Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/08—Sensitivity-increasing substances
  • G03C1/10—Organic substances
  • G03C1/12—Methine and polymethine dyes
  • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
  • G03C1/20—Methine and polymethine dyes with an odd number of CH groups with more than three CH groups
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/08—Sensitivity-increasing substances
  • G03C1/10—Organic substances
  • G03C1/12—Methine and polymethine dyes
  • G03C1/26—Polymethine chain forming part of a heterocyclic ring
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C3/00—Packages of films for inserting into cameras, e.g. roll-films, film-packs; Wrapping materials for light-sensitive plates, films or papers, e.g. materials characterised by the use of special dyes, printing inks, adhesives
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/16—X-ray, infrared, or ultraviolet ray processes
  • G03C5/164—Infra-red processes
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
  • G03C2001/03517—Chloride content

Definitions

• This invention relates to a method for storing an infrared-sensitive silver halide photographic material, and more particularly, to a storage method for preventing the change of photographic characteristics of a silver halide photographic material spectrally sensi­tized to an infrared wavelength region with the passage of time.
• the invention relates to a storage method for maintaining the photographic charac­teristics of a silver halide color photographic material spectrally sensitized to an infrared wavelength region for laser scanning exposure with the passage of time.
• the invention relates to a photographic composite composed of an infrared-sensitive silver halide photographic material and a packaging material therefor.
• Conventional means for obtaining hard copies from soft information include methods using electric or magnetic signals, using light-insensitive recording materials such as an ink jet system, etc., and using light-sensitive recording materials such as silver halide photographic materials, electrophotographic materials, etc.
• the last method is by recording using an optical system emitting light controlled with image information, and since the optical system has a high resolving power and can make not only a multi-value record but also a multi-gradient record, this method is useful for obtaining a high image quality.
• the image formation is performed chemically, the use of a silver halide photographic material gives a higher image quality and larger recorded amounts of information than when using an electrophotographic material.
• the silver halide color photographic material For quickly and easily processing silver halide color photographic materials as described above, a specific system is required. Also, the silver halide color photographic material must have sufficient performance in the light-sensitive wavelength, optimum sensitivity, color separation, and further the stability of sensitivity, matching the optical system used.
• Conventional color copying techniques include a copying system using an electrophotographic technique, a laser printer, and a combination of LED (light-emitting diode), heat development of silver halide, and a dye diffusion system.
• LED light-emitting diode
• JP-A-61-137149 discloses a silver halide color photo­graphic material having at least three silver halide emulsion layers each using an ordinary color coupler on a support, at least two emulsion layers having been spectrally sensitized for laser light of an infrared wavelength region.
• JP-A-63-197947 discloses a full color recording material having at least three light-sensitive layers each containing a color coupler on a support, at least one layer having been spectrally sensitized to a longer wavelength region than about 670 n.m. in spectral sensitivity maximum wavelength so that the layer is sensitive to LED or a semiconductor laser, a color image being obtained by a scanning exposure and subsequent development.
• This patent application also discloses a particularly high sensitive and stable spectral sensitizing method and a method of using dyes.
• JP-A-55-13505 discloses an image recording system for a color photographic material by controlling coloring of yellow, magenta, and cyan, respectively by three kinds of luminous fluxes each having a different wavelength, e.g., luminous fluxes of green, red, and infrared.
• a method using a silver halide color photo­graphic material for obtaining hard copies from soft information can easily give stable copies having a high image quality as compared to light-insensitive recording methods and those using an electrophotographic material. Also, the use of a semiconductor laser for the scanning exposure is advantageous since the exposure apparatus is compact and inexpensive.
• the wavelength of a semiconductor laser which can be used for the purpose can not be optionally selected.
• a semi­conductor laser having a wavelength of about 676 n.m. has been practically used, but many semiconductor lasers have been practically used in the infrared wavelength region.
• light-sensitive layers having spectral sensitivities to at least three different light-sensitive wavelength regions are required and hence one layer or two layers, or, as the case may be, three or more layers must have a spectral sensitivity in the infrared wavelength region.
• the photographic light-sensitive material have a high sensitivity; that stable performance is obtained even with deviations of the wavelength of the semiconductor laser, and that these features be attained in the infrared region.
• JP-A-53-144727 discloses a photographic product composed of a silver halide photographic material containing sensitizing dyes in a closed package with a packaging material having a low oxygen permeability under a low oxygen partial pressure, but it does not contain any practical description that such a system is effective for a sensitizing dye giving a spectrally sensitizing peak in the infrared region of a long wavelength as in this invention.
• a spectrally sensitizing dye selected from a tricarbocyanine sensitizing dye, a hexamethinemero­cyanine sensitizing dye, a pentamethinerhodacyanine sensitizing dye, and a heptamethinerhodacyanine sensi­tizing dye, each having a spectral sensitizing peak in the wavelength region longer than 720 n.m., the desensi­tization upon the storage of the photographic material is severe.
• a spectrally sensitizing dye selected from a tricarbocyanine sensitizing dye, a hexamethinemero­cyanine sensitizing dye, a pentamethinerhodacyanine sensitizing dye, and a heptamethinerhodacyanine sensi­tizing dye, each having a spectral sensitizing peak in the wavelength region longer than 720 n.m.
• An object of this invention is, therefore, to provide a simple method for maintaining the sensitivity during storage of a silver halide photographic material containing high silver chloride emulsion(s) sensitized by using a long wavelength infrared spectrally sensitizing dye.
• an infrared-sensitive silver halide photographic material which comprises storing in a deoxidized state an infrared-sensitive silver halide photographic material comprising a support having thereon at least one silver halide light-sensitive emulsion layer spectrally sensitized with at least one sensitizing dye selected from a tricarbocyanine sensitizing dye, a hexamethinemerocyanine sensitizing dye, a pentamethinerhodacyanine sensitizing dye, and a heptamethinerhodacyanine sensitizing dye, said light-­sensitive emulsion having a spectral sensitivity peak in the wavelength region of at least 720 n.m.
• the present invention also relates to a photographic composite i.e., a packaged photographic material comprising this infrared sensitive silver halide photographic material enclosed in a packaging material wherein the photograpic material is stored in a deoxidized state.
• a photographic composite i.e., a packaged photographic material comprising this infrared sensitive silver halide photographic material enclosed in a packaging material wherein the photograpic material is stored in a deoxidized state.
• oxygen volume ratio in this invention is as follows. That is, when the base content of oxygen atoms per unit volume of the atmosphere under 25°C and 1 atm. is defined as 21%, the content of oxygen atoms in the same unit volume under an optional temperature and pressure, i.e., the numerical value in direct proportional relation, is the oxygen volume ratio.
• the oxygen volume ratio is the product of the base oxygen ratio and the pressure, and the oxygen volume ratio is the content of oxygen per unit volume of certain gas for the atmosphere under normal conditions (25°C, 1 atm.).
• the oxygen volume ratio becomes 10.5%
• the atmosphere and nitrogen are mixed with other at 1:1 under 1 atm.
• the control of the oxygen volume ratio can be attained by generally known various methods in this invention.
• Oxygen may be removed by physical or mechanical methods, or by a chemical method.
• the air may be mixed or replaced with other gas containing no oxygen, or vacuum degassing may be employed. After vacuum degassing, the remaining air may be replaced with a gas containing no oxygen. Also, oxygen in the air may be reacted with another compound or element. Also, oxygen may be removed using a gas separating membrane or an oxygen pump.
• the term "deoxidized state” means a state in which the content of oxygen is less than that of the atmosphere, or a state in which the oxygen volume ratio is low.
• the oxygen volume ratio is preferably 2% or lower, and further is preferably as low as possible.
• the oxygen volume ratio is more preferably 1% or lower, and most preferably 0.5% or lower.
