Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/3041—Materials with specific sensitometric characteristics, e.g. gamma, density

Definitions

• the present invention relates to a color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material excellent in the graininess, sharpness and color reproducibility.
• color light-sensitive material silver halide color photographic light-sensitive material (hereinafter called color light-sensitive material) products have been markedly improved to provide high-quality images; their sharpness and graininess are on a fairly high level and have few or no problems as long as they are appreciated on service-sized color prints or slides available to customers.
• U.S. Patent Nos. 4,414,306, 4,414,310, 4,433,048, 4,434,226 and 4,459,353 disclose techniques for sensitivity improvements including color sensitizing efficiency improvement by use of sensitizing dyes, for sensitivity/graininess balance improvement, for sharpness improvement and for the use of tabular silver halide grains for covering power improvement.
• JP O.P.I. Nos. 113930/1983, 113934/1983 and 113950/1984 also disclose multilayer color light-sensitive materials improved to have a high sensitivity and excellent graininess, sharpness and color reproducibility by using tabular silver halide grains having an aspect ratio of 8:1 in the high-speed emulsion layer thereof.
• red-sensitive layer the red-sensitive silver halide emulsion layer
• the red-sensitive layer's sensitivity shift toward shorter wavelength side is important for the color reproduction of objects such as flowers having red-terminal reflection.
• the sensitivity shift of the red-sensitive layer causes lowering of chroma; particularly has brought trouble to natural skin-color reproduction that is important for the color reproduction in making portraits; i.e., it loses a healthy reddish color peculiar to the skin to result in a lifeless color.
• JP O.P.I. Nos. 20926/1978 and 131937/1979 also disclose techniques for bringing the red-sensitive layer near the green-sensitive layer or shifting the red-sensitive layer's sensitivity to shorter wavelength side, but the effect thereof is not sufficient and has the above-mentioned shortcomings. Further, JP O.P.I. No. 181144/1990 prescribes the difference in the sensitivity to 480nm between the blue-sensitive layer and the green-sensitive layer and the density of the yellow filter layer.
• JP O.P.I. 160449/1987 discloses a technique that specifies spectral sensitivity and interimage effect (IIE).
• the technique specifies the IIE's orientations to respective color-sensitive layers.
• JP O.P.I. No. 160448/1987 discloses a technique to provide a cyan-sensitive layer to produce an IIE effect upon layers up to the red-sensitive layer to create a negative spectral sensitivity falsely corresponding to the spectral sensitivity of the human eye.
• IIE IIE generating layer
• the technique is disadvantageous in that it necessarily increases the amount of silver and production cost, and yet its effect is not sufficient.
• a silver halide color photographic light-sensitive material comprising a support having thereon one or more red-sensitive silver halide emulsion layers, one or more green-sensitive silver halide emulsion layers and one or more blue-sensitive silver halide emulsion layers, in which said blue-sensitive silver halide emulsion layer is located furthest from the support and has on the outside thereof at least one non-light-sensitive layer, wherein the parallel transmission density D ⁇ 555 nm of the unit of said blue-sensitive silver halide emulsion layer and said outside non-light-sensitive layer is equal to or less than 1.05, and the spectral sensitivity distribution S B( ⁇ ) of said blue-sensitive silver halide emulsion layer satisfies the following conditions:
• the spectral sensitivity distribution is a distribution of the spectral sensitivities obtained as the functions of wavelengths by measuring the sensitivities each defined by the reciprocal of an exposure amount necessary to give a density of the minimum density Dmin + 0.7 of the color samples formed by processing after exposing a light-sensitive material to each of monochromatic lights at intervals of several nanometers within the wavelength region range of from 400 to 700nm.
• the grain diameter by volume of the silver halide grain used in the blue-sensitive layer of the invention is preferably not more than 0.80 ⁇ m, more preferably not more than 0.70 ⁇ m and most preferably not more than 0.60 ⁇ m from the graininess point of view.
• the grain diameter by volume herein, in the case of a cubic grain, is the length of a side thereof and, in the case of a noncubic grain, is the length of a side of a cube equivalent in the volume thereto.
• the color light-sensitive material of the invention is of a multilayer structure formed by superposing emulsion layers provided for separately recording blue, green and red lights, and at least one of these emulsion layers is preferably comprised of a high-speed sublayer and a low-speed sublayer; particularly, practically useful layer structure examples are as follows:
• P1 or P2 preferably contains a non-light-sensitive silver halide emulsion.
