EP1061411B1 - Photographische Silberhalogenidemulsion und diese verwendendes photographisches lichtempfindliches Material - Google Patents

Photographische Silberhalogenidemulsion und diese verwendendes photographisches lichtempfindliches Material Download PDF

Info

Publication number
EP1061411B1
EP1061411B1 EP00111917A EP00111917A EP1061411B1 EP 1061411 B1 EP1061411 B1 EP 1061411B1 EP 00111917 A EP00111917 A EP 00111917A EP 00111917 A EP00111917 A EP 00111917A EP 1061411 B1 EP1061411 B1 EP 1061411B1
Authority
EP
European Patent Office
Prior art keywords
dye
group
silver halide
emulsion
dyes
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP00111917A
Other languages
English (en)
French (fr)
Other versions
EP1061411A1 (de
Inventor
Katsumi Kobayashi
Takashi Katoh
Katsuhiro Yamashita
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Corp
Original Assignee
Fuji Photo Film Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from JP11171324A external-priority patent/JP2001005132A/ja
Priority claimed from JP36327299A external-priority patent/JP2001075222A/ja
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Publication of EP1061411A1 publication Critical patent/EP1061411A1/de
Application granted granted Critical
Publication of EP1061411B1 publication Critical patent/EP1061411B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3041Materials with specific sensitometric characteristics, e.g. gamma, density
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08Sensitivity-increasing substances
    • G03C1/10Organic substances
    • G03C1/12Methine and polymethine dyes
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/0051Tabular grain emulsions
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08Sensitivity-increasing substances
    • G03C1/09Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08Sensitivity-increasing substances
    • G03C1/10Organic substances
    • G03C1/12Methine and polymethine dyes
    • G03C1/127Methine and polymethine dyes the polymethine chain forming part of a carbocyclic ring
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08Sensitivity-increasing substances
    • G03C1/10Organic substances
    • G03C1/12Methine and polymethine dyes
    • G03C1/14Methine and polymethine dyes with an odd number of CH groups
    • G03C1/16Methine and polymethine dyes with an odd number of CH groups with one CH group
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08Sensitivity-increasing substances
    • G03C1/10Organic substances
    • G03C1/12Methine and polymethine dyes
    • G03C1/14Methine and polymethine dyes with an odd number of CH groups
    • G03C1/18Methine and polymethine dyes with an odd number of CH groups with three CH groups
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08Sensitivity-increasing substances
    • G03C1/10Organic substances
    • G03C1/12Methine and polymethine dyes
    • G03C1/14Methine and polymethine dyes with an odd number of CH groups
    • G03C1/20Methine and polymethine dyes with an odd number of CH groups with more than three CH groups
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08Sensitivity-increasing substances
    • G03C1/10Organic substances
    • G03C1/12Methine and polymethine dyes
    • G03C1/22Methine and polymethine dyes with an even number of CH groups
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08Sensitivity-increasing substances
    • G03C1/09Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • G03C2001/097Selenium

