver iodobromide having an average silver iodide content within the range of, preferably, from 1 mol% to 20 mol% and, more preferably, from 3 to 15 mol%.
  • the means for preparing a silver halide emulsion useful in the emulsion of the invention a variety of means well-known in the field of the art may be used.
  • the following means can be used in any combination, namely, a single-jet precipitation, a controlled double-jet precipitation, a controlled triple-jet precipitation and so forth.
  • a pAg value as mentioned above is preferably from 7.0 to 10.5, more preferably from 7.5 to 10.0 and, further preferably from 8.0 to 9.5.
  • the value of y is preferably as small as possible to meet the requirement.
  • the pAg is preferably from 7.5 to 10.0, more preferably from 8.0 to 9.5.
  • y is 20% or less, preferably 15% or less.
  • JP OPI Publication Nos. 54-48521/1979 and 58-49938/1983 may be referred to.
  • silver halide solvent such as ammonia, thioether and thiourea, or no silver halide solvent may be used, when preparing silver halide grains useful in the emulsion of the invention.
  • Silver halide grains useful in the invention may be either those capable of forming a latent image mainly on the surface thereof, or those capable of forming a latent image mainly inside the grain.
  • a surface latent image-forming silver halide emulsion is preferable.
  • Silver halide grains useful in the invention are prepared in the presence of a dispersion medium, that is, in an aqueous solution containing the dispersion medium.
  • a dispersion medium that is, in an aqueous solution containing the dispersion medium.
  • an aqueous solution containing a dispersion medium herein means an aqueous solution in which a protective colloid is formed of a substance capable of constituting hydrophilic colloid (that is, for example, a substance capable of serving as a binder) such as gelatin, and it also preferably means an aqueous solution containing a protective colloidal gelatin.
  • the gelatin When gelatin is used as the above-mentioned protective colloid, the gelatin may be either lime-treated or acid-treated. Details of the gelatin preparation is referred to Arthur Veis, The Macromolecular Chemistry of Gelatin, Academic Press, 1964.
  • Hydrophilic colloids other than gelatin which can be used as a protective colloid, include, for example, the following substances; namely, a protein such as a gelatin derivative, a graft polymer of gelatin and other polymer, albumin and casein; a cellulose derivative such as hydroxyethyl cellulose, carboxymethyl cellulose and a cellulose sulfate; a sugar derivative such as sodium alginate and a starch derivative; and various kinds of synthetic hydrophilic macromolecular substance such as a monomer or copolymer of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinyl pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole or polyvinyl pyrazole.
  • a protein such as a gelatin derivative, a graft polymer of gelatin and other polymer, albumin and casein
  • a cellulose derivative such as hydroxyethyl cellulose, carb
  • gelatin In the case of making use of gelatin, it is preferable to make use of those having a jelly strength of not lower than 200 in AGI's method.
  • Silver halide grains useful in the invention can contain a metal ion inside the grain and/or on the surface of the grain by adding a metal ion to the grain by making use of at least one chosen from a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iron salt, a rhodium salt, an iridium salt and an indium salt (including the complex salts thereof), in the course of forming the grain and/or growing the grain.
  • a metal ion inside the grain and/or on the surface of the grain by adding a metal ion to the grain by making use of at least one chosen from a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iron salt, a rhodium salt, an iridium salt and an indium salt (including the complex salts thereof), in the course of forming the grain and/or growing the grain.
  • a silver halide grain useful in the invention may be a grain from which any unnecessary soluble salts are optionally removed after completing the growth of the silver halide grain.
  • a desalting treatment can be performed at any point in the course of preparing silver halide.
  • they can be removed in the method described in Research Disclosure (hereinafter abbreviated to RD) No. 17643, Article II.
  • a soluble salt from an emulsion after completing precipitation or physical ripening
  • it is allowed to make use of a noodle-washing method in which gelatin is gelled, or to make use of a flocculation method in which an inorganic salt, an anionic surfactant, an anionic polymer (such as polystyrene sulfonic acid) or a gelatin derivative (such as acylated gelatin and carbamoylated gelatin) is utilized.
  • a noodle-washing method in which gelatin is gelled
  • an anionic surfactant such as polystyrene sulfonic acid
  • a gelatin derivative such as acylated gelatin and carbamoylated gelatin
  • a silver halide grain useful in the invention can be chemically sensitized in an ordinary method.