• the above non-light-sensitive silver halide emulsion may be of pure silver iodide, silver iodobromide or silver chloro-iodobromide, but is of preferably silver halide grains having a silver bromide content of not less than 60%, a silver chloride content of not more than 30% and a silver iodide content of not more than 40%, and more preferably silver iodobromide grains having a silver iodide content of not more than 10%.
• the grain size is preferably 0.05 to 0.20 ⁇ m for obtaining a high sensitivity with little or no sensitivity drop of the lower layer or sharpness deterioration.
• the non-light-sensitive silver halide emulsion of the invention is allowed to have a relatively wide grain size distribution, but preferably has a narrow grain size distribution, more preferably the distribution width is within the rang of ⁇ 40% of the grain size of the silver halide grains accounting for 90% by weight or number of the whole grains.
• the coating weight of silver of the non-light-sensitive emulsion layer is preferably 0.03 to 5g/m2, more preferably 0.05 to 1g/m2.
• the binder of the non-light-sensitive emulsion layer there may be used any hydrophilic polymers, but is preferably gelatin.
• the amount of the binder used is preferably not more than 250g per mol of silver halide.
• the parallel transmission density of the unit comprised of the blue-sensitive layer and the non-light-sensitive layer unit located on the opposite side of the blue-sensitive layer to the support as shown in the above example (2) P1/P2/BH/BL or example (6) P1/P2/BH/BM/BL can be measured in accordance with the method described in C.R.Berry, J. Opt. Soc. Am, vol.52, p.888.
• the parallel transmission density measured according to such a method is preferably not more than 1.05, more preferably not more than 0.95 and most preferably not more than 0.90 at 555nm.
• the parallel transmission density obtained by the same method at 630nm is preferably not more than 1.0, more preferably not more than 0.90.
• One of means for achieving the parallel transmission density in the invention is to decrease the coating weight of silver of the blue-sensitive layer and the non-light-sensitive unit, i.e., the parallel transmission density can be adjusted by a combination of the grain diameter and the coating weight of silver of the silver halide emulsion grains used.
• the silver content of the blue-sensitive layer is preferably 0.1 to 3.0g/m2, more preferably 0.2 to 2.0g/m2 and most preferably 0.3 to 1.5g/m2.
• the aspect ratio of the tabular silver halide grain contained in the silver halide emulsion of the invention is the diameter/thickness ratio of the grain, wherein the diameter of the silver halide grain is the diameter of a circle equivalent in the area to the projection image of the grain, while the thickness is the distance between the two parallel surface planes forming the tabular silver halide grain.
• the hexagonal tabular grain of the invention is a grain of which the ⁇ 111 ⁇ face is hexagonal and the maximum adjacent side ratio is from 1.0 to 2.0, wherein the maximum adjacent side ratio is the ratio of the longest side to the shortest side forming a hexagon. If the maximum adjacent side ratio of the hexagonal tabular grain of the invention is from 1.0 to 2.0, then the corners of the grain are allowed to be roundish. The length of each side of the hexagon having corners roundish, when the straight portion of each side is extended, is expressed as the distance between the intersecting points of these extended lines of adjacent sides.
• one half or more are preferably substantially straight lines, and more preferably 4/5 or more are substantially straight lines.
• the adjacent side ratio is preferably from 1.0 to 1.5.
• the silver halide emulsion of the invention comprises a dispersion medium and silver halide grains.
• Preferably not less than 70%, more preferably not less than 80% and most preferably not less than 90% of the number of the silver halide grains in a projection image thereof are hexagonal tabular silver halide grains each having two parallel twin faces.
• the hexagonal tabular grain of the invention is characterized by having two parallel twin faces, which may be confirmed by a transmission-type-electron-microscopic observation at a low temperature (liquid nitrogen temperature) of a cross-sectionally microtomed flake of a film coated with an emulsion of the above grains.
• the coefficient of variation of the grain diameter in the invention represents the degree of variation of grain diameters, expressed in terms of percentage of the quotient of the standard deviation of the diameters of circles equivalent in the area to projection images of hexagonal tabular grains each having a maximum adjacent side ratio of from 1.0 to 2.0 divided by the average grain diameter.
• the coefficient of variation of the grain thickness in the invention represents the degree of variation of thicknesses of hexagonal tabular grains of the invention, expressed in terms of percentage of the quotient of the standard deviation of the thicknesses of hexagonal tabular grains each having a maximum adjacent side ratio of from 1.0 to 2.0 divided by the average thickness.
