WO2005015307A1 - Silver halide color photography sensitive material - Google Patents

Silver halide color photography sensitive material Download PDF

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Publication number
WO2005015307A1
WO2005015307A1 PCT/JP2003/009980 JP0309980W WO2005015307A1 WO 2005015307 A1 WO2005015307 A1 WO 2005015307A1 JP 0309980 W JP0309980 W JP 0309980W WO 2005015307 A1 WO2005015307 A1 WO 2005015307A1
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WO
WIPO (PCT)
Prior art keywords
density
color
silver halide
exposure
illumination
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PCT/JP2003/009980
Other languages
French (fr)
Japanese (ja)
Inventor
Hiroaki Ito
Kuniaki Uezawa
Original Assignee
Konica Minolta Photo Imaging, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Konica Minolta Photo Imaging, Inc. filed Critical Konica Minolta Photo Imaging, Inc.
Priority to PCT/JP2003/009980 priority Critical patent/WO2005015307A1/en
Publication of WO2005015307A1 publication Critical patent/WO2005015307A1/en

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    • 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
    • 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
    • G03C2200/00—Details
    • G03C2200/26—Gamma

Definitions

  • the present invention relates to a novel silver halide color photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material excellent in the descriptive properties of a character image, the dependency on a viewing light source on a white background, and the gradation reproducibility.
  • Image information captured by a digital camera or image information that has been converted into digital data from a film or print using a scanner, etc. can be edited and processed on a computer, and data such as character dialing can be added. Can be done relatively easily.
  • Hard copy materials for producing hard copies based on such digitized image information include, for example, sublimation type thermal transfer prints, melt type thermal transfer prints, ink jet prints, electrostatic transfer type prints, and the like. Examples include a thermoautochrome print and a silver halide color photographic light-sensitive material.
  • a silver halide color photographic light-sensitive material having a reflective support (hereinafter also referred to as a color print or a light-sensitive material) has high sensitivity. It has extremely excellent properties compared to other print materials, such as excellent gradation, excellent image storability, and low cost. Especially for making high quality hard copies It is widely used today.
  • Digitally converted image information can be edited and edited on a computer relatively easily.For example, images based on photographic data of people, landscapes, still life, etc., and images containing character images are mixed. The opportunity to deal with is increasing.
  • silver halide color photographic materials are required to have various characteristics. Among them, character images with a large tone ratio composed of monotone and tone reproducibility from shadows to highlights. The reproducibility of images, image clarity, and whiteness are important as their basic characteristics and affect the commercial value.
  • the vertical axis represents the color density (D) and the horizontal axis represents the color density (D).
  • the gradation forming the high density area that is, the shoulder density area in the characteristic curve, in the characteristic curve composed of the logarithm of the exposure amount (L 0 g E) high contrast.
  • LED light emitting Daio one de
  • VFPH in vacuum fluorescent Purintoe' de scanning exposure scheme using a line exposure or laser first light such as the following very high 1 X 1 0- 3 seconds Since short-time illuminance exposure is required, it is assumed that a silver halide photographic material having improved high illuminance failure is used.
  • the gradation of the shoulder density region is excessively enhanced, it becomes difficult to precisely control the exposure conditions, and as a result, the occurrence of stripes and the like in the formed image is induced. Is a factor.
  • scanning light sources unique to digital exposure equipment such as LEDs, VFPHs, and lasers, especially in high-density areas, cause blur and sidelobes due to afterglow during exposure (due to aberrations in the optical lens of the exposure equipment, etc.
  • Secondary light such as illegitimate light that is generated by ripples, is generated, and stin (illegal density occurring in unexposed areas) is generated in the silver halide color photographic material. As a result, this stin May result in color bleeding and reduced image clarity in character reproduction and gradation reproduction images.
  • a method of applying an optical brightener to a color print has been proposed.
  • a method has been proposed in which a fluorescent whitening agent is contained in a water-resistant resin layer constituting a reflective support (for example, see Patent Documents 1 to 3).
  • a fluorescent whitening agent is contained in a water-resistant resin layer constituting a reflective support.
  • the UV energy is high, the reflectance near the center of gravity wavelength exceeds 100%, and a high-brightness white background can be obtained, but when viewed under a light source with low UV energy, for example, under a white light, However, there is a problem that the white background is remarkably deteriorated due to the difficulty in emitting the fluorescent light, that is, the so-called light source dependence is large. On the other hand, it has been pointed out that in places with a lot of ultraviolet rays such as under sunlight, the fluorescence is too strong and the white background is too blue.
  • the density in each wavelength nm range in the unexposed area after color development processing is specified under specific conditions, and silver halide power can be used to reproduce a stable white background regardless of whiteness and observation light source.
  • a material is disclosed (for example, see Patent Document 2).
  • image clarity is only part of the effect, and has not yet been substantially improved.
  • a first object of the present invention is to provide a silver halide color photographic light-sensitive material having improved depiction of a character image
  • a second object of the present invention is to provide a light-sensitive material regardless of the type of a viewing light source.
  • An object of the present invention is to provide a silver halide photographic material capable of reproducing a stable white background.
  • a third object of the present invention is to provide a silver halide photographic light-sensitive material excellent in tone reproducibility such as a portrait image.
  • a silver Kaginryoku color photographic light-sensitive material having a sexual colloids layer was facilities exposure with exposure time 1 X 1 0_ 6 seconds through an optical wedge, the minimum concentration that is formed by color development (unexposed portion ), And a characteristic curve consisting of density D (color density) -Log E (exposure) is created from the edge-like image including the maximum density, and at least the magenta color density in the characteristic curve is represented by the following equation [1].
  • Equation (1) A silver halide color photographic light-sensitive material characterized by satisfying the following conditions: Equation (1)
  • ra is a straight line connecting the exposure point required to obtain a density of +0.25 from the minimum density and the exposure point required to obtain a density of +0.75 from the minimum density. Represents the inclination (tan) of ]
  • White light illumination Illumination that irradiates the illumination light source directly to unexposed areas
  • Monochromatic illumination Illumination that illuminates the unexposed area after illuminating the illumination light source once and separating it into monochromatic lights.
  • the gradation (rb) in the high-density area (shoulder area) is moderately enhanced so as to be within a specific range
  • the gradation (ra) in the density area (leg area) is moderately hardened so as to be within a specific range, so that the character image descriptiveness, stable white background reproducibility regardless of the type of viewing light source,
  • the tone changes that is, the so-called white light source depends on different light sources.
  • optical brighteners are susceptible to molecular destruction due to the absorption of ultraviolet light, resulting in the problem that the white background gradually changes during the long-term storage.
  • the color tone of the white background is adjusted to the color tone specified in the present invention by a blue dye mainly referred to as a bluing agent, without depending on the fluorescent whitening agent. This makes it possible to reproduce psychologically optimal white background tones.
  • each gradation characteristic and the optimal CIE whiteness specified in the present invention improves the clarity of character quality and character reproducibility, enables recognition of complex characters, and highlights from the shadow part.
  • the tone reproducibility of the part is improved.
  • the light-sensitive material of the present invention having a hydrophilic colloid layer, the light-sensitive material is exposed through an optical wedge for an exposure time of 1 ⁇ 10- s seconds, and then formed by a color development process.
  • a characteristic curve consisting of density D (color density) -Log E (exposure amount) is created, and at least the magenta color density in the characteristic curve is minimized.
  • the slope ra of a straight line connecting the exposure point required to obtain a density of 75 satisfies the condition of the above-mentioned formula [1].
  • ra is characterized by being in the range of 2.S ⁇ ra ⁇ 3.8, but is preferably in the range of 2.3 ⁇ 3.0, and 2. More preferably, it is in the range of 3 ⁇ a ⁇ 2.7.
  • the rb force is preferably in the range of 2.0 ⁇ a ⁇ 3.8, more preferably in the range of 2.2 ⁇ ra ⁇ 3.8, and 2.5 More preferably, it is in the range of ⁇ a ⁇ 3.6.
  • a reflection type densitometer for example, an optical densitometer (X-Rite X-Rite 3 10TR) and use a blue filter and a green filter. The density is measured via a red filter. From the density (D) obtained in this way and the exposure (E) determined from the transmittance of the optical wedge and the exposure conditions, the vertical axis represents the color density (D), and the horizontal axis represents the logarithm of the exposure. The characteristic curve is plotted as the value (Log E).
  • the characteristic curve of the magenta color image satisfies the condition defined by the above formula [1]. Further, it is preferable that the magenta color image and the other one color image both satisfy the condition defined by the above formula [1]. Most preferably, all the color images satisfy the above formula [1]. ] Must be satisfied.
  • the gradation in the high-density region represented by the above-mentioned formula [2] be simultaneously satisfied. That is, the gradation defined by the formulas [1] and [2] specified in the present invention is high in a high density region in a highlight portion and a high density region in a shadow portion under high illuminance exposure conditions. It is not excessively soft or hard, and has optimal gradation characteristics in terms of character reproducibility.
  • the means for realizing the gradation characteristic defined by the above formula [1] or the gradation characteristic defined by the above formula [2] according to the present invention include the following. It can be realized by appropriately selecting or combining various tone adjusting means known in the art. In the present invention, it is preferable to use the following means among them.
  • Means 1 Improvement of high illuminance failure by incorporating heavy metal ions during preparation of silver halide emulsion used in silver halide emulsion layer.
  • Heavy metal ions that can be used for such a purpose include iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, covanolate and other Group 8-10 metals, cadmium, zinc, and the like.
  • Group 1 and 2 transition gold such as mercury Examples include metals, lead, rhenium, molybdenum, tandastene, gallium, and chromium.
  • metal ions of iron, iridium, platinum, ruthenium, gallium, and osmium are preferred. These metal ions can be added to the silver halide emulsion in the form of a salt or a complex salt.
  • the heavy metal ion forms a complex
  • its ligands include cyanide ion, thiocyanoic acid ion, cyanate ion, chloride ion, bromide ion, iodide ion, carbonyl, nitrosyl, ammonia, 1, 2, 4-triazole, thiazole and the like.
  • chloride ion, bromide ion and the like are preferable.
  • These ligands may be used alone or in combination of a plurality of ligands.
  • the silver halide emulsion used in each silver halide emulsion layer includes silver halide grains having high monodispersity, silver halide grains having high developability (particularly optimization of the halogen composition, etc.), and halogens.
  • Means 3 A method of using a high color-forming and highly reactive coupler as a coupler used in each silver halide emulsion layer and appropriately adjusting the amount of the coupler.
  • the respective densities at the exposure point which is four times the exposure amount required to obtain the image density of each color in the above-mentioned characteristic curve, are 0.2. It is preferably at least 0, more preferably from 2.0 to 3.5, and still more preferably from 2.0 to 3.0.
  • the means for realizing the density value defined above includes the above means
  • the color photographic light-sensitive material of the present invention the color photographic light-sensitive material of the present invention
  • the lightness index L * in the CIE 1976 L * a * b * color space obtained at low density (unexposed area) under white light illumination and monochromatic light illumination defined above is 85 ⁇ L * ⁇ 96, respectively. It is preferable that the chromaticity index a * is 11.0 a * 2.0 and the perceived chromaticity index b * is 18.0 ⁇ b * ⁇ -2.2.
  • the details of the CIE 1976 L * a * b * color space according to the present invention are described in “Film Imaging and Color Hard Copy” edited by The Photographic Society of Japan ⁇ The Imaging Society of Japan (Corona, 1999). Published).
  • the three-color stimulus value when using this color space is a value obtained according to the method described in JIS 8717, which defines a method for measuring the three stimulus values of the X, Y, and ⁇ coordinates of a fluorescent reflective object.