  • a sulfur sensitization method, a selenium sensitization method, a noble-metal sensitization method in which gold or other noble metal compound is used, and so forth may be used alone or in combination.
  • Silver halide grains useful in the invention can be spectrally sensitized to any desired wavelength region by making use of a dye that has been known as a sensitizing dye in the photographic field.
  • a sensitizing dye as mentioned above may be used alone or in combination.
  • an emulsion is to contain, together with a sensitizing dye, a supersensitizer capable of enhancing the sensitizing effect of a sensitizing dye, that is a dye having no spectral sensitizing function in itself, or, that is a compound substantially incapable of absorbing any visible rays of light.
  • An antifoggant or stabilizer may be added to a silver halide grain emulsion of the invention.
  • a binder applicable to the invention it is advantageous to use gelatin.
  • An emulsion layer and other hydrophilic colloidal layers may be hardened and, a plasticizer and a water-insoluble or water-soluble synthetic polymer dispersion (so-called a latex) may also be contained therein.
  • a coupler is used in an emulsion layer of a silver halide color photographic light-sensitive material of the invention. It is also allowed to use a competing coupler having a color correction effect and a compound capable of releasing such a photographically useful fragment as a development accelerator, a developing agent, a silver halide solvent, a color toner, a layer hardener, a foggant, an antifoggant, a chemical sensitizer, a spectral sensitizer and a desensitizer, through a coupling reaction with the oxidized product of a developing agent.
  • a competing coupler having a color correction effect and a compound capable of releasing such a photographically useful fragment as a development accelerator, a developing agent, a silver halide solvent, a color toner, a layer hardener, a foggant, an antifoggant, a chemical sensitizer, a spectral sensitizer and a desensitizer, through a coupling reaction with the
  • an auxiliary layer such as a filter layer, an antihalation layer and an anti-irradiation layer may be provided.
  • a filter layer such as a filter layer, an antihalation layer and an anti-irradiation layer
  • an emulsion layer it is also allowed to contain a dye capable of being dissolved out of a light-sensitive material or being bleached, in the course of carrying out the development treatment.
  • a matting agent a lubricant, an image stabilizer, a formalin scavenger, a UV absorbent, a fluorescent whitening agent, a surfactant, a development accelerator and a development retarder.
  • a sheet of paper laminated thereon with eg. polyethylene, polyethylene terephthalate film, baryta paper or cellulose triacetate film may be used.
  • Solution A was violently stirred at 40°C and Solutions B and C were added to Solution A in a double-jet method for 7 minutes so as to produce nuclei.
  • the pBr of the mixture was kept at 1.60. Thereafter, the temperature of the mixture was lowered to be 20°C by taking 30 minutes. Further, Solution D was added thereto by taking one minute and, successively, the mixture thereof was ripened for 5 minutes. While the mixture was being ripened, the KBr concentration and ammonia concentration were 0.03 mols/liter and 0.66 mols/liter, respectively.
  • the pH was adjusted to be 6.0 and a desalting treatment was carried out in an ordinary method.
  • an aqueous 10 wt% gelatin solution was then stirred to be dispersed at 60°C for 30 minutes. Thereafter, distilled water was added thereto, so that 5360 g of an emulsion was made up.
  • the average grain-size of the seed emulsion grains was 0.217 ⁇ m and that the grains having two parallel crystal planes amounted to 75% (in number) of the whole grain.
  • Tabular-shaped emulsion EM-1 of the invention was prepared by making use of the following 7 kinds of solutions, (among them, Solution A contained seed emulsion T-2 subjected to a low pAg ripening treatment).
  • Solution B An aqueous 0.5N silver nitrate solution 948 ml
  • Solution C Potassium bromide 52.88 g Ossein gelatin 35.55 g
  • An aqueous solution containing 7.06 mols of silver nitrate and an aqueous solution containing 7.06 mols of potassium iodide were each added in an amount of 2000ml to 5000ml of a 6.0 wt%-gelatin solution containing 0.06 mols of potassium iodide by taking 10 minutes, respectively.
