EP0488313A1 - A silver halide color photographic light-sensitive material - Google Patents

A silver halide color photographic light-sensitive material Download PDF

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Publication number
EP0488313A1
EP0488313A1 EP91120432A EP91120432A EP0488313A1 EP 0488313 A1 EP0488313 A1 EP 0488313A1 EP 91120432 A EP91120432 A EP 91120432A EP 91120432 A EP91120432 A EP 91120432A EP 0488313 A1 EP0488313 A1 EP 0488313A1
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Prior art keywords
sensitive
mtf
layer
mft
sensitive layer
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German (de)
French (fr)
Inventor
Yoshitaka Yamada
Hiroshi Shimazaki
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Konica Minolta Inc
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Konica Minolta Inc
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3022Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3041Materials with specific sensitometric characteristics, e.g. gamma, density

Definitions

  • oil-soluble dyes may also be used.
  • yellow, magenta and cyan dyes described in Japanese Patent Application No. 241889/1990 and JP O.P.I. No. 168148/1987.
  • a high monodisperse emulsion can be obtained by the method for growing grains in the presence of a tetrazaindene compound as disclosed in JP O.P.I. No. 122935/1985.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Abstract

A silver halide color photographic material is disclosed, which is prevented from irregular color reproduction on a photograph of gray color cloth. The photographic material comprises a support having thereon a photographic layer including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, and values of MFTB, MFTG and MFTR of dye images each formed in the blue-sensitive layer, green-sensitive layer and red-sensitive layer, respectively, satisfy the following conditions:
MTFG ≧ 0.70
MTFG + 0.20 ≧ MTFB ≧ MTFG - 0.20
MTFG + 0.20 ≧ MTFR ≧ MTFG - 0.20
in which MFTB, MFTG and MFTR are MFT values at the spatial frequency of 20 lines/mm of dye images each formed in the blue-sensitive layer, green-sensitive layer and red-sensitive layer.