  • C I ⁇ 1976 L * a * b * The chromaticity in the color space is measured using the standard white chromaticity as the international standard for standard daylight, CI ED 65 (6504K).
  • any chromaticity measuring device capable of measuring chromaticity in the CIE 1976 L * a * b * color space can be used. For example, it can be determined by measuring the unexposed part using a C-2000 color analyzer manufactured by Hitachi, Ltd. and CIED65 (650 K) as a reference light source.
  • the minimum density (unexposed portion) after the color development processing is defined as CIE whiteness Wa obtained by white light illumination defined by the above formula [3] and defined by the above formula [4].
  • the difference Wc from the CIE whiteness Wb obtained by monochromatic light illumination is 8. It is preferably 0 or less, more preferably 0.1 to 8.0, and still more preferably 1.0 to 7.0.
  • the CIE whiteness W a obtained by the white light illumination according to the present invention is a CIE whiteness obtained by white light illumination in which an illumination light source is directly applied to an unexposed portion, and more specifically, the above formula [3] ].
  • Wa is preferably 85, Wa and 91, more preferably 87 ⁇ W a ⁇ 90.
  • the CIE whiteness Wb obtained by the monochromatic light illumination according to the present invention is the CIE whiteness obtained by illumination of an illumination light source, which is obtained by irradiating the monochromatic light once separated by graying onto an unexposed portion, Specifically, it can be determined by the formula [4].
  • L 2 * rather preferably be 85 rather L 2 * Ku 9 1, more preferably 87 rather L 2 * Ku 89.
  • Wb is preferably 83, Wb and 87, and more preferably 84 ⁇ W a ⁇ 86.
  • the white light illumination includes ultraviolet light and infrared light in addition to the three primary color lights of blue, green, and red.
  • the CIE whiteness Wb obtained by the monochromatic light illumination according to the present invention refers to a monochromatic light obtained by separating an illumination light source once by graying into an unexposed portion. Defined as the CIE whiteness obtained by the illumination illuminating above.
  • the difference between the CIE whiteness W a obtained by white light illumination and the CIE whiteness W b obtained by monochromatic illumination it is possible to obtain the degree of influence of the ultraviolet light on the white background characteristics mainly. .
  • the smaller the difference the smaller the variation of the white background characteristics when observing the silver halide color photographic light-sensitive material with various illumination light sources having different ultraviolet light ratios.
  • the relationship between Wa and Wb defined in the present invention, the Wa value when observed with white light illumination or monochromatic light illumination, the Wb value, the L * value, Means for realizing the a * value and the b * value are not particularly limited, but it is preferable to appropriately select and use the following adjustment conditions.
  • means for achieving desirable white background properties include, for example, a capri inhibitor, an oil-soluble dye, a bluing agent (a bluing agent), a removal accelerator for accelerating the dissolution of pigments and sensitizing dyes, a fluorescent brightening agent, and an interface.
  • a capri inhibitor an oil-soluble dye
  • a bluing agent a bluing agent
  • a removal accelerator for accelerating the dissolution of pigments and sensitizing dyes
  • a fluorescent brightening agent and an interface.
  • improvement of the support is also being studied for the purpose of improving the white background.
  • the method and the method of adding a fluorescent whitening agent to the resin layer are both used as means for improving the support.
  • each of these color tone adjusters is added to a photosensitive emulsion layer or a non-light-sensitive emulsion layer constituting a silver halide color photographic material or a resin layer constituting a support.
  • the blueing agent that can be used in the present invention include generally known ultramarine blue, cobalt blue, cobalt oxide phosphate, quinacridone pigments and the like, and mixtures thereof.
  • oil-soluble dyes and color pigments examples include oxonol dyes, azomethine dyes, azo dyes, benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, arylidene dyes, styryl dyes, diphenyl dyes, and the like.
  • Methane dye trifluoromethane dye, xanthene dye, acridine dye, azine dye, oxazine dye, thiazine dye, perinone dye, merocyanine dye, cyanine dye, indolinyl dye, phthalocyanine dye, indigo dye, thioindigo Dyes and the like can be mentioned.
  • pigments examples include azo pigments (for example, insoluble monoazo pigments, insoluble disazo pigments, azo lake pigments, condensed azo pigments, metal complex azo pigments), phthalocyanine pigments, dyed lake pigments (for example, acid dye lakes). , Basic dye lakes), condensed polycyclic pigments (for example, quinacridone pigments, thioindigo pigments, perylene pigments, anthraquinone pigments, perinone pigments, dioxazine pigments, isoindolinone glides, diketopyrrolopyrrole pigments), and others ( Examples thereof include organic pigments such as nitroso pigments, alizarin lake pigments, and alkaline pigments.
  • azo pigments for example, insoluble monoazo pigments, insoluble disazo pigments, azo lake pigments, condensed azo pigments, metal complex azo pigments
  • phthalocyanine pigments dyed lake pigments (for example, acid dye lakes). , Basic
  • oil-soluble dye examples include compounds 1 to 27 described on pages 8 to 9 of JP-A-2-842.
  • the fluorescent whitening agent is It is preferable to use the minimum amount possible.
  • the support that can be used in the light-sensitive material of the present invention is preferably a paper support in which a resin coating layer is provided on both surfaces of a substrate.
  • a paper support in which both sides of the base paper are laminated with a polyolefin is preferable, and a paper support laminated with polyethylene is particularly preferable. It is.
  • the base paper used for the paper support is made of wood pulp as the main raw material, and if necessary, is made using synthetic pulp such as polypropylene or synthetic fibers such as Nyopen® polyester in addition to wood pulp.
  • Wood pulp can be any of L BKP, LBSP, NBKP, NB SP, LDP, NDP, LUKP and NUKP These can also be used, but it is preferable to use more LBKP, NBSP, LBSP, NDP, and LDP, which have a large amount of short fibers.
  • the ratio of LBSP and / or LDP is preferably 10% by mass or more and 0% by mass or less.
  • a chemical pulp sulfate pulp or sulfite pulp
  • pulp having improved whiteness by a bleaching treatment is also useful.
  • Base paper contains sizing agents such as higher fatty acids and alkyl ketene dimers, white pigments such as calcium carbonate, talc and titanium oxide, paper strength agents such as starch, polyacrylamide, and polyvinyl alcohol, polyethylene glycols, etc.
  • a water retention agent, a dispersant, and a softening agent such as quaternary ammonium can be added as appropriate.
  • the above-described fluorescent whitening agent according to the present invention can also be used.
  • the freeness of pulp used for papermaking is preferably 200 to 500 m1 according to the CSF standard, and the fiber length after beating is 24 mass% by mass of the residual mesh specified in JIS-P-8207. It is preferable that the sum of the mass% and the residual amount of the 42 mesh is 30 to 70%. In addition, the mass% of the 4-mesh residue is preferably 20% by mass or less.
  • the basis weight of the base paper is preferably 30 to 250 gZm 2 , particularly preferably 50 to 200 g / m 2 .
  • the thickness of the base paper is preferably 40 to 250 m.
  • the base paper can be calendered at the papermaking stage or after papermaking to provide high smoothness. Base paper density 0. 7 ⁇ 1.
  • the base paper stiffness is preferably 20 to 200 g under the conditions specified in JIS-P-8143.
  • a surface sizing agent may be applied to the surface of the base paper.
  • the surface sizing agent the same sizing agent as that which can be added to the base paper can be used.
  • the pH of the base paper is 5 to 9 when measured by the hot water extraction method specified in JIS-P-8113. Preferably.
  • the polyethylene that covers the front and back of the base paper is mainly low-density polyethylene (LDPE) and / or high-density polyethylene (HDPE), but also LLDPE (linear low density polyethylene) ⁇ polypropylene, etc. Can also be used partially.
  • LDPE low-density polyethylene
  • HDPE high-density polyethylene
  • rutile or anatase type titanium oxide is added to polyethylene to improve opacity and whiteness.
  • the content of titanium oxide is usually from 3 to 20% by mass, preferably from 4 to 13% by mass, based on polyethylene.
  • Polyethylene-coated paper can be used as glossy paper, or when polyethylene is melted and extruded onto the surface of a base paper and coated, so-called typed processing is performed to obtain matte that can be obtained with ordinary photographic printing paper. Those having a surface-to-silk surface can also be used in the present invention.
  • the amount of polyethylene used on the front and back of the base paper is usually 20 to 40 m on the side where the photosensitive layer is provided and 10 to 30 m on the back side.
  • the polyethylene-coated paper support preferably has the following properties.
  • Tensile strength The strength specified in JIS-P-8113, preferably 20-30 ON in the vertical direction and 10-20 ON in the horizontal direction.
  • the surface roughness specified in JIS-B-0601 is preferably less than 10 ⁇ m per 2.5mm of reference length.
  • Opacity 80% or more, preferably 85-98%, as measured by the method specified in JIS-P-8138
  • the 60-degree specular glossiness specified in JIS_Z—8741 is preferably 10 to 95%.
  • Clark stiffness A support having a Clark stiffness of 50 to 300 cmVl00 in the recording medium conveyance direction is preferable.
  • Moisture content of middle paper usually 2 to 100% by mass, preferably 2 to 6% by mass based on the middle paper
  • the photosensitive emulsion layer contains a silver halide emulsion.
  • the silver halide emulsion used in the present invention is preferably a high silver chloride emulsion having a silver chloride content of at least 9 mol% or more.
  • the balance is preferably made of silver bromide containing substantially no silver iodide.
  • the silver bromide content is more preferably from 0.03 to 3 mol%, particularly preferably from 0.05 to 2 mol%.
  • any shape can be used for the silver halide grains.
  • Particles having a shape such as a dodecahedron or a dodecahedron can be produced and used.
  • grains having twin planes and tabular silver halide grains may be used.
  • cubic silver halide grains having a (100) plane as a crystal surface which is excellent in productivity and production stability, may be used. It is preferable that
  • silver halide grains grains having a single shape are preferably used, but two or more monodisperse silver halide emulsions can be added to the same layer.
  • the grain size of the silver halide grains is not particularly limited, but is preferably 0.1 to 5.O jwm, more preferably 0.2 to 3.3 in consideration of other photographic properties such as rapid processing property and sensitivity. 0 ⁇ m, especially when using a cube, preferably in the range of 0.1 to 1.2 ⁇ m, more preferably in the range of 0.2 to 1.0 ⁇ m.
  • the average grain size of the silver halide emulsion used for the layer is 0.7 m or less, more preferably 0.35 to 0.65 ⁇ m, and still more preferably 0.3 to 0.6 ⁇ m. 35 to 0.60 m.
  • This particle size can be measured using the projected area of the particle or its approximate diameter. If the particles are substantially uniform in shape, the particle size distribution can represent this quite accurately as diameter or projected area.
  • the particle size distribution of the silver halide grains is preferably monodisperse silver halide grains having a coefficient of variation of 0.05 to 0.22, more preferably 0.05 to 0.15. More preferably, two or more monodispersed emulsions of 0.05 to 0.15 are added to the same layer.
  • S the standard deviation of the particle size distribution
  • R is the average particle size
  • the silver halide emulsion may be obtained by any of the acidic method, the neutral method, and the ammonia method.
  • the particles may be grown at one time or may be grown after seed particles have been produced.
  • the method of producing the seed particles and the method of growing them may be the same or different.
  • the form in which the soluble silver salt is reacted with the soluble halide may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like, but a method obtained by the simultaneous mixing method is preferable.
  • a pAg controlled double jet method described in JP-A-54-48521 can be used as one form of the double jet method.
  • water-soluble silver salts and water-soluble halides were added from an addition device disposed in the reaction mother liquid described in JP-A-57-92523 and JP-A-57-92525.