• the tabular silver halide grains each having an aspect ratio of from 3.0 to 7.0 account for preferably at least 50%, more preferably 70% of the whole projction area of silver halide grains, and the tabular silver halide grains each having an aspect ratio of 3.0 to 4.9 account for preferably 50%, more preferably 70% of the whole projection area of silver halide grains.
• the silver halide grains each having an even number of twin faces parallel with the principal plane thereof account for at least 70% of the whole projection area of silver halide grains, wherein the principal plane is in the form of a hexagon having a maximum adjacent side ratio of from 1.0 to 2.0, and the silver halide grains having such hexagonal principal planes account for preferably at least 90% of the whole projection area of silver halide grains.
• the silver halide grains with hexagonal principal planes having a maximum adjacent side ratio of from 1.0 to 1.5 account for preferably 70%, more preferably 90% of the whole projection area of silver halide grains.
• the mixing-in rate of other silver halide grains in the different form becomes high.
• Chemical sensitization is strongly affected by the form, surface characteristics, composition, defects, etc., of silver halide grains, so that if grains different in the form are thus mixedly present, the chemical sensitization degree differs depending on grains, which not only makes it unable to obtain any optimal chemical sensitization conditions with respect to the sensitivity/fog relation but allows the presence as a mixture of insufficiently chemically ripened grains poor in the pressure-desensitization characteristic and excessively chemically ripened grains poor in the pressure fog, and thus the silver halide grains become poor in the pressure-resistance as a whole.
• the silver halide emulsion of the invention there may be used pure silver bromide or silver iodobromide.
• the average silver iodide content of the silver iodobromide is preferably not more than 10 mol%, more preferably not more than 8 mol% and most preferably not more than 6 mol% from the color reproducibility point of view.
• the optimal range of the silver iodide content is preferably 0.1 to 6 mol%, more preferably 0.5 to 4 mol% and most preferably 1 to 3.5 mol% from the overall point of view.
• the silver iodide content of each individual grain can be measured by use of an XMA (X-ray microanalyzer).
• XMA X-ray microanalyzer
• the relative standard deviation value is preferably not more than 20%, more preferably not more than 15% in view of the pressure-resistant characteristic.
• the diameter of the hexagonal tabular grain of the invention is preferably not less than 0.4 ⁇ m, more preferably 0.5 to 3.0 ⁇ m and most preferably 0.5 to 1.7 ⁇ m.
• the average thickness of the tabular grain of the invention is preferably 0.05 to 0.30 ⁇ m, more preferably 0.05 to 0.25 ⁇ m and most preferably 0.05 to 0.20 ⁇ m.
• the variation of the grain diameter is preferably as much small or as much high monodisperse as possible.
• the emulsion of the invention comprises tabular low-silver-iodide-content grains rapidly developable, so it gives rise to a too contrasty gradation problem, and this problem is further accelerated by making grain diameters monodisperse.
• an optimal grain diameter distribution value is selected in the range satisfying both pressure-resistant characteristic and gradation characteristic.
• a means to spectrally sensitize an arbitrary silver halide to a desired wavelength region by use of a sensitizing dye having an absorption spectrum in the same region a means to optimize the halide composition and distribution of silver halide to cause the silver halide to have an intended spectral sensitivity without using any sensitizing dyes, and a means to use an appropriate spectral absorbent in the light-sensitive material to adjust its spectral sensitivity distribution to a desired spectral sensitivity distribution.
• a means to spectrally sensitize an arbitrary silver halide to a desired wavelength region by use of a sensitizing dye having an absorption spectrum in the same region a means to optimize the halide composition and distribution of silver halide to cause the silver halide to have an intended spectral sensitivity without using any sensitizing dyes
• a means to use an appropriate spectral absorbent in the light-sensitive material to adjust its spectral sensitivity distribution to a desired spectral sensitivity distribution.
• the following are the examples of the sensitizing dye usable in the blue-sensitive silver halide emulsion layer to obtain the spectral sensitivity distribution in the invention, but are not limited thereto.
• the light-sensitive material contain a diffusible DIR compound capable of releasing a diffusible development inhibitor or a precursor thereof upon its reaction with the oxidation product of a developing agent.
• Particularly preferred examples are the diffusible DIR compounds described in JP O.P.I. No. 110452/1990, pp.485 to 489.