Description

    FIELD OF THE INVENTION
  • The present invention relates to improvement of the color reproducibility of a silver halide color photographic light-sensitive material, and more particularly to rectification of the color photographic light-sensitive material's abnormal reproduction of a color of cloth and the like.
  • BACKGROUND OF THE INVENTION
  • Recent color photographic light-sensitive material products provide very high level of quality images having excellent graininess, sharpness and color reproducibility, but still have a problem that is pointed out by some customers.
  • An example of the problem is an abnormal reproduction of a color of cloth, which is a phenomenon wherein when one wearing a gray-colored clothe is photographed, the reproduced color of the clothe appears to be partially reddish, as described in the report of the 56th meeting of the Society for the Research of Photographic Papers. This is a complaint made not only in the above report but also often by photostudios and professional photographers, and so is a serious problem because out-of-focus photos must be made in order to avoid this phenomenon.
  • Therefore, there has been a strong demand for solution of the abnormal color reproduction problem without affecting the intrinsic color reproduciblity of color photographic light-sensitive material products.
  • SUMMARY OF THE INVENTION
  • It is an object of the invention to provide a silver halide color photographic light-sensitive material having an excellent sharpness and a color reproducibility improved so as to cause little or no abnormal color reproduction, particularly of cloths.
  • The object of the invention can be accomplished by a silver halide color photographic light-sensitive material comprising a support having thereon a blue-sensitive silver halide emulsion layer, a green-sensitive emulsion layer and a red-sensitive silver halide emulsion layer, in which said silver halide color photographic light-sensitive material satisfies the following requirements A and B:
  • Requirement A:
    MTFG ≧ 0.70,
    Requirement B:
    MTFG+0.20 ≧ MTFB ≧ MTFG-0.20 and MTFG+0.20 ≧ MTFR ≧ MTFG-0.20,
    wherein MTFB, MTFG and MTFR are the respective MTF values at 20 lines/mm of the dye images formed after processing of said blue-sensitive, green-sensitive and red-sensitive emulsion layers.
  • The invention can be more effective if the color light-sensitive material can satisfy the requirement B of
    MTFG+0.15 ≧ MTFB ≧ MTFG-0.15 and
    MTFG+0.15 ≧ MTFR ≧ MTFG-0.15,
    so that this is the preferred embodiment of the invention.
  • The above MTF values can be measured in accordance with the known method as described in the Theory of the Photographic Process (4th edition), T.H. James.. Ch 21, p.604-607. Concretely, as described in 'Fundamental of photographic Technology' Colona-sha p.417-p.419 (1974) Tokyo, there are various methods for determining MFT value such as sine curve exposure-microphotometer method, rectangular wave exposure-Fraunhofer interferometer method, slit exposure-microphotometer method. MFE values obtained by any of the above methods coincide within the error range. In this invention, MFT value is determined by a method in which rectangular wave exposure is used in place of sine wave exposure in the above sine wave exposure-microphotometer method and the value thus obtained is converted to MFT value by sine wave exposure. The processing of the sample to be determined is performed by use of the processing solutions and procedure, both described in Annual of the British Journal of Photography, p.196-198 (1988).
  • DETAILED DESCRIPTION OF THE INVENTION
  • Where a gray cloth woven with black and white threads is photographed to make a color print, there often occurs the problem of red appearing on the printed image; this is a great trouble to professional photographers. There are a variety of views about this phenomenon.
  • Some assume that it may be a special cloth reflecting an invisible red light. In fact, however, the abnormal color reproduction has occurred even though no such red light reflection was present. Another view suspects it due to the chromatic aberration of a camera lens. According to our investigation, however, it has been found that the phenomenon can not always be interpreted with the chromatic aberration of a lens.
  • Upon this, we prepared color films having blue-sensitive, green-sensitive and red-sensitive layers whose MTF (Modulation Transfer Function) values and balance were varied, as shown in the example mentioned hereinafter, to actually photograph a gray cloth woven with black and white threads and to make color prints therefrom. As a result, it has been found that only the film that satisfies the requirements of the invention can provide a very sharp image print having little or no abnormal color-forming phenomenon.
  • In order to have the MTF values of the individual color-sensitive layers meet the requirements of the invention, it is preferable to use a diffusible DIR compound.
  • The diffusible DIR compound in the invention is a compound which, upon its reaction with the oxidation product of a color developing agent, permits split-off of a development inhibitor or development inhibitor-releasing group whose diffusibility according to the evaluation method mentioned hereinafter is preferably not less than 0.34, and more preferably not less than 0.40.
  • The diffusibility is evaluated as follows:
       Light-sensitive material samples I and II having layers of the following compositions on a transparent support are prepared.
  • Sample I: Green-sensitive silver halide emulsion layer-having sample
  • A gelatin coating liquid containing green-sensitized silver iodobromide (silver iodide content: 6 mol%, average grain diameter 0.48µm) and the following coupler in an amount of 0.07 mol per mol of silver is coated to form an emulsion layer on a support so as to have a silver coating weight of 1.1g/m² and a gelatin coating weight of 3.0g/m², and on the emulsion layer is coated a gelatin liquid containing silver iodobromide neither chemically nor spectrally sensitized (silver iodide content: 2 mol%, average grain diameter: 0.08µm) to form a protective layer so as to have a silver coating weight of 0.1g/m² and a gelatin coating weight of 0.8g/m².
    Figure imgb0001
  • Sample II: Sample prepared in the same manner as the above Sample I except that the protective layer excludes the silver iodobromide.
  • Each of the above layers contains a gelatin hardener and a surface active agent in addition to the above constituents.
  • Samples I and II are exposed through an optical wedge to a white light, and then processed in accordance with the following procedure.
  • For the processing, two different developer solutions are used: one containing each of various development restrainers in an amount necessary to restrain the sensitivity of each sample to about 60% (-ΔlogE=0.22) and the other containing no development restrainers.
    Processing steps (38°C)
    Color developing 2 min. 40 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 compositions of the processing solutions used are as follows:
    Color developer
    4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate 4.75g
    Anhydrous sodium sulfite 4.25g
    Hydroxylamine 1/2 sulfate 2.0 g
    Anhydrous potassium carbonate 37.5 g
    Sodium bromide 1.3 g
    Trisodium nitrilotriacetate, monohydrate 2.5 g
    Potassium hydroxide 1.0 g
    Water to make 1 liter.
    Bleaching bath
    Ferric ammonium ethylenediaminetetraacetate 100.0 g
    Diammonium ethylenediaminetetraacetate 10.0 g
    Ammonium bromide 150.0 g
    Glacial acetic acid 10.0 ml
    Water to make 1 liter.
    Adjust pH to 6.0 with ammonia water.
    Fixing bath
    Ammonium thiosulfate 175.0 g
    Anhydrous sodium sulfite 8.5 g
    Sodium metasulfite 2.3 g
    Water to make 1 liter.
    Adjust pH to 6.0 with acetic acid.
    Stabilizing bath
    Formalin (37% aqueous solution) 1.5 ml
    Koniducks (product of KONICA Corp.) 7.5 ml
    Water to make 1 liter.
  • If the Samples I and II processed in the developer solution containing no development restrainer are denoted by S₀ and S₀', respectively, while if the Samples I and II processed in the developer solution containing the restrainer are denoted by SI and SII, respectively, then