Definitions

  • the present invention relates to a spectrally sensitized silver halide photographic emulsion and a photographic light-sensitive material using the emulsion.
  • a sensitizing dye adsorbed to the surface of a silver halide grain absorbs light entered into a light-sensitive material and transmits the light energy to the silver halide grain, whereby sensitivity can be obtained.
  • the light energy transmitted to silver halide can be increased by increasing the light absorption factor per the unit grain surface area of a silver halide grain and thereby the spectral sensitivity can be elevated.
  • the light absorption factor on the surface of a silver halide grain may be improved by increasing the amount of a spectral sensitizing dye adsorbed per the unit grain surface area.
  • the amount of a sensitizing dye adsorbed to the surface of a silver halide grain is limited and the dye chromophore cannot be adsorbed in excess of the single layer saturation adsorption (namely, one layer adsorption). Therefore, individual silver halide grains currently have a low absorption factor in terms of the quantum of incident light in the spectral sensitization region.
  • JP-A-63-138341 (the term "JP-A” as used herein means an "unexamined published Japanese patent application") and JP-A-64-84244, Sugimoto et al. disclose a technique of performing the spectral sensitization using the energy transfer from a light-emitting dye.
  • R. Steiger et al. disclose a technique of performing the spectral sensitization using the energy transfer from a gelatin-substituted cyanine dye.
  • Ikegawa et al. disclose a technique of performing the spectral sensitization using the energy transfer from a cyclodextrin-substituted dye.
  • Ukai, Okazaki and Sugimoto disclose a technique of bonding at least one substantially non-adsorptive dye such as cyanine dye, merocyanine dye and hemicyanine dye containing at least two sulfo and/or carboxyl groups to a spectral sensitizing dye which can adsorb to silver halide.
  • JP-A-6-57235 L.C. Vishwakarma discloses a method of synthesizing a linked dye by a dehydrating condensation reaction of two dyes. Furthermore, in JP-A-6-27578, it is disclosed that the linked dye of monomethinecyanine and pentamethineoxonol has red sensitivity. However, in this case, the light emission of oxonol and the absorption of cyanine do not overlap and the spectral sensitization using the Forster-type excitation energy transfer does not occur, failing in attaining higher sensitivity owing to the light-gathering action of oxonol linked.
  • the spectral sensitivity must be rendered to fall within an objective wavelength region.
  • the spectral sensitization of a silver halide light-sensitive material usually does not use the absorption of sensitizing dye in the monomer state but uses the J-band formed when the dye is adsorbed to the surface of a silver halide grain.
  • the J-band is very useful for laying the light absorption and the spectral sensitivity in a desired wavelength region because it has absorption acutely shifted to the longer wavelength side than that in the monomer state.
  • each color sensitization region has a width of about 100 nm and it is disadvantageous to cause unnecessarily large difference in the sensitivity to light in that range.
  • One object of the present invention is to provide a silver halide photographic emulsion prevented from coagulation of grains and having high sensitivity.
  • Another object of the present invention is to provide a photographic light-sensitive material using the emulsion.
  • the present invention is a silver halide photographic light-sensitive material using a silver halide grain sensitized by a dye, which has large light absorption intensity, proper spectral absorption waveform and proper sensitivity distribution.
  • the light absorption intensity is an integrated intensity of light absorption by a sensitizing dye per unit grain surface area and defined as a value obtained, assuming that the quantity of light entered into the unit surface area of a grain is I 0 and the quantity of light absorbed into a sensitizing dye on the surface is I, by integrating the optical density Log (I 0 /(I 0 -I)) with respect to the wave number (cm -1 ).
  • the integration range is from 5,000 cm -1 to 35,000 cm -1 .
  • the silver halide photographic emulsion of the present invention preferably contains a silver halide grain having a light absorption intensity of 100 or more in the case of a grain having a spectral absorption maximum wavelength of 500 nm or more in a proportion of a half or more of the entire projected area of all silver halide grains.
  • the light absorption intensity is preferably 150 or more, more preferably 170 or more, still more preferably 200 or more.
  • the upper limit is not particularly limited but it is preferably 2,000 or less, more preferably 1,000 or less, still more preferably 500 or less.
  • the microspectrophotometer is a device capable of measuring an absorption spectrum of a microscopic area and can measure the transmission spectrum of one grain.
  • the measurement of absorption spectrum of one grain by the microspectrometry is described in the report by Yamashita et al (Nippon Shashin Gakkai, 1996 Nendo Nenji Taikai Ko'en Yoshi Shu (Lecture Summary at Annual Meeting of Japan Photographic Association in 1996) , page 15). From this absorption spectrum, an absorption intensity per one grain can be obtained. However, the light transmitting the grain is absorbed on two surfaces of upper surface and lower surface.
  • the absorption intensity per unit area on the grain surface can be obtained as a half (1/2) of the absorption intensity per one grain obtained by the above-described method.
  • the segment for the integration of absorption spectrum is definably from 5,000 to 35,000 cm -1 . however, in experiments, the segment for the integration may contain the region of 500 cm -1 shorter or longer than the segment having absorption by the sensitizing dye.
  • the light absorption intensity may also be obtained by not using the microspectrometry but using a method of aligning grains while preventing the grain from lying one on another, and measuring the transmission spectrum.
  • the light absorption intensity is a value indiscriminately determined by the oscillator strength of sensitizing dye and the number of molecules adsorbed per unit area. Therefore, it may be possible to obtain the oscillator strength of sensitizing dye, the amount of dye adsorbed and the surface area of grain and convert these into the light absorption intensity.
  • the oscillator strength of sensitizing dye can be experimentally obtained as a value in proportion to the absorption integrated intensity (optical density ⁇ cm -1 ) of a sensitizing dye solution. Therefore, assuming that the absorption integrated intensity of a dye per 1 M is A (optical density ⁇ cm -1 ), the amount of sensitizing dye adsorbed is B (mol/mol-Ag) and the surface area of grain is C (m 2 /mol-Ag), the light absorption intensity can be obtained according to the following formula within an error of about 10%: 0.156 ⁇ A ⁇ B / C
  • the light absorption intensity calculated from this formula is substantially the same as the light absorption intensity measured based on the above-described definition (a value obtained by the integration of Log(I 0 /(I 0 -I)) with respect to the wave number (cm -1 )).
  • a method of adsorbing a dye chromophore in one or more layers onto the grain surface a method of increasing the molecular extinction coefficient of dye and a method of reducing the dye occupation area may be used. Any of these methods may be used but preferred is the method of adsorbing a dye chromophore in one or more layers onto the grain surface.
  • the state where a dye chromophore is adsorbed in one or more layers onto the grain surface means that the dye bounded to the vicinity of a silver halide grain is present in one or more layers. Dyes present in the dispersion medium are not included in this dye. Also, the case where a dye chromophore is connected to a substance adsorbed to the grain surface through a covalent bond is not regarded as the adsorption in one or more layers, because the connecting group is long, when the dye chromophore is present in the dispersion medium, and the effect increasing the light absorption intensity is less.
  • the number of stages necessary for the dye to form a color per one molecule is preferably from 1 to 3.
  • Examples thereof include cyanine dyes, styryl dyes, hemicyanine dyes, merocyanine dyes, trinuclear merocyanine dyes, tetranuclear merocyanine dyes, rhodacyanine dyes, complex cyanine dyes, complex merocyanine dyes, allopolar dyes, oxonol dyes, hemioxonol dyes, squarium dyes, croconium dyes, azomethine dyes, coumarin dyes, allylidene dyes, anthraquinone dyes, triphenylmethine dyes, azo dyes, azomethine dyes, spiro compounds, metallocene dyes, fluorenone dyes, fulgide dyes, perylene dyes, phenazine dyes, phenothiazine dyes, quinone dyes, indigo dyes, diphenylmethane dye
  • cyanine dyes preferred are cyanine dyes, styryl dyes, hemicyanine dyes, merocyanine dyes, trinuclear merocyanine dyes, tetranuclear merocyanine dyes, rhodacyanine dyes, complex cyanine dyes, complex merocyanine dyes, allopolar dyes, oxonol dyes, hemioxonol dyes, squarium dyes, croconium dyes and polymethine chromophores such as azamethine dyes, more preferred are cyanine dyes, merocyanine dyes, trinuclear merocyanine dyes, tetranuclear merocyanine dyes and rhodacyanine dyes, still more preferred are cyanine dyes, merocyanine dyes and rhodacyanine dyes, and most preferred are cyanine dyes.
  • the dye chromophore adsorbed to a silver halide grain is preferably in 1.5 or more layers, more preferably 1.7 or more layers, still more preferably in 2 or more layers.
  • the upper limit of the layer number is not particularly limited, however, it is preferably 10 or less layers, more preferably 5 or less layers.
  • the state where a chromophore is adsorbed in one or more layers onto the surface of a silver halide grain means that when saturation adsorption achieved by a dye having a smallest dye occupation area on a silver halide grain surface of sensitizing dyes added to an emulsion is defined as a single layer saturation coverage, the adsorption amount of a dye chromophore per unit layer is large based on the single layer saturation coverage.
  • the adsorption layer number means an adsorption amount based on the single layer saturation coverage.
  • the adsorption layer number may be based on the dye occupation area of individual dyes in the state such that these dye chromophores are not connected.
  • the dye occupation area may be obtained from an adsorption isotherm showing the relationship between the free dye concentration and the dye adsorption amount, and a grain surface area.
  • the adsorption isotherm may be obtained by referring, for example, to A. Herz et al., Adsorption from Aqueous Solution, Advances in chemistry Series , No. 17, page 173 (1968).
  • two methods may be used, namely, one is a method of centrifuging an emulsion having adsorbed thereto a dye to separate emulsion grains from supernatant aqueous gelatin solution, measuring the spectral absorption of the supernatant to obtain a non-adsorbed dye concentration, subtracting the concentration from the amount of dye added and thereby determining the dye adsorption amount, and another is a method of drying emulsion grains precipitated, dissolving a predetermined weight of the precipitate in a 1:1 mixed solution of aqueous sodium thiosulfate solution and methanol, measuring the spectral absorption and thereby determining the dye adsorption amount.
  • the adsorption amount of individual dyes may also be obtained by a means such as high-speed liquid chromatography.
  • the method of determining the dye adsorption amount by quantitating the amount of dye in the supernatant is described, for example, in W. West et al., Journal of Physical Chemistry , Vol. 56, page 1054 (1952). However, under the conditions that the amount of dye added is large, even non-adsorbed dyes may precipitate and exact determination of the adsorption amount may not be obtained by the method of quantitating the dye concentration in the supernatant.
  • the amount of only the dye adsorbed to grains can be exactly determined because the emulsion grain is by far higher in the precipitation rate and the dye precipitated with grains can be easily separated. This method is most reliable for determining the dye adsorption amount.
  • a method of taking a transmission electron microscopic photograph by a replica process and calculating the shape and size of individual grains may be used.
  • the thickness of a tabular grain is calculated from the length of a shadow of the replica.
  • the transmission electron microscopic photograph may be taken, for example, by referring to Denshi Kenbikyo Shiryo Gijutsu Shu (Electron Microscopic Sample Technologies) , Nippon Denshi Kenbikyo Gakkai Kanto Shibu (compiler), Seibundo Shinko Sha (1970), P.B. Hirsch et al., Electron Microscopy of Thin Crystals , Butterworths, London (1965).
  • the dye occupation area of individual grains may be experimentally determined by the above-described methods, however, the molecular occupation area of sensitizing dyes usually used is mostly in the vicinity of 80 ⁇ 2 . therefore, the adsorption layer number may be roughly estimated by a simple method of counting the dye occupation area as 80 ⁇ 2 .
  • the dye chromophore directly adsorbing to the silver halide grain namely, dye chromophore in the first layer
  • the dye chromophores in the second and subsequent layers may have any reduction potential and any oxidation potential.
  • the reduction potential of the dye chromophore in the first layer is preferably more positive than the value obtained by subtracting 0.2 V from the reduction potential of the dye chromophore in the second or subsequent layer.
  • the reduction potential and the oxidation potential may be measured by various methods. However, these are preferably measured by phase discrimination-type second harmonic a.c. polarography for determining exact values.
  • phase discrimination-type second harmonic a.c. polarography The method for determining the potential by phase discrimination-type second harmonic a.c. polarography is described in Journal of Imaging Science , Vol. 30, page 27 (1986).
  • the dye chromophore in the second or subsequent layer is preferably a light-emitting dye.
  • the light-emitting dye preferably has a skeleton (i.e., a basic) structure of dyes used for dye laser. These are described, for example, in Mitsuo Maeda, Laser Kenkyu (Study of Laser) , Vol. 8, page 694, page 803 and page 958 (1980), ibid. , Vol. 9, page 85 (1981), and F. Shaefer, Dye Lasers , Springer (1973).
  • the absorption maximum wavelength of the dye chromophore in the first layer in a silver halide photographic light-sensitive material is preferably longer than the absorption maximum wavelength of the dye chromophore in the second or subsequent layer.
  • the light emission of the dye chromophore in the second or subsequent layer preferably overlaps the absorption of the dye chromophore in the first layer.
  • the dye chromophore in the first layer preferably forms J-association product (i.e., J-aggregate).
  • the dye chromophores in the second and subsequent layers also preferably form a J-association product.
  • the distance between the shortest wavelength showing 50% of a maximum value Amax of the spectral absorption factor by a sensitizing dye and showing 50% of a maximum value Smax of the spectral sensitivity and the longest wavelength showing 50% of Amax and 50% of Smax is preferably 120 nm or less, more preferably 100 nm or less.
  • the distance between the shortest wavelength showing 80% of Amax and 80% of Smax and the longest wavelength showing 80% of Amax and 80% of Smax is 20 nm or more and is preferably 100 nm or less, more preferably 80 nm or less, still more preferably 50 nm or less.
  • the distance between the shortest wavelength showing 20% of Amax and 20% of Smax and the longest wavelength showing 20% of Amax and 20% of Smax is preferably 180 nm or less, more preferably 150 nm or less, still more preferably 120 nm or less, and most preferably 100 nm or less.
  • the longest wavelength showing 50% of Amax and 50% of Smax is preferably from 500 to 510 nm, from 560 nm to 610 nm, or from 640 to 730 nm.
  • a first preferred method is a method of using a specific dye described below.
  • a method of using a dye having at least one aromatic group preferred is a method of using only a positively charged dye, a dye cancelled in the electric charge within the molecule or a dye having no electric charge, or a method of using a positively charged dye and a negative charged dye in combination where at least one of the positively charged dye and the negatively charged dye is a dye having at least one aromatic group as a substituent.
  • the aromatic group is described in detail below.
  • the aromatic group includes a hydrocarbon aromatic group and a heterocyclic aromatic group.
  • the group may have a polycyclic condensation structure obtained by condensing a hydrocarbon aromatic ring and a heterocyclic aromatic ring to each other or a polycyclic condensation structure obtained by combining an aromatic hydrocarbon group and an aromatic heterocyclic ring, and may be substituted by a substituent V which will be described later.
  • aromatic ring which is preferably contained in the aromatic group include benzene, naphthalene, anthracene, phenanthrene, fluorene, triphenylene, naphthacene, biphenyl, pyrrole, furane, thiophene, imidazole, oxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, indolizine, indole, benzofurane, benzothiophene, isobenzofurane, quinolizine, quinoline, phthalazine, naphtylidine, quinoxaline, quinoxazoline, quinoline, carbazole, phenanthridine, acridine, phenanthroline, thianthrene, chromene, xanthene, phenoxathine, phenothiazine and phenazine.
  • hydrocarbon aromatic rings preferred are benzene and naphthalene, and most preferred is benzene.
  • Examples of the dye include the dyes described above as examples of the dye chromophore. Among these, preferred are dyes described above as examples of the polymethine dye chromophore.
  • cyanine dyes More preferred are cyanine dyes, styryl dyes, hemicyanine dyes, merocyanine dyes, trinuclear merocyanine dyes, tetranuclear merocyanine dyes, rhodacyanine dyes, complex cyanine dyes, complex merocyanine dyes, allopolar dyes, oxonol dyes, hemioxonol dyes, squarium dyes, croconium dyes and azamethine dyes, still more preferred are cyanine dyes, merocyanine dyes, trinuclear merocyanine dyes, tetranuclear merocyanine dyes and rhodacyanine dyes, particularly preferred are cyanine dyes, merocyanine dyes and rhodacyanine dyes, and most preferred are cyanine dyes.
  • the methods (1) and (2) are preferred. Of the methods (1) and (2), the method (2) is more preferred.
  • R 1 is preferably a group having an aromatic ring.