  • a device for supplying an aqueous solution a device for continuously changing the concentration of an aqueous solution of a water-soluble silver salt and a water-soluble halide described in German Patent No. 2,921,164, etc.
  • the reaction mother liquor was taken out of the reactor described in Table 5, No. 56-501, 776, etc.
  • An apparatus for forming grains while keeping the distance between silver halide grains constant by concentration may be used. Further, if necessary, a silver halide solvent such as thioether may be used.
  • the silver halide grains of the present invention can contain various polyvalent metal ions alone or in combination during the grain formation or physical ripening.
  • salts such as potassium, zinc, copper, thallium, and gallium, or salts or complex salts of Group VIII transition metal ions such as iron, ruthenium, rhodium, palladium, osmium, iridium, and platinum.
  • Group VIII transition metal ions such as iron, ruthenium, rhodium, palladium, osmium, iridium, and platinum.
  • the silver halide grains of the present invention preferably have a chemical sensation.
  • Chemical sensitization methods include gold sensitization with gold compounds (for example, U.S. Pat. Nos. 2,48,060 and 3,320,069) or sensitization with metals such as iridium, platinum, and palladium. (For example, US Pat. Nos. 2,448,060, 2,566,245, and 2,566,263) or a sulfur sensitization method using a sulfur-containing compound (for example, US Pat. , No. 264), or a combination of two or more of these.
  • a silver halide emulsion can be optically spectrally sensitized to a desired wavelength region by adding a dye (spectral sensitizing dye) that absorbs light in a wavelength region corresponding to a target spectral sensitivity.
  • a dye spectral sensitizing dye
  • the spectral sensitizing dye used at this time for example, a compound described in FM Hamerti eterocycl—iccompounds—Cyaninedyesandrelatedcompounds (John Wileyand Sons; New York, 1964) Can be mentioned.
  • the spectral sensitizing dye used in the present invention include a cyanine dye, a merocyanine dye, and a complex merocyanine dye.
  • cyanine dyes there are complex cyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes.
  • cyanine dye simple cyanine dye, carbocyanine dye, and dicarbocyanine dye are preferably used.
  • silver halide photographic light-sensitive material of the present invention components other than those described above, for example, other silver halide photographic emulsions, emulsion additives, sensitization methods, anti-capri agents, stabilizers, and erasures Inhibiting dyes, yellow couplers, magenta couplers, cyan couplers, spectral sensitizing dyes, emulsifying dispersion methods, surfactants, color turbidity inhibitors, binders, hardeners, slip agents and matting agents, coating methods, coloring
  • the image recorded on the negative must be printed.
  • the image may be formed optically on a silver halide color photographic light-sensitive material and printed.
  • the image is once converted into digital information, and then the image is formed on a CRT (cathode ray tube).
  • the image may be printed on a silver halide color photographic material to be printed and printed, or printed by changing the intensity of the laser beam based on digital information and scanning.
  • the exposure time per pixel is not particularly limited, but is often in the range of 100 nanoseconds to 100 microseconds.
  • the exposure time per pixel is defined as the outer edge of the light beam where the light intensity becomes half of the maximum value in the spatial change of the light beam intensity.
  • the distance between two points where the line passing through the point where the intensity is maximum and the outer edge of the light beam intersect is defined as the light beam diameter
  • (light beam diameter) / (scanning speed) is defined as the exposure time per pixel.
  • Examples of a laser printer device that can be applied to such a system include, for example, JP-A-55-4071, JP-A-59-11062, JP-A-63-197794, JP-A-74942, and JP-A-2-236538.
  • No. 56-14963 Japanese Patent Publication No. 56-40822, European wide-area patent 77410, Department of Electronics and Communication Technology Technical Report 80, No. 244, and Cinema Television Engineering 1984Z6 (382), pp. 34-36 There are those described in such as.
  • a light source for exposing the silver halide photographic light-sensitive material of the present invention in addition to the Xe flash light, a light emitting diode, a gas laser, a solid-state laser, a semiconductor laser, a HeNe Laser, Ar laser, dye laser and the like. Furthermore, it can be used in either vertical single mode or horizontal multi mode, and it is possible to use a light source modulated by electric modulation by superposition of high frequency and SHG (second harmonic element).
  • a semiconductor laser is preferably used to design a compact, inexpensive device having a long life and high stability, and it is preferable to use a semiconductor laser as at least one of the exposure light sources.
  • the exposure time for such scanning exposure is assuming a pixel density of 400 dpi. Defined as the time necessary to expose the pixel size, the preferred exposure time 1 0 one 3 seconds or less, and more preferably not more than 10 6 seconds. In the present invention, dpi refers to the number of dots per 2.54 cm.
  • the curl degree at 23 and 20% RH may be +15 or less.
  • it is more preferably 0 to 10.
  • Each silver halide emulsion was prepared by the following method.
  • Emulsion II-1 is a monodisperse cubic emulsion having an average particle size of 0.40 ⁇ ⁇ , a coefficient of variation of the particle size distribution of 0.07, and a silver chloride content of 99.5 mol%.
  • Emulsion EMP-1B was obtained as a monodisperse cubic emulsion having a coefficient of variation of particle size distribution of 0.07 and a silver chloride content of 99.5 mol%.
  • emulsion EMP-1 was optimally chemically sensitized at 60 ° C using the following compounds.
  • sensitized emulsion EMP-1 and emulsion EMP-1B were mixed at a silver ratio of 1: 1.
  • a red-sensitive silver halide emulsion (Em-R) was obtained.
  • Emulsion EMP-1 In the preparation of emulsion EMP-1, the average particle size was 0.40 m in the same manner except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed.
  • Emulsion EMP-2 was obtained as a monodisperse cubic emulsion having a coefficient of variation of 0.08 and a silver chloride content of 99.5 mol%.
  • the average particle size was reduced in the same manner except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed.
  • Emulsion EMP-2B was obtained as a monodisperse cubic emulsion having a particle diameter of 50 m, a coefficient of variation of 0.08 and a silver chloride content of 99.5 mol%.
  • the emulsion EMP-2 prepared above was subjected to optimal chemical sensation at 55 ° C using the following compound.
  • the sensitized emulsion EMP-2 and emulsion EMP-2B were mixed at a silver ratio of 1: 1.
  • a green light-sensitive silver halide emulsion (Em-G) was obtained.
  • Emulsion EMP-3 was obtained as a monodisperse cubic emulsion having a length of 1 m, a coefficient of variation of 0.08 and a silver chloride content of 99.5 mol%.
  • EMP-3 was optimally chemically sensitized at 60 ° C using the following compound to obtain a blue-sensitive silver halide emulsion (Em-B).
  • High-density polyethylene was laminated on both sides of a paper pulp having a basis weight of 180 gZm 2 to produce a paper support.
  • a reflective support was prepared by laminating a molten polyethylene containing a surface-treated anatase-type titanium oxide dispersed at a content of 15% by mass. After the reflective support was subjected to a corona discharge treatment, a gelatin undercoat layer was provided thereon, and each layer having the following constitution was further provided thereon, to prepare Sample 101 as a silver halide photographic light-sensitive material.
  • H-1 As the hardener, H-1,
  • H-2 and F-1 were used as preservatives.
  • DIDP 0.002 Blue tinting agent (WB-1) 0.0002 Blue tinting agent (WB-2) 0.002 Silicon dioxide 0.003 6th layer (UV absorbing layer) Gelatin 0 40
  • AI-1 0 01 UV absorber (uV-1) 0 084 UV absorber (UV-2) 0 027 UV absorber (UV-3) 0 1 1 Sting inhibitor (HQ-5) 0 04 PVP 0 0 1 5 Fifth layer (Red-sensitive layer)
  • UV absorber (UV-1) 0.196 UV absorber (UV-2) 0.063 UV absorber (UV-3) 0.266 AI-1 0.02 Sting inhibitor (HQ-5) ) 0. 10 Third layer (green photosensitive layer)
  • HQ-5 2,5-di [(1,1-dimethyl-41-hexyloxycarbonyl) butyl] hydroquinone
  • Image stabilizer A P-t-octylphenol
  • Samples 102 to L10 were prepared by appropriately selecting or combining the following gradation correcting means so that ra shown in the following table was obtained.
  • the following table shows the characteristic values of the third layer as representative examples.
  • Means 1 the first layer, and have contact during the preparation of silver halide emulsions used in the third layer and the fifth layer, the use of K 2 I r C 1 6 and K 4 F e (CN) 6 was used in solution C The amount was adjusted.
  • Means 2 The chemical sensitization conditions of the silver halide emulsions used in the first, third and fifth layers were adjusted.
  • Means 3 The amounts of the silver halide emulsions of the first, third and fifth layers and the amount of each coupler were adjusted. Sample number r a ⁇ b Remarks
  • the amount of the optical brightener (W-1) used in the second layer and the amount of the bluing agent (WB-1) and bluing agent (WB-2) used in the seventh layer were appropriately adjusted.
  • a xenon flash light source through an optical wedge was subjected to exposure light in an exposure time 1 X 10- 6 seconds, using Noritsu Co., Ltd.
  • CSR type sheet automatic processing machine as an automatic developing machine, by the following method
  • a running process was performed, and the process was performed using a process name CP K-22 QA (manufactured by Koni Riki Co., Ltd.) that stabilized the state of the processing solution.
  • CP K-22 QA manufactured by Koni Riki Co., Ltd.
  • each photosensitive material is exposed imagewise with a color negative film having an average density, and is continuously processed until the volume of the color developing replenisher becomes twice the volume of the color developing tank. The properties of the processing solution were converged.
  • the obtained developed sample was measured for density using an optical densitometer (X-Rite 31 OTR manufactured by X-Rite), and the vertical axis was the color density (D) and the horizontal axis was the exposure.
  • a characteristic curve composed of the quantities (Log E) was prepared, and ra and ⁇ b were determined from the obtained characteristic curve.
  • Each sample was subjected to laser-exposure using 1 to 6 points of alphabetic characters and Japanese characters using a 1 ambda 76 manufactured by Durst (lambda 76 manufactured by Durst). Development was performed using a CSR type sheet automatic developing machine manufactured by Konica Corporation in accordance with the process name CPK-22 QA (manufactured by KONiki Co., Ltd.). Each sample on which the character image obtained as described above was printed was used as an observation light source, such as tungsten light (observation light source 1), a fluorescent lamp for observation at 500 ° K (observation light source 2), and a sunny day. Under the three conditions of outdoor daylight (observation light source 3), visual evaluation was performed by 20 general evaluators, character reproducibility was evaluated according to the following criteria, and the average value was obtained.
  • observation light source 1 tungsten light
  • observation light source 2 a fluorescent lamp for observation at 500 ° K
  • observations light source 3 Under the three conditions of outdoor daylight (observation light source 3), visual evaluation was performed by 20 general
  • the white background has a clear color tone, the density difference between the character image and the white background is poor, and it is difficult to identify even a 6-point character image. Also, clear character collapse and color blur are observed. Quality that is extremely problematic in practical use
  • Image data of a portrait scene (scene of a woman in an edging dress) where the skin color gradation can be confirmed is input to the media using a CD-R, and this image is used to apply a 1 ambda made by Durst to each sample. (Lastrda 76 manufactured by Durst Co., Ltd.), and then developed using the above-mentioned automatic CSR type sheet developing machine manufactured by Noritz Co., Ltd. according to the process name CPK-22 QA (manufactured by KONiki). Processing was performed.
  • observation light source 2 For each of the obtained portlet images, a view at 500 ° K was used as an observation light source. Under a fluorescent light for observation (observation light source 2), 20 general evaluators visually observed and evaluated the tone reproducibility according to the following criteria, and the average value was obtained.
  • ⁇ The face, hair, etc. of the person, from highlight to shadow, sharp image, very good tone reproduction, and high clarity of hair, etc.