    the desensitized degree of Sample: ΔS₀ = S₀ - S I
    Figure imgb0002


    the desensitized degree of Sample: ΔS = S₀' - S II
    Figure imgb0003


    Diffusibility = ΔS/ΔS₀,
    Figure imgb0004


    wherein each sensitivity is shown in terms of the logarithm of the recprocal of the exposure amount (-logE) necessary to form the density of fog + 0.3.
  • The diffusibilities of the foregoing several development restrainers found according to the above method are listed in the following table.
    Figure imgb0005
    Figure imgb0006
  • In the invention, there may be used any diffusible DIR compound regardless of its chemical structure as long as the diffusibility of the group released therefrom is in the above range.
  • The typical formula of the compound is as follows:
  • Formula D-1


  •         A-(Y)m



    wherein A represents a coupler residue; m is an integer of 1 or 2; and Y is 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, the group being one capapble of releasing a development inhibitor residue or development inhibitor having a diffusibility of not less than 0.34.
  • In Formula D-1, Y includes those typically represented by the following Formulas D-2 to D-19.
    Figure imgb0007
    Figure imgb0008
  • In Formulas D-2 through D-7, Rd₁ is a hydrogen atom, a halogen atom or an alkyl, alkoxy, acylamino, alkoxycarbonyl, thiazolidinylideneamino, aryloxycarbonyl, acyloxy, carbamoyl, N-alkylcarbamoyl, N,N-dialkylcarbamoyl, nitro, amino, N-arylcarbamoyloxy, sulfamoyl, N-alkylcarbamoyloxy, hydroxyl, alkoxycarbonylamino, alkylthio, arylthio, aryl, heterocyclic, cyano, alkylsulfonyl or aryloxycarbonylamino group; and n is an integer of 0, 1 or 2, provided that when n is 2, the respective Rd₁ may be the same or different and the total number of carbon atoms contained in the n number of Rd₁s is from 0 to 10.
  • The number of carbon atoms contained in the Rd₁ of Formula D-6 is 0 to 15.
  • In Formula D-6, X represents an oxygen atom or a sulfur atom.
  • In Formula D-8, Rd₂ represents an alkyl group, an aryl group or a heterocyclic group.
  • In Formula D-9, Rd₃ represents a hydrogen atom or an alkyl, cycloalkyl, aryl or heterocyclic group; Rd₄ is a hydrogen atom, a halogen atom or an alkyl, cycloalkyl, aryl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkanesulfonamido, cyano, heterocyclic, alkylthio or amino group.
  • Where Rd₁, Rd₂, Rd₃ or Rd₄ represents an alkyl group, the alkyl group includes those having a substituent which may be either straight-chain or branched-chain.
  • Where Rd₁, Rd₂, Rd₃ or Rd₄ represents an aryl group, the aryl group includes those having a substituent.
  • Where Rd₁, Rd₂, Rd₃ or Rd₄ represents a heterocyclic group, the group includes those having a substituent and is preferably a 5- or 6-member single or condensed ring containing at least one hetero atom selected from the class consisting of nitrogen, oxygen and sulfur atoms. The heterocyclic group is selected from among, e.g., pyridyl, quinolyl, furyl, benzothiazolyl, oxazolyl, imidazolyl, thiazolyl, triazolyl, benzotriazolyl, imido and oxazine.
  • The number of carbon atoms contained in the Rd₂ of Formula D-8 is 0 to 15.
  • The total number of carbon atoms contained in the Rd₃ and Rd₄ of Formula D-9 is 0 to 15.
  • Formula D-10
  • -TIME-INHIBIT
    Figure imgb0009