  • R 1 and R 2 are a group having an aromatic ring, and more preferably, R 1 and R 2 both are a group having an aromatic ring.
  • the cationic dye for use in the present invention may be any as long as the electric charge of the dye exclusive of the counter ion is cationic, but a dye having no anionic substituent is preferred.
  • the anionic dye for use in the present invention may be any as long as the electric charge of the dye exclusive of the counter ion is anionic, but a dye having one or more anionic substituents is preferred.
  • the betaine dye for use in the present invention is a dye having an electric charge within the molecule, where an inner salt is formed and the molecule as a whole has no electric charge.
  • the nonionic dye for use in the present invention is a dye not having an electric charge at all within the molecule.
  • anionic substituent means a substituent having a negative charge.
  • examples thereof include a proton-dissociative acidic group having a dissociation ratio of 90% or more at a pH of from 5 to 8.
  • Specific examples thereof include a sulfo group, a carboxyl group, a sulfate group, a phosphoric acid group, a boric acid group, an alkylsulfonylcarbamoylalkyl group (e.g., methanesulfonylcarbamoylmethyl group), an acylcarbamoylalkyl group (e.g., acetylcarbamoylmethyl group), an acylsulfamoylalkyl group (e.g., acetylsulfamoylmethyl group) and an alkylsulfonylsulfamoylalkyl group (e.g., methanesulfonylsulfulf
  • Examples of the cationic substituent include a substituted or unsubstituted ammonium group and a pyridium group.
  • the dye represented by formula (I) is more preferably represented by the following formula (I-1), (I-2) or (I-3): wherein L 5 , L 6 , L 7 , L 8 , L 9 , L 10 and L 11 each represents a methine group, p 3 and p 4 each represents 0 or 1, n 1 represents 0, 1, 2, 3 or 4, Z 3 and Z 4 each represents an atomic group necessary for forming a nitrogen-containing heterocyclic ring, provided that a ring may be condensed to Z 3 and Z 4 , R 3 and R 4 each represents an alkyl group, an aryl group or a heterocyclic group, and M 1 and m 1 have the same meanings as in formula (I), provided that R 3 , R 4 , Z 3 , Z 4 and L 5 to L 11 each has no anionic substituent when the compound (I-1) is a cationic dye, and has an anionic substituent so as to balance the electric charge within the dye molecule, preferably one anionic substituent, when the compound
  • the anionic dye represented by formula (II) is more preferably represented by the following formula (II-1), (II-2) or (II-3): wherein L 25 , L 26 , L 27 , L 28 , L 29 , L 30 and L 31 each represents a methine group, p 8 and p 9 each represents 0 or 1, n 5 represents 0, 1, 2, 3 or 4, Z 10 and Z 11 each represents an atomic group necessary for forming a nitrogen-containing heterocyclic ring, provided that a ring may be condensed to Z 10 and Z 11 , R 10 and R 11 each represents an alkyl group, an aryl group or a heterocyclic group, and M 2 and m 2 have the same meanings as in formula (II), provided that R 10 and R 11 each has an anionic substituent; wherein L 32 , L 33 , L 34 and L 35 each represents a methine group, p 9 represents 0 or 1, n 6 represents 0, 1, 2, 3 or 4, Z 12 and Z 13 each represents an atomic group
  • R 3 and R 4 is(are) a group having an aromatic ring
  • at least one and preferably both of R 5 and R 6 is (are) a group having an aromatic ring
  • at least one, preferably two and more preferably all three of R 7 , R 8 and R 9 is (are) a group having an aromatic ring.
  • At least one, preferably two, more preferably three and still more preferably four or more of R 3 to R 9 or R 10 to R 16 is(are) a group having an aromatic group.
  • a silver halide grain having a spectral absorption maximum wavelength of 500 nm or more and a light absorption intensity of 100 or more may be obtained.
  • the dye in the second layer is usually adsorbed in the state of a monomer and the absorption width and the spectral sensitivity width thereof are broader than respective desired ranges in most cases.
  • the dye adsorbed in the second layer must form a J-association product (i.e., J-aggregate).
  • J-aggregate has high fluorescence yield and small Stokes' shift. Therefore, this is advantageous in transferring the light energy absorbed by the dye in the second layer to the dye in the first layer, which are approximated in the light absorption wavelength, utilizing the Forster-type energy transfer.
  • the dye in the second and subsequent layers means a dye which is adsorbed to a silver halide grain but not adsorbed directly to the silver halide.
  • the J-aggregate of dye in the second or subsequent layer is defined as a product such that the absorption width in the longer wavelength side of absorption shown by a dye adsorbed to the second or subsequent layer is 2 times or less of the absorption width in the longer wavelength side of absorption shown by the dye solution in the monomer state where interaction between dye chromophores does not occur.
  • the absorption width in the longer wavelength side as used herein means an energy width between the absorption maximum wavelength and the wavelength being longer than the absorption maximum wavelength and showing absorption as small as 1/2 of the absorption maximum. It is well-known that when a J-aggregate is formed, the absorption width in the longer wavelength side is generally reduced as compared with the case in the monomer state.
  • the absorption width increases as much as 2 times or more the absorption width in the longer wavelength side of absorption shown by the dye solution in the monomer state because the adsorption site and the adsorption state are not uniform. Accordingly, the dye in the second or subsequent layer can be defined as above.
  • the spectral absorption of dye adsorbed to the second and subsequent layers can be obtained by subtracting the spectral absorption attributable to the dye in the first layer from the entire spectral absorption of the emulsion.
  • the spectral absorption attributable to the dye in the first layer can be determined by measuring the absorption spectrum when only the dye in the first layer is added.
  • the spectral absorption spectrum may also be measured by adding a dye desorbing agent to the emulsion having adsorbed thereto a sensitizing dye in multiple layers and thereby desorbing the dyes in the second and subsequent layers.
  • the dye in the first layer is usually desorbed after the dyes in the second and subsequent layers are desorbed. Therefore, by selecting appropriate desorption conditions, the spectral absorption attributable to the dye in the first layer can be obtained and thereby the spectral absorption of dye in the second and subsequent layers may be obtained.
  • the method of using a dye desorbing agent is described in Asanuma et al., Journal of Physical Chemistry B , Vol. 101, pp. 2149-2153 (1997).
  • the dye adsorbed to form the first layer and the dye adsorbed to form the second or subsequent layer are preferably added separately and it is more preferred that the dye used for the first layer and the dye used for the second or subsequent layer have different structures from each other.
  • the dye in the second or subsequent layer preferably comprises a cationic dye, a betaine dye or a nonionic dye alone or comprises a combination of a cationic dye and an anionic dye.
  • any dye may be used, however, the dye represented by formula (I) or (II) is preferred and the dye represented by formula (I) is more preferred.
  • the cationic dye, betaine dye or nonionic dye represented by formula (I) is preferably used alone.
  • either one of the dyes used is preferably the cationic dye represented by formula (I) or the anionic dye represented by formula (II), and it is more preferred that the cationic dye represented by formula (I) and the anionic dye represented by formula (II) both are contained.
  • the ratio of cationic dye/anionic dye as the dye in the second layer is preferably from 0.5 to 2, more preferably from 0.75 to 1.33, most preferably from 0.9 to 1.11.
  • a dye other than the dyes represented by formulae (I) and (II) may be added, however, the dye represented by formula (I) or (II) preferably occupies 50% or more, more preferably 70% or more, most preferably 90% or more, of the total amount of dyes added.
  • the interaction between dyes in the second layer can be increased while promoting rearrangement of the dyes in the second layer and thereby, the J-association product (i.e., J-aggregate) can be formed.
  • the J-association product i.e., J-aggregate
  • Z 1 and Z 2 is preferably a basic nucleus substituted by an aromatic group or a basic nucleus resulting from condensation of three or more rings.
  • Z 1 and Z 2 is preferably a basic nucleus resulting from condensation of three or more rings.
  • the number of rings condensed in the basic nucleus is, for example, 2 in the benzoxazole nucleus and 3 in the naphthoxazole nucleus. Even if the benzoxazole nucleus is substituted by a phenyl group, the number of rings condensed is 2.
  • the basic nucleus resulting from condensation of three or more rings may be any as long as it is a polycyclic condensation-type heterocyclic basic nucleus obtained by the condensation of three or more rings. However, a tricyclic condensation-type heterocyclic ring and a tetracyclic condensation-type heterocyclic ring are preferred.
  • Preferred examples of the tricyclic condensation-type heterocyclic ring include naphtho[2,3-d]-oxazole, naphtho[1,2-d]oxazole, naphtho[2,1-d]oxazole, naphtho[2,3-d]thiazole, naphtho[1,2-d]thiazole, naphtho-[2,1-d]thiazole, naphtho[2,3-d]imidazole, naphtho[1,2-d]-imidazole, naphtho[2,1-d]imidazole, naphtho[2,3-d]selenazole, naphtho[1,2-d]selenazole, naphtho[2,1-d]selenazole, indolo[5,6-d]oxazole, indolo[6,5-d]oxazole, indolo[2,3-d]oxazole, indolo[5,6-d
  • Preferred examples of the tetracyclic condensation-type heterocyclic ring include anthra[2,3-d]oxazole, anthra[1,2-d]oxazole, anthra-[2,1-d]oxazole, anthra[2,3-d]thiazole, anthra[1,2-d]-thiazole, phenanthro[2,1-d]oxazole, phenanthro[2,3-d]-imidazole, anthra[1,2-d]imidazole, anthra[2,1-d]imidazole, anthra[2,3-d]selenazole, phenanthro[1,2-d]selenazole, phenanthro[2,1-d]selenazole, carbazolo[2,3-d]oxazole, carbazolo[3,2-d]oxazole, dibenzofuro[2,3-d]oxazole, dibenzofuro[3,2-d
  • More preferred examples of the basic nucleus resulting from condensation of three or more rings include naphtho[2,3-d]oxazole, naphtho[1,2-d]oxazole, naphtho[2,1-d]oxazole, naphtho[2,3-d]thiazole, naphtho[1,2-d]thiazole, naphtho-[2,1-d]thiazole, indolo[5,6-d]oxazole, indolo[6,5-d]oxazole, indolo[2,3-d]oxazole, indolo[5,6-d]thiazole, indolo[2,3-d]-thiazole, benzofuro[5,6-d]oxazole, benzofuro[6,5-d]oxazole, benzofuro[2,3-d]oxazole, benzofuro[5,6-d]thiazole, benzofuro[2,3-d]thi
  • naphtho[2,3-d]oxazole naphtho[1,2-d]oxazole, naphtho[2,3-d]thiazole, indolo[5,6-d]oxazole, indolo[6,5-d]oxazole, indolo[5,6-d]thiazole, benzofuro[5,6-d]oxazole, benzofuro-[5,6-d]thiazole; benzofuro[2,3-d]thiazole, benzothieno[5,6-d]oxazole, carbazolo[2,3-d]oxazole, carbazolo[3,2-d]oxazole, dibenzofuro[2,3-d]oxazole, dibenzofuro[3,2-d]oxazole, carbazolo[2,3-d]thiazole, carbazolo[3,2-d]thiazole, dibenzofuro[2,3-d]dazole,
  • Another preferred example of the method for realizing an adsorption state such that a dye chromophore is coated in multiple layers on a silver halide grain surface is a method of using a dye compound having two or more dye chromophore moieties connected by covalent bonding though a linking group.
  • the dye chromophore which can be used may be any and examples thereof include the dye chromophores described above.
  • cyanine dyes preferred are the polymethine dye chromophores described above for the dye chromophore, more preferred are cyanine dyes, merocyanine dyes, rhodacyanine dyes and oxonol dyes, still more preferred are cyanine dyes, rhodacyanine dyes and merocyanine dyes, and most preferred are cyanine dyes.
  • Preferred examples of the above-described method include a method of using a dye connected by a methine chain described in JP-A-9-265144, a method of using a dye having connected thereto an oxonol dye described in JP-A-10-226758, a method of using a linked dye having a specific structure described in JP-A-10-110107, JP-A-10-307358, JP-A-10-307359 and JP-A-10-310715, a method of using a linked dye having a specific linking group described in JP-A-9-189986 and JP-A-10-204306, a method of using a linked dye having a specific structure described in JP-A-2000 231174, JP-A-2000 231172 and JP-A-2000 231173, and a method of using a dye having a reactive group and producing a linked dye in an emulsion described in JP-A-2000 81678.
  • the linked dye is preferably a dye represented by the following formula (III): D 1 ⁇ ( L a ⁇ [ D 2 ] q ) r M 3 m 3 wherein D 1 and D 2 each represents a dye chromophore, La represents a linking group or a single bond, q and r each represents an integer of from 1 to 100, M 3 represents a charge-balancing counter ion, and m 3 represents a number necessary for neutralizing the electric charge of molecule.
  • formula (III) D 1 ⁇ ( L a ⁇ [ D 2 ] q ) r M 3 m 3
  • D 1 and D 2 each represents a dye chromophore
  • La represents a linking group or a single bond
  • q and r each represents an integer of from 1 to 100
  • M 3 represents a charge-balancing counter ion
  • m 3 represents a number necessary for neutralizing the electric charge of molecule.
  • the chromophore represented by D 1 or D 2 may be any. Specific examples thereof include the dye chromophores described above. Among those, preferred are the polymethine dye chromophores described above for the dye chromophore, more preferred are cyanine dyes, merocyanine dyes, rhodacyanine dyes and oxonol dyes, still more preferred are cyanine dyes, merocyanine dyes and rhodacyanine dyes, and most preferred are cyanine dyes.
  • D 2 is preferably a chromophore not directly adsorbed to silver halide.
  • D 2 is preferably lower than D 1 in the adsorption strength to a silver halide grain.
  • the adsorption strength to a silver halide grain is most preferably in the order of D 1 >La>D 2 .
  • D 1 is preferably a sensitizing dye moiety having adsorptivity to a silver halide grain,
  • the adsorption may also be attained by either physical adsorption or chemical adsorption.
  • D 2 is preferably weak in the adsorptivity to a silver halide grain and is also preferably a light-emitting dye.
  • the light-emitting dye those having a skeleton structure (i.e., a basic structure) of dyes used for dye laser are preferred. These are described, for example, in Mitsuo Maeda, Laser Kenkyu (Study of Laser) , Vol. 8, page 694, page 803 and page 958 (1980), ibid. , Vol. 9, page 85 (1981), and F. Shaefer, Dye Lasers , Springer (1973).
  • the absorption maximum wavelength of D 1 in a silver halide photographic light-sensitive material is preferably longer than the absorption maximum wavelength of D 2 . Furthermore, the light emission of D 2 preferably overlaps the absorption of D 1 . In addition, D 1 preferably forms a J-aggregate. In order to allow the linked dye represented by formula (I) to have absorption and spectral sensitivity in a desired wavelength range, D 2 also preferably forms a J-aggregate.
  • D 1 and D 2 each may have any reduction potential and any oxidation potential, however, the reduction potential of D 1 is preferably more positive than the value obtained by subtracting 0.2 V from the reduction potential of D 2 .
  • La represents a linking group (preferably a divalent linking group) or a single bond.
  • This linking group preferably comprises an atom or atomic group containing at least one of carbon atom, nitrogen atom, sulfur atom and oxygen atom.
  • La preferably represents a linking group having from 0 to 100 carbon atoms, more preferably from 1 to 20 carbon atoms, constituted by one or a combination of two or more of an alkylene group (e.g., methylene, ethylene, propylene, butylene, pentylene), an arylene group (e.g., phenylene, naphthylene,), an alkenylene group (e.g., ethenylene, propenylene), an alkynylene group (e.g., ethynylene, propynylene), an amide group, an ester group, a sulfoamido group, a sulfonic acid ester group, a ureido group, a
  • linking groups each may have a substituent represented by V which is described later. Furthermore, these linking groups each may contain a ring (aromatic or non-aromatic hydrocarbon or heterocyclic ring).
  • La more preferably represents a divalent linking group having from 1 to 10 carbon atoms, constituted by one or a combination of two or more of an alkylene group having from 1 to 10 carbon atoms (e.g., methylene, ethylene, propylene, butylene), an arylene group having from 6 to 10 carbon atoms (e.g., phenylene, naphthylene), an alkenylene group having from 2 to 10 carbon atoms (e.g., ethenylene, propenylene), an alkynylene group having from 2 to 10 carbon atoms (e.g., ethynylene, propynylene), an ether group, an amide group, an ester group, a sulfonamido group and a sulfonic acid ester group.
  • These linking groups each may be substituted by V which is described later.
  • La is a linking group which may perform energy transfer or electron transfer by the through-bond interaction.
  • the through-bond interaction includes tunnel interaction and super-exchange interaction, Of these, a through-bond interaction based on the super-exchange interaction is preferred.
  • the through-bond interaction and the super-exchange interaction are interactions defined in Shammai Weinr, Chem. Rev. , Vol. 96, pp. 1960-1963 (1996).
  • As the linking group which can allow the occurrence of energy transfer or electron transfer by such an interaction those described in Shammai Weiner, Chem. Rev. , Vol. 96, pp. 1967-1969 (1996) are preferred.
  • q and r each represents an integer of from 1 to 100, preferably from 1 to 5, more preferably from 1 to 2, still more preferably 1.
  • a plurality of linking groups La contained may be different from each other and a plurality of dye chromophores D 2 contained may also be different from each other.
  • the dye represented by formula (III) as a whole preferably has an electric charge of -1.
  • the dye is more preferably a methine dye where D 1 and D 2 in formula (III) each is independently represented by the following formula (IV), (V) or (VI): wherein L 45 , L 46 , L 47 , L 48 , L 49 , L 50 and L 51 each represents methine group, p 12 and p 13 each represents 0 or 1, n 9 represents 0, 1, 2, 3 or 4, Z 17 and Z 18 each represents an atomic group necessary for forming a nitrogen-containing heterocyclic ring, provided that a ring may be condensed to Z 17 and Z 18 , M 4 represents a charge-balancing counter ion, m 4 represents a number of 0 or more necessary for neutralizing the electric charge of molecule, and R 17 and R 18 each represents an alkyl group, an aryl group or a heterocyclic group; wherein L 52 , L 53 , L 54 and L 55 each represents a methine group, p 14 represents 0 or 1, n 10 represents 0, 1, 2, 3 or 4, Z 19 and Z
  • Q 1 and Q 2 each represents a group necessary for forming a methine dye.
  • any methine dye can be formed but examples thereof include methine dyes described above as examples of the dye chromophore.
