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
  • G03C7/3029—Materials characterised by a specific arrangement of layers, e.g. unit layers, or layers having a specific function

Definitions

• the present invention relates to improvement of a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material capable of forming a high-quality image and having an excellent preservability.
• Recent silver halide color photographic light-sensitive material products are so improved as to form remarkably highquality images.
• the three major elements of an image quality - graininess, sharpness and color reproducibility - are all on a considerably high level, so that most customers appear to be contended with their prints or slide photos reproduced.
• the color reproducibility has two major factors: the spectral sensitivity distribution and interimage effect.
• the effect can be attained by adding to a silver halide multilayer color photographic light-sensitive material a compound called DIR compound capable of releasing a development inhibitor or a precursor thereof upon its coupling reaction with a color developing agent, wherein the development inhibitor inhibits the development of different color-forming layers to thereby create an interimage effect for color reproducibility improvement.
• the compound it is difficult for the compound to control the directivity of the interimage effect, so that the compound has a drawback of causing color alteration although it can raise color purity.
• the control of the directivity of the interimage effect is described in U.S. Patent No. 4,725,529.
• U.S. Patent No. 3,672,898 discloses a proper spectral sensitivity distribution for reducing the color reproducibility variation due to the different light sources used in photographing.
• JP O.P.I. No. 034541/1986 makes an attempt to improve the foregoing color film's reproduction of certain colors hard to be reproduced, and its effect appears to have been obtained to some extent.
• the attempt is to exert not only the respective effects of the conventional blue-sensitive layer, green-sensitive layer and red-sensitive layer but also the interimage effect from the outside of the wavelengths to which the above color-sensitive layers are sensitive.
• the above technique is considered useful to a certain extent for improving the reproducibility of specific colors, but the technique, for interimage effect generation, needs an interimage effect-generating layer and a light-sensitive silver halide layer in addition to the conventional blue-sensitive, green-sensitive and red-sensitive emulsion layers, which requires increasing the amount of silver and the number of production processes to thus result in a high production cost. Besides, its effect is not sufficient.
• U.S. Patent No. 3,672,898 discloses a spectral sensitivity distribution for reducing the color reproducibility variation due to different light sources used in photographing; this intends to reduce the color variation by bringing the spectral sensitivity distributions of the blue-sensitive and red-sensitive layers close to that of the green-sensitive layer to thereby lessen the changes in the sensitivities of these layers corresponding to different light sources, particularly different color temperatures, in photographing.
• the three color-sensitive layers are so close to one another as to overlap their spectral sensitivity distributions to cause a color purity deterioration.
• the color purity deterioration can be prevented to a certain extent, as is well known, by emphasizing the interimage effect by use of the foregoing diffusible DIR compound.
• British Patent No. 923,045 discloses a method in which a color-sensitive layer is separated into substantially the same color-forming nondiffusible coupler-containing high-speed and low-speed emulsion sublayers, and the high-speed sublayer's maximum color density is set low, whereby the sensitivity of the layer can be raised high without coarsening the grains of the layer. This method, however, is still not sufficient for the graininess.
• U.S. Patent No. 3,843,469 discloses a high-sensitivity multilayer color light-sensitive material in which at least one of its red-sensitive, green-sensitive and blue-sensitive layers is comprised of three different-speed sublayers - a high-speed upper sublayer, a medium-speed middle sublayer and a low-speed lower sublayer. This light-sensitive material, however, is still not sufficient, either, although its graininess is improved to some extent.
• the two-equivalent coupler having a good color-forming characteristic is conventionally known as one of the sharpness-improving techniques; for example, German Patent No. 1,121,470 describes a light-sensitive material having light-sensitive units each composed of two sublayers each containing a two-equivalent coupler.
• German Patent No. 1,121,470 describes a light-sensitive material having light-sensitive units each composed of two sublayers each containing a two-equivalent coupler.