  • ⁇ Face, hair of the person In the highlight part to the part of the shadow, the image is almost sharp, with good tone reproduction, and also has favorable characteristics such as hair clarity
  • ⁇ A person's face, hair, etc., which is slightly excessively hard or soft over the highlight area to part of the shadow, but reproduces almost acceptable tone, and the sharpness of hair etc. is also within the acceptable range. is there
  • X A person's face, hair, etc., from highlights to shadows, where the tone is excessively hard or too soft, causing undesired tone reproduction, and poor clarity of hair etc.
  • the sample of the present invention having the gradation characteristics (ra, ⁇ b) specified in the present invention was different from the comparative example in the observation of the character image under the environment of different light sources. It can be seen that the character reproducibility is excellent even under the illumination conditions of, and the tone reproducibility from the part of the shadow of the port image to the highlight part is in a preferable range. However, among the above results, exposure control was somewhat difficult for samples whose ra value was close to 3.8.
  • Example 1 The samples 101 to 110 prepared in Example 1 are described in paragraph numbers [0243:] to [0246] of JP-A-2003-43604 using a digital minilab frontier 350 manufactured by Fuji Photo Film Co., Ltd. Characteristic reproducibility and tone reproducibility were evaluated in the same manner as in Example 1 except that the development processing was performed.As a result, the samples of the present invention differed in light source as in Example 1. When observing character images in an environment, it was confirmed that the character reproducibility was excellent under any lighting conditions, and that the tone reproducibility from the shadow part to the highlight part of the portrait image was in a preferable range. Was. Industrial potential
  • the silver halide color photographic light-sensitive material of the present invention has excellent character reproducibility and favorable tone reproducibility in observation under various lighting conditions, and has excellent tone reproducibility. Material can be provided.

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Abstract

A silver halide color photography sensitive material, characterized in that when a wedged image containing a minimum density (unexposed part) and a maximum density is formed by the exposure via an optical wedge for an exposure time of 1 X 10-6 sec, followed by color development and a characteristic curve of density (D) - Log E (exposure) is prepared from the wedged image, at least a magenta coloring density in the characteristic curve satisfies the requirement of the following formula [1]: formula [1] 2.3 ≤ Ϝa ≤ 3.8 wherein Ϝa represents a gradient of a straight line joining a point for an exposure required for achieving a density of +0.25 from the minimum density and a point for an exposure required for achieving a density of +0.75 from the minimum density. The silver halide color photography sensitive material is excellent in letter reproducibility even in the observation under various lighting conditions and exhibits satisfactory gradation reproducibility.

Description

明細書 ハ口ゲン化銀力ラ一写真感光材料 技術分野  Description Hachigen silver halide photographic material
本発明は、 新規のハロゲン化銀カラ一写真感光材料に関し、 詳しくは文字画 像の描写性、 白地の鑑賞光源依存性及び階調再現性に優れたハロゲン化銀力ラ —写真感光材料に関する。 背景技術  The present invention relates to a novel silver halide color photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material excellent in the descriptive properties of a character image, the dependency on a viewing light source on a white background, and the gradation reproducibility. Background art
近年、 コンピュータ一の演算能力の向上ゃネッ トワーク技術の進歩に合わせ て、 画像をデジタルデータとして取り扱う機会が急速に増加している。 デジタ ルカメラで撮影された画像情報、 あるいはフィルム、 プリントからスキャナな どを用いてデジタルデータ化された画像情報は、 コンピュ一タ一上で編集加工 したり、 さらには文字ゃィラスト等のデータを付加したりすることも比較的容 易に行える。 このようなデジタル化された画像情報に基づいたハ一ドコピ一を 作成するハ一ドコピー材料には、 例えば、 昇華型熱転写プリ ント、 溶融型熱転 写プリント、 インクジヱッ トプリント、 静電転写型プリント、 サーモオートク ロームプリ ント、ハロゲン化銀カラー写真感光材料等が挙げられるが、中でも、 反射支持体を有するハロゲン化銀カラー写真感光材料（以下、 カラープリ ント あるいは感光材料ともいう）は、高感度であること、階調性に優れていること、 画像保存性に優れていること、 低コストであること等、 他のプリ ント材料に比 ベて非常に優れた特性を有している。 特に高品質なハ一ドコピーの作成用とし て、 今日盛んに用いられている。 In recent years, the number of opportunities for handling images as digital data has been rapidly increasing in accordance with the improvement in the computing power of computers and network technology. Image information captured by a digital camera or image information that has been converted into digital data from a film or print using a scanner, etc., can be edited and processed on a computer, and data such as character dialing can be added. Can be done relatively easily. Hard copy materials for producing hard copies based on such digitized image information include, for example, sublimation type thermal transfer prints, melt type thermal transfer prints, ink jet prints, electrostatic transfer type prints, and the like. Examples include a thermoautochrome print and a silver halide color photographic light-sensitive material. Among them, a silver halide color photographic light-sensitive material having a reflective support (hereinafter also referred to as a color print or a light-sensitive material) has high sensitivity. It has extremely excellent properties compared to other print materials, such as excellent gradation, excellent image storability, and low cost. Especially for making high quality hard copies It is widely used today.
デジタルデータ化された画像情報は、 コンピュ一ター上での編集加工が比較 的容易に行えるため、 例えば、 人物、 風景、 静物等の写真撮影データに基づい た画像等と、 文字画像が混在する画像を扱う機会が増加している。  Digitally converted image information can be edited and edited on a computer relatively easily.For example, images based on photographic data of people, landscapes, still life, etc., and images containing character images are mixed. The opportunity to deal with is increasing.
また、 デジタルデータ化された画像情報に基づいて露光を行うデジタル露光 装置として、 現在多くの機種が販売されており、 また、 露光光源や制御装置等 の進歩と相まつて新しいデジタル露光装置も数多く研究開発されている。 これ らのデジタル露光装置の中でも、 露光光源としてレーザーや L E Dのように光 源波長分布がシャープなものを用いる装置が主流になりつつある。  In addition, many models are currently being sold as digital exposure devices that perform exposure based on digitalized image information, and a number of new digital exposure devices have been researched along with advances in exposure light sources and control devices. Is being developed. Among these digital exposure apparatuses, apparatuses using a sharp light source wavelength distribution such as a laser or LED as an exposure light source are becoming mainstream.
近年のハロゲン化銀カラ一写真感光材料においては、 種々の特性が要求され るが、 その中でも、 シャ ドー部からハイライ ト部にかけての調子再現性、 モノ トーンで構成される濃度比の大きな文字画像等の再現性、 画像鮮明度あるいは 白地性はその基本的特性として、 重要であり商品価値を左右する。  In recent years, silver halide color photographic materials are required to have various characteristics. Among them, character images with a large tone ratio composed of monotone and tone reproducibility from shadows to highlights. The reproducibility of images, image clarity, and whiteness are important as their basic characteristics and affect the commercial value.
従来、 シャ ドー部からハイライ ト部にかけての調子再現性、 モノ トーンで構 成される濃度比の大きな文字画像等の再現性を向上させる方法としては、 縦軸 が発色濃度（ D )、横軸が露光量の対数（ L 0 g E )からなる特性曲線において、 高濃度領域、 すなわち特性曲線における肩部濃度領域を構成する階調を硬調化 させることにより達成してきた。特に、 L E D (発光ダイォ一ド）、 V F P H (真 空蛍光プリントへッ ド） 等のライン露光やレーザ一光等を用いた走査型露光方 式では、 1 X 1 0— 3秒以下の極めて高照度短時間露光となるため、 高照度不軌 が改良されたハロゲン化銀力ラ一写真感光材料の使用が前提となる。 しかしな がら、 過度に、 肩部濃度領域の階調を硬調化させると、 露光条件を精密に制御 することが困難となり、 その結果、 形成した画像のスジムラ等の発生を誘引す る要因となる。 また、 L E D、 V F P H、 レーザーといったデジタル露光機器 特有の走査型光源は、 特に高濃度領域において、 露光時に残光によるにじみや サイ ドローブ （露光装置の光学レンズの収差などに起因し、 ビームの中心から 波及的に発生する不正光） の様な二次光が発生し、 ハロゲン化銀カラ一写真感 5光材料に、 スティン （未露光部に生じる不正濃度） を発生させ、 その結果、 こ のスティンが文字再現や階調再現画像において色にじみや画像鮮明度の低下を 招く結果となる。 Conventionally, to improve the tone reproducibility from the shadow area to the highlight area and the reproducibility of character images composed of monotone and having a high density ratio, the vertical axis represents the color density (D) and the horizontal axis represents the color density (D). Has been achieved by making the gradation forming the high density area, that is, the shoulder density area in the characteristic curve, in the characteristic curve composed of the logarithm of the exposure amount (L 0 g E) high contrast. In particular, LED (light emitting Daio one de), VFPH in (vacuum fluorescent Purintoe' de) scanning exposure scheme using a line exposure or laser first light such as the following very high 1 X 1 0- 3 seconds Since short-time illuminance exposure is required, it is assumed that a silver halide photographic material having improved high illuminance failure is used. However, if the gradation of the shoulder density region is excessively enhanced, it becomes difficult to precisely control the exposure conditions, and as a result, the occurrence of stripes and the like in the formed image is induced. Is a factor. In addition, scanning light sources unique to digital exposure equipment such as LEDs, VFPHs, and lasers, especially in high-density areas, cause blur and sidelobes due to afterglow during exposure (due to aberrations in the optical lens of the exposure equipment, etc. Secondary light, such as illegitimate light that is generated by ripples, is generated, and stin (illegal density occurring in unexposed areas) is generated in the silver halide color photographic material. As a result, this stin May result in color bleeding and reduced image clarity in character reproduction and gradation reproduction images.
一方、 画像鮮明度の中でも、 基本的な画像の組み合わせである黒画像や色画 像をバックとした白文字、 あるいは白画像をバックとした黒文字あるいは色文0字などが明瞭に再現できないという課題が顕在化してきた。 ユーザーは、 白地 の白いプリントを高級感があると認識し、 また、 白地が白いほど文字の明瞭感 が高まるため、高い白地性を有するカラ一プリ ントが求められる傾向にある。、 その要求に応えるために様々な方法が考案されてきた。  On the other hand, among image clarity, there is a problem that a black image or a white character with a color image as a background, or a black character or a color character with a white image as a background, which is a combination of basic images, cannot be clearly reproduced. Has become apparent. Users perceive white prints on a white background as having a high-grade feel, and the whiter the white background, the higher the clarity of characters. Therefore, color prints with high whiteness tend to be required. However, various methods have been devised to meet the demand.