  • cyanine dyes preferred are cyanine dyes, merocyanine dyes, rhodacyanine dyes, trinuclear merocyanine dyes, tetranuclear merocyanine dyes, allopolar dyes, hemicyanine dyes and styryl dyes, more preferred are cyanine dyes, merocyanine dyes and rhodacyanine dyes, still more preferred are cyanine dyes.
  • These dyes are described in detail in F.M. Harmer, Heterocyclic Compounds-Cyanine Dyes and Related Compounds , John Wiley & Sons, New York, London (1964), D.M. Sturmer, Heterocyclic Compounds - Special topics in heterocyclic chemistry , Chap. 18, Section 14, pp. 482-515.
  • cyanine dyes merocyanine dyes and rhodacyanine dyes, formulae (XI), (XII) and (XIII) described in U.S. Patent 5,340,694, columns 21 to 22, are preferred on the condition that the numbers of n12, n15, n17 and n18 are not limited and each is an integer of 0 or more (preferably 4 or less).
  • formulae (I) and (II) may be expressed by the following resonance formulae:
  • Z 1 , Z 2 , Z 3 , Z 4 , Z 5 , Z 7 , Z 9 , Z 10 , Z 11 , Z 12 , Z 14 , Z 16 , Z 17 , Z 18 , Z 19 , Z 21 and Z 23 each represents an atomic group necessary for forming a nitrogen-containing heterocyclic ring, preferably a 5- or 6-membered nitrogen-containing heterocyclic ring. However, a ring may be condensed to each of these groups.
  • the ring may be either an aromatic ring or a non-aromatic ring, but an aromatic ring is preferred and examples thereof include hydrocarbon aromatic rings such as benzene ring and naphthalene ring, and heteroaromatic rings such as pyrazine ring and thiophene ring.
  • nitrogen-containing heterocyclic ring examples include thiazoline nucleus, thiazole nucleus, benzothiazole nucleus, oxazoline nucleus, oxazole nucleus, benzoxazole nucleus, selenazoline nucleus, selenazole nucleus, benzoselenazole nucleus, 3,3-dialkylindolenine nucleus (e.g., 3,3-dimethylindolenine), imidazoline nucleus, imidazole nucleus, benzimidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus, 2-quinoline nucleus, 4-quinoline nucleus, 1-isoquinoline nucleus, 3-isoquinoline nucleus, imidazo[4,5-b]quinoxaline nucleus, oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus and pyrimidine nucleus.
  • benzothiazole nucleus preferred are benzothiazole nucleus, benzoxazole nucleus, 3,3-dialkylindolenine nucleus (e.g., 3,3-dimethylindolenine), benzimidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus, 2-quinoline nucleus, 4-quinoline nucleus, 1-isoquinoline nucleus and 3-isoquinoline nucleus; more preferred are benzothiazole nucleus, benzoxazole nucleus, 3,3-dialkylindolenine nucleus (e.g., 3,3-dimethylindolenine) and benzimidazole nucleus; still more preferred are benzoxazole nucleus, benzothiazole nucleus and benzimidazole nucleus; and most preferred are benzoxazole nucleus and benzothiazole nucleus.
  • the substituent represented by V is not particularly limited, however.
  • examples thereof include a halogen atom (e.g., chlorine, bromine, iodine, fluorine), a mercapto group, a cyano group, a carboxy group, a phosphoric acid group, a sulfo group, a hydroxy group, a carbamoyl group having from 1 to 10, preferably from 2 to 8, more preferably from 2 to 5, carbon atoms (e.g., methylcarbamoyl, ethylcarbamoyl, morpholinocarbonyl), a sulfamoyl group having from 0 to 10, preferably from 2 to 8, more preferably from 2 to 5, carbon atoms (e.g., methylsulfamoyl, ethylsulfamoyl, piperidino-sulfonyl), a nitro group, an halogen atom (e.g., chlorine, bromine,
  • ring an aromatic or non-aromatic hydrocarbon or heterocyclic ring, e.g., benzene ring, naphthalene ring, anthracene ring, quinoline ring
  • a ring an aromatic or non-aromatic hydrocarbon or heterocyclic ring, e.g., benzene ring, naphthalene ring, anthracene ring, quinoline ring
  • the substituent represented by V may be further substituted by V.
  • alkyl group preferred are the alkyl group, the aryl group, the alkoxy group, the halogen atom, the aromatic ring condensation product, the sulfo group, the carboxy group and the hydroxy group.
  • the substituent V on Z 1 , Z 2 , Z 3 , Z 4 , Z 5 , Z 7 , Z 9 , Z 10 , Z 11 , Z 12 , Z 14 and Z 16 is more preferably the aromatic group and the aromatic ring condensation product.
  • the chromophore represented by D 1 in formula (III) is the methine dye represented by formula (IV), (V) or (VI)
  • the substituent V on Z 17 , Z 18 , Z 19 , Z 21 and Z 23 is more preferably the aromatic group or the aromatic ring condensation product.
  • the substituent V on Z 17 , Z 18 , Z 19 , Z 21 and Z 23 is more preferably the carboxy group, the sulfo group or the hydroxy group, still more preferably the sulfo group.
  • Z 6 , Z 13 and Z 20 each represents an atomic group necessary for forming an acidic nucleus, however, an acidic nucleus form of any general merocyanine dye may also be formed.
  • the term "acidic nucleus” as used herein is defined, for example, in James (compiler), The Theory of the Photographic Process , 4th ed., page 198, Macmillan (1977). Specific examples thereof include those described in U.S. Patents 3,567,719, 3,575,869, 3,804,634, 3,837,862, 4,002,480 and 4,925,777, and JP-A-3-167546.
  • the acidic nucleus preferably forms a 5- or 6-membered nitrogen-containing heterocyclic ring comprising carbon, nitrogen and chalcogen (typically oxygen, sulfur, selenium or tellurium) atoms. Examples thereof include the following nuclei:
  • Z 6 , Z 13 and Z 20 each is preferably hydantoin, 2- or 4-thiohydantoin, 2-oxazolin-5-one, 2-thiooxazoline-2,4-dione, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dione, barbituric acid or 2-thiobarbituric acid, more preferably hydantoin, 2- or 4-thiohydantoin, 2-oxazolin-5-one, rhodanine, barbituric acid or 2-thiobarbituric acid, still more preferably 2- or 4-thiohydantoin, 2-oxazolin-5-one, rhodanine or barbituric acid.
  • the 5- or 6-membered nitrogen-containing heterocyclic ring formed by Z 8 , Z 15 or Z 22 is the heterocyclic ring represented by Z 6 , Z 13 or Z 20 from which an oxo or thioxo group is excluded, preferably hydantoin, 2- or 4-thiohydantoin, 2-oxazolin-5-one, 2-thiooxazoline-2,4-dione, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, barbituric acid or 2-thiobarbituric acid from which an oxo or thioxo group is excluded, more preferably hydantoin, 2- or 4-thiohydantoin, 2-oxazolin-5-one, rhodanine, barbituric acid or 2-thiobarbituric acid from which an oxo or thioxo group is excluded, still more preferably 2- or 4-thiohydantoin
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 and R 23 each represents an alkyl group, an aryl group or a heterocyclic group.
  • R 1 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 each is preferably a group having an aromatic ring.
  • the aromatic ring include a hydrocarbon aromatic ring and a heteroaromatic ring. These rings each may be a polycyclic condensation ring resulting from the condensation of hydrocarbon aromatic rings or heteroaromatic rings to each other, or a polycyclic condensation ring resulting from an aromahydrocarbon ring and an aromatic heterocyclic ring being combined. These rings each may be substituted by the above-described substituent V or the like.
  • Preferred examples of the aromatic ring include those described above as examples of the aromatic ring for the aromatic group.
  • the group having an aromatic ring may also be expressed by -Lb-A 1 , wherein Lb represents a single bond or a linking group, and A 1 represents an aromatic group.
  • Preferred examples of the linking group represented by Lb include the linking groups described above for La and the like.
  • Examples of the aromatic group represented by A 1 include those described above as examples of the group having an aromatic ring.
  • Preferred examples of the group having an aromatic ring containing no anionic group include an alkyl group having a hydrocarbon aromatic ring, such as an aralkyl group (e.g., benzyl, 2-phenylethyl, naphthylmethyl, 2-(4-biphenyl) ethyl), an aryloxyalkyl group (e.g., 2-phenoxyethyl, 2-(1-naphthoxy)ethyl, 2-(4-biphenyloxy)ethyl, 2- (o-, m- or p-halophenoxy) ethyl, 2-(o-, m- or p-methoxyphenoxy)ethyl) and an aryloxycarbonylalkyl group (e.g., 3-phenoxycarbonylpropyl, 2-(1-naphthoxycarbonyl)ethyl); an alkyl group having a heteroaromatic ring, such as 2-(2-pyri
  • alkyl group having a substituted or unsubstituted hydrocarbon aromatic ring or the heteroaromatic ring more preferred are the alkyl group having a substituted or unsubstituted hydrocarbon aromatic ring.
  • R 2 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 each is preferably a group having an aromatic ring. Both of R 10 and R 11 , at least one of R 12 and R 13 , and at least one of R 14 , R 15 and R 16 have an anionic substituent. R 2 preferably has an anionic substituent.
  • the aromatic ring include a hydrocarbon aromatic ring and a heteroaromatic ring. These rings each may be a polycyclic condensation ring resulting from the condensation of hydrocarbon aromatic rings or heteroaromatic rings with each other, or a polycyclic condensation ring resulting from an aromahydrocarbon ring and an aromatic heterocyclic ring being combined. These rings each may be substituted by the above-described substituent V or the like.
  • Preferred examples of the aromatic ring include those described above as examples of the aromatic ring for the aromatic group.
  • the group having an aromatic ring may also be expressed by -Lc-A 2 , wherein Lc represents a single bond or a linking group, and A 2 represents an aromatic group.
  • Preferred examples of the linking group represented by Lc include the linking groups described for La.
  • Preferred examples of the aromatic group represented by A 2 include those described above as examples of the aromatic group.
  • Lc or A 2 is preferably substituted by at least one anionic substituent.
  • Preferred examples of the group having an aromatic ring substituted by an anionic substituent include an alkyl group having a hydrocarbon aromatic ring, such as an aralkyl group substituted by a sulfo group, a phosphoric acid group or a carboxyl group (e.g., 2-sulfobenzyl, 4-sulfobenzyl, 4-sulfophenethyl, 3-phenyl-3-sulfopropyl, 3-phenyl-2-sulfopropyl, 4,4-diphenyl-3-sulfobutyl, 2-(4'-sulfo-4-biphenyl)ethyl, 4-phosphobenzyl), an aryloxycarbonylalkyl group substituted by a sulfo group, a phosphoric acid group or a carboxyl group (e.g., 3-sulfophenoxycarbonylpropyl) and an aryloxyalkyl group substituted by a sulf
  • alkyl group having a hydrocarbon aromatic or heteroaromatic group substituted by a sulfo group, a phosphoric acid group or a carboxyl group still more preferred is the alkyl group having a hydrocarbon aromatic ring substituted by a sulfo group, a phosphoric acid group or a carboxyl group, and most preferred are 2-sulfobenzyl, 4-sulfobenzyl, 4-sulfophenethyl, 3-phenyl-3-sulfopropyl and 4-phenyl-4-sulfobutyl.
  • the substituents represented by R 17 , R 18 , R 19 , R 20 , R 21 , R 22 and R 23 each is preferably the above-described unsubstituted alkyl group or substituted alkyl group (an alkyl group such as carboxyalkyl, sulfoalkyl, aralkyl and aryloxyalkyl).
  • the substituents represented by R 17 , R 18 , R 19 , R 20 , R 21 , R 22 and R 23 each is preferably the above-described unsubstituted alkyl group or substituted alkyl group, more preferably an alkyl group having an anionic substituent (an alkyl group such as carboxyalkyl and sulfoalkyl), still more preferably a sulfoalkyl group.
  • the methine group represented by L 1 to L 64 may have a substituent.
  • the substituent include V described above, such as a substituted or unsubstituted alkyl group having from 1 to 15, preferably from 1 to 10, more preferably from 1 to 5, carbon atoms (e.g., methyl, ethyl, 2-carboxyethyl), a substituted or unsubstituted aryl group having from 6 to 20, preferably from 6 to 15, more preferably from 6 to 10, carbon atoms (e.g., phenyl, o-carboxyphenyl), a substituted or unsubstituted heterocyclic group having from 3 to 20, preferably from 4 to 15, more preferably from 6 to 10, carbon atoms (e.g., N,N-dimethylbarbituric acid), a halogen atom (e.g., chlorine, bromine, iodine, fluorine), an alkoxy group having from 1 to 15, preferably from 1 to 10, more preferably from
  • L 1 , L 2 , L 3 , L 4 , L 5 , L 6 , L 10 , L 11 , L 12 , L 13 , L 16 , L 17 , L 23 , L 24 , L 25 , L 26 , L 30 , L 31 , L 32 , L 33 , L 36 , L 37 , L 43 , L 44 , L 45 , L 46 , L 50 , L 51 , L 52 , L 53 , L 56 , L 57 , L 63 and L 64 each is preferably an unsubstituted methine group.
  • n 1 , n 2 , n 3 , n 4 , n 5 , n 6 , n 7 , n 8 , n 9 , n 10 , n 11 and n 12 each independently represents 0, 1, 2, 3 or 4, preferably 0, 1, 2 or 3, more preferably 0, 1 or 2, still more preferably 0 or 1.
  • n 1 , n 2 , n 3 , n 4 , n 5 , n 6 , n 7 , n 8 , n 9 , n 10 , n 11 and n 12 each is 2 or more, the methine group is repeated but these methine groups need not be the same.
  • p 1 , p 2 , p 3 , p 4 , p 5 , p 6 , p 7 , p 8 , p 9 , p 10 , p 11 , p 12 , p 13 , p 14 , p 15 and p 16 each independently represents 0 or 1, preferably 0.
  • M 1 , M 2 , M 3 , M 4 , M 5 and M 6 each is included in the formulae so as to show the presence of a cation or anion when the ion charge of the dye is necessary to be neutralized.
  • Typical examples of the cation include inorganic cation such as hydrogen ion (H + ), alkali metal ion (e.g., sodium ion, potassium ion, lithium ion) and alkaline earth metal ion (e.g., calcium ion), and organic cation such as ammonium ion (e.g., ammonium ion, tetraalkylammonium ion, pyridinium ion, ethylpyridinium ion).
  • H + hydrogen ion
  • alkali metal ion e.g., sodium ion, potassium ion, lithium ion
  • alkaline earth metal ion e.g., calcium ion
  • the anion may be either inorganic anion or organic anion and examples thereof include halogen anion (e.g., fluoride ion, chloride ion, iodide ion), substituted arylsulfonate ion (e.g., p-toluenesulfonate ion, p-chlorobenzenesulfonate ion), aryldisulfonate ion (e.g., 1,3-benzenesulfonate ion, 1,5-naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion), alkylsulfate ion (e.g., methylsulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion and trifluoromethanes
  • m 1 , m 2 , m 3 , m 4 , m 5 and m 6 each represents a number of 0 or greater necessary for balancing the electric charge, preferably a number of from 0 to 4, more preferably from 0 to 1, and is 0 when an inner salt is formed.
  • both midpoint sensitivity and foot sensitivity on the photographic characteristic curve can be elevated and a sharp spectral sensitivity spectrum can be obtained.
  • Z24 represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring
  • Z25 represents an atomic group necessary for forming an aliphatic or aromatic ring and necessary for forming a polycyclic condensation structure comprising three or more rings including the nitrogen-containing heterocyclic ring formed by Z24
  • Q represents a group necessary for allowing the compound represented by formula (IV') to form a methine dye
  • R24 represents an alkyl group, an aryl group or a heterocyclic group
  • L65 and L66 each represents a methine group
  • p17 represents 0 or 1
  • M7 represents a counter ion for balancing the electric charge
  • m7 represents a number of from 0 to 10 necessary for neutralizing the electric charge of the molecule.
  • the cationic dye means a dye having no anionic substituent and the anionic dye means a dye having an anionic substituent.
  • the anionic substituent referred to in the present invention is a substituent having a negative charge and this substituent is an atomic group capable of readily dissociating under neutral or weakly alkaline conditions, particularly a substituent having hydrogen atom.
  • substituents having a negative charge include a sulfo group (-SO 3 - ), a sulfuric acid group (-OSO 3 - ), a carboxyl group (-CO 2 - ), a phosphoric acid group (-PO 3 - ), an alkylsulfonylcarbamoylalkyl group (e.g., methanesulfonylcarbamoylmethyl), an acylcarbamoylalkyl group (e.g., acetylcarbamoylmethyl), an acylsulfamoylalkyl group (e.g., acetylsulfamoylmethyl) and an alkylsulfonylsulfam
  • Light-sensitive materials using silver halide grains obtained by adsorbing a dye chromophore in one or more layers on a silver halide grain as described above exhibit a broad spectral sensitivity distribution in many cases.
  • the present inventors have found out that this problem can be improved by allowing the dye in the first layer and also the dyes in the second and subsequent layers to have spectral sensitivity due to absorption attributable to the J-association (i.e., J-aggregation).
  • any methine dye can be formed.
  • Preferred examples thereof include cyanine dyes, merocyanine dyes, rhodacyanine dyes, oxonol dyes, trinuclear merocyanine dyes, tetranuclear merocyanine dyes, allopolar dyes, styryl dyes, styryl base dyes, hemicyanine dyes, streptocyanine dyes and hemioxonol dyes.
  • cyanine dyes cyanine dyes
  • merocyanine dyes merocyanine dyes and rhodacyanine dyes
  • cyanine dyes in which the electric charge may be any of cation, anion and betaine.
  • F.M. Harmer Heterocyclic Compounds - Cyanine Dyes and Related Compounds , John Wiley & Sons, New York, London (1964), and D.M. Sturmer, Heterocyclic Compounds - Special Topics in Heterocyclic Chemistry , Chap. 18, Sec. 14, pp. 482-515, John Wiley & Sons, New York, London (1977).
  • formula (IV') may be expressed by the following resonance formula:
  • the number of methine groups in Q, Q3 or Q4 is preferably from 0 to 7, more preferably from 0 to 5, still more preferably 3.
  • Q, Q3 or Q4 forms the above-described dye (e.g., cyanine dye, merocyanine dye, rhodacyanine dye, trinuclear merocyanine dye, allopolar dye, hemicyanine dye, styryl dye)
  • the number of methine groups may be 0 (for example, simple merocyanine).
  • the methine group is preferably substituted by a substituent (e.g., heterocyclic group, aliphatic group, aromatic group) necessary for forming a methine dye.
  • the substituent is preferably a heterocyclic group, an aliphatic group or an aromatic group, more preferably a heterocyclic group.
  • the aromatic group includes a substituted or unsubstituted aromatic group (e.g., 4-dimethylaminophenyl, 4-methoxyphenyl, phenyl, 4-dimethylaminonaphthyl).
  • a substituted or unsubstituted aromatic group e.g., 4-dimethylaminophenyl, 4-methoxyphenyl, phenyl, 4-dimethylaminonaphthyl.
  • Preferred examples of the aliphatic group include an alkoxy carbonyl group (e.g., ethoxycarbonyl) and an acyl group (e.g., acetyl).
  • Other examples include the substituents represented by V described above.
  • a substituted or unsubstituted amino group e.g., amino, dimethylamino
  • a cyano group an alkoxycarbonyl group (e.g., ethoxycarbonyl), a substituted or unsubstituted alkylsulfonyl group (e.g., methylsulfonyl) and a substituted or unsubstituted acyl group (e.g., acetyl).
  • Z24 represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring.
  • the nitrogen-containing heterocyclic ring formed by Z24 may be condensed with an aromatic ring.