• the light-sensitive material can be stored or packed in an oxygen-free atmosphere, e.g., a nitrogen atmosphere, from production, or when the light-sensitive materials are stored in a closed vessel or closely packed in the air, the light-sensitive materials can be stored or packed with a deoxidizing agent such as an iron powder. This method is preferred to easily form a deoxidized state in a package form.
• an oxygen-free atmosphere e.g., a nitrogen atmosphere
• Such a deoxidized state may be maintained at any time after coating silver halide emulsions until the step of forming the product, or may be introduced to the when the product is packaged.
• the deoxidized state is maintained after opening the package for using the light-sensitive materials.
• the deoxidized state in this invention may be achieved in any step from the production of the light-sensitive materials to use thereof or throughout, whereby the charge of the performance or the light-sensitive materials can be prevented.
• a vacuum pump for keeping the deoxidized state for preventing the change of the photographic performance of the light-­sensitive materials after opening the package a vacuum pump, an oxygen separating membrane, or a solid oxygen pump can be used.
• a vacuum pump for keeping the deoxidized state for preventing the change of the photographic performance of the light-­sensitive materials after opening the package a vacuum pump, an oxygen separating membrane, or a solid oxygen pump can be used.
• Such a device can be incorporated in the apparatus for exposing and processing the light-­sensitive materials, or the device can be used individually.
• water contained in the light-sensitive material is also removed, which may retard the hardening reaction of gelatin, or cause the formation of fog, or curling of the light-sensitive material, but this technique is useful for stably storing the light-sensitive materials.
• a polymer or a metal foil substantially impermeable to oxygen is used as a packaging material, the light-sensitive material is closely packed by the packaging material, and before or after closely packaging, the deoxidized state is formed in the package.
• the polymer which can be used for this purpose includes polyvinylidene chloride, polyethylene tere­phthalate, nylon, and polyvinyl alcohol, as a polymer having a low oxygen permeability. Also, even a polymer having a high oxygen permeability, such as polyethylene, or the material obtained by copolymerizing or blending polyethylene with polyvinyl alcohol, is preferably used. Furthermore, polyvinyl chloride, polyvinyl acetate, polypropylene can be used.
• a metal foil an aluminum foil or a lead foil can be used.
• two or more packaging materials are preferably used as double or multiple package form.
• a conventional method of heat-welding the polymer film may be used.
• At least one silver halide light-sensitive emulsion layer of a silver halide photo­graphic material is spectrally sensitized by a tricarbo­cyanine sensitizing dye, a hexamethinemerocyanine sensitizing dye, a pentamethinerhodacyanine sensitizing dye, or a heptamethinerhodacyanine sensitizing dye, each providing a spectral sensitivity peak in the wavelength region of at least 720 n.m., i.e. 720 n.m. or longer.
• these sensitizing dyes can be used with other sensi­tizing dyes such as ordinary cyanine dyes, merocyanine dyes, or complex cyanine dyes.
• complex cyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, or hemioxonol dyes can be also used in combination.
• Cyanine dyes include simple cyanine dyes, carbocyanine dyes, and dicarbocyanine dyes.
• merocyanine dyes include zerimethinemerocyanine dyes, dimethinemerocyanine dyes, and tetramethinemerocyanine dyes.
• At least one light-sensitive emulsion layer is spectrally sensitized by at least one sensitizing dye selected from a tricarbocyanine sensitizing dye, a hexamethine­merocyanine sensitizing dye, a pentamethinerhodacyanine sensitizing dye, and a heptamethinerhodacyanine sensitizing dye each having a spectral sensitivity peak in the wavelength region of at least 720 n.m. and other light-sensitive emulsion layers may be layers having a spectral sensitivity peak shorter than 720 n.m.
• an ordinary color photographic light-­sensitive material is composed of plural light-sensitive emulsion layers containing a cyan coupler, a magenta coupler, and a yellow coupler respectively and in this invention, at least one of the coloring coloring light-­sensitive layers is required to be spectrally sensitized by a tricarbocyanine sensitizing dye, a hexamethine­merocyanine sensitizing dye, a pentamethinerhodacyanine sensitizing dye, or a heptamethinerhodacyanine sensi­tizing dye each having a spectral sensitivity peak in the wavelength region of at least 720 n.m. It is preferable that two different coloring light-sensitive emulsion layers are each spectrally sensitized to have a spectral sensitivity peak in the wavelength region of at least 720 n.m.
• three or more different coloring light-sensitive emulsion layers are all spectrally sensitized to have a spectral sensitivity peak in the region of at least 720 n.m.
• At least one light-sensitive emulsion layer must be spectrally sensitized with a tricarbocyanine sensitizing dye, a hexamethinemero­cyanine sensitizing dye, a pentamethinerhodacyanine sensitizing dye, or a heptamethinerhodacyanine sensi­tizing dye giving spectral sensitivity peak in the region of at least 720 n.m.
• a silver halide photographic material has light-sensitive emulsion layer(s) having a spectral sensitivity peak in the region shorter than 720 n.m.
• each color light-sensitive emulsion layer may be selectively spectrally sensitized for matching with a laser diode emitting light having a wavelength in a different wavelength region of, for example, 650 n.m. to 690 n.m., 720 n.m. to 790 n.m., or 770 n.m. to 850 n.m.
• selectively spectrally sensitized means that when the light-sensitive material having the light-­sensitive layer thus sensitized is exposed by the main wavelength of one laser diode, the sensitivity of the light-sensitive layer thus sensitized is sufficiently separated from that of other color light-sensitive layers to avoid mixing of colors is spectral sensi­tivity, which would cause an improper color reproduc­tion.
• the spectrally sensitizing dye which is preferably used in this invention that is, the spectrally sensitizing dye which is used for visible sensitization to infrared sensitization, can be selected from the compounds represented by formulae (I), (II), and (III) shown below.
• At least one light-sensitive emulsion layer is spectrally sensitized to have a spectral sensitivity peak in the wavelength region of at least 720 n.m. with at least one sensitizing dye selected from a tricarbocyanine sensi­tizing dye typified by a compound shown by following formula (I) wherein m11 is 3; a pentamethinerhodacyanine sensitizing dye or a heptamethinerhodacyanine sensiti­zing dye typified by a compound shown by following formula (II) wherein m21 + m22 is 3 or 4, and a hexa­methinemerocyanine sensitizing dye typified by a compound shown by following formula (III) wherein m31 is 3.
• a sensitizing dye selected from a tricarbocyanine sensi­tizing dye typified by a compound shown by following formula (I) wherein m11 is 3; a pentamethinerh
• a sensitizing dye compound represented by formula (I) wherein m11 is 3 is called a tricarbocyanine sensitizing dye
• a sensitizing dye compound represented by formula (III) wherein m31 is 3 is called a hexa­methinemerocyanine sensitizing dye
• a sensitizing dye compound represented by formula (II) wherein m21 + m22 is 3 is called a penta­methinerhodacyanine sensitizing dye
• a sensitizing dye typified by the compound shown by formula (II) wherein m21 + m22 is 4 is called a hepta­methinerhodacyanine sensitizing dye.
• these definitions of the terms "pentamethinerhodacyanine dye” and "heptamethinerhodacyanine dye” in terms of formula (II) are employed for simplicity.
• the light-sensitive emulsion layer is spectrally sensitized by the specific sensitiz­ing dye to give a spectral sensitivity peak in the wavelength region preferably of at least 735 n.m., more preferably of at least 750 n.m., and most preferably of at least 770 n.m.
• two or more different color light-sensitive layers are spectrally sensitized to have a spectral sensitivity peak in the region of at least 720 n.m., each with a sensitizing dye selected from the compounds represented by formulae (I), (II), and (III) shown below.
• the compounds represented by formulae (I), (II), and (III) below include compounds which adsorb onto silver halide grains to spectrally sensitize the silver halide emulsion so that the emulsion has a spectral sensitivity peak in the region of at least 720 n.m. as described above but also include compounds capable of spectrally sensitizing such an emulsion to have a spectral sensitivity peak in the region shorter than 720 n.m.