• this technique although useful for improving the sharpness, has the problem of conspicuously deteriorating the graininess and increasing the fog of the light-sensitive unit.
• U.S. Patent No. 3,516,831 describes a light-sensitive material comprising emulsion layer units of which at least one emulsion layer unit is comprised of two different-speed sublayers - a high-speed sublayer and a low-speed sublayer each sensitive to the same spectral region, in which the high-speed emulsion sublayer contains a four-equivalent coupler, while the low-speed emulsion sublayer contains a two-equivalent coupler to thereby improve both sharpness and graininess. It is, however, difficult for the above coupler combination to provide a sufficiently high sensitivity.
• a silver halide color photographic light-sensitive material comprising a support having thereon a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer, in which said red-sensitive layer is comprised of a high-speed emulsion sublayer, a medium-speed emulsion sublayer and a low-speed emulsion sublayer, which are provided in the low-speed to high-speed order from the support, wherein said high-speed emulsion sublayer contains a two-equivalent cyan coupler and said medium-speed and low-speed emulsion sublayers each contain a four-equivalent cyan coupler and a diffusible DIR compound, and the maximum cyan color transmission density of said medium-speed emulsion sublayer is not more than 0.35.
• the high-speed sublayer is preferably adjacent to the medium-speed sublayer, and the medium-speed sublayer adjacent to the low-speed sublayer as well.
• the high-speed sublayer's sensitivity is 0.1 to 1.0 log E higher than the medium-speed sublayer's, while the medium-speed sublayer's sensitivity is 0.1 to 1.0 log E higher than the low-speed sub-layer's.
• the high-speed emulsion sublayer in the red-sensitive layer of the invention contains a two-equivalent cyan coupler, and may also contain a four-equivalent cyan coupler. Where the four-equivalent coupler is contained, the amount of the two-equivalent coupler accounts for preferably 50 to 100 mol% of the whole coupler content of the high-speed sublayer and the four-equivalent coupler accounts for the rest; more preferably 80 to 100 mol%; and most preferably 100 mol%.
• the whole coupler content of the high-speed emulsion sublayer of the invention is preferably 1x10- 4 to 1 mol, more preferably 1x10- 3 to 1 mol, and most preferably 3x10- 3 to 8x10 ⁇ mol per mol of silver.
• the two-equivalent coupler used in the invention is repre sented by the following Formula I: wherein Cp represents a coupler residue, * represents the coupling position of the coupler, and X is a group that splits off upon the coupler's coupling reaction with the oxidation product of an aromatic primary amine developing agent to form a dye.
• cyan coupler residue represented by Cp of the above formula are described in U.S. Patent Nos. 2,367,531, 2,423,730, 2,474,293, 2,772,162, 2,895,826, 3,002,836 and 3,034,892; and Agfa Mitannon (Band II), pp.156 to 175 (1961).
• the split-off group represented by X is a monovalent group such as a halogen atom or an alkoxy, aryloxy, heterocyclic oxy, acyloxy, alkylthio, arylthio, heterocyclic thio; wherein X is a group of atoms necessary to form a 5- or 6-member ring together with at least one atom selected from the group consisting of a carbon atom, an oxygen atom, a nitrogen atom and a sulfur atom; a monovalent group such as acylamino or sulfonamido, or a bivalent group such as alkylene. In the case of a bivalent group, a dimer is formed with X.
• the preferred as the two-equivalent cyan coupler are the compounds having the following Formulas II, III and IV, and the most preferred are those having Formula III.
• R 2 and R 3 each represent a hydrogen atom or a substituent
• R 4 represents a substituent
• m is an integer of 1 to 3
• n is an integer of 1 or 2
• p is an integer of 1 to 5, provided that m, n and p each are 2 or more, the respective R 2 s may be either the same or different.
• the substituent represented by R 4 is a halogen atom or an alkyl, cycloalkyl, aryl or heterocyclic group attached directly or through a bivalent atom or a group to the nucleus.