  • Examples thereof include thiazoline nucleus, thiazole nucleus, oxazoline nucleus, oxazole nucleus, selenazoline nucleus, selenazole nucleus, 3,3-dialkyl-3H-pyrrole nucleus (e.g., 3, 3-dimethyl-3H-pyrrole), imidazoline nucleus, imidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus, imidazo[4,5-b]quinoxaline nucleus, oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus, pyrimidine nucleus, pyridazine nucleus and pyrazine nucleus.
  • thiazole nucleus preferred are thiazole nucleus, oxazole nucleus, selenazole nucleus, 3,3-dialkyl-3H-pyrrole nucleus, imidazole nucleus and 2-pyridine nucleus, and more preferred are thiazole nucleus, oxazole nucleus, imidazole nucleus and 2-pyridine nucleus.
  • the substituent represented by V is not particularly limited. Examples thereof include a halogen atom (e.g., chlorine, bromine, iodine, fluorine), a mercapto group, a cyano group, a carboxyl group, a phosphoric acid group, a sulfo group, a hydroxy group, a carbamoyl group having from 1 to 10, preferably from 2 to 8, more preferably from 2 to 5, carbon atoms (e.g., methylcarbamoyl, ethylcarbamoyl, morpholinocarbonyl), a sulfamoyl group having from 0 to 10, preferably from 2 to 8, more preferably from 2 to 5, carbon atoms (e.g., methylsulfamoyl, ethylsulfamoyl, piperidinosulfonyl), a nitro group, an alkoxy
  • a halogen atom e.g., chlorine, bromine
  • alkyl group preferred are the alkyl group, the aryl group, the alkoxy group, the halogen atom and benzene ring condensation products thereof, and more preferred are methyl group, phenyl group, methoxy group, chlorine atom, bromine atom, iodine atom and benzene ring condensation products thereof.
  • Z25 represents an atomic group necessary for forming an aliphatic or aromatic cyclic compound and necessary for forming a polycyclic condensation structure comprising three or more rings including the nitrogen-containing heterocyclic ring formed by Z24.
  • the cyclic structure formed by Z25 include an unsubstituted aliphatic cyclic structure having a bicyclic or greater polycyclic condensation ring structure (e.g., decahydronaphthalene), a substituted aliphatic cyclic structure having a bicyclic or greater polycyclic condensation structure (examples of the substituent include those described above as examples of the substituent V), an unsubstituted aromatic cyclic structure having a bicyclic or greater polycyclic condensation ring structure (e.g., pentalene, indene, naphthalene, azulene, anthracene, phananthrene, anthracene), a substituted aromatic cyclic structure having a bicyclic or greater polycyclic condensation ring structure
  • an unsubstituted aromatic ring structure having a bicyclic or greater polycyclic condensation ring structure e.g., pentalene, indene, naphthalene, azulene, anthracene, phenanthrene
  • a substituted aromatic ring structure having a bicyclic or greater polycyclic condensation ring structure e.g., pentalene, indene, naphthalene, azulene, anthracene, phenanthrene
  • a substituted aromatic ring structure having a bicyclic or greater polycyclic condensation ring structure e.g., pentalene, indene, naphthalene, azulene, anthracene, phenanthrene
  • a substituted aromatic ring structure having a bicyclic or greater polycyclic condensation ring structure e.g., pentalene, indene, naphthalene, azulene, anthracene, phenanthrene
  • Z26, Z27, Z28, Z29, Z30 and Z31 each represents an atomic group necessary for forming a nitrogen-containing heterocyclic ring, provided that an aromatic ring may be condensed thereto.
  • the aromatic ring include a benzene ring, a naphthalene ring and a heteroaromatic ring such as pyrazine ring and thiophene ring.
  • nitrogen-containing heterocyclic ring examples include thiazoline nucleus, thiazole nucleus, benzothiazole nucleus, oxazoline nucleus, oxazole nucleus, benzoxazole nucleus, selenazoline nucleus, selenazole nucleus, benzoselenazole nucleus, 3,3-dialkylindolenine nucleus (e.g., 3,3-dimethylindolenine), imidazoline nucleus, imidazole nucleus, benzimidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus, 2-quinoline nucleus, 4-quinoline nucleus, 1-isoquinoline nucleus, 3-isoquinoline nucleus, imidazo[4,5-b]quinoxaline nucleus, oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus and pyrimidine nucleus.
  • benzothiazole nucleus preferred are benzothiazole nucleus, benzoxazole nucleus, 3,3-dialkylindolenine nucleus (e.g., 3,3-dimethylindolenine), benzimidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus, 2-quinoline nucleus, 4-quinoline nucleus, 1-isoquinoline nucleus and 3-isoquinoline nucleus; more preferred are benzothiazole nucleus, benzoxazole nucleus, 3,3-dialkylindolenine nucleus (e.g., 3,3-dimethylindolenine) and benzimidazole nucleus; still more preferred are benzoxazole nucleus, benzothiazole nucleus and benzimidazole nucleus; and most preferred are benzoxazole nucleus and benzothiazole nucleus.
  • the nitrogen-containing heterocyclic ring may be further substituted by a substituent V described above.
  • the substituent V on Z26, Z27, Z28, Z29, Z30 or Z31 is preferably an aryl group, an aromatic heterocyclic ring or an aromatic ring condensation product.
  • L65 to L84 each independently represents a methine group.
  • the methine group represented by L65 to L84 may have a substituent and examples of the substituent include a substituted or unsubstituted alkyl group having from 1 to 15, preferably from 1 to 10, more preferably from 1 to 5, carbon atoms (e.g., methyl, ethyl, 2-carboxyethyl), a substituted or unsubstituted aryl group having from 6 to 20, preferably from 6 to 15, more preferably from 6 to 10, carbon atoms (e.g., phenyl, o-carboxyphenyl), a substituted or unsubstituted heterocyclic group having from 3 to 20, preferably from 4 to 15, more preferably from 6 to 10, carbon atoms (e.g., N,N-dimethylbarbituric acid), a halogen atom (e.g., chlorine, bromine, iodine, fluorine), an alkoxy group having from 1 to
  • L65 to L72, L76 to L79, L83 and L84 each is preferably an unsubstituted methine group.
  • p17, p18, p19, p20, p21, p22 and p23 each represents 0 or 1 and is preferably 0.
  • R24, R25, R26, R27, R28, R29 and R30 each represents an alkyl group, an aryl group or a heterocyclic group. Specific examples thereof include an unsubstituted alkyl group having from 1 to 18, preferably from 1 to 7, more preferably from 1 to 4, carbon atoms (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), a substituted alkyl group having from 1 to 18, preferably from 1 to 7, more preferably from 1 to 4, carbon atoms ⁇ for example, an alkyl group substituted by a substituent V described above, preferably an aralkyl group (e.g., benzyl, 2-phenylethyl), an unsaturated hydrocarbon group (e.g., allyl), a hydroxyalkyl group (e.g., 2-hydroxy
  • R25 and at least one of R27 and R28 represent an alkyl group substituted by an aromatic group (an aryl group or an aromatic heterocyclic group), an aryl group or an aromatic heterocyclic group and that R25 and both of R27 and R28 have no anionic substituent.
  • the substituent include the substituents V.
  • the dye in formula (IV'-1) or (IV'-3) must form a cationic dye.
  • aryl-substituted alkyl group examples include an aralkyl group (e.g., benzyl, 2-phenylethyl, naphthylmethyl, 2-(4-biphenyl)ethyl), an aryloxyalkyl group (e.g., 2-phenoxyethyl, 2-(1-naphthoxy)ethyl, 2-(4-biphenyloxy)ethyl, 2-(o,m,p-halophenoxy)ethyl, 2-(o,m,p-methoxyphenoxy)ethyl) and an aryloxycarbonylalkyl group (e.g., 3-phenoxycarbonylpropyl, 2-(1-naphthoxycarbonyl)-ethyl).
  • aralkyl group e.g., benzyl, 2-phenylethyl, naphthylmethyl, 2-(4-biphenyl)ethyl
  • Preferred examples of the aromatic heterocyclic ring-substituted alkyl group include 2-(2-pyridyl)ethyl, 2-(4-pyridyl)ethyl, 2-(2-furyl)ethyl, 2-(2-thienyl)ethyl and 2-(2-pyridylmethoxy)ethyl.
  • Preferred examples of the aryl group include 4-methoxyphenyl, phenyl, naphthyl and biphenyl.
  • Preferred examples of the aromatic heterocyclic group include 2-thienyl, 4-chloro-2-thienyl, 2-pyridyl and 3-pyrazolyl.
  • alkyl group substituted by an aromatic group aryl group or aromatic heterocyclic group
  • substituted or unsubstituted aryl group aryl group or aromatic heterocyclic group
  • R26 and at least one of R29 and R30 represent an alkyl group substituted by an aromatic group (an aryl group or an aromatic heterocyclic group), an aryl group or an aromatic heterocyclic group and that R26 and both of R29 and R30 have an anionic substituent.
  • the substituent include the substituents V.
  • the dye in formula (IV'-2) or (IV'-4) must form an anionic dye.
  • the alkyl group include an alkyl group having from 1 to 15, preferably from 1 to 10, carbon atoms and substituted by a sulfo group, a phosphoric acid group or a carboxyl group (for example, sulfomethyl, sulfoethyl, 2,2-difluoro-2-carboxyethyl, 2-phosphoethyl), an unsaturated hydrocarbon group substituted by a sulfo group, a phosphoric acid group or a carboxyl group (for example, 3-sulfo-2-propenyl), an alkoxyalkyl group substituted by a sulfo group, a phosphoric acid group or a carboxyl group (for example, 2-sulfomethoxyethyl), an alkoxycarbonylalkyl group substituted by a sulfo group, a phosphoric acid group or a carboxyl group (for example, sulfoethoxycarbonylethy
  • alkyl group substituted by an aryl group examples include an aralkyl group substituted by a sulfo group, a phosphoric acid group or a carboxyl group (for example, 2-sulfobenzyl, 4-sulfobenzyl, 4-sulfophenethyl, 3-phenyl-3-sulfopropyl, 3-phenyl-2-sulfopropyl, 4,4-diphenyl-3-sulfobutyl, 2-(4'-sulfo-4-biphenyl)ethyl, 4-phosphobenzyl), an aryloxycarbonylalkyl group substituted by a sulfo group, a phosphoric acid group or a carboxyl group (for example, 3-sulfophenoxycarbonylpropyl), an aryloxyalkyl group substituted by a sulfo group and a phosphoric acid group or a carboxyl group (for example, 2-(4
  • alkyl group substituted by an aromatic heterocyclic group examples include an aromatic heterocyclic group-substituted alkyl group substituted by a sulfo group, a phosphoric acid group or a carboxyl group (for example, 3-(2-pyridyl)-3-sulfopropyl, 3-(2-furyl)-3-sulfopropyl, 2-(2-thienyl)-2-sulfopropyl).
  • Preferred examples of the aryl group include an aryl group substituted by a sulfo group, a phosphoric acid group or a carboxyl group (for example, 4-sulfophenyl, 4-sulfonaphthyl).
  • Preferred examples of the aromatic heterocyclic group include an aromatic heterocyclic group substituted by a sulfo group, a phosphoric acid group or a carboxyl group (for example, 4-sulfo-2-thienyl, 4-sulfo-2-pyridyl).
  • aralkyl substituted by a sulfo group, a phosphoric acid group or a carboxyl group and the aryloxyalkyl group substituted by a sulfo group, a phosphoric acid group or a carboxyl group
  • n13 and n14 each independently represents 0, 1, 2, 3 or 4, preferably 0, 1, 2 or 3, more preferably 0, 1 or 2, still more preferably 0 or 1.
  • n13 and n14 each is 2 or more, the methine group is repeated but these methine groups need not be the same.
  • p17, p18, p19, p20, p21, p22 and p23 each independently represents 0 or 1, preferably 0.
  • M7, M8 and M9 each is included in the formulae so as to show the presence of a cation or anion when the ion charge of the dye is necessary to be neutralized.
  • Typical examples of the cation include inorganic cation such as hydrogen ion (H + ), alkali metal ion (e.g., sodium ion, potassium ion, lithium ion) and alkaline earth metal ion (e.g., calcium ion), and organic cation such as ammonium ion (e.g., ammonium ion, tetraalkylammonium ion, pyridinium ion, ethylpyridinium ion).
  • H + hydrogen ion
  • alkali metal ion e.g., sodium ion, potassium ion, lithium ion
  • alkaline earth metal ion e.g., calcium ion
  • organic cation such as ammonium i
  • the anion may be either inorganic anion or organic anion and examples thereof include halogen anion (e.g., fluoride ion, chloride ion, iodide ion), substituted arylsulfonate ion (e.g., p-toluenesulfonate ion, p-chlorobenzenesulfonate ion), aryldisulfonate ion (e.g., 1,3-benzenesulfonate ion, 1,5-naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion), alkylsulfate ion (e.g., methylsulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion and trifluoromethanes
  • n7, m8 and m9 each represents a number necessary for balancing the electric charge, and is 0 when an inner salt is formed.
  • the dyes of the present invention can be synthesized according to the methods described in F.M. Harmer, Heterocyclic Compounds - Cyanine Dyes and Related Compounds , John Wiley & Sons, New York, London (1964), D.M. Sturmer, Heterocyclic Compounds - Special topics in heterocyclic chemistry , Chap. 18, Sec. 14, pp. 482-515, John Wiley & Sons, New York, London (1977), Rodd's Chemistry of Carbon Compounds , 2nd ed., Vol. IV, Part B, Chap. 15, pp. 369-422, Elsevier Science Publishing Company Inc., New York (1977), and patents and literatures described above (cited for describing specific examples).
  • the present invention is not limited only to the use of sensitizing dyes of the present invention but a spectral sensitizing dye other than those of the present invention may also be used in combination.
  • any nucleus usually used as a basic heterocyclic nucleus in cyanine dyes may be applied.
  • the nucleus include a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrol nucleus, a oxazole nucleus, a thiazole nucleus, a selenazole nucleus, a imidazol nucleus, a tetrazole nucleus and a pyridine nucleus; nuclei obtained by fusing an alicyclic or aromatic hydrocarbon ring to the above-described nuclei (e.g., indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselen
  • a 5- or 6-membered heterocyclic nucleus may be applied as a nucleus having a ketomethylene structure, such as pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidine-2,4-dione nucleus, thiazolidine-2, 4-dione nucleus, rhodanine nucleus, thiobarbituric acid nucleus and 2-thioselenazoline-2,4-dione nucleus may be applied.
  • a ketomethylene structure such as pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidine-2,4-dione nucleus, thiazolidine-2, 4-dione nucleus, rhodanine nucleus, thiobarbituric acid nucleus and 2-thioselenazoline-2,4-dione nucleus may be applied.
  • the sensitizing dye for use in the present invention may be incorporated into the silver halide photographic emulsion of the present invention by directly dispersing the sensitizing dye in the emulsion or may be added to the emulsion after dissolving it in a solvent such as water, methanol, ethanol, propanol, acetone, methyl cellosolve, 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol, acetonitrile, tetrahydrofuran and N,N-dimethylformamide, or a mixed solvent thereof.
  • a solvent such as water, methanol, ethanol, propanol, acetone, methyl cellosolve, 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-meth
  • a method of dissolving a dye in a volatile organic solvent, dispersing the solution in water or hydrophilic colloid and adding the dispersion in the emulsion described in U.S. Patent 3,469,987 a method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving the dye, and adding this dispersion to the emulsion described in JP-B-64-24185 (the term "JP-B" as used herein means an "examined Japanese patent publication")
  • an ultrasonic wave may also be used.
  • the anionic dye and the cationic dye both preferably occupy 30% or more in the total amount of sensitizing dyes added.
  • either one of the cationic dye and the anionic dye is added in an amount corresponding to 80% or more of the saturation coverage and also added in an amount such that the total amount of sensitizing dyes added corresponds to 160% or more of the saturation coverage.
  • the dyes may be added after previously mixing those two dyes, however, the cationic dye and the anionic dye are preferably added separately.
  • the cationic dye is added earlier, in a more preferred embodiment, the cationic dye is added in an amount corresponding to 80% or more of the saturation coverage and then the anionic dye is added, and in a still more preferred embodiment, the cationic dye is added in an amount corresponding to 80% or more of the saturation coverage and then the anionic dye is added in an amount corresponding to 50% of the saturation coverage.
  • the dye added later preferably has a fluorescence yield in gelatin dry film, of 0.5 or more, more preferably 0.8 or more.
  • the dyes may be added at any time during the preparation of emulsion. Also, the dyes may be added at any temperature, however, the emulsion temperature at the addition of dyes is preferably from 10 to 75°C, more preferably from 30 to 65°C.
  • any of silver bromide, silver iodobromide, silver chlorobromide, silver iodide, silver iodochloride, silver iodobromochloride and silver chloride may be used.
  • the halogen composition on the outermost surface of emulsion grain preferably has an iodide content of 0.1 mol% or more, more preferably 1 mol% or more, still more preferably 5 mol% or more, whereby the multi-layer adsorption structure can be more firmly constructed.
  • the grain size distribution may be either broad or narrow but narrow distribution is preferred.
  • the silver halide grain of the photographic emulsion may be a grain having a regular crystal form such as cubic, octahedral, tetradecahedral or rhombic dodecahedral form, a grain having an irregular crystal form such as spherical or tabular form, a grain having a (hkl) face, or a mixture of grains having these crystal forms, however, a tabular grain is preferred.
  • the tabular grain is described in detail later.
  • the grain having a (hkl) face is described in Journal of Imaging Science , Vol. 30, pp. 247-254 (1986).
  • the above-described silver halide grains may be used either individually or in mixture of a plurality of grains.
  • the silver halide grain may have different phases between the interior and the surface layer, may have a multi-phase structure, for example, with a conjugation structure, may have a localized phase on the grain surface or may have a uniform phase throughout the grain. These grains may also be present together.
  • These various emulsions each may be either a surface latent image-type emulsion in which a latent image is mainly formed on the surface, or an internal latent image-type emulsion in which a latent image is formed inside the grain.
  • the silver halide emulsion for use in the present invention is preferably a tabular silver halide grain having a higher ratio of surface area/volume and having adsorbed thereto a sensitizing dye disclosed in the present invention.
  • the aspect ratio of the grain is 2 or more (preferably 100 or less), preferably from 5 to 80, more preferably from 8 to 80, and the thickness of the tabular grain is preferably less than 0.2 ⁇ m, more preferably less than 0.1 ⁇ m, still more preferably less than 0.07 ⁇ m.
  • a silver halide tabular grain having a halogen composition of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide or silver iodochloride is preferably used.
  • the tabular grain preferably has a main plane of (100) or (111).
  • the tabular grain having a (111) main plane is hereinafter referred to as a (111) tabular grain and this grain usually has a triangular or hexagonal face. In general, when the distribution becomes more uniform, tabular grains having a hexagonal face occupy a higher ratio.