上記白地性を改良するために種々の方法が提案されており、 その際、 未露光5部の発色が少ないことは最低限の条件であり、 そのためハロゲン化銀乳剤の未 露光部の発色 （カプリ ） を最低限に抑えるため、 例えば、 特開平 2— 1 4 6 0 3 6号公報等に記載の化合物でカプリ防止効果があることが知られている。 し かしながら、 カプリは処理液の温度、 ハロゲンイオン濃度、 現像主薬の種類、 濃度や処理液中の着色成分の染着により変化し、 これらを調整する必要がある 〇 ことが広く知られている。しかし、カプリを抑えることは最低限の条件であり、 また理想的状態でも発色、 着色をゼロにするところまでが限界である。 カラ一 プリ ントの白地性の厳しい要求を満たすには、 白地部の発色、 着色を抑えるこ と以外に、 白地性を改良する方法を工夫することが必要である。 このための一 つの方法としては、 カラ一プリ ントに蛍光増白剤を適用する方法が提案されて いる。 例えば、 反射型支持体を構成する耐水性樹脂層中に蛍光增白剤を含有す る方法が提案されている （例えば、 特許文献 1〜3参照。）。 この方法では、 反 射支持体に蛍光増白剤を含有せしめることにより、 紫外線ェネルギーの一部を 吸収して短波長域で蛍光を発し、 白地を改良する方法であるが、 この方法を用 いると紫外線エネルギーが多い場合には、 重心波長付近での反射率が 1 0 0 % を越え、高輝度の白地を得ることができるが、紫外線エネルギーの少ない光源、 例えば、 白色灯下で鑑賞した際には、 蛍光が出にくいため、 著しく見た目の白 地が劣化する、 いわゆる光源依存性が大きいという問題を抱えている。 また、 太陽光下など紫外線の多い場所では、 逆に蛍光が強調されすぎるため白地が青 すぎると言う問題が指摘されている。 また、 発色現像処理後の未露光部におけ る各波長 n m域での濃度を特定の条件に規定し、 白地性及び観察光源によら ず安定した白地を再現できるハロゲン化銀力ラ一写真感光材料が開示されてい る （例えば、 特許文献 2参照。）。 しかしながら、 イエロ一最低濃度、 マゼンタ 最低濃度及びシアン最低濃度を規定するだけでは、 シャ ド一部からハイライ ト 部にかけての調子再現性、 モノ トーンで構成される濃度比の大きな文字画像等 の再現性、 画像鮮明度に対しては、 その一部の効果であって、 本質的な改良に は至っていないのが現状である。 Various methods have been proposed to improve the above-mentioned white background. In this case, it is a minimum condition that the color development of the unexposed 5 parts is small. ) Is minimized, for example, the compounds described in JP-A-2-14636 are known to have an anti-capri effect. However, it is widely known that capri changes depending on the temperature of the processing solution, the halogen ion concentration, the type and concentration of the developing agent, and the coloring of the coloring component in the processing solution, and it is necessary to adjust these. I have. However, minimizing the capri is the minimum condition, and even under ideal conditions, there is a limit up to the point where color development and coloring become zero. In order to meet the strict requirements of the white background of color prints, it is necessary to devise ways to improve the white background, in addition to suppressing the coloring and coloring of the white background. One for this As one method, a method of applying an optical brightener to a color print has been proposed. For example, a method has been proposed in which a fluorescent whitening agent is contained in a water-resistant resin layer constituting a reflective support (for example, see Patent Documents 1 to 3). In this method, by incorporating a fluorescent whitening agent into the reflective support, a part of the ultraviolet energy is absorbed to fluoresce in a short wavelength range and the white background is improved, but this method is used. If the UV energy is high, the reflectance near the center of gravity wavelength exceeds 100%, and a high-brightness white background can be obtained, but when viewed under a light source with low UV energy, for example, under a white light, However, there is a problem that the white background is remarkably deteriorated due to the difficulty in emitting the fluorescent light, that is, the so-called light source dependence is large. On the other hand, it has been pointed out that in places with a lot of ultraviolet rays such as under sunlight, the fluorescence is too strong and the white background is too blue. In addition, the density in each wavelength nm range in the unexposed area after color development processing is specified under specific conditions, and silver halide power can be used to reproduce a stable white background regardless of whiteness and observation light source. A material is disclosed (for example, see Patent Document 2). However, simply specifying the minimum density of yellow, the minimum density of magenta, and the minimum density of cyan, the tone reproducibility from the part of the shadow to the highlight part, and the reproducibility of character images composed of monotone and having a large density ratio, etc. On the other hand, image clarity is only part of the effect, and has not yet been substantially improved.
従って、 本発明の第 1の目的は、 文字画像の描写性を改良したハロゲン化銀 カラ一写真感光材料を提供することにあり、 本発明の第 2の目的は、 鑑賞光源 の種類に関わらず安定した白地を再現できるハロゲン化銀力ラ一写真感光材料 を提供することである。 更に、 本発明の第 3の目的は、 ポートレート画像等の 調子再現性に優れたハ口ゲン化銀力ラ一写真感光材料を提供することである。 (特許文献 1 ) Accordingly, a first object of the present invention is to provide a silver halide color photographic light-sensitive material having improved depiction of a character image, and a second object of the present invention is to provide a light-sensitive material regardless of the type of a viewing light source. An object of the present invention is to provide a silver halide photographic material capable of reproducing a stable white background. Further, a third object of the present invention is to provide a silver halide photographic light-sensitive material excellent in tone reproducibility such as a portrait image. (Patent Document 1)
特開 200 2— 35 1 0 2 2号公報  Japanese Patent Application Laid-Open No. 200 2—35 1 0 2 2
(特許文献 2 )  (Patent Document 2)
特開 200 2— 35 1 0 25号公報 発明の開示  Japanese Patent Application Laid-Open No. 2002-35 1 025 Disclosure of the Invention
本発明の上記目的は、 下記の各々の構成により達成される。  The above object of the present invention is achieved by each of the following constitutions.
( 1 ) 反射支持体上に、 それぞれ少なくとも一層のイエロ一発色感光性ハロ ゲン化銀乳剤層、 マゼンタ発色感光性ハロゲン化銀乳剤層及びシアン発色感光 性ハロゲン化銀乳剤層と、 非感光性親水性コロイ ド層を有するハロゲン化銀力 ラー写真感光材料において、 光学楔を介して露光時間 1 X 1 0_6秒で露光を施 した後、 発色現像処理して形成された最小濃度 （未露光部） 及び最大濃度を含 むゥエッジ状画像より、 濃度 D (発色濃度） 一 L o g E (露光量） からなる特 性曲線を作成し、 該特性曲線における少なくともマゼンタ発色濃度が、 下式 〔 1〕 の条件を満たすことを特徴とするハロゲン化銀カラー写真感光材料。 式 〔 1〕 (1) On a reflective support, at least one yellow-color-sensitive silver halide emulsion layer, a magenta-color-sensitive silver halide emulsion layer, a cyan-color-sensitive silver halide emulsion layer, and a non-photosensitive hydrophilic layer a silver Kaginryoku color photographic light-sensitive material having a sexual colloids layer was facilities exposure with exposure time 1 X 1 0_ 6 seconds through an optical wedge, the minimum concentration that is formed by color development (unexposed portion ), And a characteristic curve consisting of density D (color density) -Log E (exposure) is created from the edge-like image including the maximum density, and at least the magenta color density in the characteristic curve is represented by the following equation [1]. A silver halide color photographic light-sensitive material characterized by satisfying the following conditions: Equation (1)
2. 3≤ a≤ 3. 8  2. 3≤a≤3.8
〔式中、 r aは、最小濃度から + 0. 2 5の濃度を得るのに要する露光量点と、 最小濃度から + 0. 7 5の濃度を得るのに要する露光量点とを結んだ直線の傾 き （ t a n ） を表す。〕  (In the formula, ra is a straight line connecting the exposure point required to obtain a density of +0.25 from the minimum density and the exposure point required to obtain a density of +0.75 from the minimum density. Represents the inclination (tan) of ]
( 2 ) 前記特性曲線における少なく ともマゼンタ発色濃度が、 下式 〔 2〕 の 条件を満たすことを特徴とする （ 1 ) に記載のハロゲン化銀カラ一写真感光材 料。 (2) The silver halide color photographic material according to (1), wherein at least the magenta color density in the characteristic curve satisfies the condition of the following formula [2]. Fees.
式〔 2〕  Equation [2]
2. 0≤ γ b≤ 3. 8  2.0≤γb≤3.8
〔式中、 r bは、最小濃度から + 0. 75の濃度を得るのに要する露光量点と、 最小濃度から + 1. 75の濃度を得るのに要する露光量点とを結んだ直線の傾 き （ t a n ） を表す。〕  (Where rb is the slope of the straight line connecting the exposure point required to obtain a density of +0.75 from the minimum density and the exposure point required to obtain a density of +1.75 from the minimum density. (Tan). ]
( 3 ) 前記発色現像処理後の最小濃度（未露光部） の下記で定義する白色光 照明時及び単色光照明時に得られる C I E 1976 L* a * b *色空間における明 度指数 L*がそれぞれ 85≤ L* 96で、知覚色度指数 a *がそれぞれ一 1. 0 ≤ a *≤ 2. 0で、 かつ知覚色度指数 b *がそれぞれ一 8. 0≤ b *≤- 2. 2で あることを特徴とする （ 1 ) または （ 2 ) に記載のハロゲン化銀カラ一写真感 光材料。  (3) The CIE 1976 L * a * b * lightness index L * in the color space obtained at the time of white light illumination and monochromatic light illumination defined below, of the minimum density (unexposed area) after the color development processing, respectively 85 ≤ L * 96, the perceived chromaticity index a * is 1 1.0 ≤ a * ≤ 2.0, and the perceived chromaticity index b * is 1 8.0 ≤ b * ≤-2.2, respectively. The silver halide photographic light-sensitive material according to (1) or (2), wherein
白色光照明：照明光源を直接未露光部に照射する照明  White light illumination: Illumination that irradiates the illumination light source directly to unexposed areas
単色光照明：照明光源を、一旦グレーディングにより各単色光に分離した後、 未露光部に照射する照明  Monochromatic illumination: Illumination that illuminates the unexposed area after illuminating the illumination light source once and separating it into monochromatic lights.
( ) 前記発色現像処理後の最小濃度 （未露光部） 、 下式〔 3〕 で定義す る前記白色光照明により得られる C I E白色度 W aと、 下式 〔4〕 で定義する 前記単色光照明により得られる C I E白色度 W bとの差 W cが 8. 0以下であ ることを特徴とする （ 1 )乃至（ 3 ) のいずれか 1項に記載のハ σゲン化銀力 ラー写真感光材料。  () The minimum density (unexposed area) after the color development processing, the CIE whiteness Wa obtained by the white light illumination defined by the following equation [3], and the monochromatic light defined by the following equation [4] (1) to (3), wherein the difference Wc from the CIE whiteness Wb obtained by illumination is 8.0 or less. Photosensitive material.
式〔 3〕  Equation [3]
W a = 2. 1 L i*- 4. 4 5 b ι*{ 1 ~ 0. 0 0 9 0 X ( L i * - 9 6 ) } - 1 1. 〔式中、 L は白色光照明により得られる未露光部の C I E 1976 L*a*b *色空間における明度指数であり、 は白色光照明により得られる C I EL* a 色空間における知覚色度指数を表す。〕 W a = 2. 1 L i *-4.45 b ι * {1 ~ 0.0.0 9 0 X (L i *-9 6)}-1 1. (Where L is the lightness index in the CIE 1976 L * a * b * color space of the unexposed area obtained by white light illumination, and is the perceived chromaticity index in the CIEL * a color space obtained by white light illumination. Represents ]
式〔4〕  Equation [4]
W b = 2. 1 L2*-4. 45 b 2*{ 1 - 0. 0090 X ( L 2* - 96 )}W b = 2.1 L 2 * -4. 45 b 2 * {1-0. 0090 X (L 2 *-96)}
- 1 1. -1 1.
〔式中、 L2*は単色光照明により得られる未露光部の C I E 1976 L*a*b *色空間における明度指数であり、 b 2*は単色光照明により得られる C I EL* a *b*色空間における知覚色度指数を表す。〕 (Where L 2 * is the lightness index in the CIE 1976 L * a * b * color space of the unexposed portion obtained by monochromatic illumination, and b 2 * is the CIEL * a * b obtained by monochromatic illumination. * Represents the perceived chromaticity index in the color space. ]
( 5 ) 前記発色現像処理後の未露光部の前記白色光照明により得られる C I E L* a * b*色空間における色度 L が 80 < Li*< 9 1であって、かつ前記式 (5) The chromaticity L in the CIE L * a * b * color space obtained by the white light illumination of the unexposed part after the color development processing is 80 <Li * <91, and the above formula
〔 3〕 で求められる C I E白色度 W aが 85く W aく 9 1であることを特徴と する （ 4 ) に記載のハロゲン化銀カラー写真感光材料。 The silver halide color photographic light-sensitive material according to (4), wherein the CIE whiteness Wa determined in [3] is 85 or 91.