• bivalent atom and group examples include oxygen, nitrogen and sulfur atoms and groups such as carbonylamino, aminocarbonyl, sulfonylamino, aminosulfonyl, amino, carbonyl, carbonyloxy, oxycarbonyl, ureylene, thioureylene, thiocarbonylamino, sulfonyl and sulfonyloxy.
• alkyl, cycloalkyl, aryl and heterocyclic groups include those having a substituent such as a halogen atom or a nitro, cyano, alkyl, alkenyl, cycloalkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, carboxy, sulfo, sulfamoyl, carbamoyl, acylamino, ureido, urethane, sulfonamido, heterocyclic, arylsulfonyl, alkylsulfonyl, arylthio, alkylthio, alkylamino, anilino, hydroxy, imido or acyl group.
• a substituent such as a halogen atom or a nitro, cyano, alkyl, alkenyl, cycloalkyl, aryl, alkoxy, aryloxy, alk
• alkyl, cycloalkyl, aryl and heterocyclic groups each represented by R 3 include those having a substituent, examples of which substituent include those previously exemplified as the substituent to the groups of R 2 .
• R 4 is as defined and exemplified for R 3
• X is as previously defined for the X or Formula I, and is preferably a halogen atom or an alkoxy, aryloxy or sulfonamido group.
• the cyan couplers having Formulas I and II include those forming polymers beyond dimers with R 2 , R 3 or X, while the couplers having Formula III include those forming polymers beyond dimers with R 2 , R 3 , R 4 or X.
• the four-equivalent cyan coupler used in the red-sensitive medium-speed emulsion sublayer and low-speed emulsion sublayer is preferably one having Formula I in which the X is a hydrogen atom, and more preferably one having Formula III in which the X is a hydrogen atom.
• the medium and low-speed emulsion sublayers of the invention contain a four-equivalent cyan coupler, and may also contain a two-equivalent cyan coupler in combination.
• the amount of the four-equivalent cyan coupler used accounts for preferably 50 to 100 mol% of the whole coupler content of the medium and low-speed sublayers and the two-equivalent coupler accounts for the rest, more preferably 80 to 100 mol%, and most preferably 100 mol%, i.e., it is most preferable that the four-equivalent cyan coupler alone be used.
• All the coupler amount contained in the medium and low-speed emulsion sublayers of the invention is preferably 1x10 -4 to 1 mol, more preferably 1x10 -3 to 1 mol and most preferably 3x10- 3 to 8x10 -1 mol per mol of silver.
• a diffusible DIR compound is added to the medium and low-speed emulsion sublayers of the red-sensitive emulsion layer.
• the diffusible DIR compound is a compound which is capable of releasing a development inhibitor or a development inhibitor precursor upon its reaction with the oxidation product of a color developing agent and of which the diffusibility according to the following evaluation method is preferably not less than 0.34 and more preferably not less than 0.40.
• the diffusibility evaluation method is as follows:
• Sample I Sample having a Green-sensitive silver halide emulsion layer
• a green-sensitive gelatino silver iodobromide emulsion layer (silver iodide content: 6mol%, average grain size: 0.48 ⁇ m) containing 0.07 mol/mol Ag of the following coupler is coated so as to have a silver coating weight of 1.1 g/m 2 and a gelatin coating weight of 3.0g/m 2 , and on the emulsion layer is coated a protective gelatin layer containing chemically, spectrally unsensitized silver iodobromide (silver iodide content: 2mol%, average grain size: 0.08 ⁇ m) so as to have a silver coating weight of 0.1 g/m 2 and a gelatin coating weight of 0.8g/m 2 .
• Sample II Sample the same as Sample I except that the protective layer contains no silver iodide.
• Each of the layers of the above samples contains a gelatin hardener and a surfactant in addition to the above components.