• the silver halide emulsion used in the color light-sensitive material of the invention may be chemically sensitized in the usual manner.
• an antifoggant and a stabilizer may be added to the silver halide emulsion.
• a binder of the emulsion gelatin is advantageously used (but is not limited to it).
• the emulsion layer and other hydrophilic layer may be hardened, and may contain a plasticizer and a synthetic polymer dispersion (latex) which is insoluble or hardly soluble in water.
• the invention is suitably applicable to light-sensitive materials for photographing use such as color negative films, color reversal films, and the like.
• couplers having a color correction effect there may be used arbitrarily colored couplers having a color correction effect, competing couplers, and chemical substances capable of releasing photographically useful fragments such as development accelerator, bleaching accelerator, developing agent, silver halide solvent, toning agent, hardener, fogging agent, antifoggant, chemical sensitizer, spectral sensitizer and desensitizer upon the coupling reaction thereof with the oxidation product of a developing agent.
• the light-sensitive material may have auxiliary layers such as a filter layer, an antihalation layer and an antiirradiation layer. These layers and/or emulsion layers may contain a dye which, during processing, is dissolved out of the light-sensitive material or is bleached.
• To the light-sensitive material may be added formalin scavenger, brightening agent, matting agent, lubricant, image stabilizer, surfactant, anti-color-stain agent, development accelerator, development retarder and bleaching accelerator.
• the support there may be used discretionarily polyethylene-laminated paper, polyethylene terephthalate film, baryta paper, cellulose triacetate, or the like.
• the color light-sensitive material of the invention to obtain a dye image, is imagewise exposed and then processed according to a generally known color photographic processing method.
• Solution A1 After stopping the addition of Solutions B1 and C1, the temperature of Solution A1 was raised spending 30 minutes to 60°C, and again Solutions B1 and C1 were added at a flow rate of 19.5ml/min for 25 minutes in the double-jet method. In the meantime, the electric potential of silver (measured with a silver ion selection electrode, using a saturated silver-silver chloride electrode as a comparative electrode) was controlled to +6mV by using Solution D1.
• the prepared seed emulsion EM-O is of silver halide grains in which the hexagonal tabular grains accounting for 90% or more of the whole projection area thereof were found by electron-microscopic observation to each have a maximum adjacent side ratio of 1.0 to 2.0, an average thickness of 0.07 ⁇ m and an average diamter (equivalent to a circle diameter) of 0.5 ⁇ m.
• the emulsion EM-O in an amount of 0.6215 mol is contained in 4612ml of the silver halide.
• Solutions B2 and C2 were added at a flow rate of 45ml/min spending 95.14 minutes by a double-jet method to Solution A2 by using the mixing stirrer described in JP E.P. Nos. 58288/1983 and 58289/1983 to thereby grow silver halide grains.
• the grown grains were washed in the usual sedimentation manner (with use of phenylcarbamoylated gelatin) to remove the excessive salts therefrom, and thereafter an aqueous gelatin solution containing 47.57g of osein gelatin was added thereto for redispersion by stirring.
• Emulsion EM-1 in its amount of 2445ml contains 5.65 mol of silver halide, and pH and pAg of its emulsion liquid at 40°C are adjusted to 5.8 and 8.06, respectively.
• EM-1 Approximately 3,000 grains of EM-1 were subjected to electron-microscopic observation/measurement for configuration analysis. As a result, it was found that in EM-1, 50% or more of the whole silver halide grains in the projection area are silver halide grains each having an aspect ratio of not less than 4.34, 70% or more of the whole projection area are tabular grains each having an aspect ratio of not less than 3.86, and 90% or more of the above tabular grains in the whole prejction area are hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0.
• the hexagonal tabular grains have an average grain diameter of 0.92 ⁇ m (equivalent to circle diameter), a diameter distribution variation coefficient of 21.8%, an average thickness of 0.218 ⁇ m, and a thickness variation coefficient of 15%.
• the grown grains were washed in the usual sedimentation manner (with use of phenyl-carbamoylated gelatin) to remove the excessive salts therefrom, and thereafter an aqueous gelatin solution containing 29.3g of osein gelatin was added thereto for redispersion by stirring.
• Emulsion EM-2 in its amount of 2660ml contains 4.94 mol of silver halide grain, and pH and pAg of the emulsion liquid are adjusted at 40°C to 5.8 and 8.06, respectively.