    wherein TIME is a group which is attached to the coupling position of A and cleavable upon the coupler's reaction with the oxidation product of a color developing agent and, after its cleavage, properly controls and releases the INHIBIT group.
  • The INHIBIT group is a group which, after being released, becomes a development inhibitor and which is represented by the foregoing Formulas D-2 through D-9.
  • The above -TIME-INHIBIT
    Figure imgb0010
    group of Formula D-10 is further typically represented by the following Formulas D-11 to D-19:
    Figure imgb0011
    Figure imgb0012
    Figure imgb0013
  • In Formulas D-11 to D-15 and D-18, Rd₅ represents a hydrogen atom, a halogen atom or an alkyl, cycloalkyl, alkenyl, aralkyl, alkoxy, alkoxycarbonyl, anilino, acylamino, ureido, cyano, nitro, sulfonamido, sulfamoyl, carbamoyl, aryl, carboxyl, sulfo, hydroxyl or alkanesulfonyl group. In Formulas D-11 to D-13, D-15 and D-18, the Rd₅s may combine with each other to form a condensed ring. In Formulas D-11, D-14, D-15 and D-19, Rd₆ represents an alkyl, alkenyl, aralkyl cycloalkyl, heterocyclic or aryl group. In Formulas D-16 and D-17, Rd₇ represents a hydrogen atom or an alkyl, alkenyl, aralkyl, cycloalkyl, heterocyclic or aryl group. In Formula D-19, Rd₈ and Rd₉ each represent a hydrogen atom or an alkyl group preferably having 1 to 4 carbon atoms. In Formulas D-11 and D-15 to D-18, k is an integer of 0, 1 or 2. In Formulas D-11 to D-13, D-15 and D-18, l is an integer of 1 to 4. In Formula D-16, m is an integer of 1 or 2, provided that when m is 2, the Rd₇s may be either the same or different. In Formula D-19, n is an integer of 2 to 4, provided that the n numbers of Rd₈ and Rd₉ may be either the same or different. In Formulas D-16 to D-18, B represents an oxygen atom or a Rd₆-N<, wherein Rd₆ is as defined previously. In Formula D-16, ---- implies that it may be either a single bond or double bond, provided that if it is a single bond, m is 2, while if it is a double bond, m is 1; and INHIBIT group is as defined previously except the formulas and number of carbon atoms in Formulas D-2 to D-9.
  • In the INHIBIT group, the total number of carbon atoms contained in the Rd₁s in one molecule of Formula D-2 to D-7 is 0 to 32. In Formula D-8, the number of carbon atoms contained in Rd₂ is 1 to 32. In Formula D-9, the total number of carbon atoms contained in Rd₃ and Rd₄ is 0 to 32.
  • Where Rd₅, Rd₆ and Rd₇ each represent an alkyl, aryl or cycloalkyl group, they include those having a substituent.
  • The preferred among these diffusible DIR compounds are those in which Y is represented by Formulas D-2, D-3 or D-10. Among the groups represented by D-10, the preferred are those in which the INHIBIT is represented by Formulas D-2, D-6 (particularly where the X thereof is an oxygen atom), or D-8 (particularly where the Rd₂ thereof is a hydroxyaryl group or an alkyl group having 1 to 5 carbon atoms).
  • Examples of the coupler constituent represented by A in Formula D-1 include a yellow dye image-forming coupler residue, a magenta dye image-forming coupler residue and a cyan dye image-forming coupler residue.
  • The following are useful examples of the diffusible DIR compound of the invention, but are not limited thereto.
  • Exemplified compounds
  • Figure imgb0014
    Figure imgb0015
  • Exemplified compound No. R ₁ R ₂ Y
    D - 2 ( 1 ) ( 1 ) (30)
    D - 3 ( 2 ) ( 3 ) (30)
    D - 4 ( 2 ) ( 4 ) (30)
    D - 5 ( 7 ) ( 6 ) (31)
    D - 6 ( 2 ) ( 4 ) (32)
    D - 7 ( 2 ) ( 5 ) (36)
    D - 8 ( 7 ) ( 8 ) (33)
    D - 33 ( 2 ) ( 4 ) (55)
    Figure imgb0016
    Exemplified compound No. R ₁ R ₂ Y
    D - 9 ( 9) (10) (30)
    D - 10 (11) (10) (30)
    D - 11 (12) ( 7) (34)
    D - 12 (12) (13) (35)
    D - 13 ( 9) (14) (36)
    D - 14 (15) (16) (37)
    Figure imgb0017
    Exemplified compound No. R ₁ Y
    D - 15 (17) (38)
    D - 16 (17) (39)
    D - 17 (18) (40)
    D - 18 (20) (41)
    D - 19 (18) (42)
    D - 20 (18) (43)
    D - 21 (18) (44)
    D - 22 (19) (45)
    D - 23 (18) (46)
    D - 24 (21) (47)
    D - 25 (21) (48)
    D - 26 (22) (49)
    D - 27 (22) (50)
    D - 28 (22) (51)
    D - 29 (23) (52)
    D - 30 (18) (53)
    D - 31 (18) (54)
    D - 32 (23) (49)
    D - 33 (18) (55)
    D - 34 (18) (56)
  • The R₁, R₂ and Y in the table represent the following groups:
    Figure imgb0018
    Figure imgb0019
    Figure imgb0020
    Figure imgb0021
    Figure imgb0022
    Figure imgb0023