  • JP-B-5-61205 describes the monodisperse hexagonal tabular grains.
  • the tabular grain having a (100) face as the main plane is hereinafter called a (100) tabular grain and this grain has a rectangular or square form.
  • a grain having a ratio of adjacent sides of less than 5:1 is called a tabular grain rather than an acicular grain.
  • the tabular grain is silver chloride or a grain having a high silver chloride content
  • the (100) tabular grain is higher in the stability of the main plane than that of the (111) tabular grain. Therefore, the (111) tabular grain must be subjected to stabilization of the (111) main plane, and the method therefor is described in JP-A-9-80660, JP-A-9-80656 and U.S. Patent 5,298,388.
  • the (111) tabular grain comprising silver chloride or having a high silver chloride content for use in the present invention is disclosed in the following patents:
  • the silver halide emulsion is generally subjected to chemical sensitization before use.
  • the chemical sensitization is performed using chalcogen sensitization (e.g., sulfur sensitization, selenium sensitization, tellurium sensitization), noble metal sensitization (e.g., gold sensitization) and reduction sensitization individually or in combination.
  • chalcogen sensitization e.g., sulfur sensitization, selenium sensitization, tellurium sensitization
  • noble metal sensitization e.g., gold sensitization
  • reduction sensitization individually or in combination.
  • the silver halide emulsion is preferably subjected to at least selenium sensitization. More specifically, selenium sensitization alone or a combination of selenium sensitization with another chalcogen sensitization and/or noble metal sensitization (particularly gold sensitization) is preferred, and a combination of selenium sensitization and noble metal sensitization is more preferred.
  • a labile selenium compound is used as a sensitizer.
  • the labile selenium compound is described in JP-B-43-13489, JP-B-44-15748, JP-A-4-25832, JP-A-4-109240, JP-A-4-271341 and JP-A-5-40324.
  • selenium sensitizer examples include colloidal metal selenium, selenoureas (e.g., N,N-dimethylselenourea, trifluoromethylcarbonyl-trimethylselenourea, acetyltrimethylselenourea), selenoamides (e.g., selenoamide, N,N-diethylphenylselenoamide), phosphine selenides (e.g., triphenylphosphineselenide, pentafluorophenyltriphenylphosphineselenide), selenophosphates (e.g., tri-p-tolylselenophosphate, tri-n-butylselenophosphate), selenoketones (e.g., selenobenzophenone), isocyanates, selenocarboxylic acids, selenoesters and diacyl selenides.
  • selenoureas e.g., N
  • selenium sensitizer relatively stable selenium compounds such as selenious acid, potassium selenocyanate, selenazoles and selenides (described in JP-B-46-4553 and JP-B-52-34492) may also be used as a selenium sensitizer.
  • a labile sulfur compound is used as a sensitizer.
  • the labile sulfur compound is described in P. Glafkides, Chimie et Physique Photographiques , 5th ed. , Paul Montel (1987), and Research Disclosure , Vol. 307, No. 307105.
  • sulfur sensitizer examples include thiosulfates (e.g., hypo), thioureas (e.g., diphenylthiourea, triethylthiourea, N-ethyl-N'-(4-methyl-2-thiazolyl)thiourea, carboxymethyltrimethylthiourea), thioamides (e.g., thioacetamide), rhodanines (e.g., diethylrhodanine, 5-benzylidene-N-ethyl-rhodanine), phosphinesulfides (e.g., trimethylphosphinesulfide), thiohydantoins, 4-oxo-oxazolidine-2-thiones, dipolysulfides (e.g., dimorpholinedisulfide, cystine, hexathiocane-thione), mercapto compounds (cysteine), polythionic acid
  • a labile tellurium compound is used as a sensitizer.
  • the labile tellurium compound is described in Canadian Patent 800,958, British Patents 1,295,462 and 1,396,696, JP-A-4-204640, JP-A-4-271341, JP-A-4-333043 and JP-A-5-303157.
  • tellurium sensitizer examples include telluroureas (e.g., tetramethyltellurourea, N,N'-dimethylethylenetellurourea, N,N'-diphenylethylenetellurourea), phosphinetellurides (e.g., butyldiisopropylphosphinetelluride, tributylphosphinetelluride, tributoxyphosphinetelluride, ethoxydiphenylphophinetelluride), diacyl(di)tellurides (e.g., bis(diphenylcarbamoyl)ditelluride, bis(N-phenyl-N-methylcarbamoyl)ditelluride, bis(N-phenyl-N-methylcarbamoyl)-telluride, bis(ethoxycarbonyl)telluride), isotellurocyanates, telluroamides, tellurohydrzides, telluroesters (e.g.
  • a salt of noble metals such as gold, platinum, palladium and iridium is used as a sensitizer.
  • the noble metal salt is described in P. Glafkides, Chimie et Physique Photographiques , 5th ed., Paul Montel (1987) and Research Disclosure , Vol. 307, No. 307105.
  • gold sensitization is preferred.
  • the present invention is particularly effective in the embodiment where gold sensitization is performed.
  • gold sensitizer examples include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide and gold selenide.
  • the gold compounds described in U.S. Patents 2,642,361, 5,049,484 and 5,049,485 may also be used.
  • a reducing compound is used as a sensitizer.
  • the reducing compound is described in P. Glafkides, Chimie et Physique Photographiques , 5th ed., Paul Montel, (1987), and Research Disclosure , Vol. 307, No. 307105.
  • the reducing sensitizer examples include aminoiminomethanesulfinic acid (i.e., thiourea dioxide), borane compounds (e.g., dimethylaminoborane), hydrazine compounds (e.g., hydrazine, p-tolylhydrazine), polyamine compounds (e.g., diethylenetriamine, triethylenetetramine), stannous chloride, silane compounds, reductones (e.g., ascorbic acid), sulfites, aldehyde compounds and hydrogen gas.
  • the reduction sensitization may also be performed by an atmosphere of high pH or excess silver ion (so-called silver ripening).
  • the reduction sensitization is preferably applied at the formation of silver halide grains.
  • the amount of the sensitizer used is generally determined according to the kind of silver halide grain and the conditions of chemical sensitization.
  • the amount of the chalcogen sensitizer used is from 10 -8 to 10 -2 mol, preferably from 10 -7 to 5 ⁇ 10 -3 mol, per mol of silver halide.
  • the amount of the noble metal sensitizer used is preferably from 10 -7 to 10 -2 mol per mol of silver halide.
  • the conditions for chemical sensitization are not particularly limited.
  • the pAg is generally from 6 to 11, preferably from 7 to 10.
  • the pH is preferably from 4 to 10.
  • the temperature is preferably from 40 to 95°C, more preferably from 45 to 85°C
  • JP-A-10-239789, column 63, line 36 to column 65, line 2 may be applied.
  • additives such as color coupler
  • additives to the photographic light-sensitive material the kind of light-sensitive material to which the present invention can be applied, the processing of the light-sensitive material, and the like, JP-A-10-239789, column 65, line 3 to column 73, line 13 may be applied.
  • the temperature of the thus-obtained emulsion was lowered and after adding thereto a copolymer of isobutene and maleic acid sodium salt as a coagulant, desalted by precipitation washing. Subsequently, 95 g of deionized ossein gelatin and 430 ml of water were added thereto and the resulting solution was adjusted to have a pH of 6.5 and a pAg of 8.3 at 50°C. Thereto, potassium thiocyanate, chloroauric acid and sodium thiosulfate were added to give optimal sensitivity, and then this emulsion was ripened at 55°C for 50 minutes. The emulsion obtained was designated as Emulsion A.
  • Emulsion B While again keeping the temperature at 40°C, 45.6 g of gelatin, 10 ml of an aqueous sodium hydroxide solution in a concentration of 1 mol/l, 167 ml of water and 1.66 ml of 35% phenoxy ethanol were added and the pAg and the pH were adjusted to 8.3 to 6.20, respectively. Thereto, potassium thiocyanate, chloroauric acid and sodium thiosulfate were added to give an optimal sensitivity, and then this emulsion was ripened at 55°C for 50 minutes. The emulsion obtained was designated as Emulsion B.
  • an emulsion was prepared by performing the chemical sensitization using potassium thiocyanate, chloroauric acid, pentafluorophenyldiphenylphosphineselenide and sodium thiosulfate in place of potassium thiocyanate, chloroauric acid and sodium thiosulfate, and designated as Emulsion C. Assuming that the dye occupation area is 80 ⁇ 2 , the single layer saturation coverage amounts of Emulsion A and B were 5.4 ⁇ 10 -4 mol/mol-Ag and 1.42 ⁇ 10 -3 mol/mol-Ag, respectively.
  • a first dye shown in Table 1 was added while keeping the emulsion at 50°C, and then each emulsion was stirred for 30 minutes. Thereafter, a second dye and a third dye were continuously added and each emulsion was further stirred at 50°C for 30 minutes.
  • the amount of dye adsorbed was determined as follows. Each liquid emulsion obtained was centrifuged and thereby precipitated at 10,000 rpm for 10 minutes, the precipitate was freeze-dried, 25 ml of a 25% aqueous sodium thiosulfate solution and methanol were added to 0.05 g of the precipitate to form 50 ml of solution, the solution obtained was analyzed by high-speed liquid chromatography, and the dye density was quantitated.
  • the light absorption intensity per unit area was measured as follows.
  • the emulsions obtained each was thinly coated on a slide glass and the transmission spectrum and reflection spectrum of individual grains were determined using a microspectrophotometer MSP65 manufactured by Carl Zeiss K.K. by the following method to determine the absorption spectrum.
  • the transmission spectrum the area where grains were not present was used as the reference, and the reference for the reflection spectrum was obtained by measuring silicon carbide of which reflectance is known.
  • the measured area is a circular aperture part having a diameter of 1 ⁇ m. After adjusting the position not to allow the aperture part to overlap the contour of a grain, the transmission spectrum and the reflection spectrum were measured in the wave number region of from 14,000 cm -1 (714 nm) to 28,000 cm -1 (357 nm).
  • the absorption spectrum was determined from the absorption factor A which is 1 - T (transmittance) - R (reflectance).
  • the absorption factor A' obtained by subtracting the absorption of silver halide, -Log(1-A') was integrated with respect to the wave number (cm -1 ) and the value obtained was halved and used as a light absorption intensity per unit area.
  • the integration range is from 14,000 to 28,000 cm -1 .
  • the light source used was a tungsten lamp and the light source voltage was 8 V.
  • a monochromator in the primary side was used and the wavelength distance and the slit width were set to 2 nm and 2.5 nm, respectively.
  • the infinite diffusion reflectance of a finished emulsion was converted according to the Kubelka-Munk equation using as a control an emulsion in which a dye was not added, and absorption spectrum of only the dye was obtained.
  • the spectral sensitivity of the coated film was determined from the amount of exposure necessary for giving a density of fog + 0.2 when exposure was performed using a spectral exposing machine adjusted such that the photon numbers of respective wavelengths can be the same in the exposure wavelength region.
  • a gelatin hardening agent and a coating aid were added to each emulsion obtained and the emulsions each was coated on a cellulose acetate film support simultaneously with the gelatin protective layer to have a coated silver amount of 3.0 g-Ag/m 2 .
  • the film formed was exposed to a tungsten bulb (color temperature: 285°K) for 1 second through a continuous wedge color filter.
  • tungsten bulb color temperature: 285°K
  • Fuji Gelatin Filter SC-50 manufactured by Fuji Photo Film Co., Ltd.
  • the developed film was measured on the optical density by Fuji Automatic Densitometer.
  • the sensitivity is a reciprocal of light intensity necessary for giving an optical density of fog+0.2 and shown by a value while assuming that the sensitivity when only the first dye was added is 100.
  • the sensitizing dye can be adsorbed in multiple layers on the grain surface to form J-aggregate, so that the light absorption intensity can be increased within a narrow wavelength range. Furthermore, by using a silver halide emulsion having such absorption intensity and wavelength properties, the silver halide light-sensitive material obtained can have high sensitivity only to the objective wavelength region and can have good color separation and high color reproducibility.
  • the dye in the second or subsequent layers must form J-aggregate and it has been found that by realizing such an adsorption state, there is provided an effect that the coagulation of grains is reduced. This is considered to occur because the interaction of grains on the surface is reduced as a result of formation of J-aggregate by the dye in the second or subsequent layers. This effect is quite an unexpected result.
  • a pure silver chloride tabular grain emulsion was prepared in the same manner as Emulsion D in Example 2 of JP-A-8-227117.
  • the grain surface area was 5.15 ⁇ 10 2 m 2 /mol Ag and when the dye occupation area was taken as 80 ⁇ 2 , the single layer saturation coverage was 1.07 ⁇ 10 -3 mol/mol-Ag.
  • 1.1 ⁇ 10 -3 mol/mol-Ag of Sensitizing Dye I-6 was added at 56°C and after stirring the solution for 30 minutes, 6.0 ⁇ 10 -4 mol/mol-Ag of Sensitizing Dye I-6 and 6.0 ⁇ 10 -4 mol/mol-Ag of Sensitizing Dye II-7 were added.
  • Emulsion 2A Comparative
  • 1.1 ⁇ 10 -3 mol/mol-Ag of Sensitizing Dye I-6 was added at 56°C and after stirring the solution for 30 minutes, 6.0 ⁇ 10 -4 mol/mol-Ag of Sensitizing Dye I-4 and 6.0 ⁇ 10 -4 mol/mol-Ag of Sensitizing Dye II-4 were added.
  • Emulsion 2B Reference
  • Emulsion 2C Comparative
  • Coated Samples were prepared in the same manner as Coated Sample F in Example 3 of JP-A-8-227117.
  • a sample obtained by using Emulsion 2A in place of Emulsion F of Coated Sample F in Example 3 of JP-A-8-227117 was designated as Sample 2A, and samples obtained by similarly using Emulsion 2B or Emulsion 2C in place of Emulsion F were designated as Sample 2B and Sample 2C, respectively.
  • the amount of dye adsorbed, the adsorption layer number and the light absorption intensity were determined in the same manner as in Example 1. Furthermore, the absorption spectrum and the spectral sensitivity distribution of each emulsion were measured in the same manner as in Example 1.
  • the coated samples were each exposed through an optical wedge and a blue filter for 1/100 second using Fuji FW-Type Sensitometer (manufactured by Fuji Photo Film Co., ltd.), subjected to Fuji Photo Film CN16 processing, and compared on the photographic properties.
  • the sensitivity is a reciprocal of an exposure amount necessary for giving a density of fog+0.2 and shown by a relative value based on the sensitivity of Sample 2C.
  • Emulsion A-1 octahedral internal latent image-type direct positive emulsion
  • core grain octahedral silver bromide crystals having an average grain size (equivalent sphere diameter) of about 0.7 ⁇ m and equalized in the grain size were produced.
  • the core grain obtained was subjected to chemical sensitization using the following container and formulation.
  • a propeller-style seamless integrated blade made of a metal of which surface was teflon-coated.
  • the resulting emulsion was washed with water by an ordinary flocculation method and thereto, the gelatin prepared above, 2-phenoxyethanol and methyl p-hydroxybenzoate were added to obtain octahedral silver bromide crystals having an average grain size (equivalent sphere diameter) of about 1.4 ⁇ m and equalized in the grain size (hereinafter referred to as an "internal latent image-type core/shell grain").
  • Emulsions B to G octahedral internal latent image-type direct positive emulsions
  • Octahedral internal latent image-type direct positive silver halide emulsions each having an average grain size (equivalent sphere diameter) shown in Table 4 and equalized in the grain size were obtained by changing respective addition times of the aqueous silver nitrate solution and the aqueous potassium bromide solution and further changing the amounts of chemicals added in the preparation of Emulsion A-1.
  • Table 4 Name of Emulsion Average Grain Size, ⁇ m B 1.20 C 0.93 D 1.20 E 0.94 F 0.74 G 0.66
  • a comparative light-sensitive element having a structure shown below was prepared.
  • the sensitizing dyes were added at the completion of chemical sensitization of the shell and the kind of dye, the dispersion form, the addition temperature and the amount are shown in Table 5.
  • Carboxymethyl cellulose (CMC CELLOGEN 6A, produced by Daiichi Kogyo Seiyaku K.K.)
  • polyvinyl alcohol (PVA-220E) Polymerization degree: about 2,000, saponification degree: 88%.
  • Polymethyl methacrylate spherical latex (average particle size: 3 ⁇ m)
  • Emulsions A-2 to A-4 were prepared by adding dyes in the second and subsequent layers (first dye + second dye) after adding the first layer dye as shown in Table 6 in place of adding dyes (7), (4) and (6) to Emulsion A-1 of the fourteenth layer, and light-sensitive elements obtained by using these emulsions were designated as Samples 102 to 104, respectively. TABLE 6 Sample No.
  • a cover sheet was prepared as follows.
  • the light piping preventing dye used was a 3:1 mixture of KAYASET GREEN A-G produced by Nippon Kayaku K.K. and a compound shown below:
  • An alkali processing composition was prepared as follows.
  • These light-sensitive elements (Samples 101 to 104) were subjected to spectrum exposure from the emulsion layer side through a continuous wedge in an equi-energy spectrum exposing machine and then superposed on the cover sheet prepared above. Between two materials, the above-described processing solution was developed to have a thickness of 62 ⁇ m by a pressure roller. The processing was performed at 25°C and after 10 minutes, the transfer density was measured by a color densitometer.
  • samples 103 and 104 were compared with respect to the equi-energy spectral sensitivity spectrum obtained.
  • the samples of the present invention (Samples 103 and 104) exhibited a sharp spectral sensitivity spectrum distribution as compared with the conventional multi-layer system (Sample 102).
  • the light-sensitive elements (Samples 101 to 104) were exposed from the emulsion layer side through a gray continuous wedge and superposed on the cover sheet prepared above.
  • the above-described processing solution was developed between two materials by a pressure roller to have a thickness of 62 ⁇ m.
  • the exposure was performed for 1/100 second while controlling the exposure illuminance to give a constant exposure amount.
  • the processing was performed at 25°C and after 10 minutes, the transfer density was measured by a color densitometer. Subsequently, a characteristic curve was drawn by denoting the logarithm of exposure amount on the abscissa and each color density on the ordinate.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Claims (12)