• EM-2 Approximately 3,000 grains of EM-2 were subjected to electron-microscopic observation/measurement for configuration analysis. As a result, it was found that in EM-2, 50% or more of the whole silver halide grains in the projection area are silver halide grains having an aspect ratio of not less than 4.07, 70% or more of the whole projection area are tabular grains having an aspect ratio of not less than 3.33, and 90% or more of the above tabular grains in the whole projection area are hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0.
• the hexagonal tabular grains have an average grain diameter (equivalent to circle diameter) of 0.62 ⁇ m, a diameter distribution variation coefficient of 24.2%, an average thickness of 0.163 ⁇ m and an average thickness variation coefficient of 9%.
• Table 1 Emulsion name Diameter by volume ( ⁇ m) Grain form Aspect ratio Average AgI content (%) EM-1 0.53 Tabular grain 3.86 2.46 EM-2 0.37 Tabular grain 3.33 3.18 EM-3 0.70 Tabular grain 5.12 3.70 EM-4 0.30 Tabular grain 4.01 2.30 EM-5 0.42 Cubic grain 1.00 5.25 EM-6 0.28 Cubic grain 1.00 4.00 EM-7 0.65 Cubic grain 1.00 5.50 EM-8 0.78 Cubic grain 1.00 5.50
• added amounts of additives to the silver halide photographic light-sensitive material samples are shown in grams per m2 except that silver halide and colloidal silver are in silver equivalent and sensitizing dyes are in moles per mol of the silver halide of the same layer.
• coating aid Su-1 dispersing aid Su-2, viscosity adjusting agent, hardeners H-1 and H-2, stabilizer ST-1, antifoggant AF-1 and two different compounds AF-2 having weight average molecular weights of 10,000 and 100,000.
• Samples-102 to -111 were prepared in the same manner as in Sample-101 except that the sensitizing dye for the blue-sensitive emulsion layer of Sample-101 was changed as shown in Table 2 for optimal chemical sensitization.
• Samples-101 to -111 were used to photograph a color rendition chart, manufactured by Macbeth Co., and then processed according to the following color processing steps. Processing step (38°C) Color developing 3 min. 10 sec. Bleaching 6 min. 30 sec. Washing 3 min. 15 sec. Fixing 6 min. 30 sec. Washing 3 min. 15 sec. Stabilizing 1 min. 30 sec. Drying
• the film of each processed sample was used to make a color paper print (KONICA Color PC Paper Type SR) therefrom so that the photographed gray scale image of an optical density of 0.7 is reproduced in the same density on the print, whereby the reproducibity thereof was evaluated.
• a color paper print KONICA Color PC Paper Type SR
• the maximum sensitivity As for the spectral sensitivity distribution, from the distribution of minimum density + 0.7, comparison of the maximum sensitivity at the minimum density + 0.7 in the spectral sensitivity distribution of the blue-sensitive layer (hereinafter referred to as the maximum sensitivity) with the spectral sensitivity at the minimum sensitivity + 0.7 to 480nm (hereinafter referred to as the sensitivity to 480nm) was performed.
• the sensitivity comparison is defined by the following formula: (maximum sensitivity/sensitivity to 480nm) x 100(%)
• the ⁇ max(nm) column of Table 2 shows a wavelength which provides the maximum sensitivity in the spectral sensitivity distribution at the minimum density + 0.7 of the blue-sensitive layer of each sample.
• the parallel transmission density was obtained by measuring with a Hitachi automatic-recording spectrophotometer U-3210 each sample prepared by coating on a triacetyl cellulose film support a unit of Layers 10 to 13 of each of the above multilayer light-sensitive materials.
• the value obtained by subtracting the uncoated support density from the above parallel transmission density is given as the parallel transmission density of each coated unit in Table 2.
• the RMS value is expressed in terms of a 1.000-fold value of the standard deviation of the variation of density values obtained by scanning 1,000 or more sampled densitiy areas to be measured of each light-sensitive material sample with a microdensitometer having a scanning head opening area of 1800 ⁇ m2 (slit width: 10 ⁇ m, slit length: 180 ⁇ m) and is shown in a relative value to the value of Sample-101 set at 100.

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• 1991
  • 1991-03-12 JP JP3046756A patent/JPH05249626A/ja active Pending
• 1992
  • 1992-03-09 US US07/848,381 patent/USH1243H/en not_active Abandoned
  • 1992-03-10 EP EP92104048A patent/EP0503549A1/de not_active Withdrawn

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