    Figure imgb0024
    Figure imgb0025
  • Including these compounds, examples of the diffusible DIR compounds usable in the invention are disclosed in U.S. Patent Nos. 4,234,678, 3,227,554, 3,617,291, 3,958,993, 4,149,886, 3,933,500, 2,072,363 and 2,070,266; JP O.P.I. Nos. 56837/1982 and 13239/1976; and Research Disclosure No. 21228, Dec. 1981.
  • The diffusible DIR compound is preferably added to blue-sensitive, green-sensitive and red-sensitive emulsion layers, and preferably used in an amount of 0.0001 to 1.0 mol, and more preferably 0.001 to 0.5 mol per mol of silver halide.
  • Dyes may be preferably used in order to fit the respective MTF values of the blue-, green- and red-sensitive layers in the requirements of the invention. A variety of dyes may be used, but the most useful dyes are those having their absorption maximums in the respective ranges of from -20nm to + 20nm with respect to the wavelengths to which the blue-sensitive, green-sensitive and red-sensitive layers have their maximum sensitivities.
  • To lower the light scattering and improve the sharpness, various dyes may be used. For this purpose there may be used colored couplers, which are usually applied to color negative films. A colored magenta coupler, when applied to the invention, is not intended for the magenta color formation but can be used as a yellow dye because it assumes a yellow color prior to working in processing. A colored cyan coupler can be used likewise as a red dye. Examples of the colored couplers' applications are found in Japanese Patent Application No. 10967/1990.
  • Further, a variety of oil-soluble dyes may also be used. For example, there may be used the yellow, magenta and cyan dyes described in Japanese Patent Application No. 241889/1990 and JP O.P.I. No. 168148/1987.
  • The water-soluble dyes described in Japanese Patent O.P.I. Publication No. 215851/1991 are favorable in respect that they become colorless after being processed.
  • As the water-soluble dye for the light-sensitive material of the invention there may be utilized those known dyes normally used for silver halide color photographic light-sensitive materials. The preferred among them are oxonol, merocyanine, benzilidene, anthraquinone, cyanine, styryl, azo and hemioxonol dyes, particularly those having acid groups such as a sulfonic acid group, a carboxylic acid group. etc. Further, the most useful dyes for the invention are those having their maximum absorption wavelength in the range of 420nm to 480nm, 520nm to 580nm or 600nm to 680nm.
  • The following are examples of the dyes usable in the invention, but are not limited thereto.
  • Exemplified dyes
  • Figure imgb0026
    Figure imgb0027
    Figure imgb0028
    Figure imgb0029
    Figure imgb0030
    Figure imgb0031
    Figure imgb0032
    Figure imgb0033
    Figure imgb0034
  • Any of these dyes may be incorporated into any discretionary layers, but the dye, because it permits easy control of the sharpness, is more preferably added to a non-light-sensitive layer adjacent to a light-sensitive layer having its sensitivity to the light which the dye absorbs or to a layer on the side nearer to an object than the light-sensitive layer.
  • The adding amount of the dye used depends on the controllable ranges of the molar extinction coefficient, molecular weight and solubility of the dye, the layer to which the dye should be added, and the sharpness, but is preferably 0.1 to 1000mg/m², and more preferably 0.5 to 500mg/m².
  • In the invention, a monodisperse silver halide emulsion is preferably used for the blue-sensitive, green-sensitive and red-sensitive layers.
  • The monodisperse silver halide emulsion in the invention is an emulsion having a grain diameter distribution width of preferably not more than 20%, more preferably not more than 15%, and most preferably not more than 12%, wherein the grain diameter distribution width is defined by
    Figure imgb0035
  • The grain diameter herein is the diameter of a circular image equivalent in the area to the projection image of a silver halide grain.
  • The grain diamter can be obtained by actually measuring the diamter of a photographed and printed grain image magnified 10,000 to 50,000 times by an electron microscope or the area of an enlarged grain image projected onto a screen (the number of grains to be measured should be not less than 1000 at random).
  • The average grain diameter is defined by
    Figure imgb0036