• At least one light-sensitive emulsion layer is spectrally sensitized to have a spectral sensitivity peak in the wavelength region of at least 720 n.m. by the sensitizing dye
• other light-sensitive emulsion layer(s) spectrally sensitized to have a spectral sensitivity peak in the region shorter than 720 n.m. may be spectrally sensitized by a compound included in the compounds represented by formulae (I), (II), and (III), or may be spectrally sensitized by other compounds not represented by these formulae.
• the present invention relates to a method for retaining the storage performance of the silver halide photographic material after coating the silver halide emulsion(s) spectrally sensitized to have a spectral sensitivity peak in the region of at least 720 n.m. by the specific sensitizing dye according to the invention, and the spectrally sensitizing dyes for use in this invention are not to be construed as being limited to the compounds represented by formulae (I), (II), and (III).
• the sensitising dyes represented by formulae (I), (II), and (III) are as follows:
• Z11 and Z12 each represents an atomic group necessary for forming a heterocyclic nucleus.
• heterocyclic nucleus a 5- or 6-membered heterocyclic nucleus containing nitrogen, sulfur, oxygen, selenium, or tellurium is preferred and the ring may be further combined with a condensed ring or may have a substituent.
• heterocyclic nucleus examples include a thiazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a selenazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, an oxazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, an imidazole nucleus, a benzimidazole nucleus, a naphthimidazole nucleus, a 4-quinoline nucleus, a pyrroline nucleus, a pyridine nucleus, a tetrazole nucleus, an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a tellurazole nucleus, a benzotellurazole nucleus and a naphthotellurazol
• R11 and R12 each represents an alkyl group, an alkenyl group, an alkynyl group, or an aralkyl group. These groups and the groups described below may be substituted or unsubstituted.
• the alkyl group include an unsubstituted alkyl group and a substituted alkyl group, and the alkyl group may be a straight chain, branched, or cyclic alkyl group.
• the carbon atom number of the alkyl group is preferably from 1 to 8.
• substituent of the substituted alkyl group include a halogen atom (e.g., chlorine, bromine, and fluorine), a cyano group, an alkoxy group, a substituted or unsubstituted amino group, a carboxylic acid group, a sulfonic acid group, and a hydroxy group, and alkyl group may have one or plural substituents.
• halogen atom e.g., chlorine, bromine, and fluorine
• alkenyl group examples include a vinylmethyl group.
• aralkyl group examples include benzyl and phenetyl.
• m11 represents 1, 2, or 3; R13 represents hydrogen; R14 represents hydrogen, a lower alkyl group, or an aralkyl group, and further R14 may combine with R12 to form a 5- or 6-membered ring. Also, when R14 represents hydrogen and m11 is 2 or 3, R13 may combine with other R13 to form a hydrocarbon ring or a heterocyclic ring such as, preferably, a 5- or 6-­membered ring; j11 and k11 each represents 0 or 1; X11 represents an acid anion; and n11 represents 0 or 1.
• Z31 represents an atomic group necessary for forming a heterocyclic ring.
• the heterocyclic ring include those described above for to Z11 and Z12 in formula (I), and in addition, nuclei of thiazolidine, thiazoline, benzo­thiazoline, naphthothiazoline, selenazolidine, sele­nazoline, benzoselenazoline, naphthoselenazoline, benz­oxazoline, naphthoxazoline, dihydropyridine, dihydro­quinoline, benzimidazoline, and naphthimidazoline.
• Q31 has the same meaning as Q21 in formula (II); R31 has the same meaning as R11 or R12 in formula (I); and R32 has the same meaning as R23 in formula (II); m31 represents 2 or 3; R33 has the same meaning as R24 in formula (II) and R33 may combine with other R33 to form a hydrocarbon ring or a heterocyclic ring; and j31 has the same meaning as j11 in formula (I).
• the sensitizing dye represented by formula(I) wherein Z11 and/or Z12 comprises a naphthothiazole nucleus, a naphthoselenazole nucleus, a naphthoxazole nucleus, a naphthimidazole nucleus, or a 4-quinoline nucleus is preferred.
• Sensitizing dyes represented by formula (II) wherein Z21 and/or Z22 in formula (II) is selected from the same nuclei, and those represented by formula (III) wherein Z31 is selected from the same nuclei are also preferred.
• sensitizing dyes wherein the methine chain forms a hydrocarbon ring or a heterocyclic ring are preferred.
• the spec­tral sensitivity distribution is generally broader than the sensitization by the J band.
• it is preferred to correct the spectral sensitivity distribution by forming a colored layer containing a dye on a colloid layer closer to the exposed side than a definite light-­sensitive layer.
• the colored layer is effective for inhibiting color mixing by a filter effect.
• a red-sensitive or infrared-sensitive sensi­tizing dye As a red-sensitive or infrared-sensitive sensi­tizing dye, a compound having a reduction potential of - 1,00 (VvsSCE) or lower is preferred.
• the sensitizing dye having this characteristic is useful for increasing the sensitivity, in particular, for stabilizing the sensitivity and latent images.
• the reduction potential can be measured by phase discrimination type second harmonics AC polarography.
• a dropping mercury electrode is used, as a reference electrode, a saturated calomel electrode is used, and as a counter electrode, platinum is used.
• the combination of a compound selected from compounds represented by formulae (IV), (V), (VI) and (VII) described in JP-A-2-157749 and a compound selected from the formaldehyde condensation products of the compounds represented by formulae (VIII-­a), (VIII-b) and (VIII-c) described in JP-A-2-157749 is preferably used together with the sensitizing dye according to the present invention.
• sensitizing dyes represented by formulae (I), (II), and (III) are as follows, but the present invention is not to be construed as being limited thereto.
• the sensitizing dye for use in this invention is contained in a silver halide emulsion in an amount, per mol of silver halide, of from 5x10 ⁇ 7 mol to 5x10 ⁇ 3 mol, preferably from 1x10 ⁇ 6 mol to 1x10 ⁇ 3 mol, and particularly preferably from 2x10 ⁇ 6 mol to 5x10 ⁇ 4 mol
• the sensitizing dye for use in this invention can be directly dispersed in a silver halide emulsion.
• the sensitizing dye can be added to an emulsion as a solution thereof in a proper solvent such as methanol, ethanol, methylcellosolve, acetone, water, pyridine or a mixture thereof.
• a proper solvent such as methanol, ethanol, methylcellosolve, acetone, water, pyridine or a mixture thereof.
• ultrasound can be used in the case of dissolving the sensitizing dye.
• methods of adding the infrared sensitizing dye include a method of dissolving the dye in a volatile organic solvent, dispersing the solution in an aqueous solution of a hydrophilic colloid, and adding the dispersion to a silver halide emulsion as described in U.S. Patent 3,469,987; a method of dispersing the water-insoluble dye in a water-soluble solvent without dissolving the dye and adding the dispersion to an emulsion as described in JP-B-46-24185 (the term "JP-B" as used herein means an "examined published Japanese patent application”), a method of dissolving the dye in a surface active agent and adding the solution to an emulsion as described in U.S.
• Patent 3,822,135 a method of dissolving the dye in a solvent using a compound capable of red-shifting the dye and adding the solution to an emulsion as described in JP-A-­51-74624; and a method of dissolving the dye in an acid containing substantially no water and adding the solution to an emulsion as described in JP-A-50-80826.
• the infrared sensitizing dye may be uniformly dispersed in a silver halide emulsion before the emulsion is coated on a proper support. Furthermore, the dye may be added to a silver halide emulsion before the chemical sensitization or during the latter half of the formation of silver halide grains.