• Each of Samples I and II is exposed through an optical wedge to a white light, and then processed in the following manner.
• two different developers are used; one containing various development inhibitors in an amount necessary to decrease the sensitivity of Sample II to 60%, and the other containing no development inhibitor.
• compositions of the processing solutions used in the above processing steps are as follows:
• any diffusible DIR compound regardless of its chemical structure as long as the diffusibility of the group released therefrom is in the above prescribed range.
• Formula D-1 A-(Y) m wherein A represents a coupler residue, m is an integer of 1 or 2, and Y represents a group attached to the coupling position of the coupler residue A and capable of splitting off upon the compound's reaction with the oxidation product of a color developing agent to release a development-inhibiting group or a development inhibitor having a diffusibility of more than 0.34.
• Y is typically represented by the following Formulas D-2 to D-19.
• Rd 1 is a hydrogen atom, a halogen atom or an alkyl, alkoxy, acylamino, alkoxycarbonyl, thiazolydinilidenamino, aryloxycarbonyl, acyloxy, carbamoyl, N-alkylcarbamoyl, N,N-dialkylcarbamoyl, nitro, amino, N-arylcarbamoyloxy, sulfamoyl, N-alkylcarbamoyloxy, hydroxy, alkoxycarbonylamino, alkylthio, arylthio, aryl, heterocyclic, cyano, alkylsulfonyl or aryloxycarbonylamino group; n is an integer of 0, 1 or 2, provided that when n is 2, the Rd 1 s may be either the same or different. The total number of carbon atoms contained in the n number of Rd 1 s is from
• X represents an oxygen atom or a sulfur atom.
• Rd 2 represents an alkyl group, aryl group or a heterocyclic group.
• Rd 3 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group
• Rd 4 represents a hydrogen atom, a halogen atom, or an alkyl, cycloalkyl, aryl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkanesulfonamido, cyano, heterocyclic, alkylthio or amino group.
• alkyl groups represented by Rd,, Rd 2 , Rd 3 and Rd 4 include those having a substituent, which may be either straight-chain or branched-chain.
• the aryl groups represented by Rd,, Rd 2 , Rd 3 and Rd 4 include those having a substituent.
• the heterocyclic groups represented by Rd 1 , Rd 2 , Rd 3 and Rd 4 include those having a substituent, and are in the form of preferably a single or condensed 5- or 6-member ring containing at least one hetero atom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom.
• Examples of the heterocyclic group include pyridyl, quinolyl, furyl, benzothiazolyl, oxazolyl, imidazolyl, thiazolyl, triazolyl, benzotriazolyl, imido and oxazine groups.
• the number of carbon atoms contained in the Rd 2 of Formulas D-6 and D-8 is 0 to 15.
• Formula D-9 the total number of carbon atoms contained in Rd 3 and Rd 4 is 0 to 15.
• Formula D-10 -TIME-INHIBIT wherein TIME is a group attached to the coupling position of A and cleavable upon the coupler's reaction with the oxidation product of a color developing agent, and thereafter capable of controlling and releasing the INHIBIT group.
• the INHIBIT group is a group represented by the foregoing Formulas D-2 to D-9 which, after being released, becomes a development inhibitor.
• the -TIME-INHIBIT group is typically represented by the following Formulas D-11 to D-19.
• Rd 5 represents a hydrogen atom, a halogen atom or an alkyl, cycloalkyl, alkenyl, aralkyl, alkoxy, alkoxycarbonyl, anilino, acylamino, ureido, cyano, nitro, sulfonamido, sulfamoyl, carbamoyl, aryl, carboxy, sulfo, hydroxy or alkanesulfonyl group.
• the Rdss may combine with each other to form a condensed ring.
• Rd 6 is an alkyl, alkenyl, aralkyl, cycloalkyl, heterocyclic or aryl group.
• Rd 7 is a hydrogen atom or an alkyl, alkenyl, aralkyl, cycloalkyl, heterocyclic or aryl group.