  • the pH and temperature were controlled with nitric acid so as to be 2.0 and 40°C while the fine grains were being produced. After the grains were formed, the pH was adjusted with an aqueous sodium carbonate solution so as to be 6.0. The finished amount by weight was proved to be 12.53 kg.
  • Solution A was added to a reactor vessel.
  • Solutions B through F were added thereto, with stirring, by a double-jet method in accordance with the combination shown in Table 1, and the seed crystals were grown up, so that a core/shell type silver halide grain emulsion was prepared.
  • the temperature and pAg of each of the solutions were controlled to be 75°C and 8.8 in the reactor vessel, respectively.
  • Solution G was added when necessary.
  • Table 1 shows the grain-sizes at the points of time corresponding to each of the time of adding the solutions, and the silver iodide contents of the silver halide phases capable of forming each of the grain surfaces.
  • a desalting treatment was carried out according to the method described in JP Application No. 3-41314/1991 and a redispersion treatment was carried out by adding gelatin.
  • the pH and pAg of the emulsion were controlled to be 5.80 and 8.06 at 60°C, respectively. From the electronmicrograph of the resulting emulsion grains, the resulting grains were proved to be the tabular-shaped grains having an average grain-size of 1.23 ⁇ m, an average aspect ratio of 2.0 and an average grain-size distribution of 12.0%.
  • Emulsion EM-2 was prepared in the same manner as in the process of preparing emulsion EM-1, except that 10 ml of an aqueous solution containing 2.0 g of potassium hydroxide was added to seed emulsion T-1 at the point of time 65 minutes after starting the addition of a solution for growing the crystals so that the pH of the emulsion was adjusted to be 8.7 in a reaction system. At the point of time when completing the addition of the reactive solution for growing the crystals, the pH of the emulsion was lowered to be 5.8.
  • the grains were proved to be the tabular-shaped grains having an average grain-size of 1.24 ⁇ m, an average aspect ratio of 2.1 and a grain-size distribution of 12.5%.
  • emulsion EM-3 for comparative use was prepared in the same manner as in the case of emulsion EM-1, except that seed emulsion T-1 was used and the pAg in the course of growing the crystals was controlled to be 11.0.
  • emulsion EM-4 for comparison use was prepared in the same manner as in emulsion EM-2, except that potassium hydroxide was not added in the course of growing the crystals.
  • Emulsions EM-5 through EM-9 were each prepared by replacing seed emulsions, by changing the conditions for ripening the seed emulsions at a low pAg, by omitting or applying a high-pH ripening treatment in the course of growing the crystals, by altering the positions of adding potassium hydroxide in the course of growing the crystals or by varying the pAg control values in the course of growing the crystals.
  • twin planes and the grain thickness were observed at a temperature of -120°C, through a transmission type electron microscope Model JEM-2000FX manufactured by Japan Electron Co., Ltd at an acceleration voltage of 200KV.
  • Table 2 collectively shows the conditions for preparing emulsions EM-1 through EM-9 and the results obtained.
  • the KOH adding positions represent in terms of (the volume of a grain at the point of time when adding KOH / the volume of the grain after growing the crystal) ⁇ 100; and y/x represents a variation coefficient (y) of a grain thickness / a variation coefficient (x) of a distance between twinned crystal planes.
  • a silver halide color photographic light-sensitive material of the invention was prepared in the following manner. An optimum gold-sulfur sensitization was applied to each of emulsions EM-1 to EM-9. By making use of the resulting emulsions, each of the layers having the following compositions was formed on a tricetyl cellulose support in order from the side of the support.
  • the constitution of silver halide color photographic light-sensitive material sample 101 of the invention (in which emulsion EM-1 of the invention was used) was as follows.