• a coupler having a high mol ratio of the colored coupler to developed silver halide for a silver halide color photographic material in this invention for quick color photographic processing, whereby the amount of a light-sensitive silver halide can be reduced.
• two equivalent couplers are preferably used.
• a one-equivalent coupler wherein a one-electron oxidation coloring step subsequent to the coupling reaction of the quinonediimine compound of the aromatic amine of a color developing agent and a color coupler is performed with an other oxidizing agent than silver halide may be used in combination.
• a color coupler is used such that the maximum coloring color density is at least 3 as a transmission density and at least 2 as a reflection density.
• color gradation conversion processing is conducted with color correction processing by an image processing apparatus, and hence an excellent color image can be obtained at the maximum coloring reflection density of about 1.2, and preferably from about 1.6 to 2.0. Accordingly, the amounts of color couplers and light-sensitive silver halide can be decreased.
• the amounts of yellow coupler, magenta coupler, and cyan coupler for the color photographic light-­sensitive material, in particular, a reflection color photographic light-sensitive material in this invention are from 2.5x10 ⁇ 4 to 10x10 ⁇ 4; from 1.5x10 ⁇ 4 to 8x10 ⁇ 4; and from 1.5x10 ⁇ 4 to 7x10 ⁇ 4 mol/m2, respectively.
• Color couplers suitable for the color photo­graphic light-sensitive material in this invention are now described in greater detail.
• the cyan couplers, magenta couplers, and yellow couplers which are preferably used in this invention are represented by formulae (C - I), (C - II); (M - I), (M - II); and (Y), respectively.
• R1, R2, and R4 each represents a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aromatic group, or a substituted or unsubstituted heterocyclic group
• R3, R5, and R6 each represents hydrogen, a halogen atom, an aliphatic group, an aromatic group, or an acylamino group
• R3 and R2 together may form a non-metallic atomic group forming a nitrogen-containing 5- or 6-membered ring
• Y1 and Y2 each represents hydrogen or a coupling-­off group capable of being cleaved upon the coupling reaction with the oxidation product of a color developing agent
• n represents 0 or 1.
• R5 is preferably an aliphatic group such as, for example, methyl, ethyl, propyl, butyl, pentadecyl, tert-butyl, cyclohexyl, cyclohexylmethyl, phenylthiomethyl, dodecyloxyphenyl­thiomethyl, butaneamidomethyl, and methoxymethyl.
• R1 is preferably an aryl group or a heterocyclic group, and is more preferably an aryl group substituted by a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group, a carbamoyl group, a sulfonamido group, a sulfamoyl group, a sulfonyl group, a sulfamido group, an oxycarbamoyl group, or a cyano group.
• R2 is preferably a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group and particularly preferably an alkyl group substituted by a substituted aryloxy group and R3 is preferably hydrogen.
• R4 is preferably a substituted or unsubstituted alkyl group or a substi­tuted or unsubstituted aryl group, and particularly preferably an alkyl group substituted by a substituted aryloxy group.
• R5 is preferably an alkyl group having from 2 to 15 carbon atoms or a methyl group having a substituent of one or more carbon atoms.
• Preferred examples of the substituent are an arylthio group, an alkylthio group, an acylamino group, an aryloxy group, and an alkyloxy group.
• R5 is more preferably an alkyl group having from 2 to 15 carbon atoms, and particularly preferably an alkyl group having from 2 to 4 carbon atoms.
• R6 is preferably hydrogen or a halogen atom, and particularly preferably chlorine or fluorine.
• Y1 and Y2 each is preferably hydrogen, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, or a sulfonamido group.
• R7 and R9 each represents an aryl group
• R8 represents hydrogen, an aliphatic acyl group, an aromatic acyl group, an aliphatic sulfonyl group, or an aromatic sulfonyl group
• Y3 represents hydrogen or a coupling-off group.
• the substituent for the aryl group (preferably a phenyl group) shown by R7 and R9 is same as the above substituent for R1 and when two or more substituents exist, they may be the same or different.
• R8 is preferably hydrogen, an aliphatic acyl group or an aliphatic sulfonyl group, and particularly preferably hydrogen.
• Y3 is preferably a coupling-off group of a type released by sulfur, oxygen, or nitrogen and the sulfur atom-releasing type magenta couplers described in U.S. Patent 4,351,897 and PCT WO088/04795 are particularly preferred.
• R10 represents hydrogen or a substituent
• Y4 represents hydrogen or a releasable group, and is particularly preferably a halogen atom or an arylthio group
• the double bond can be part of an aromatic ring.
• the coupler includes a dimer or higher polymer formed at R10 or Y4 and when Za, Zb, and Zc is a substituted methine, the coupler includes a dimer or higher polymer formed at the substituted methine.
• imidazo[1,2-b]pyrazoles described in U.S. Patent 4,500,630 are preferred for reduced yellow side absorption and light fastness of colored dyes formed and also pyrazolo[1,5-b][1,2,4]tri­azoles described in U.S. patent 4,540,654 are particularly preferred.
• pyrazolotriazole couplers having a branched alkyl group directly bonded to the 2-, 3-, or 6-position of the pyrazolotriazole ring as described in JP-A-61-65245 pyrazoloazole couplers containing a sulfonamido group in the molecule as described in JP-A-­61-65246, pyrazoloazole couplers having an alkoxyphenyl­sulfonamido ballast group as described in JP-A-61-­147254, and pyrazolotriazole couplers having an alkoxy group or an aryloxy group at the 6-position as described in European Patent Applications (unexamined published) 226,849 and 294,785 can be preferably used in this invention.
• R11 represents a halogen atom, an alkoxy group, a trifluoromethyl group, or an aryl group
• R12 represents hydrogen, a halogen atom, or an alkoxy group
• A represents -NHCOR13, -NHSO2-R13, -SO2NHR13, -COOR13, or (wherein R13 and R14 each represents an alkyl group, an aryl group, or an acyl group)
• Y5 represents a coupling-off group.
• the substituents for R12, R13, and R14 are same as the substituents for R1 and Y5 is preferably a coupling-off group of the type of being released by oxygen or nitrogen, and is particularly preferably of a nitrogen atom-releasing type.
• Couplers represented by formulae (C - I), (C - II), (M - I), (M - II) and (Y) are illustrated below, but the present invention is not to be construed as being limited thereto.
• Each of the couplers shown by the aforesaid formulae (C-I), (C-II), (M-I), (M-II), and (Y) is contained in a silver halide emulsion constituting the light-sensitive emulsion layer in an amount of from 0.1 to 1.0 mol, and preferably from 0.1 to 0.5 mol per mol of silver halide.
• the coupler can be added by an oil drop-in-water dispersion method known as an "oil product" method. That is, after dissolving a coupler in an organic solvent, the solution is dispersed by emulsification in an aqueous gelatin solution containing a surface active agent. Or water or an aqueous gelatin solution is added to a coupler solution containing a surface active agent and an oil drop-in-water dispersion may be formed from the mixture with phase inversion.
• the coupler when a coupler is alkali soluble, the coupler can be dispersed by a Fischer's dispersion method. After removing a low-boiling organic solvent from a coupler dispersion by distillation, a noodle washing method, or ultrafiltration, the dispersion may be added to a silver halide emulsion.
• a high-boiling organic solvent and/or a water-insoluble polymer each having a dielectric constant of from 2 to 20 (25°C), and a refractive index of from 1.5 to 1.7 (25°C) is preferably used.
• the high-boiling organic solvent represented by formulae (A) to (E) is preferably used.
• W1, W2, and W3 each represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and each may be substituted;
• W4 represents W1, OW1, or S-W1; and
• n represents an integer of from 1 to 5.
• W4s may be the same or different.
• W1 and W2 may form a condensed ring.
• high-boiling organic solvents than those represented by formulae (A) to (E) can be also used in this invention, if they are compounds immiscible with water having a melting point of up to 100°C and a boiling point of at least 140°C, and are a good solvent for the coupler.