( 6 ) 前記特性曲線における各色画像濃度 0. 75を得るのに要する露光量 の 4倍の露光量点におけるそれぞれの濃度が、 2. 0以上であることを特徴と する （ 1 )乃至（ 5 ) のいずれか 1項に記載のハロゲン化銀カラ一写真感光材 料。 発明を実施するための最良の形態  (6) The density at each exposure point four times the exposure required to obtain 0.75 of each color image density in the characteristic curve is 2.0 or more. (1) to (5) ). The silver halide color photographic light-sensitive material as described in any one of 1) to 1) above. BEST MODE FOR CARRYING OUT THE INVENTION
発明者は上記課題に鑑み鋭意研究を行った結果、 光学楔を介して露光時間 1 X 10— 6秒で露光を施した後、 発色現像処理して形成された最小濃度 （未露光 部）及び最大濃度を含むゥエッジ状画像より、 濃度 D (発色濃度） 一 L 0 g E (露光量） からなる特性曲線を作成し、 該特性曲線における少なくともマゼン タ発色濃度において、 最小濃度から + 0 . 2 5の濃度を得るのに要する露光量 点と、 最小濃度から + 0. 7 5の濃度を得るのに要する露光量点とを結んだ直 線の傾き r a、 あるいは最小濃度から + 0 . 7 5の濃度を得るのに要する露光 量点と、 最小濃度から + 1 . 7 5の濃度を得るのに要する露光量点とを結んだ 直線の傾き bを特定の条件範囲に規定することにより、 文字画像の描写性、 鑑賞光源の種類に関わらず安定した白地再現性、 あるいはポートレート画像等 の調子再現性に優れたハ口ゲン化銀力ラ一写真感光材料を実現できることを見 出したものである。 Inventor result of extensive research in view of the above problems, was subjected to exposure with an exposure time 1 X 10- 6 seconds through an optical wedge, the minimum concentration that is formed by color development (unexposed portion) and From the edge-shaped image containing the maximum density, a characteristic curve consisting of density D (color density) -L 0 g E (exposure) is created, and at least In the color density, a straight line connecting the exposure point required to obtain a density of +0.25 from the minimum density and the exposure point required to obtain a density of +0.75 from the minimum density Slope ra or slope b of a straight line connecting the exposure point required to obtain a density of +0.75 from the minimum density and the exposure point required to obtain a density of +1.75 from the minimum density b Is defined as a specific range of conditions, so that the character image is easy to describe, the white background is stable regardless of the type of viewing light source, or the tone reproduction of portrait images is excellent. It has been found that photographic photosensitive materials can be realized.
具体的には、 観賞用のハロゲン化銀カラ一写真感光材料において、 高濃度領 域（肩部領域）での階調（ r b )を特定の範囲となるように適度に硬調化させ、 また低濃度領域 （脚部領域） での階調 （ r a ) を特定の範囲となるように適度 に硬調化させることにより、 文字画像の描写性、 鑑賞光源の種類に関わらず安 定した白地再現性、 あるいはポ一トレ一ト画像等の調子再現性を向上させると 共に、 画像のスジムラ等の発生を抑制することができる。 これは、 デジタルプ リ ンタ一の露光方式が、 8 b i tではなく、 1 2〜1 6 b i tで制御されるよ うになつたことにより可能となった。 すなわち、 最適なルックアップテーブル ( L U ) の設計により、 ハロゲン化銀カラ一写真感光材料特有のォリジナル の階調特性から、作製者が意図する目標階調への変換が可能となり、その結果、 ハイライ ト部 （低濃度領域） に適度な階調 （曲率形状） を付与させた設計とす ることにより、 文字再現性の向上と滑らかな低濃度域の階調再現性を雨立する を可能としたものである。  Specifically, in an ornamental silver halide color photographic light-sensitive material, the gradation (rb) in the high-density area (shoulder area) is moderately enhanced so as to be within a specific range, The gradation (ra) in the density area (leg area) is moderately hardened so as to be within a specific range, so that the character image descriptiveness, stable white background reproducibility regardless of the type of viewing light source, Alternatively, it is possible to improve the tone reproducibility of a portray image and the like, and to suppress the occurrence of uneven streaks and the like in the image. This was made possible by the fact that the exposure method of the digital printer was controlled by 12 to 16 bits instead of 8 bits. In other words, by designing an optimal look-up table (LU), it is possible to convert from the original gradation characteristics specific to silver halide color photographic light-sensitive materials to the target gradation intended by the creator. With the design that gives an appropriate gradation (curvature shape) to the bottom part (low-density area), it is possible to improve the character reproducibility and make the gradation reproducibility in the smooth low-density area rainy. It was done.
更に、 文字再現性を向上させる手段として、 白地の改良による心理的なコン トラスト差を利用して文字の表現を改良できる方法が知られている。 従来の白 地改良技術の多くは、 ハロゲン化銀カラ一写真感光材料の支持体や、 ハロゲン 化銀乳剤層あるいは非感光性層中に蛍光增白剤を含有させ青色蛍光を発するこ とにより白地の黄ばみを補正している。 しかしながら、 ここで用いられている 蛍光增白剤による蛍光発光には、 紫外線の吸収を必要とするため、 画像を観察 する光源の種類、 例えば、 タングステン光、 蛍光灯、 太陽光等により、 白地色 調が変化する、 いわゆる白地の異種光源依存性が生じる。 更に、 紫外線の吸収 により、 蛍光増白剤は分子破壊を起こしやすく、 その結果、 長期保存の過程で 白地が徐々に変化していく問題も抱えている。 本発明では、 蛍光増白剤によら ず、 主に青味剤といわれている青色染料により、 白地の色調を本発明で規定す る色調に調整することにより、 観察照明に依存せずに、 心理的に最適の白地色 調を再現できることを可能としたものである。 Furthermore, as a means for improving the character reproducibility, a method is known in which the expression of characters can be improved using a psychological contrast difference due to the improvement of the white background. Conventional white Many of the ground improvement techniques use a silver halide color photographic light-sensitive material support or a silver halide emulsion layer or a non-photosensitive layer to contain a fluorescent whitening agent to emit blue fluorescence, thereby reducing yellowing of the white background. It has been corrected. However, since the fluorescent light emitted by the fluorescent whitening agent used here requires absorption of ultraviolet light, the type of light source for observing an image, for example, tungsten light, fluorescent light, sunlight, etc., causes a white background color. The tone changes, that is, the so-called white light source depends on different light sources. In addition, optical brighteners are susceptible to molecular destruction due to the absorption of ultraviolet light, resulting in the problem that the white background gradually changes during the long-term storage. In the present invention, the color tone of the white background is adjusted to the color tone specified in the present invention by a blue dye mainly referred to as a bluing agent, without depending on the fluorescent whitening agent. This makes it possible to reproduce psychologically optimal white background tones.
本発明で規定する各階調特性と最適の C I E白色度との設計により、 文字品 質の鮮明度、 文字再現性が向上し、 複雑な文字でも認知が可能となり、 かつシ ャ ドー部からハイライ ト部にかけての階調再現性を向上したものである。 以下、 本発明の詳細について説明する。  The design of each gradation characteristic and the optimal CIE whiteness specified in the present invention improves the clarity of character quality and character reproducibility, enables recognition of complex characters, and highlights from the shadow part. The tone reproducibility of the part is improved. Hereinafter, details of the present invention will be described.
反射支持体上に、 それぞれ少なくとも一層のイエロ一発色感光性ハロゲン化 銀乳剤層、 マゼンタ発色感光性ハ口ゲン化銀乳剤層及びシァン発色感光性ハ口 ゲン化銀乳剤層と、 非感光性親水性コロイ ド層を有する本発明のハロゲン化銀 カラ一写真感光材料においては、 光学楔を介して露光時間 1 X 1 0— s秒で露光 を施した後、 発色現像処理して形成された最小濃度（未露光部） 及び最大濃度 を含むゥエッジ状画像より、 濃度 D (発色濃度） 一 L o g E (露光量） からな る特性曲線を作成し、 該特性曲線における少なくともマゼンタ発色濃度が、 最 小濃度から + 0 . 2 5の濃度を得るのに要する露光量点と、最小濃度から + 0 . 75の濃度を得るのに要する露光量点とを結んだ直線の傾き r aが、 前記式 〔 1〕 の条件を満たすことを特徴とする。 On a reflective support, at least one layer each of yellow-color-sensitive photosensitive silver halide emulsion layer, magenta-color-sensitive photosensitive silver halide emulsion layer, cyan-sensitive photosensitive silver halide emulsion layer, and non-photosensitive hydrophilic layer In the silver halide color photographic light-sensitive material of the present invention having a hydrophilic colloid layer, the light-sensitive material is exposed through an optical wedge for an exposure time of 1 × 10- s seconds, and then formed by a color development process. From the edge-shaped image including the density (unexposed area) and the maximum density, a characteristic curve consisting of density D (color density) -Log E (exposure amount) is created, and at least the magenta color density in the characteristic curve is minimized. The exposure point required to obtain a density of +0.25 from a small density and +0.25 from the minimum density. The slope ra of a straight line connecting the exposure point required to obtain a density of 75 satisfies the condition of the above-mentioned formula [1].
すなわち、 前記式 〔 1〕 において、 r aが 2. S≤ r a≤ 3. 8の範囲にあ ることが特徴であるが、 2. 3≤ ≤ 3. 0の範囲にあることが好ましく、 2. 3≤ a≤ 2. 7の範囲にあることがより好ましい。  That is, in the above formula [1], ra is characterized by being in the range of 2.S≤ra≤3.8, but is preferably in the range of 2.3≤≤3.0, and 2. More preferably, it is in the range of 3≤a≤2.7.
更に、 上記式 〔 1〕 で規定する条件に加えて、 該特性曲線における少なくと もマゼンタ発色濃度が、 最小濃度から + 0. 75の濃度を得るのに要する露光 量点と、 最小濃度から + 1. 75の濃度を得るのに要する露光量点とを結んだ 直線の傾き r が、 前記式 〔 2〕 の条件を満たすことが好ましい。  Furthermore, in addition to the conditions defined by the above equation (1), at least the exposure point required to obtain a density of at least magenta color development density of +0.75 from the minimum density and + It is preferable that the slope r of a straight line connecting the exposure point required to obtain the density of 1.75 satisfies the condition of the above formula [2].
すなわち、 前記式 〔 2〕 において、 r b力 2. 0≤ a≤ 3. 8の範囲にあ ることが好ましく、 2. 2≤ r a≤ 3. 8の範囲にあることがより好ましく、 2. 5≤ a≤ 3. 6の範囲にあることが更に好ましい。  That is, in the above formula [2], the rb force is preferably in the range of 2.0 ≦ a ≦ 3.8, more preferably in the range of 2.2 ≦ ra ≦ 3.8, and 2.5 More preferably, it is in the range of ≤a≤3.6.