    wherein di is each grain diameter, and ni is its frequency.
  • The monodisperse emulsion can be obtained in the manner that an aqueous silver salt solution and an aqueous halide solution are added by a double-jet process to a gelatin solution containing seed grains with its pAg and pH under control. For determination of the adding rate, reference can be made to JP O.P.I. Nos. 48521/1979 and 49938/1983.
  • Further, a high monodisperse emulsion can be obtained by the method for growing grains in the presence of a tetrazaindene compound as disclosed in JP O.P.I. No. 122935/1985.
  • The monodisperse emulsion of the invention may be of any arbitrary composition comprising silver chloride, silver bromide, silver chlorobromide, silver iodobromide or silver chloroiodobromide, but preferably silver iodobromide, particularly having a silver iodide content of not less than 1 mol% and not more than 10 mol%.
  • The monodisperse emulsion of the invention is preferably of core/shell-type grains each consisting of an internal core and a surface shell, in which the silver iodide content of the core is higher than that of the shell.
  • The core/shell-type emulsion used in the invention can be prepared in accordance with any of the known methods disclosed in JP O.P.I. Nos. 177535/1984, 138538/1985, 52238/1984, 143331/1985, 35726/1985 and 258536/1985.
  • The silver halide grain contained in the monodisperse emulsion of the invention may be either a regular crystal or a twin crystal.
  • The average grain diameter of the monodisperse emulsion of the invention is preferably 0.08µm to 5µm, more preferably 0.2µm to 3µm, and most preferably 0.3µm to 1µm.
  • The silver halide emulsion used in the invention may be one of those described in Research Disclosure (hereinafter abbreviated to RD) 308119.
  • The silver halide emulsion of the invention is subjected to physical ripening, chemical ripening and spectral sensitization treatments. The additives which should be used in the processes of the treatments are described in RD17643, RD18716 and RD308119.
  • The known photographic additives usable in the invention are also described in the above RD numbers.
  • In the invention, a variety of couplers may be used, which are exemplified in the above RD numbers.
  • The additives used in the invention may be added in accordance with the dispersing method described in RD308119 XIV.
  • In the invention there may be used a support made of one of the materials described in the foregoing RD17643 p.28, RD-18716 p.647-648, and RD308119 XIV.
  • The light-sensitive material of the invention may have auxiliary layers such as filter layers and intermediate layers as 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.
  • In the light-sensitive material of the invention, the total coating weight of silver is preferably 2.0 to 5.0g/m² and the total coating weight of gelatin is preferably 8 to 13g/m².
  • The present invention may apply to various color photographic light-sensitive materials such as color negative films for general use and 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 according to ordinary methods as described in RD17643 p.28-29, RD18716 p.615, and RD308119 XIV.
  • EXAMPLES
  • In the following examples, the adding amount of each of the constituents of the silver halide light-sensitive material samples is indicated in grams per m² except that silver halide and colloidal silver are indicated in silver equivalent and sensitising dyes in moles per mole of silver halide.
  • Example 1
  • On a triacetyl cellulose film support were coated the following compositions-having layers in order from the support side, whereby a multilayer color photographic light-sensitive material Sample 1 was prepared.
  • Sample 1 (comparative)
  • Figure imgb0037
    Figure imgb0038
    Figure imgb0039
    Figure imgb0040
    Figure imgb0041
  • In addition to the above constituents, to each of the above layers were added appropriate amounts of a dispersing aid SU-1 and hardeners H-1 and H-2.
  • The emulsions used in the above sample are as follows. The emulsions Em-1 to Em-4 are internal-high-iodide-type core/shell monodisperse emulsions.
  • Em-1...
    Average AgI content: 7.5 mol%, octahedral grains. cube-equivalent diameter: 0.38µm.
    Em-2...
    Average AgI content: 2.5 mol%, octahedral grains, cube-equivalent diameter: 0.30µm.