• the melting point of the high-boiling organic solvent is preferably up to 80°C and the boiling point of the high boiling organic solvent is preferably at least 160°C, and more preferably at least 170°C.
• the coupler can be dispersed by emulsification in an aqueous gelatin solution by impregnating a loadable latex polymer (described, e.g., in U.S. Patent 4,203,716) with the coupler in the presence or absence of the high-boiling organic solvent or by dissolving in a polymer which is insoluble in water and soluble in an organic solvent.
• a loadable latex polymer described, e.g., in U.S. Patent 4,203,716
• the silver halide photographic material in this invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, or an ascorbic acid derivative as a color fogging inhibitor.
• Organic fading inhibitors for cyan, magenta, and/or yellow images include hydroquinones, 6-­hydroxychromans, 5-hydroxycoumarans, spirochromans, p-­alkoxyphenols, hindered phenols (such as bisphenols), gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and the ether or ester derivatives thereof formed by silylating or alkylating the phenolic hydroxy groups of these compounds.
• metal complexes such as (bis-salicylaldoximate)nickel complex and (bis-N,N-dialkyldithiocarbamate)nickel complex can be used.
• Hydroquinones are described in U.S. Patents 2,360,290, 2,418,613, 2,700,453, 2,701,197, 2,728,659, 2,732,300, 2,735,765, 3,982,944, and 4,430,425, British Patent 1,363,921, U.S. Patents 2,710,801, and 2,816,028; 6-hydroxychromans, 5-hydroxycoumarans, and spirochromans are described in U.S. Patents 3,432,300, 3,573,050, 3,574,627, 3,698,909, and 3,764,337, and JP-A-52-152225; spiroindanes are described in U.S. Patent 4,360,589; p-­alkoxyphenols are described in U.S.
• Patents 3,336,135 and 4,268,593 British patents 1,326,889, 1,354,313, and 1,410,846, JP-­B-51-1420, JP-A-58-114036, JP-A-59-53846, and JP-A-59-­78344; and metal complexes are described in U.S. Patents 4,050,938 and 4,241,155, and British Patent 2,027,731(A).
• the aforesaid compound is coemulsified with each corresponding color coupler in an amount of from 5 to 100% by weight to the coupler and added to a silver halide emulsion.
• Examples of the ultraviolet absorbent which can be used in this invention are benzotriazole compounds substituted by an aryl group described, e.g., in U.S. Patent 3,533,794, 4-thiazolidone compounds described, e.g., in U.S. Patents 3,314,794 and 3,352,681, benzophenone compounds described, e.g., in JP-A-46-2784, cinnamic acid ester compounds described, e.g., in U.S. Patents 3,705,805 and 3,707,395, butadiene compounds described, e.g., in U.S. Patent 4,045,229, and benzoxazole compounds described, e.g., in U.S. Patents 3,406,070, 3,677,762, and 4,271,307.
• Ultraviolet absorptive couplers e.g., ⁇ -­naphtholic cyan dye-forming couplers
• ultraviolet absorptive polymers may be used.
• ultraviolet absorbents may be mordanted in a specific layer.
• benzotriazole compounds substituted by an aryl group are preferred.
• a compound (F) which causes chemical bonding with an aromatic amine color developing agent remaining after color development processing to form a chemically inactive and substantially colorless compound and/or a compound (G) which causes chemical bonding with the oxidized aromatic amino color developing agent remaining after color development processing is preferred for preventing the occurrence of stains by the formation of colored dyes by the reaction of the color developing agent or the oxidation product thereof remaining in the emulsion layers with couplers, or the occurrence of other side reaction during the storage of the photographic materials after processing.
• a compound which reacts with p-anisidine at a secondary reaction rate constant k z (in trioctyl phosphate at 80°C) in the range of from 1.0 liter/mol ⁇ sec. to 1x10 ⁇ 5 liter/mol ⁇ sec. is preferably used.
• the secondary reaction rate constant can be measured by the method described in JP-A-63-158545.
• the compound itself becomes unstable and may decomposed by causing a reaction with gelatin or water.
• the value of k z is less than this range, the reaction with the remaining aromatic amine developing agent is delayed, which reduces the prevention of the side reaction of the remaining aromatic amine developing agent.
• R1-(A) n -X (FI) R2- Y (FII) wherein R1 and R2 each represents an aliphatic group, an aromatic group, or a heterocyclic group; n represents 0 or 1; A represents a group forming a chemical bond by reacting with an aromatic amino developing agent; X represents a group capable of being cleaved by reacting with an aromatic amino developing agent; B represents hydrogen, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group; and Y represents a group capable of accelerating the addition of an aromatic amino developing agent to the compound of formula (FII).
• R1 and X or Y and R2 or B may be linked with each other to form a cyclic structure.
• the typical system of chemically bonding with a remaining aromatic amino developing agent is a sub­stitution reaction and an addition reaction.
• Preferred compounds among the compounds (G) which cause chemical bonding with the oxidation product of an aromatic amino developing agent remaining after color development processing are represented by formula (GI): R-Z (GI) wherein R represents an aliphatic group, an aromatic group, or a heterocyclic group and Z represents a nucleophilic group or a group which is decomposed in a photographic light-sensitive material to release a nucleophilic group.
• Z is preferably a group having a Pearson's nucleophilic n CH3I value (R.G. Pearson, et al, Journal of Americal Chemical Society , 90 , 319 (1968)) of at least S or a group derived from this group.
• the photographic light-sensitive material in this invention may contain ultraviolet absorbent(s) in the hydrophilic colloid layer(s).
• the ultraviolet absorbent are benzotriazole compounds substituted by an aryl group described, e.g., in U.S. Patent 3,533,794, 4-thiazolidone compounds described, e.g., in U.S. Patents 3,314,794 and 3,352,681, benzophenone compounds described, e.g., in JP-A-46-2784, cinnamic acid ester compounds described, e.g., in U.S. Patents 3,705,805 and 3,707,375, butadiene compounds described, e.g., in U.S.
• Patent 4,045,229 and benzooxidol compounds described, e.g., in U.S. Patent 3,700,455.
• An ultraviolet absorptive coupler e.g., ⁇ -­naphtholic cyan dye-forming couplers
• an ultraviolet absorptive polymer may be used.
• the ultraviolet absorbent may be mordanted in a specific hydrophilic colloid layer.
• colloidal silver or dyes are used for anti-irradiation, anti-halation, and in particular, the separation of the spectral sensitivity distribution of each light-sensitive emulsion layer and ensuring safety to a safelight of a visible wavelength region.
• dyes which are used for this purpose are oxonol dyes, hemioxonol dyes, styryl dyes, mero­cyanine dyes, cyanine dyes, and azo dyes. Of these dyes, oxonol dyes, hemioxonol dyes, and merocyanine dyes are useful. Also, indolenine dyes are particularly useful.
• decolorable dyes described in JP-A-62-3250, JP-A-62-­181381, JP-A-62-123454, and JP-A-63-197947 and dyes for backing layers are described in JP-A-62-39682, JP-A-62-­123192, JP-A-62-158779, and JP-A-62-174741, or dyes introduced with a water-soluble group which can flow out during processing can be used.
• the infrared dye for use in this invention may be a colorless dye having substantially no light absorption in a visible wavelength region.
• the infrared dye for use in this invention is mixed with a silver halide emulsion spectrally sensitized to the longest wavelength side of red region or infrared wavelength region, occasionally the emulsion is desensitized, fog is formed, or in some cases, the dye itself adsorbs to silver halide grains to cause a weak and broad spectral sensitization.
• the infrared dye is incorporated in other colloid layer(s) only than light-sensitive emulsion layers.
• the dye is incorporated in a specific colored layer in a nondif­fusible state.
• the dye is rendered non­diffusible by introducing a ballast group into the dye.