  • Layer 1 An antihalation layer Black colloidal silver 0.16 UV absorbent (UV-1) 0.20 High boiling solvent (OIL-1) 0.16 Gelatin 1.60
  • Layer 2 An intermediate layer Compound (SC-1) 0.14 High boiling solvent (OIL-2) 0.17 Gelatin 0.80
  • Layer 3 A low-speed red-sensitive layer Silver iodobromide emulsion A 0.15 Silver iodobromide emulsion B 0.35 Sensitizing dye (SD-1) 2.0x10 -4 Sensitizing dye (SD-2) 1.4x10 -4 Sensitizing dye (SD-3) 1.4x10 -5 Sensitizing dye (SD-4) 0.7x10 -4 Cyan coupler (C-1) 0.53 Colored cyan coupler (CC-1) 0.04 DIR compound (D-1) 0.025 High boiling solvent (OIL-3) 0.48 Gelatin 1.09
  • Layer 4 A medium-speed red-sensitive layer Silver iodobromide emulsion B 0.30 Silver iodobromide e
  • coating aid Su-1 for example, coating aid Su-2, dispersion aid Su-2, a viscosity controller, layer hardeners H-1 and H-2, stabilizer ST-1, antifoggants AF-1 having an average molecular weight of 10,000 and AF-2 having an average molecular weight of 1,100,000, and preservative DI-1, respectively.
  • Emulsion Average AgI content (in mol%) Average grain-diameter (in ⁇ m) Crystal shape Ratio of Diameter/ Thickness Remarks Emulsion A 4.0 0.41 Regular crystal 1 Emulsion B 6.0 0.57 Regular crystal 1 Emulsion C 6.0 0.75 Regular crystal 1 Emulsion D 6.0 1.16 Tabular twinned crystal 4 Emulsion E 6.0 1.30 Tabular twinned crystal 4
  • Silver halide color photographic light-sensitive material samples 102 to 109 were also prepared in the same manner as described above, except that emulsion EM-1 of sample 101 was replaced by emulsions EN-2 to EM-9 as shown in Table 4: Sample 102 103 104 105 106 107 108 109 Emulsion used EM-2 EM-3 EM-4 EM-5 EM-6 EM-7 EM-8 EM-9
  • compositions of the processing solutions used in the above-mentioned processing steps were as follows.
  • Each of the resulting samples was exposed (for 1/200") to red light (R) through a sensitometric wedge, and the resulting relative sensitivity and latent image preservability of the samples were evaluated.
  • the relative sensitivity of a fresh sample was obtained in such a manner that the sample was color-developed within one minute after exposure and a relative value of the reciprocal of the exposure amount capable of giving a density of Dmin (the minimum density)+0.15 is obtained as the relative sensitivity of the sample.
  • the sensitivity of the sample is indicated by a value relative to the sensitivity of sample 101 that is set to 100, (in other words, it means that the more is a value, the higher is the sensitivity.)
  • the latent image preservability of a sample was obtained in such a manner that the sample was exposed to light and then allowed to stand at a relative humidity of 80% for 7 days.
  • Sample Invention or Comparison Red-sensitive layer Real-time relative sensitivity Relative sensitivity obtained after preserving a latent image 101 Invention 100 92 102 Invention 101 93 103 Comparison 77 42 104 Comparison 97 61 105 Comparison 75 65 106 Comparison 76 67 107 Invention 99 86 108 Invention 100 88 109 Invention 102 99
  • samples 101, 102 and 107 to 109 each relating to the invention, which contained an emulsion of the invention, have a high sensitivity and are improved in latent image preservability.
  • sample 109 is particularly superior, because it uses emulsion EM-9 satisfying the best combination of the invention.
  • the invention can provide a silver halide photographic light-sensitive material and a silver halide color photographic light-sensitive material high in sensitivity and excellent in latent image preservability.

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  • Physics & Mathematics (AREA)
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Claims (9)

  1. Lichtempfindliches farbphotographisches Silberhalogenid-Aufzeichnungsmaterial, das einen Träger und eine darauf befindliche, eine Silberhalogenidemulsion aufweisende Silberhalogenidemulsionsschicht aufweist, wobei die Silberhalogenidemulsion tafelförmige Silberhalogenidkörnchen aus im wesentlichen Silberiodbromid umfaßt, wobei die Körnchen eine gerade Zahl von Zwillingsflächen aufweisen, das Seitenverhältnis Korndurchmesser/Dicke weniger als 5 beträgt, der mittlere Zwillingsflächenabstand der tafelförmigen Körnchen 0,01 bis 0,05 µm beträgt und die mittlere Dicke der tafelförmigen Körnchen 0,05 bis 1,5 µm beträgt, wobei die tafelförmigen Körnchen nicht weniger als 50% der gesamten Projektionsfläche der Körnchen in der Emulsionsschicht ausmachen und die folgenden Bedingungen (a) bis (c) erfüllen:
    (a) Der Variationskoeffizient der Korngrößenverteilung beträgt nicht mehr als 20%,
    (b) 0,7 ≤ y/x ≤ 2,0, worin x der Variationskoeffizient der Zwillingsflächenabstände der Körnchen ist und y der Variationskoeffizient der Körnchendicken ist, und
    (c) die Körnchen sind in einem inneren Bereich von 90% oder weniger, bezogen auf das Volumen des Körnchens, intern reduktionssensibilisiert.