• Rd 8 and Rd s each represent a hydrogen atom or an alkyl group preferably having 1 to 4 carbon atoms.
• k is an integer of 0, 1 or 2.
• 1 is an integer of 1 to 4.
• m is an integer of 1 or 2, provided that when m is 2, the Rd 7 s may be either the same or different.
• n is an integer of 2 to 4, provided that the n number of Rd 8 and of Rd 9 may be either the same or different, respectively.
• B represents an oxygen atom or wherein Rd 6 is as defined previously, and ---- implies that it may be either a single bond or double bond; in the case of a single bond, m is 2, while in the case of a double bond, m is 1.
• the total number of carbon atoms contained in the Rdis in one molecule of the INHIBIT group represented by Formula D-2 to D-7 is 0 to 32
• the number of carbon atoms contained in the Rd 2 of Formula D-8 is 1 to 32
• the total number of carbon atoms contained in the Rd 3 and Rd 4 of Formula D-9 is 0 to 32.
• alkyl, aryl and cycloalkyl groups represented by Rd s , Rd 6 and Rd 7 include those having a substituent.
• the preferred among the diffusible DIR compounds are those in which Y is represented by Formulas D-2, D-3 and D-10, and the preferred among the Y groups of Formula D-10 are those of which the INHIBIT group is represented by Formulas D-2, D-6 in which X is an oxygen atom, and D-8 in which Rd 2 is hydroxyaryl or alkyl having 1 to 5 carbon atoms.
• Examples of the coupler component represented by A of Formula D-1 include a yellow dye-image forming coupler residue, a magenta dye-image forming coupler residue, a cyan dye-image forming coupler residue and a colorless coupler residue.
• the diffusible DIR compound is used in the amount range of preferably 0.0001 to 0.1 mol, and more preferably 0.001 to 0.05 mol per mol of silver halide.
• the incorporation of the foregoing two-equivalent cyan coupler, four-equivalent cyan coupler and diffusible DIR compound into the emulsion layer may be carried out by adding to the emulsion a solution of them dissolved in a water-miscible organic solvent; adding to the emulsion an oil-in-water-type dispersion prepared by dissolving them in a water-nonmiscible organic solvent, particularly a high-boiling solvent, and dispersedly mixing the solution with a hydrophilic colloid liquid; adding to the emulsion a suspension/dispersion of them in the milled solid state; or by the deposition-precipitation dispersion method as disclosed in JP O.P.I. No. 120848/1990, European Patent No. 374,837 and World Patent No. 90/08345.
• the maximum cyan color transmission density of the medium-speed emulsion sublayer of the red-sensitive layer is obtained in the following manner:
• the maximum cyan color transmission density of the medium-speed red-sensitive emulsion layer is preferably not more than 0.35, more preferably 0.05 to 0.30, and most preferably 0.10 to 0.25.
• the maximum color transmission density of the high-speed emulsion sublayer of the red-sensitive layer of the invention is preferably 0.3 to 1.0, and more preferably 0.4 to 0.9.
• the maximum color transmission density of the low-speed emulsion sublayer of the red-sensitive layer is preferably 0.6 to 2.0, and more preferably 0.7 to 1.8.
• compositions of the processing solutions used in the above processing steps are as follows:
• the silver halide color photographic light-sensitive material of the invention preferably has an ISO speed of not less than 100.
• the method for determining an ISO speed is specified in JIS K 7614-1981.
• the silver halide color photographic light-sensitive material of the invention preferably has a monodisperse silver halide emulsion.
• the monodisperse silver halide emulsion is an emulsion comprising silver halide grains, in which the weight of the silver halide grains confined within the average grain diameter d ⁇ 20% range accounts for preferably 70% or more, more preferably 80% or more, and most preferably 90% or more of the whole silver halide weight.