• residual color or processing stain is liable to form.
• the anionic dye for use in this invention is mordanted using a polymer or a polymer latex providing a cation site.
• a dye which is insoluble in water having pH of 7 or lower and decolored and dissolved off during processing is used as a dispersion of fine particles thereof.
• the dye is dissolved in a low-boiling organic solvent or solubilized in a surface active agent and dispersed in an aqueous solution of a hydrophilic protective colloid such as gelatin.
• the solid dye is kneaded with an aqueous solution of a surface active agent, the mixture is mechanically ground by a mill to fine particles and the fine particles are dispersed in an aqueous solution of a hydrophilic colloid such as gelatin.
• gelatin is advantageously used but other hydrophilic colloids can be used singly or together with gelatin.
• Gelatin for use in this invention may be lime-­processed gelatin or acid-processed gelatin. Details of the production process of gelatin are described in Arther Weiss, The Macromolecular Chemistry of Gelatin (published by Academic Press, 1964).
• the halogen composition for a silver halide emulsion which is used for the silver halide light-­sensitive emulsion layers of the silver halide photographic material in this invention may be silver chloride, silver bromide, silver chlorobromide, silver chloroiodo-bromide, or silver iodochloride, but a high silver chloride content such as that of a silver chlorobromide emulsion containing at least 90 mol% silver chloride is preferred for rapid development processing and increasing the storage stability of this invention.
• a silver chlorobromide emulsion containing at least 96 mol% silver chloride or a silver chloride emulsion is more preferably used.
• silver bromide When silver bromide is contained in the emulsion, it is preferred that silver bromide exist in the interior of silver halide grain or at the surface of the grain as a local phase.
• silver halide grains when silver halide grains have a local partial structure having a different silver bromide content at least in the inside of the grain or localized in the surface thereof, the silver halide grain has a "local phase".
• the silver chloride grains are said to have a "local phase" in this invention. JP-A-1-183647 dis­closes that high silver chloride grains having a silver bromide local phase were doped with iron ions.
• silver chlorobromide when silver halide grains are composed of silver chlorobromide, silver chlorobromide having a mean silver chloride content of at least 96 mol% and having local phases having a silver bromide content of over 15 mol% is preferred.
• Such a local phase having a high content of silver bromide may be optionally disposed as required, i.e., may be in the inside of the silver halide grains, at the surface of the grain, near the surface of the grain, or may simultaneously exist at two or more positions. Also, the local phase may have a layer structure surrounding the grain, a discontinuous isolated structure, a network structure, or a composite structure thereof.
• silver chlorobromide having a silver bromide content of at least 15 mol% is present locally at the surface of silver chlorobromide grains. It is preferred that the silver bromide content of the local phase is over 15 mol% but less than 70 mol%. If the silver bromide content of the local phase is too high, pressure desensitization occurs when exposing the light-­ sensitive material using the silver halide emulsion after applying a mechanical pressure, or the photo­graphic properties of the photographic light-sensitive material are varied with changes in the composition of a processing solution.
• the silver bromide content in the local phase is preferably in the range of from 15 to 70 mol%, more preferably from 20 to 60 mol%, and particularly preferably from 30 to 50 mol%.
• the local phases are preferably composed of silver in an amount from 0.01 to 20 mol% of the total silver constituting the silver halide grains for use in this invention, and are more preferably composed of silver of from 0.02 to 7 mol% of total silver.
• the interface between the local phase having a high silver bromide content and other phase may have a distinct boundary or may have a boundary wherein the halogen composition is gradually and continuously changed.
• the silver bromide content in such a local phase can be analyzed using an X-ray diffraction method (described, e.g., in Shin Jikken Kagaku Koza (New Experimental Chemical Course) 6 Kozokaiseki (Structure Analysis) , edited by Chemical Society of Japan, published by Maruzen) or an XPS method (described, e.g., in Hyomen Bunseki (Surface Analysis)-IMA , Application of Auger Electron. Photoelectric Spectrum- , published by Kodansha).
• the existence of the local phase can be seen by an electromicroscope.
• the local phase can be formed by reacting a soluble silver salt and a soluble bromide or metal salt by a single jet method or a double jet method.
• the local phase can be also formed using a halogen conversion method including a step of converting a silver halide already formed into a silver halide having a lower solubility product.
• the local phase can be also formed by mixing silver halides each having a different halogen composition followed by ripening to cause recrystallization.
• the silver chlorobromide local phase is formed at the surface of silver chloride grains, it is preferred to form the local phase by adding fine silver bromide grains having relatively small grain sizes to silver chloride grains already formed followed by ripening to cause recrystallization.
• the extent of the halogen conversion or the recrystallization is changed, thereby the silver halide emulsion formed can be controlled to have a desired performance.
• the silver halide emulsion having the aforesaid local phases may contain silver iodide. In this case, it is preferred that silver iodide is present locally. In this case, the content of silver iodide is preferably from 0 to 3 mol%, more preferably from 0 to 1 mol%, and most preferably from 0 to 0.6 mol%.
• the silver halide emulsion for use in this invention may further contain an inorganic silver salt other than silver halide as described above, such as silver rhodanate or silver phosphate.
• the form of the crystal grains of the silver halide for use in this invention may be a regular grain form such as cubic, octahedral, tetradecahedral, or rhombic dodecahedral, or may be an irregular grain for such as sphere or tabular. Also, the grain form may be a complicated form having a combination of these crystal planes or may be grains having higher crystal planes. Furthermore, a mixture of these silver halide grains may be used.
• the silver halide emulsion for use in this invention contains tabular grains having a mean aspect ratio (the ratio of the circle equivalent diameter of the main plane of the grain to the thickness of the grain) of at least 5, and particularly preferably at least 8 account for at least 50% of the total projected area of the grains, the emulsion is useful for quick processing.
• the grain size distribution of the silver halide grains may be broad or narrow but a monodisperse silver halide emulsion is preferable for sensitivity stability.
• the value S/d obtained by dividing the standard deviation S of the distribution of the circle equivalent diameters from the projected areas of the silver halide grains by the mean diameter d is preferably 20% or less, and more preferably 15% of less.
• a monodisperse silver halide emulsion containing silver halide grains having a regular crystal form in a grain number or weight of at least 50%, preferably at least 70%, and more preferably at least 90% is preferably used in this invention, and a silver halide emulsion containing silver halide grains of cubic or tetrahedral form having a (100) crystal plane and having the aforesaid local phase at the corner portions or edge portions if particularly preferred in this invention.
• the local phase of a metal salt may preferably exist at another portion than the edge and the corner, such as, at the (100) plane in this invention.
• Such discontinuous isolated local phases existing at the surfaces of silver halide grains can be formed by supplying a bromide ion or a metal ion to a silver halide emulsion containing the silver halide grains as the case material while controlling the silver ion concentration, hydrogen ion concentration, temperature or time, to cause halogen conversion.
• a bromide ion or a metal ion to a silver halide emulsion containing the silver halide grains as the case material while controlling the silver ion concentration, hydrogen ion concentration, temperature or time, to cause halogen conversion.
• it is necessary to uniformly supply the ion to each silver halide grain in the system it is preferred to supply the ion while stirring the system. It is also preferred to simultaneously supply the ions at a low concentration or gradually supply the ions.
• an organic halogen compound such as bromosuccinimide or bromopropionic acid or a halogen compound covered by a semipermeable capsule can be used
• the local phases can be formed by supplying a silver ion and a halogen ion to a silver halide emulsion containing silver halide grains as a base material while controlling the silver ion concentration, to grow silver halide at limited sites of the grains, or by mixing silver halide grains as the base material with fine grain silver halide crystals having a finer grain size than the base material to grow silver halide at limited sites of the silver halide grains as the base material, such as the edges or corners thereof.
• a silver halide solvent can be used together.