  2. Farbphotographisches Material nach Anspruch 1, wobei die tafelförmigen Körnchen aus Silberiodbromidkörnchen mit einem mittleren Iodidgehalt von 1 bis 20 Mol-% bestehen.
  3. Farbphotographisches Aufzeichnungsmaterial nach Anspruch 2, wobei die Körnchen eine Silberiodbromidphase mit 5 Mol-% oder mehr Iodid im Körnchen aufweisen.
  4. Photographische Silberhalogenidemulsion, wobei die Silberhalogenidemulsion tafelförmige Halogenidkörnchen aus im wesentlichen Silberiodbromid umfaßt, wobei die Körnchen eine gerade Zahl von Zwillingsflächen aufweisen, das Seitenverhältnis Korndurchmesser/Dicke weniger als 5 beträgt, der mittlere Zwillingsflächenabstand der tafelförmigen Körnchen 0,01 bis 0,05 µm beträgt und die mittlere Dicke der tafelförmigen Körnchen 0,05 bis 1,5 µm beträgt, wobei die tafelförmigen Körnchen nicht weniger als 50% der gesamten Projektionsfläche der Körnchen in der Emulsionsschicht ausmachen und die folgenden Bedingungen (a) bis (c) erfüllen:
    (a) ein Variationskoeffizient der Korngrößenverteilung von nicht mehr als 20%,
    (b) 0,7 ≤ y/x ≤ 2,0, worin x der Variationskoeffizient der Zwillingsflächenabstände der Körnchen ist und y der Variationskoeffizient der Korndicken ist, und
    (c) die tafelförmigen Körnchen sind intern reduktionssensibilisiert,
    und wobei die tafelförmigen Körnchen nach einem Verfahren erhältlich sind, das die folgenden Stufen umfaßt:
    (i) Herstellen von Kernkörnchen durch Eintragen eines wasserlöslichen Silbersalzes und eines wasserlöslichen Halogenids in eine Mutterlauge,
    (ii) Herstellen von Impfkörnchen durch Reifenlassen der Kernkörnchen und
    (iii) Wachsenlassen der Impfkörnchen zur Herstellung der tafelförmigen Körnchen durch Eintragen eines wasserlöslichen Silbersalzes und eines wasserlöslichen Halogenids oder Silberhalogenids,
    wobei in Stufe (iii) eine Reduktionssensibilisierung durchgeführt wird, bevor 90% der Endvolumens des Körnchens erreicht sind.
  5. Silberhalogenidemulsion nach Anspruch 4, wobei während der Kernkörnchenbildung in Stufe (i) der pBr-Wert der Mutterlauge bei 2,5 oder weniger gehalten wird.
  6. Silberhalogenidemulsion nach Anspruch 4 oder 5, wobei in Stufe (ii) die Reifung in Gegenwart eines Silberhalogenidlösungsmittels durchgeführt wird.
  7. Silberhalogenidemulsion nach Anspruch 6, wobei nach Bildung der Impfkörnchen die Körnchen weiter bei einem pAg-Wert von 7,0 oder weniger reifen gelassen werden.
  8. Silberhalogenidemulsion nach einem der Ansprüche 4 bis 7, wobei in Stufe (iii) die Impfkörnchen bei einem pAg-Wert von 7,0 bis 10,5 wachsen gelassen werden.
  9. Silberhalogenidemulsion nach einem der Ansprüche 4 bis 8, wobei in Stufe (iii) eine Reduktionssensibilisierung durch Zugeben eines Reduktionsmittels, eines wasserlöslichen Silbersalzes oder einer Alkaliverbindung durchgeführt wird.
EP94309680A 1993-12-27 1994-12-22 Farbphotographisches lichtempfindliches Silberhalogenidmaterial Expired - Lifetime EP0660176B1 (de)

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