• the average grain diameter d is defined by the grain diameter di in the case where n x d 3 i , the product of the frequency n of grains having a grain diameter d ; and d 3 i , is the maximum (rounded to three decimal places).
• the grain diameter herein is the diameter of a circular image equivalent in the areal to the projection image of a grain.
• the grain diameter can be obtained by actually measuring the diameter or the area of the grain image formed on a photographic print or projected on a screen by magnifying a silver halide grain 10,000 to 50,000 times through an electron microscope (the number of grains subjected to the measurement shall be 1000 or more selected at random).
• the highly monodisperse emulsion suitable for the invention has a grain diameter distribution width of preferably not more than 20%, and more preferably not more than 15%, wherein the grain diameter distribution width is defined by
• the method for measuring grain diameters complies with the aforementioned method, and the average grain diameter is an arithmetic mean.
• the silver halide emulsion of the invention comprises silver iodobromide emulsion of which the average silver iodide content is preferably 4 to 20 mol%, and more preferably 5 to 15 mol%.
• the silver halide emulsion used in the invention may contain silver chloride in an amount not to impair the effect of the invention.
• the silver halide grain used in the invention has thereinside a high silver halide-content phase.
• the silver halide content of the high silver iodide-content phase is preferably 15 to 45 mol%, more preferably 20 to 42 mol%, and most preferably 25 to 40 mol%.
• the silver halide grain of the invention has the internal high silver iodide-content phase covered with an external low silver iodide-content phase.
• the average silver iodide content of the external low silver iodide-content phase that forms the outermost phase of the grain is preferably not more than 6 mol%, and more preferably 0 to 4 mol%.
• a medium silver iodide-content phase (intermediate phase) may be present between the outermost phase and the internal high silver iodide-content phase.
• the silver iodide content of the intermediate phase is preferably 10 to 22 mol%, and more preferably 12 to 20 mol%.
• Each of the differences in the silver iodide content between the outermost phase and the intermediate phase and between the intermediate phase and the high silver iodide-content phase is preferably not less than 6 mol%, and more preferably not less than 10 mol%.
• the volume of the outermost phase accounts for preferably 4 to 70%, more prefeably 10 to 50%, that of the high silver iodide-content phase accounts for preferably 10 to 80%, more preferably 20 to 50% and most preferably 20 to 45%, and that of the intermediate phase accounts for 5 to 60%, and more preferably 20 to 55% of the whole volume of the grain.
• the above phases each may be a single phase of a homogeneous composition, a complex phase of a homogeneous composition or a group of phases having stepwise varied compositions, and besides arbitrary one of these phases may have a continuously varied composition.
• Another embodiment of the silver halide emulsion of the invention is such that the silver iodide content continuously changes from the core toward the external of the grain rather than the silver iodide present locally forms substantially stepwise uniform phases.
• the silver iodide content preferably decreases monotonously from its maximum content point inside the core to the external of the grain.
• the silver iodide content at its maximum content point is preferably 15 to 45 mol%, and more preferably 25 to 40 mol%.
• the silver iodide content of the surface phase of the silver iodobromide grain is preferably not more than 6 mol%, and more preferably 0 to 4 mol%.
• the silver halide emulsion used in the invention preferably satisfies at least one of the following requirements (1) to (4):
• the grain diameter herein is the diameter of the circumcircle where the projection image area of the grain is maximum.
• the emulsion is pretreated as follows prior to measurement by the X-ray photoelectron spectral analysis. Firstly, the emulsion, after adding a pronase solution thereto, is stirred for one hour at 40°C for gelatin decomposition, and then centrifuged to deposit the emulsion grains. After removing the supernatant in the decantation manner, the pronase solution is added to the grains to repeat gelatin decomposition under the same conditions as the above. This sample is again centrifuged to remove its supernatant therefrom, then distilled water is added thereto to redisperse the emulsion grains into water, then again centrifuged to remove its supernatant therefrom...., thus repeating this washing operation three times. After that, the emulsion grains are redispersed into ethanol, which is then thinly coated on a mirror-like polished silicon wafer to thereby prepare a sample for measurement.