詳しくは、 ハロゲン化銀カラ一写真感光材料を、 高照度露光条件である I X 1 6秒で階段状の光学濃度 （透過率） を変化させた光学楔を介して露光を与 えた後、 所定の発色現像処理を施して、 主に、 最小濃度 （未露光部） から最高 濃度まで階段状の濃度変化をしているイエロ一色画像、 マゼンタ色画像及びシ アン画像を形成する。 この様にして得られた各色画像を、 反射型濃度計、 ある いは透過型濃度計で測定するが、 本発明のハ口ゲン化銀力ラ一写真感光材料の ような観賞用ハ口ゲン化銀力ラ一写真感光材料である場合には、反射型濃度計、 例えば、光学濃度計（ X— R i t e社製 X— R i t e 3 10 TR)を用いて、 ブルーフィルタ一、 グリーンフィルタ一、 レッ ドフィルタ一を介して濃度測定 を行う。 この様にして得られた濃度 （ D ) と、 光学楔の各透過率と露光条件に より求められる露光量（ E ) より、 縦軸を発色濃度（D )、 横軸を露光量の対数 値 （ L o g E ) としてプロッ トしたものが、 特性曲線である。 Specifically, after exposing a silver halide color photographic light-sensitive material through an optical wedge in which the optical density (transmittance) is changed in a stepwise manner at IX 16 seconds, which is a high-illumination exposure condition, By performing color development processing, it mainly forms yellow one-color images, magenta-color images, and cyan images that have a stepwise density change from the minimum density (unexposed area) to the maximum density. Each color image obtained in this way is measured with a reflection densitometer or a transmission densitometer, and the ornamental hachigen like the silver halide photographic light-sensitive material of the present invention is used. In the case of a silver halide photographic material, use a reflection type densitometer, for example, an optical densitometer (X-Rite X-Rite 3 10TR) and use a blue filter and a green filter. The density is measured via a red filter. From the density (D) obtained in this way and the exposure (E) determined from the transmittance of the optical wedge and the exposure conditions, the vertical axis represents the color density (D), and the horizontal axis represents the logarithm of the exposure. The characteristic curve is plotted as the value (Log E).
本発明では、 イエロ一色画像、 マゼンタ色画像及びシアン色画像により得ら れた特性曲線の内、 少なくともマゼンタ色画像の特性曲線が、 前記式 〔 1〕 で 規定する条件を満たしていることが特徵であり、 更に、 マゼンタ色画像と他の 1色の色画像が前記式 〔 1〕 で規定する条件を共に満たしていることが好まし く、 最も好ましくは、 全ての色画像が前記式 〔 1〕 で規定する条件を満たして いることである。  According to the present invention, among the characteristic curves obtained from the yellow single color image, the magenta color image, and the cyan color image, at least the characteristic curve of the magenta color image satisfies the condition defined by the above formula [1]. Further, it is preferable that the magenta color image and the other one color image both satisfy the condition defined by the above formula [1]. Most preferably, all the color images satisfy the above formula [1]. ] Must be satisfied.
更に、 上記式 〔 1〕 で表される低濃度域の階調性を規定する条件に加え、 前 記式〔 2〕 で表される高濃度域の階調性を同時に満足することが好ましい。 すなわち、 本発明で規定する式 〔 1〕 及び式 〔 2〕 で規定する階調性は、 高 照度露光条件下で、 低濃度領域であるハイライ ト部及び高濃度領域であるシャ ド一部において、 過度に軟調、 あるいは硬調でなく、 文字再現性上最適の階調 特性を有しているものである。  Further, in addition to the conditions for defining the gradation in the low-density region represented by the above formula [1], it is preferable that the gradation in the high-density region represented by the above-mentioned formula [2] be simultaneously satisfied. That is, the gradation defined by the formulas [1] and [2] specified in the present invention is high in a high density region in a highlight portion and a high density region in a shadow portion under high illuminance exposure conditions. It is not excessively soft or hard, and has optimal gradation characteristics in terms of character reproducibility.
本発明のハロゲン化銀カラー写真感光材料において、 本発明に係る前記式 〔 1〕 で規定する階調特性、 あるいは前記式 〔 2〕 で規定する階調特性を実現 するための手段としては、 当業界公知の各階調調整手段を適宜選択、 あるいは 組み合わせることにより実現することができるが、 本発明においては、 その中 でも以下に示す手段を用いることが好ましい。  In the silver halide color photographic light-sensitive material of the present invention, the means for realizing the gradation characteristic defined by the above formula [1] or the gradation characteristic defined by the above formula [2] according to the present invention include the following. It can be realized by appropriately selecting or combining various tone adjusting means known in the art. In the present invention, it is preferable to use the following means among them.
手段 1 ：ハロゲン化銀乳剤層で用いるハロゲン化銀乳剤の調製時に、 重金属 イオンを含有せしめることによる高照度不軌の改良。  Means 1: Improvement of high illuminance failure by incorporating heavy metal ions during preparation of silver halide emulsion used in silver halide emulsion layer.
このような目的で用いることのできる重金属イオンとしては、 鉄、 イ リジゥ ム、 白金、 パラジウム、 ニッケル、 ロジウム、 オスミウム、 ルテニウム、 コバ ノレト等の第 8〜1 0族金属や、 カ ドミウム、 亜鉛、 水銀などの第 1 2族遷移金 属ゃ、 鉛、 レニウム、 モリブデン、 タンダステン、 ガリウム、 クロムの各ィォ ンを挙げることができる。 中でも鉄、 ィ リジゥム、 白金、 ルテニウム、 ガリウ ム、 オスミウムの金属イオンが好ましい。 これらの金属イオンは、 塩や、 錯塩 の形でハ口ゲン化銀乳剤に添加することができる。 前記重金属ィォンが錯体を 形成する場合には、その配位子としてシァン化物ィォン、チオシァン酸ィォン、 シアン酸イオン、 塩化物イオン、 臭化物イオン、 沃化物イオン、 カルボニル、 ニトロシル、 アンモニア、 1 , 2， 4一トリァゾ一ル、 チアゾール等を挙げる ことができる。 中でも、 塩化物イオン、 臭化物イオン等が好ましい。 これらの 配位子は単独であつても複数の配位子が併用されてもよい。 Heavy metal ions that can be used for such a purpose include iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, covanolate and other Group 8-10 metals, cadmium, zinc, and the like. Group 1 and 2 transition gold such as mercury Examples include metals, lead, rhenium, molybdenum, tandastene, gallium, and chromium. Among them, metal ions of iron, iridium, platinum, ruthenium, gallium, and osmium are preferred. These metal ions can be added to the silver halide emulsion in the form of a salt or a complex salt. When the heavy metal ion forms a complex, its ligands include cyanide ion, thiocyanoic acid ion, cyanate ion, chloride ion, bromide ion, iodide ion, carbonyl, nitrosyl, ammonia, 1, 2, 4-triazole, thiazole and the like. Among them, chloride ion, bromide ion and the like are preferable. These ligands may be used alone or in combination of a plurality of ligands.
手段 2 ：各ハロゲン化銀乳剤層で用いるハロゲン化銀乳剤として、 高い単分 散度を有するハロゲン化銀粒子、 高現像性のハロゲン化銀粒子 （特に、 ハロゲ ン組成の最適化等）、ハロゲン化銀粒子の添加量、ハロゲン化銀粒子の平均粒子 径、 粒径の異なる 2種以上のハロゲン化銀粒子を混合する方法、 化学增感法等 を適宜選択、 あるいは組み合わせる方法。  Means 2: The silver halide emulsion used in each silver halide emulsion layer includes silver halide grains having high monodispersity, silver halide grains having high developability (particularly optimization of the halogen composition, etc.), and halogens. A method of appropriately selecting or combining a method of mixing two or more kinds of silver halide grains having different addition amounts of silver halide grains, an average grain size of silver halide grains, and different grain sizes, and a chemical sensitization method.
手段 3 ：各ハロゲン化銀乳剤層で用いるカプラーとして、 高発色性、 高反応 性カプラーを使用し、 その添加量を適宜調整する方法。  Means 3: A method of using a high color-forming and highly reactive coupler as a coupler used in each silver halide emulsion layer and appropriately adjusting the amount of the coupler.
また、 本発明のハロゲン化銀カラ一写真感光材料においては、 上記特性曲線 における各色画像画像濃度 0 . Ί 5を得るのに要する露光量の 4倍の露光量点 におけるそれぞれの濃度が、 2 . 0以上であることが好ましく、 より好ましく は 2 . 0〜3 . 5であり、 更に好ましくは 2 . 0〜3 . 0である。  Further, in the silver halide color photographic light-sensitive material of the present invention, the respective densities at the exposure point, which is four times the exposure amount required to obtain the image density of each color in the above-mentioned characteristic curve, are 0.2. It is preferably at least 0, more preferably from 2.0 to 3.5, and still more preferably from 2.0 to 3.0.
本発明において、 上記で規定する濃度値を実現する手段としては、 上記手段 In the present invention, the means for realizing the density value defined above includes the above means
1〜 3に記載の各手段を適宜調整することにより実現することができる。 It can be realized by appropriately adjusting each means described in 1 to 3.
本発明のハロゲン化銀カラー写真感光材料においては、 発色現像処理後の最 小濃度 （未露光部） が前記で定義した白色光照明時及び単色光照明時に得られ る C I E 1976 L* a* b*色空間における明度指数 L*がそれぞれ 85≤L*≤ 96で、 知覚色度指数 a*がそれぞれ一 1. 0 a* 2. 0で、 知覚色度指数 b*がそれぞれ一 8. 0≤ b *≤- 2. 2であることが好ましい。 In the silver halide color photographic light-sensitive material of the present invention, the color photographic light- The lightness index L * in the CIE 1976 L * a * b * color space obtained at low density (unexposed area) under white light illumination and monochromatic light illumination defined above is 85≤L * ≤96, respectively. It is preferable that the chromaticity index a * is 11.0 a * 2.0 and the perceived chromaticity index b * is 18.0≤b * ≤-2.2.
本発明でいう明度指数 L*、 知覚色度指数 a *、 b*とは、 C I EL AB ( C 0 mm i s s i o n I n t e r n a t i o n a l e d e 1 E c h a i r a g e " 奨励の L=\ a *、 b*色彩系略語） による明度指数 L*、 知覚色度 指数 a*、 b*であり、詳細は「新編 色彩科学ハンドブック （日本色彩学会編） 267ページ」 の C I E L* a* b*の項目に記載されている。 The lightness index L * and the perceived chromaticity index a *, b * in the present invention are based on CI EL AB (C = 0 mm ission Internationalede 1 E chairage "L = \ a *, b * color abbreviation recommended") These are the lightness index L * and the perceived chromaticity index a * and b *, and are described in detail in the CIEL * a * b * section of the “New Edition of Color Science Handbook (edited by the Japan Society of Color Society), page 267”
また、本発明に係る C I E 1976 L* a* b*表色空間の詳細は、 日本写真学 会 · 日本画像学会編「フアインィメージングとカラーハ一ドコピー」 354ぺ —ジ （ 1999年、 コロナ社刊行） にも詳記されている。 この表色空間を用い る際の 3色刺激値は、 蛍光性反射物体の X、 Y、 Ζ座標の 3刺激値測定方法を 規定した J I S Ζ 8717記載の方法に従って求められた値である。 C I Ε 1976 L* a *b*表色空間上の色度は、基準となる白色の色度を標準昼光の 国際標準である C I ED 65 ( 6504K) に用いて測定する。 測定機器とし ては、 C I E 1976 L* a *b*表色空間上の色度を測定できるいずれの色度測 定装置を用いることができる。 例えば、 日立製作所社製の C— 2000カラー アナライザ一および基準光源として C I E D65 ( 650 K) を用い未露 光部を測定することにより求めることができる。  The details of the CIE 1976 L * a * b * color space according to the present invention are described in “Film Imaging and Color Hard Copy” edited by The Photographic Society of Japan · The Imaging Society of Japan (Corona, 1999). Published). The three-color stimulus value when using this color space is a value obtained according to the method described in JIS 8717, which defines a method for measuring the three stimulus values of the X, Y, and Ζ coordinates of a fluorescent reflective object. C I Ε 1976 L * a * b * The chromaticity in the color space is measured using the standard white chromaticity as the international standard for standard daylight, CI ED 65 (6504K). As the measuring device, any chromaticity measuring device capable of measuring chromaticity in the CIE 1976 L * a * b * color space can be used. For example, it can be determined by measuring the unexposed part using a C-2000 color analyzer manufactured by Hitachi, Ltd. and CIED65 (650 K) as a reference light source.