• controlling compounds for halogen conversion or recrystallization described in JP-A-1-­105940, JP-A-1-26840, and JP-A-1-183647 can be used.
• the silver halide grains having such local phases can be also prepared using fine crystals of silver iodobromide, silver chlorobromide, as in the case of using fine silver bromide crystals.
• the grain sizes of the silver halide grains contained in the silver halide emulsion for use in this invention are preferably from 0.05 ⁇ m to 2 ⁇ m, and more preferably from 0.1 ⁇ m to 1.5 ⁇ m as the mean value of the diameters of spheres corresponding to the volumes thereof.
• the silver halide emulsions for use in this invention can be prepared by utilizing the methods described in P. Glafkides, Chemie et Phisique Photographique , (Paul Montel Co., 1967); G.F. Duffin, Photographic Emulsion Chemistry , (Focal Press Co., 1966); and V.L. Zelikman et al, Making and Coating of Photographic Emulsion , (Focal Press Co., 1964).
• an acid method, a neutralization method, or an ammonia method can be used for the preparation of the emulsion but an acid method and a neutralization method are preferred in this invention for reducing the formation of fog.
• an acid method and a neutralization method are preferred in this invention for reducing the formation of fog.
• a single jet method, a double jet method or a combination thereof may be used for obtaining a silver halide emulsion by reacting a soluble silver salt and a soluble halide.
• a reverse mixing method of forming silver halide grains in an excess of silver ion can be also used.
• a double jet method is preferably used.
• a double jet method keeping a constant silver ion concentration in a liquid phase while forming silver halide grains is more preferably used.
• this method a preferred silver halide emulsion containing silver halide grains having a regular crystal form and a narrow grain size distribution can be obtained.
• a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, or an iron salt or a complex salt thereof may be present.
• a silver halide solvent e.g., ammonia, thiocyanates, or the ethers and the thione compounds described in U.S. Patent 3,271,157, JP-A-51-12360, JP-A-53-82408, JP-A-53-144319, JP-A-54-­100717, and JP-A-54-155828
• a silver halide solvent e.g., ammonia, thiocyanates, or the ethers and the thione compounds described in U.S. Patent 3,271,157, JP-A-51-12360, JP-A-53-82408, JP-A-53-144319, JP-A-54-­100717, and JP-A-54-155828
• a noodle washing method For removing soluble salts from the silver halide emulsion after physical ripening, a noodle washing method, a flocculation method, or an ultra-­filtration method can be utilized.
• the silver halide emulsion for use in this invention can be chemically sensitized by sulfur sensitization, selenium sensitization, reduction sensitization, or noble metal sensitization, alone or as a combination thereof.
• a sulfur sensitization method using active gelatin or a compound containing a sulfur compound capable of reacting with a silver ion e.g., a thiosulfate, a thiourea compound, a mercapto compound, a rhodanine compound
• a reduction sensitization method using a reducing material e.g., stannous salts, amines, hydrazine derivatives, formamidinesulfinic acid, silane compounds, ascorbic acid
• a noble metal sensitization method using a noble metal compound e.g., a gold complex salt, a salt of a metal belonging to group VIII of the periodic table, such as platinum, iridium, palladium, rhodium, iron
• silver halide emulsion for use in this invention sulfur sensitization or a selenium sensitization is preferably used and it is also preferred to use gold sensitization together with this sensitization. Also, it is preferred for controlling the sensitivity and gradation to perform the chemical sensitization in the presence of a hydroxyazaindene compound or nucleic acid.
• the silver halide grains for use in this invention contain a metal ion other than a silver ion (e.g., a metal ion belonging to group VIII of the periodic table, a transition metal ion of group II, a lead ion of group IV, or a gold ion or a copper ion of group I) or a complex ion thereof.
• a metal ion other than a silver ion e.g., a metal ion belonging to group VIII of the periodic table, a transition metal ion of group II, a lead ion of group IV, or a gold ion or a copper ion of group I
• the metal ion or the complex ion thereof may be incorporated uniformly in the silver halide grains, the local phases or other phases.
• an iridium ion, a zinc ion, an iron ion, a palladium ion, a rhodium ion, a platinum ion, a gold ion, and a copper ion are preferred.
• metal ions or complex ions When these metal ions or complex ions are used as a combination thereof, desired photographic properties are frequently obtained, and also it is preferred to change the kind and the amount of the addition ion between the local phases and other portions of the grains. It is particularly preferred that an iridium ion or a rhodium ion be present in the local phases.
• the metal ion or the complex ion may be directly added to a reaction vessel before or during the formation of the silver halide grains or at physical ripening after formation of the grains, or may be previously added to a solution of a water-soluble halide or a water-soluble silver salt.
• the metal ion or complex ion is incorporated in the fine grains of silver bromide or silver iodide and they may be added to a silver chloride emulsion or a high-silver chloride emulsion.
• the metal ion may be incorporated while forming the local phases.
• A91 represents a divalent aromatic residue
• -A91- represents a divalent aromatic group which may be substituted with -SO3M (wherein M represents hydrogen or a cation providing water solubility (e.g., sodium and potassium)).
• -A91- Useful examples of -A91- are those selected from -A92- or -A93- shown below. However, when R91, R92, R93, or R94 does not contain -SO3M, -A91- is represented by -­A92-.
• A92 represents the following groups: (wherein M represents a hydrogen atom or a cation giving water solubility).
• A93 represents the following groups:
• R91, R92, R93, and R94 each represents hydrogen, a hydroxy group, an alkyl group (having preferably from 1 to 8 carbon atoms, e.g., methyl, ethyl, n-propyl, and n-butyl), an alkoxy group (having preferably from 1 to 8 carbon atoms, e.g., methoxy, ethoxy, propoxy, and butoxy), an aryloxy group (e.g., phenoxy, naphthoxy, o-tolyloxy, and p-sulfo­phenoxy), a halogen atom (e.g., chlorine and bromine), a heterocyclic nucleus (e.g., morpholinyl and piperidyl), an alkylthio group (e.g., methylthio and ethylthio), a heterocyclicthio group (e.g., benzothiazolylthio, benz­imi
• R91, R92, R93, and R94 may be the same or different.
• R91, R92, R93, and R94 must have at least one sulfo group (which may be a free acid group or form a salt).
• (A-1) to (A-6) are preferred and also, (A-1), (A-2), (A-4), (A-5), (A-9), (A-15), and (A-20) are particularly preferred.
• the compound represented by formula (IX) is used in an amount of from 0.01 to 5 g per mol of silver halide and also, advantageously used in an amount of from about 5 times to 2,000 times, and preferably from 20 times to 1,500 times by weight the amount of a sensitizing dye.
• a mercaptoazole represented by following formula (X), (XI), or (XII) to the coating compositions for an interlayer and a silver halide emulsion layer.
• the addition amount thereof is preferably from 1x10 ⁇ 5 to 5x10 ⁇ 2 mol, and more preferably from 1x10 ⁇ 4 to 1x10 ⁇ 2 mol per mol of silver halide.
• R101 represents an alkyl group, an alkenyl group, or an aryl group
• X101 represents hydrogen, an alkali metal atom, an ammonium group, or a precursor thereof.
• alkali metal atom examples of the alkali metal atom ate sodium and potassium and examples of the ammonium group are tetramethylammonium and trimethylbenzylammonium.
• the alkyl group and the alkenyl group include unsubstituted groups and substituted groups, and further include alicyclic groups.
• the substituent of the substituted alkyl group include a halogen atom, a nitro group, a cyano group, a hydroxy group, an alkoxy group, an aryl group, an acylamino group, an alkoxycarbonylamino group, a ureido group, an amido group, a heterocyclic group, an acyl group, a sulfamoyl group, a sulfonamido group, a thioureido group, a carbamoyl group, an alkylthio group, an arylthio group, a heterocyclic thio group, a carboxylic acid group, a sulfonic acid group, and the salt thereof.