• a measuring instrument such as an ESCA/SAM560, manufactured by PHI Co., provided with Mg-Ka rays as an excitation X-ray source, which is operated under conditions of an X-ray source power of 15KV, an X-ray source current of 40mA and a pass energy of 50eV.
• composition ratio is calculated according to a relative speed coefficient method by using the respective peaks' integral intensities.
• the composition ratio is rendered in atomic percentages by using 5.10, 0.81 and 4.592 as the relative speed coefficients of Ag3d, Br3d and 13d3/2.
• Silver halide grains are dispersed in an electron-microscopic observation grid of an electron microscope equipped with an energy-dispersion-type X-ray analyzer, the grid is cooled by liquid nitrogen, the magnification is set so as to get one grain in the CRT field of view, and the intensities of AgLa and ILa rays are integrated for a given period of time. From the intensity ratio of ILa/AgLa and an in advance prepared calibration curve, a silver iodide content can be calculated.
• the emulsion is characterized by having a continuous signal over a diffraction angle of more than 1.5; preferably has a continuous signal over a diffraction angle of more than 1.5 at the signal's maximum peak height x 0.15; more preferably has a continuous signal over a diffraction angle of more than 1.8; and most preferably has a continuous signal over a diffraction angle of more than 2.0. That the emulsion has the signal means that at the maximum peak height x 0.13 or 0.15, it has a signal intensity more than the height.
• a more preferred embodiment of the silver halide emulsion of the invention is such that it has two or three peaks, more preferably three peaks, in the above (420) X-ray diffraction signal with CuKa rays as the X-ray source.
• the X-ray diffractometry is known as a method useful for examining the structure of silver halide crystals.
• the X-ray source for the method there may be used various characteristics-having X rays. Particularly. CuLa rays with Cu used as a target is most widely used.
• Silver iodobromide has a rock-salt structure, which shows a diffraction angle 2 of 71 to 74° in the (420) X-ray diffraction signal with CuKa rays.
• the X-ray diffractometry generates a relatively high- intensity signal at a high angle and a good resolution, so that it is suitable for examining crystal structures.
• the measured values' relative standard deviation shall be preferably not more than 20%, more preferably not more than 15%, and most preferably not more than 12%.
• the silver halide crystal used in the invention may be a regular crystal such as a cubic, tetradecahedral or octadecahedral crystal, or a tabular twin crystal, or a mixture of these crystals.
• the projected image area of ones each in which the ratio of the diameter of a circular image equivalent in the area to that of its projection image and its thickness is in the range of from 1 to 20 accounts for preferably more than 60% of the whole projected image area of the twin crystal grains in a scene.
• the above ratio range is preferably less than 8.0, and more preferably not less than 1.5 and less than 5.0.
• the monodisperse regular crystal grains-containing emulsion of the invention can be prepared by making reference to the methods described in JP O.P.I. Nos. 177535/1984, 138538/1985, 52238/1984, 143331/1985, 35726/1985, 258536/1985 and 14636/1986.
• the monodisperse twin crystals emulsion may be prepared making reference to the spherical seed grains growing method disclosed in JP O.P.I. No. 14636/1986.
• a silver nitrate aqueous solution and a halide aqueous solution by a double-jet process.
• An iodide may be provided in the form of silver iodide to the system. The addition should be made at a speed not to generate new nuclei and not to cause a grain size distribution extension due to Ostwald ripening: i.e., at a speed in the range of from 30 to 100% of the speed to generate new nuclei.
• the growth of the silver halide emulsion is preferably carried out under conditions of a pAg of 5 to 11, a temperature of 40 to 85 ° C and a pH of 1.5 to 12.
• the silver halide emulsion is subjected to physical ripening, chemical ripening and spectral sensitization.