    Em-3...
    Average AgI content: 8.0 mol%, octahedral grains, cube-equivalent diameter: 0.65µm.
    Em-4...
    Average AgI content: 8.5 mol%, octahedral grains, cube-equivalent diameter: 0.80µm.
    Em-5...
    Average AgI content: 2.0 mol%, octahedral grains, diameter: 0.08µm.
  • The compounds used in Sample 1 are given below:
    Figure imgb0042
    Figure imgb0043
    Figure imgb0044
    Figure imgb0045
    Figure imgb0046
    Figure imgb0047
    Figure imgb0048
    Figure imgb0049
  • Samples 2 to 9 were prepared in the same manner as in Sample 1 except that the constituents of Sample 1 were partially modified as shown in Table 1. Each of these samples was exposed through an optical wedge for sharpness measurement in contact therewith to a white light, and then processed in the procedure described hereinafter. Each processed sample was subjected to MTF measurement with use of blue, green and red lights in the usual manner to obtaine its MTF values with respect to 20 lines/mm.
  • On the other hand, each of the same samples was used to photograph a gray cloth woven with black and white threads, and the image was printed on KONICA SR paper. Then, the degree of the formed color's abnormality of the cloth image on each print was visually examined. The results are shown in Table 2. Table 1
    Sample No. Modification
    2 Second protective layer PRO-2: 60mg/m² of dye S-1 added
    3 Second protective layer PRO-2: 1.5mg/m² of dye S-9 added
    4 Second protective layer PRO-2: 3.0mg/m² of dye S-9 added
    5 Second protective layer PRO-2: 4.0mg/m² of dye S-7 and 3.0mg/m² of dye S-9 added
    6 Second protective layer PRO-2: 4.0mg/m² of dye S-7 and 4.5mg/m² of dye S-9 added
    7 Yellow filter layer YC: Gelatin increased to 1mg/m²
    8 Second protective layer PRO-2 of Sample 7 1.5mg/m² of dye S-9 added
    9 Second protective layer PRO-2 of Sample 7 60mg/m² of dye S-1 added
    Processing step Time Temperature
    Color developing (monobath) 3 min. 15 sec. 38°C
    Bleaching (monobath) 45 sec. 38°C
    Fixing (monobath) 1 min. 30 sec. 38°C
    Stabilizing (tribath, cascade) 1 min. 38°C
    Drying 1 min. 40 to 80°C
  • The compositions of the processing solutions used are as follows:
    Color developer
    Potassium carbonate 30 g
    Sodium hydrogencarbonate 2.5 g
    Potassium sulfite 4.0 g
    Sodium bromide 0.6 g
    Potassium iodide 1.2 mg
    Hydroxylamine sulfate 2.5 g
    Sodium chloride 0.6 g
    Diethylenetriamine pentaacetic acid 1.0 g
    4-Amino-3-methyl-N-ethyl-N-(β-hydroxylethyl)-aniline sulfate 4.8 g
    Potassium hydroxide 1.2 g
    Water to make 1 liter.
    Adjust pH to 10.6 with potassium hydroxide or 50% sulfuric acid.
    Bleaching bath
    Ferric-ammonium 1,3-propylenediaminetetraacetate 0.3 mol
    1,3-Propylenediaminetetraacetic acid 5 g
    Ammonium bromide 100 g
    Glacial acetic acid 30 ml
    Ammonium nitrate 50 g
    Water to make 1 liter.
    Adjust pH to 4.5 with ammonia water or glacial acetic acid.
    Fixing bath
    Ammonium thiosulfate 120 g
    Ammonium thiocyanate 2.0 mols
    Ammonium sulfite 5 g
    Disodium ethylenediaminetetraacetate 0.5 g
    Sodium carbonate 10 g
    The above bleaching solution 100 ml
    Water to make 1 liter.
    Adjust pH to 7.0 with acetic acid or ammonia water.
    Figure imgb0050
    Figure imgb0051
    Table 2
    Sample No. MTF Degree of abnormal reproduction of cloth color on print
    B G R
    1 (Comp.) 1.00 0.85 0.60 Abnormal: apparently reddish.
    2 (Comp.) 1.10 0.85 0.60 Abnormal: apparently reddish.
    3 (Inv.) 1.00 0.86 0.68 Abnormal: slightly reddish.
    4 (Inv.) 1.00 0.87 0.75 Normal
    5 (Comp.) 1.00 0.98 0.75 Abnormal: apparently reddish.
    6 (Inv.) 1.00 0.98 0.84 Normal
    7 (Comp.) 0.98 0.80 0.55 Abnormal: apparently reddish.
    8 (Inv.) 0.98 0.80 0.65 Abnormal: slightly reddish.
    9 (Comp.) 1.10 0.80 0.65 Abnormal: apparently reddish.
  • As is apparent from Table 2, Samples 3, 4, 6 and 8, which meet the requirements of the invention, show little or no abnormal color, and form very sharp images with excellent color reproducibility as compared to the comparative samples.
  • In addition, the above samples were processed as described in the aforementioned Annual of the British Journal of Photography and then subjected to MTF measurement. As a result, similar MTF values to those in Table 2 were obtained.