  1. Photographische Silberhalogenidemulsion, die ein Silberhalogenidkorn mit einer Wellenlänge des spektralen Absorptionsmaximums von 500 nm oder mehr und einer Lichtabsorptionsintensität von 100 oder mehr umfasst, worin unter der Annahme, dass der maximale Wert des spektralen Absorptionsfaktors der Emulsion durch einen Sensibilisierungsfarbstoff Amax ist, der Abstand zwischen der kürzesten Wellenlänge, die 80 % von Amax zeigt, und der längsten Wellenlänge, die 80 % von Amax zeigt, 20 nm oder mehr ist und der Abstand zwischen der kürzesten Wellenlänge, die 50 % von Amax zeigt, und der längsten Wellenlänge, die 50 % von Amax zeigt, 120 nm oder weniger ist, und worin die photographische Silberhalogenidemulsion mehrschichtig adsorbierte Sensibilisierungsfarbstoffschichten aufweist und der Farbstoff in der zweiten oder nachfolgenden Schicht in den mehrschichtig adsorbierten Farbstoffschichten ein J-Aggregat bildet.
  2. Photographische Silberhalogenidemulsion, die ein Silberhalogenidkorn mit einer Wellenlänge des spektralen Absorptionsmaximums von 500 nm oder mehr und einer Lichtabsorptionsintensität von 100 oder mehr umfasst, worin unter der Annahme, dass der maximale Wert der spektralen Empfindlichkeit der Emulsion durch einen Sensibilisierungsfarbstoff Smax ist, der Abstand zwischen der kürzesten Wellenlänge, die 80 % von Smax zeigt, und der längsten Wellenlänge, die 80 % von Smax zeigt, 20 nm oder mehr ist und der Abstand zwischen der kürzesten Wellenlänge, die 50 % von Smax zeigt, und der längsten Wellenlänge, die 50 % von Smax zeigt, 120 nm oder weniger ist, und worin die photographische Silberhalogenidemulsion mehrschichtig adsorbierte Sensibilisierungsfarbstoffschichten aufweist und der Farbstoff in der zweiten oder nachfolgenden Schicht in den mehrschichtig adsorbierten Farbstoffschichten ein J-Aggregat bildet.
  3. Photographische Silberhalogenidemulsion gemäß
    Anspruch 1, worin die längste Wellenlänge, die einen spektralen Absorptionsfaktor von 50 % von Amax zeigt, im Bereich von 500 bis 510 nm, von 560 bis 610 nm oder von 640 bis 730 nm liegt.
  4. Photographische Silberhalogenidemulsion gemäß
    Anspruch 2, worin die längste Wellenlänge, die eine spektrale Empfindlichkeit von 50 % von Smax zeigt, im Bereich von 500 bis 510 nm, von 560 bis 610 nm oder von 640 bis 730 nm liegt.
  5. Photographische Silberhalogenidemulsion gemäß
    Anspruch 1, 2, 3 oder 4, worin die Silberhalogenidemulsion einen Farbstoff mit wenigstens einer aromatischen Gruppe enthält.
  6. Photographische Silberhalogenidemulsion gemäß Anspruch 1 oder 2, worin die Wellenlänge des Absorptionsmaximums des Farbstoffchromophors in der ersten Schicht in den mehrschichtig adsorbierten Farbstoffschichten länger als diejenige des Farbstoffchromophors in der zweiten oder nachfolgenden Schicht in den mehrschichtig adsorbierten Farbstoffschichten ist.
  7. Photographische Silberhalogenidemulsion gemäß Anspruch 1 oder 2, worin der Farbstoff in der zweiten oder nachfolgenden Schicht eine vom Farbstoff in der ersten Schicht in den mehrschichtig adsorbierten Farbstoffschichten unterschiedliche Struktur hat und die zweite oder nachfolgende Schicht sowohl einen kationischen als auch einen anionischen Farbstoff enthält.
  8. Photographische Silberhalogenidemulsion gemäß einem der Ansprüche 1 bis 7, die einen Sensibilisierungsfarbstoff mit einem Grundkern enthält, der durch die Kondensation von drei oder mehr Ringen gebildet wird.
  9. Photographische Silberhalogenidemulsion gemäß einem der Ansprüche 1 bis 8, worin das Silberhalogenidkorn mit einer Wellenlänge des spektralen Absorptionsmaximums von 500 nm oder mehr und einer Lichtabsorptionsintensität von 100 oder mehr ein Tafelkorn mit einem Seitenverhältnis von 2 oder mehr ist.
  10. Photographische Silberhalogenidemulsion gemäß einem der Ansprüche 1 bis 9, worin das Silberhalogenidkorn mit einer Wellenlänge des spektralen Absorptionsmaximums von 500 nm oder mehr und einer Lichtabsorptionsintensität von 100 oder mehr einer Selensensibilisierung unterworfen ist.
  11. Photographisches lichtempfindliches Silberhalogenidmaterial, das wenigstens eine photographische Silberhalogenidemulsion umfasst und das eine in einem der Ansprüche 1 bis 10 beschriebene photographische Silberhalogenidemulsion enthält.
  12. Photographische Silberhalogenidemulsion gemäß Anspruch 1 oder 2, worin der in mehrfachen Schichten adsorbierte Sensibilisierungsfarbstoff ein durch Formel (III) dargestellter verknüpfter Farbstoff ist: D 1 ( L a [ D 2 ] q ) r M 3 m 3
    Figure imgb0358