• the ureido group, thioureido group, sulfamoyl group, carbamoyl group, and amino group each includes an unsubstituted group, an N-alkyl-substituted group, and an N-aryl-substituted group.
• Examples of the aryl group are a phenyl group and a substituted phenyl group, and examples of the substituent of the substituted phenyl group are an alkyl group and the substituents illustrated above for the substituted alkyl group.
• Y111 represents oxygen or sulfur
• L represents a divalent linkage group
• R111 represents hydrogen, an alkyl group, an alkenyl group, or an aryl group.
• X111 has the same meaning as X101 in formula (X), and the alkyl group and alkenyl group represented by R111 are the same as those in formula (X).
• divalent linkage group shown by L are and a combination thereof (wherein R0, R1, and R2 each represents hydrogen, an alkyl group, or an aralkyl group).
• n 0 or 1. wherein R121 and X121 have the same meaning as R101 and X101 in formula (X); L and n have the same meaning as L and n in formula (XI); R3 has the same meaning as R121, and they may be the same or different.
• a silver halide color photographic material having the layer structure shown below was prepared as Sample A.
• the silver halide emulsion use for each emulsion layer was prepared as follows.
• di-potassium iridium hexachloride and hexacyano iron(II) potassium were added in amounts of 1x10 ⁇ 8 mol/mol-Ag and 1.5x10 ⁇ 5 mol/mol-Ag, respectively, based on the total silver halide amount.
• the emulsion obtained was observed by an electromicroscope, the emulsion contained silver halide grains having a mean side length of about 0.46 ⁇ m and a variation coefficient of the grain size distribution of 0.09.
• nucleic acid and a monodisperse silver bromide emulsion (containing 1.2x10 ⁇ 4 mol/mol-Ag of di-potassium iridium hexachloride) having a mean grain size of 0.05 ⁇ m in an amount of 1.0 mol% as silver halide were added to the above emulsion, the emulsion was chemically sensitized with about 2x10 ⁇ 6 mol/mol-Ag of tri-­ethylthiourea, and then 5x10 ⁇ 6 mol/mol-Ag of compound (V-­23), 1.1x10 ⁇ 3 mol/mol-Ag of compound (I-1), and 1.8x10 ⁇ 3 mol/mol-Ag of compound (F-1) were added thereto to provide the desired emulsion.
• Emulsion for Magenta Coupler-Containing Layer is a
• di-potassium iridium hexachloride and hexacyano iron(II) potassium were added thereto in amounts of 1.2x10 ⁇ 8 mol/mol-Ag and 1.8x10 ⁇ 5 mol/mol-Ag, respectively, based on the total silver halide amount.
• the emulsion obtained was observed by means of an electromicroscope, the emulsion contained silver halide grains having a mean side length of about 0.44 pm and a variation coefficient of grain size distribution of 0.08.
• nucleic acid and a monodisperse silver bromide emulsion (containing 1.5x10 ⁇ 4 mol/mol-Ag) having a mean grain size of 0.05 ⁇ m of 0.5 mol% as silver halide were added to the emulsion, the emulsion was chemically sensitized with about 2.4x10 ⁇ 6 mol/mol-Ag of triethylurea, and further, 1.1x10 ⁇ 5 mol/mol-Ag of compound (V-46), 0.6x10 ⁇ 3 mol/mol-Ag of compound (I-1), and 0.9x10 ⁇ 3 mol/mol-Ag of compound (F-1) were added thereto to provide the desired emulsion.
• Emulsion for Yellow Coupler-Containing Layer is a
• hardening agents for gelatin the following 3 compounds were used in a 3:2:1 by mol ratio.
• Sample A was kept for 3 days under conditions of 25°C and 60% RH, then stored for 4 weeks at 25°C under the storage conditions shown in Table 1, and the photographic properties were compared.
• the layer structure of Sample A was as follows, wherein the coating amount is shown in g/m2, and the silver halide emulsion and colloidal silver are calculated in terms of silver.
• compositions of the processing solutions were as follows. Color Developer Ethylenediamine-N,N,N′,N′-tetramethylenesulfonic acid 3.0 g N,N-Di(carboxymethyl)hydrazine 4.5 g N,N-Diethylhydroxylamine oxalate 2.0 g Triethanolamine 8.5 g Sodium sulfite 0.14 g Potassium chloride 1.6 g Potassium bromide 0.01 g Potassium carbonate 25.0 g N-Ethyl-N-( ⁇ -methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.0 g WHITEX-4 (made by Sumitomo Chemical Company, Limited) 1.4 g Water to make 1000 ml pH adjusted to 10.05 Blix Solution Ammonium thiosulfate (50 wt%) 100 ml Sodium sulfite 17.0 g Ethylenediaminetetraace
• Ion-exchanged water (calcium ion concentration less than 3 ppm, magnesium ion concentration less than 2 ppm).
• the sensitivities were determined as relative values with the sensitivity of each coloring layer of the sample stored in a refrigerator for at -16°C being defined as 100.
• TABLE 2 Storing Condition Cyan Sensitivity Magenta Sensitivity Yellow Sensitivity Remark 1 76 85 96 Comparison 2 81 91 96 Comparison 3 91 95 100 Comparison 4 98 100 100 Invention 5 100 102 102 Invention 6 100 102 102 Invention 7 102 100 100 Invention 8 100 100 100 Invention 9 105 105 100 Invention 10 105 105 102 Invention
• the samples stored under storage conditions 4 to 10 of this invention had almost the same sensitivity as that of the samples stored in a refrigerator, while the samples stored under comparison conditions 1 to 3 clearly showed loss of sensitivity.
• the improvement in storage stability of this invention was more remarkable in the cyan coloring layer spectrally sensitized by a tricarbocyanine sensitizing dye giving a spectral sensitivity peak at a long wavelength, 835 n.m., than in the yellow coloring layer, spectrally sensitized by a carbocyanine sensitizing dye giving a spectral sensitivity peak at a short wavelength, about 670 n.m.
• oxygen volume ratio useful for obtaining the effect of this invention was less than about 2%, by comparing storage conditions 1, 3, and 4.
• this invention is effective for stably maintaining the performance of silver halide photographic materials using the infrared spectrally sensitizing dyes specified in this invention.
• Samples 1 to 10 prepared in Example 1 were processed by the following processing step 2 in place of the step 1 in Example 1. The exposure was same as in Example 1. Processing step Temperature Time (°C) Color Development 35 45 sec. Blix 35 45 sec. Rinse 1 25 30 sec. Rinse 2 25 30 sec. Rinse 3 25 30 sec. Drying 80 60 sec.
• compositions of the processing solutions were the same as in Example 1.
• Example 1 In the processing step 1 in Example 1, the processing time was 45 seconds and images were very quickly formed, while in processing step 2, 4 minutes were required. In this example as well, the sensitivities obtained under the test storage conditions were almost same as in Example 1.
• the sensitivity difference between samples was larger in the processing step in Example 1.
• ⁇ max shows the spectral sensitivity peak wavelength in n.m.
• Example 2 For samples B to G, the same test applied to the samples stored under the storage conditions 1 and 6 in Example 1 was applied. The processing was the same as in Example 2.
• the tricarbocyanine sensitizing dye or the hexamethinemerocyanine sensitizing dye which was used for the cyan coloring layer has a spectral sensitivity of a longer wavelength than the sensitivity dye used for the magenta coloring layer, and it is seen that when using such a sensitizing dye, the improvement in storage stability of this invention was large.
• the change in the photographic properties of a silver halide photographic material spectrally sensitized to the infrared wavelength region can be prevented during storage over a period of time.
• the invention provides a photographic light-sensitive material spectrally sensitized to infrared wavelength region having constant high sensitivity.

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• 1990
  • 1990-05-09 JP JP11925590A patent/JPH03213844A/ja active Pending
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