Claims (9)

  1. A silver halide color photographic light-sensitive material comprising a support having thereon a photographic layer including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, wherein values of MFTB, MFTG and MFTR of dye images each formed in said blue-sensitive layer, green-sensitive layer and red-sensitive layer, respectively, satisfy the following requirements:
    MTFG ≧ 0.70
    MTFG + 0.20 ≧ MTFB ≧ MTFG - 0.20
    MTFG + 0.20 ≧ MTFR ≧ MTFG - 0.20
    in which MFTB, MFTG and MFTR are MFT values at the spatial frequency of 20 lines/mm of dye images each formed in said blue-sensitive layer, green-sensitive layer and red-sensitive layer.
  2. A light-sensitive material of claim 1, wherein said MFT values satisfy the following requirements:
    MTFG ≧ 0.70
    MTFG + 0.15 ≧ MTFB ≧ MTFG - 0.15
    MTFG + 0.15 ≧ MTFR ≧ MTFG - 0.15
  3. A light-sensitive material of claim 1, wherein said blue-sensitive layer, green-sensitive layer and red-sensitive layer each contain a diffusible DIR compound having a diffusibility of not lower than 0.34.
  4. A light-sensitive material of claim 3, wherein said blue-sensitive layer, green-sensitive layer and red-sensitive layer each contain a diffusible DIR compound having a diffusibility of not lower than 0.40.
  5. A light-sensitive material of claim 1, wherein at least one of said blue-sensitive layer, green-sensitive layer and red-sensitive layer and other layers included in said photographic layer contains a dye.
  6. A light-sensitive material of claim 1, wherein said blue-sensitive layer, green-sensitive layer and red-sensitive layer each contain core/shell type monodisperse silver halide grains which have higher iodide content at the internal portion than that at the external portion thereof.
  7. A light-sensitive material of claim 1, wherein the total amount of silver contained in said photographic layer is within the range of from 2 to 5 gram per square meter.
  8. A light-sensitive material of claim 1, wherein the total amount of gelatin contained in said photographic layer is within the range of from 8 to 13 gram per square meter.
  9. A silver halide color photographic light-sensitive material comprising a support having thereon a photographic layer including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, wherein said blue-sensitive layer, green-sensitive layer and red-sensitive layer each contain core/shell type monodisperse silver halide grains, which have higher iodide content at the internal portion than that at the external portion thereof, and a diffusible DIR compound having a diffusibility of not lower than 0.40, the total amount of silver and the total amount of gelatin contained in said photographic layer are 2 to 5 g per square meter and 8 to 13 g per square meter, respectively, wherein values of MFTB, MFTG and MFTR of dye images each formed in said blue-sensitive layer, green-sensitive layer and red-sensitive layer, respectively, satisfy the following requirements:
    MTFG ≧ 0.70
    MTFG + 0.15 ≧ MTFB ≧ MTFG - 0.15
    MTFG + 0.15 ≧ MTFR ≧ MTFG - 0.15
    in which MFTB, MFTG and MFTR are MFT values at the spatial frequency of 20 lines/mm of dye images each formed in said blue-sensitive layer, green-sensitive layer and red-sensitive layer.
EP91120432A 1990-11-30 1991-11-28 A silver halide color photographic light-sensitive material Withdrawn EP0488313A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0589694A1 (en) * 1992-09-24 1994-03-30 Konica Corporation Silver halide light-sensitive photographic material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0214832A2 (en) * 1985-09-03 1987-03-18 Konica Corporation Light-sensitive silver halide color photographic material
GB2180359A (en) * 1985-07-17 1987-03-25 Fuji Photo Film Co Ltd Silver halide color reversal photographic materials
US4686176A (en) * 1984-09-25 1987-08-11 Konishiroku Photo Industry Co., Ltd. Multilayer multi-color photographic material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4686176A (en) * 1984-09-25 1987-08-11 Konishiroku Photo Industry Co., Ltd. Multilayer multi-color photographic material
GB2180359A (en) * 1985-07-17 1987-03-25 Fuji Photo Film Co Ltd Silver halide color reversal photographic materials
EP0214832A2 (en) * 1985-09-03 1987-03-18 Konica Corporation Light-sensitive silver halide color photographic material

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0589694A1 (en) * 1992-09-24 1994-03-30 Konica Corporation Silver halide light-sensitive photographic material
USH1450H (en) * 1992-09-24 1995-06-06 Konica Corporation Silver halide light-sensitive photographic material

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