• the additives used in the invention can be added according to the dispersing method described in RD308119 X IV.
• the support of the light-sensitive material of the invention there may be used one of the materials described in the foregoing RD17643 p.28, RD18716 p.647-8, and RD308119 XVII.
• the light-sensitive material of the invention may have auxiliary layers such as the filter layer and intermediate layer described in RD308119 VII-K.
• the light-sensitive material of the invention may take various layer structures such as the normal layer structure, inverted layer structure and unit structure described in RD 308119 VII-K.
• the invention may apply to various color light-sensitive materials such as color negative films for general or movie use, color reversal films for slide or TV use, color photographic papers, color positive films and color reversal papers.
• the light-sensitive material of the invention may be processed in the usual manner as described in RD17643 p.28-29, RD18716 p.647, and RD308119 XVII.
• adding amounts to the silver halide light-sensitive material are shown in grams per m 2 except that those of silver halide and colloidal silver are shown in silver equivalents and those of sensitizing dyes in mols per mol of silver halide.
• a coating aid Su-2 a dispersing aid Su-1, hardeners H-1 and H-2, dyes AI-1 and AI-2, a stabilizer ST-1, antifoggants AF-1 and AF-2 and an antiseptic DI-1 in addition to the above compounds.
• a sample 102 was prepared in the same manner as in Sample 101 except that the DIR compound of Layer 4 of Sample 101 was removed and the following Layer 3A was provided between the Layer 3 and Layer 4 of Sample 101.
• Samples 103 to 108 were prepared in the same manner as in Sample 102 except that the coating weights (g/m 2 ) of the cyan coupler C-1 and the DIR compound D-1 contained in Layer 3A of Sample 102 were varied as shown in Table 1.
• Samples 101 to 108 were exposed through an optical stepwedge for sensitometric evaluation; imagewise exposed for image-quality evaluation; and then processed in the following procedure.
• a separate set of the samples, prepared for different sensitometric evaluation were allowed to stand for 20 days under atmospheric conditions of 35 ° C/70%RH, and then exposed and processed in like manner.
• compositions of the processing solutions used in the above processing steps are as follows:
• the graininess of each sample was evaluated in terms of an RMS granularity value.
• the RMS value is the standard deviation of the fluctuation of density values obtained when measuring the red density + 0.5 area with a SAKURA microdensitometer PDM-5AR having a head slit opening of 250u.m 2 , manufactured by KONICA Corp.
• Table 2 the RMS values of the samples are shown in relative values to the value of Sample 101 set at 100.
• MTF modulation transfer function
• the samples having the construction of the invention have better improved graininess, sharpness and preservability than the comparative samples.
• a coating aid Su-2 In addition to the above compounds, to each of the above layers were added a coating aid Su-2, a dispersing aid Su-1, a viscosity-control agent, hardeners H-1 and H-2, a stabilizer ST-1, two different antifoggants AF-1 having a Mw of 10,000 and AF-2 having a Mw of 1,100,000 and an antiseptic DI-1.
• Samples 202 to 208 were prepared in the same manner as in Sample 201 except that the cyan coupler and DIR compound contained in the Layers 3, 4 and 5 of Sample 201 were changed as shown in Table 3, provided that cyan coupler C-1 was added in an amount of 0.8g/ M 3 to layer 3 and in an amount of 0.56g/m 2 to Layer 4 of each of Samples 203, 204 and 205, and added as shown in Table 3 to Samples 206, 207 and 208; and DIR compound D-1 was added in an amount of 0.003g/m 2 to Layer 4.
• the samples having the construction of the invention have better improved graininess, sharpness and preservability than the comparative samples.

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• 1990
  • 1990-09-03 JP JP23265990A patent/JPH04113354A/ja active Pending
• 1991
  • 1991-09-02 EP EP91114764A patent/EP0474166A1/de not_active Withdrawn

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