    worin D1 und D2 jeweils einen Farbstoffchromophor darstellen, La eine Verknüpfungsgruppe oder eine Einfachbindung darstellt, q und r jeweils eine ganze Zahl von 1 bis 100 darstellen, M3 ein ladungsausgleichendes Gegenion darstellt und m3 eine Zahl darstellt, die zur Neutralisierung der elektrischen Ladung des Moleküls notwendig ist.
EP00111917A 1999-06-17 2000-06-14 Photographische Silberhalogenidemulsion und diese verwendendes photographisches lichtempfindliches Material Expired - Lifetime EP1061411B1 (de)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP11171324A JP2001005132A (ja) 1999-06-17 1999-06-17 ハロゲン化銀写真感光材料
JP17132499 1999-06-17
JP19471499 1999-07-08
JP19471499 1999-07-08
JP36327299A JP2001075222A (ja) 1999-07-08 1999-12-21 ハロゲン化銀写真乳剤およびそれを用いた写真感光材料
JP36327299 1999-12-21

Publications (2)

Publication Number Publication Date
EP1061411A1 EP1061411A1 (de) 2000-12-20
EP1061411B1 true EP1061411B1 (de) 2006-10-11

Family

ID=27323476

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00111917A Expired - Lifetime EP1061411B1 (de) 1999-06-17 2000-06-14 Photographische Silberhalogenidemulsion und diese verwendendes photographisches lichtempfindliches Material

Country Status (3)

Country Link
EP (1) EP1061411B1 (de)
AT (1) ATE342523T1 (de)
DE (1) DE60031203T2 (de)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003121956A (ja) 2001-10-11 2003-04-23 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
US6699652B1 (en) 2003-01-17 2004-03-02 Eastman Kodak Company Color photographic material with improved sensitivity comprising a pyrazolotriazole coupler
US6908730B2 (en) 2003-01-17 2005-06-21 Eastman Kodak Company Silver halide material comprising low stain antenna dyes
US6794121B2 (en) 2003-01-17 2004-09-21 Eastman Kodak Company Method of making a silver halide photographic material having enhanced light absorption and low fog and containing a scavenger for oxidized developer
US6811963B2 (en) 2003-01-17 2004-11-02 Eastman Kodak Company Color photographic material with improved sensitivity
US6790602B2 (en) 2003-01-17 2004-09-14 Eastman Kodak Company Method of making a silver halide photographic material having enhanced light absorption and low fog
US6787297B1 (en) 2003-05-12 2004-09-07 Eastman Kodak Company Dye-Layered silver halide photographic elements with low dye stain

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3622317A (en) * 1965-03-08 1971-11-23 Polaroid Corp Photoresponsive articles comprising pseudo-polymeric spectral sensitization systems
EP0985965A1 (de) * 1998-09-11 2000-03-15 Eastman Kodak Company Photographisches Material mit erhöhter Lichtabsorption

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2802693B2 (ja) * 1991-08-14 1998-09-24 富士写真フイルム株式会社 ハロゲン化銀乳剤
US5609978A (en) * 1995-06-06 1997-03-11 Eastman Kodak Company Method for producing an electronic image from a photographic element
JPH10239789A (ja) * 1996-10-24 1998-09-11 Fuji Photo Film Co Ltd ハロゲン化銀写真乳剤及び該ハロゲン化銀写真乳剤を含むハロゲン化銀写真感光材料
US6117629A (en) * 1996-10-24 2000-09-12 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion and silver halide photographic material containing said silver halide photographic emulsion
DE19711142A1 (de) * 1997-03-18 1998-09-24 Agfa Gevaert Ag Hochempfindliches farbfotografisches Aufzeichnungsmaterial mit erhöhter Empfindlichkeit im blauen Spektralbereich

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3622317A (en) * 1965-03-08 1971-11-23 Polaroid Corp Photoresponsive articles comprising pseudo-polymeric spectral sensitization systems
EP0985965A1 (de) * 1998-09-11 2000-03-15 Eastman Kodak Company Photographisches Material mit erhöhter Lichtabsorption

Also Published As

Publication number Publication date
DE60031203T2 (de) 2007-08-23
DE60031203D1 (de) 2006-11-23
EP1061411A1 (de) 2000-12-20
ATE342523T1 (de) 2006-11-15

Similar Documents

Publication Publication Date Title
US6331385B1 (en) Photographic material having enhanced light absorption
JPH08220681A (ja) 写真要素
EP1061411B1 (de) Photographische Silberhalogenidemulsion und diese verwendendes photographisches lichtempfindliches Material
US6582894B1 (en) Silver haide photographic emulsion and photographic light-sensitive material using same
US7161010B2 (en) Methine compound and silver halide photographic material containing the same
JPH10171058A (ja) ハロゲン化銀写真乳剤及び該ハロゲン化銀写真乳剤を含むハロゲン化銀写真感光材料
US6465166B1 (en) Methine compound and silver halide photographic material
US6521401B1 (en) Silver halide photographic emulsion and silver halide photographic material
US6458524B1 (en) Silver halide photographic light-sensitive material
JP3929616B2 (ja) ハロゲン化銀写真乳剤
JP2001075222A (ja) ハロゲン化銀写真乳剤およびそれを用いた写真感光材料
JP2001075226A (ja) ハロゲン化銀写真感光材料
JP2001075221A (ja) ハロゲン化銀写真乳剤、及びそれを用いたハロゲン化銀写真感光材料
JP3587332B2 (ja) ハロゲン化銀写真感光材料
JP3522962B2 (ja) ハロゲン化銀写真感光材料
JPH10239789A (ja) ハロゲン化銀写真乳剤及び該ハロゲン化銀写真乳剤を含むハロゲン化銀写真感光材料
EP1251395B1 (de) Photographisches Silberhalogenidmaterial enthaltend einen Methinfarbstoff
JP3476315B2 (ja) ハロゲン化銀乳剤
JP2001255615A (ja) ハロゲン化銀写真感光材料
JP3781307B2 (ja) ハロゲン化銀写真乳剤及び該ハロゲン化銀写真乳剤を含むハロゲン化銀写真感光材料
JP2001166413A (ja) 色素化合物およびそれを用いたハロゲン化銀写真感光材料
JP3791721B2 (ja) ハロゲン化銀写真感光材料
JP2000345060A (ja) メチン化合物、ハロゲン化銀乳剤及びハロゲン化銀写真感光材料
JP2001152037A (ja) メチン化合物およびそれを用いたハロゲン化銀写真感光材料
JP2001075220A (ja) ハロゲン化銀写真乳剤及びハロゲン化銀写真感光材料

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

17P Request for examination filed

Effective date: 20010515

AKX Designation fees paid

Free format text: AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

17Q First examination report despatched

Effective date: 20031127

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20061011

Ref country code: LI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20061011

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20061011

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20061011

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20061011

Ref country code: CH

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20061011

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20061011

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 60031203

Country of ref document: DE

Date of ref document: 20061123

Kind code of ref document: P

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070111

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070111

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070122

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: FUJIFILM CORPORATION

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070319

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

EN Fr: translation not filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20070712

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070630

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20070614

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070112

Ref country code: FR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070601

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070614

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070614

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20061011

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20061011

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070614

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20100519

Year of fee payment: 11

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 60031203

Country of ref document: DE

Effective date: 20120103

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120103