また、 本発明においては、 癸色現像処理後の最小濃度 （未露光部） が、 前記 式 〔 3〕 で定義する白色光照明により得られる C I E白色度 W aと、 前記式 〔 4〕で定義する単色光照明により得られる C I E白色度 W bとの差 W cが 8. 0以下であることが好ましく、 より好ましくは 0. 1〜8. 0であり、 更に好 ましくは 1. 0〜7. 0である。 Further, in the present invention, the minimum density (unexposed portion) after the color development processing is defined as CIE whiteness Wa obtained by white light illumination defined by the above formula [3] and defined by the above formula [4]. The difference Wc from the CIE whiteness Wb obtained by monochromatic light illumination is 8. It is preferably 0 or less, more preferably 0.1 to 8.0, and still more preferably 1.0 to 7.0.
本発明に係る白色光照明により得られる C I E白色度 W aとは、 照明光源を 直接未露光部に照射する白色光照明により求められる C I E白色度であり、 具 体的には、 前記式 〔 3〕 により求めることができる。  The CIE whiteness W a obtained by the white light illumination according to the present invention is a CIE whiteness obtained by white light illumination in which an illumination light source is directly applied to an unexposed portion, and more specifically, the above formula [3] ].
前記式 〔 3〕 において、 として、 85 < L く 9 1であることが好まし く、 より好ましくは 87< 1^*く 89である。  In the above formula [3], it is preferable that the following expression is satisfied: 85 <L <91, more preferably 87 <1 ** <89.
また、 W aとしては、 85く Waく 9 1であることが好ましく、 より好まし くは 87<W a < 90である。  Further, Wa is preferably 85, Wa and 91, more preferably 87 <W a <90.
また、 本発明に係る単色光照明により得られる C I E白色度 Wbとは、 照明 光源を、 一旦グレーデイングにより分離した単色光を、 未露光部上に照射する 照明により得られる C I E白色度であり、 具体的には、 前記式 〔 4〕 により求 めることができる。  Further, the CIE whiteness Wb obtained by the monochromatic light illumination according to the present invention is the CIE whiteness obtained by illumination of an illumination light source, which is obtained by irradiating the monochromatic light once separated by graying onto an unexposed portion, Specifically, it can be determined by the formula [4].
前記式 〔 4〕 において、 L2*として、 85く L2*く 9 1であることが好まし く、 より好ましくは 87く L2*く 89である。 In Formula (4), as L 2 *, rather preferably be 85 rather L 2 * Ku 9 1, more preferably 87 rather L 2 * Ku 89.
また、 Wbとしては、 83く Wbく 87であることが好ましく、 より好まし くは 84<W a < 86である。  Further, Wb is preferably 83, Wb and 87, and more preferably 84 <W a <86.
本発明では、 具体的には、 日立製作所製の C一 2000カラ一アナライザ一 を用いて、 タングステン光源を直接試料に照射して測定される C I E白色度を 白色光照明により得られる C I E白色度 W aと定義する。 ここでいう、 白色光 照明には、 ブル一、 グリーン、 レッ ドの 3原色光の他に、 紫外光及び赤外光が 含まれている。 一方、 本発明に係る単色光照明により得られる C I E白色度 W bとは、 照明光源を、 一旦グレーデイングにより分離した単色光を、 未露光部 上に照射する照明により得られる C I E白色度と定義する。 In the present invention, specifically, the CIE whiteness W obtained by irradiating a tungsten light source directly onto a sample using a C-2000 color analyzer manufactured by Hitachi, Ltd. Define as a. Here, the white light illumination includes ultraviolet light and infrared light in addition to the three primary color lights of blue, green, and red. On the other hand, the CIE whiteness Wb obtained by the monochromatic light illumination according to the present invention refers to a monochromatic light obtained by separating an illumination light source once by graying into an unexposed portion. Defined as the CIE whiteness obtained by the illumination illuminating above.
従って、 白色光照明により得られる C I E白色度 W aと、 単色光照明により 得られる C I E白色度 W bとの差を求めることにより、 主に紫外光による白地 特性への影響度を求めることができる。 この差が小さいほど、 紫外光比率の異 なる様々な照明光源で、 ハロゲン化銀カラー写真感光材料を観察した際、 白地 特性の変動が小さく観察されることを意味している。  Therefore, by determining the difference between the CIE whiteness W a obtained by white light illumination and the CIE whiteness W b obtained by monochromatic illumination, it is possible to obtain the degree of influence of the ultraviolet light on the white background characteristics mainly. . The smaller the difference, the smaller the variation of the white background characteristics when observing the silver halide color photographic light-sensitive material with various illumination light sources having different ultraviolet light ratios.
本発明のハロゲン化銀カラ—写真感光材料において、 本発明で規定する W a と W bの関係、白色光照明あるいは単色光照明で観察した際の W a値、 W b値、 L *値、 a *値、 b *値を実現する手段としては、 特に制限はないが、 以下の調整 条件を適宜選択して用いることが好ましい。  In the silver halide color photographic light-sensitive material of the present invention, the relationship between Wa and Wb defined in the present invention, the Wa value when observed with white light illumination or monochromatic light illumination, the Wb value, the L * value, Means for realizing the a * value and the b * value are not particularly limited, but it is preferable to appropriately select and use the following adjustment conditions.
通常、 望ましい白地特性を達成する手段としては、 例えば、 カプリ抑制剤、 油溶性染料、 ブルーィング剤（青み剤）、顔料ゃ增感色素の溶出を促進する除去 促進剤、 蛍光増白剤、 界面活性剤などをハロゲン化銀カラー写真感光材料又は 処理剤に用いる技術が知られている。 更には、 白地改良の目的から支持体の改 良も検討されており、 例えば、 二酸化チタン等の白色顔料を樹脂層中に添加す る方法、 群青等の色味付けにより白地の色味を調節する方法、 また蛍光増白剤 を樹脂層中に添加する方法は、 いずれも支持体による改良手段として用いられ ている。  Usually, means for achieving desirable white background properties include, for example, a capri inhibitor, an oil-soluble dye, a bluing agent (a bluing agent), a removal accelerator for accelerating the dissolution of pigments and sensitizing dyes, a fluorescent brightening agent, and an interface. There is known a technique in which an activator or the like is used for a silver halide color photographic light-sensitive material or a processing agent. Further, improvement of the support is also being studied for the purpose of improving the white background.For example, a method of adding a white pigment such as titanium dioxide to the resin layer, or adjusting the tint of the white background by tinting ultramarine blue or the like. The method and the method of adding a fluorescent whitening agent to the resin layer are both used as means for improving the support.
本発明においては、 上記白地改良技術の中でも、 油溶性染料、 ブルーイング 剤等の色調調整剤を適宜選択、 あるいは組み合わせて、 所望の白地特性を達成 することが好ましい。 また、 これらの各色調調整剤は、 ハロゲン化銀カラー写 真感光材料を構成する感光性乳剤層、 非感光性乳剤層あるいは支持体を構成す る樹脂層等に添加することが好ましい。 本発明で用いることのできるブルーィング剤としては、一般に知られる群青、 コバルトブルー、 酸化リン酸コバルト、 キナクリ ドン系顔料等とその混合物が 挙げられる。 In the present invention, among the above-described white background improvement techniques, it is preferable to appropriately select or combine color tone adjusting agents such as oil-soluble dyes and bluing agents to achieve desired white background characteristics. It is preferable that each of these color tone adjusters is added to a photosensitive emulsion layer or a non-light-sensitive emulsion layer constituting a silver halide color photographic material or a resin layer constituting a support. Examples of the blueing agent that can be used in the present invention include generally known ultramarine blue, cobalt blue, cobalt oxide phosphate, quinacridone pigments and the like, and mixtures thereof.
本発明において用いることのできる油溶性染料や着色顔料としては、例えば、 ォキソノール染料、 ァゾメチン染料、 ァゾ染料、 ベンゾキノン染料、 ナフ トキ ノン染料、 アントラキノン染料、 ァリ一リデン染料、 スチリル染料、 ジフヱ二 ルメタン染料、 ト リフヱニルメタン染料、 キサンテン染料、 ァクリジン染料、 ァジン染料、 ォキサジン染料、 チアジン染料、 ペリノ ン染料、 メロシアニン染 料、 シァニン染料、 ィ ンドア二リ ン染料、 フタロシア二ン染料、 ィ ンジゴ染料、 チォインジゴ染料などを挙げることができる。  Examples of the oil-soluble dyes and color pigments that can be used in the present invention include oxonol dyes, azomethine dyes, azo dyes, benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, arylidene dyes, styryl dyes, diphenyl dyes, and the like. Methane dye, trifluoromethane dye, xanthene dye, acridine dye, azine dye, oxazine dye, thiazine dye, perinone dye, merocyanine dye, cyanine dye, indolinyl dye, phthalocyanine dye, indigo dye, thioindigo Dyes and the like can be mentioned.
顔料については、 例えば、 ァゾ顔料 （例えば、 不溶性モノァゾ顔料、 不溶性 ジスァゾ顔料、 ァゾレーキ顔料、 縮合ァゾ顔料、 金属錯塩ァゾ顔料）、 フタロシ ァ二ン顔料、染付けレーキ顔料（例えば、酸性染料レーキ、塩基性染料レーキ）、 縮合多環顔料（例えば、キナクリ ドン顔料、チオインジゴ顔料、ペリ レン顔料、 アントラキノン系顔料、 ぺリノン顔料、 ジォキサジン顔料、 イソインドリノ ン 攀料、 ジケトピロロピロール顔料）、 その他（例えば、 ニトロソ顔料、 ァリザリ ンレーキ顔料、 アルカ リブル一） などの有機顔料を挙げることができる。  Examples of pigments include azo pigments (for example, insoluble monoazo pigments, insoluble disazo pigments, azo lake pigments, condensed azo pigments, metal complex azo pigments), phthalocyanine pigments, dyed lake pigments (for example, acid dye lakes). , Basic dye lakes), condensed polycyclic pigments (for example, quinacridone pigments, thioindigo pigments, perylene pigments, anthraquinone pigments, perinone pigments, dioxazine pigments, isoindolinone glides, diketopyrrolopyrrole pigments), and others ( Examples thereof include organic pigments such as nitroso pigments, alizarin lake pigments, and alkaline pigments.
また、 油溶性染料の代表的具体例として、 特開平 2— 842号 8ページ〜 9 ページに記載の化合物 1〜 27が挙げられる。  Further, typical examples of the oil-soluble dye include compounds 1 to 27 described on pages 8 to 9 of JP-A-2-842.
その他の具体的な化合物については、 「新版染料便覧」 （有機合成化学協会編 ；丸善， 1970 )、「カラ一インデックス」（ T h e S o c i e t y o f D e r s a n d c o l o u r i s t s )、「色材工学ノヽンドブック」（色材 協会編；朝倉書店、 1989 )、 「改訂新版顔料便覧」 などに記載されている。 また、本発明に用いられる青顔料の具体例としては、「カラーイ ンデックス」 において、 C. I . P i g m e n t B 1 u eとして分類されている顔料が挙 げられ、 同様に、 本発明に用いられる赤顔料としては、 C. I . P i g m e n t R e d、 本発明に用いられる紫顔料としては、 C. I. P i g m e n t V i o 1 e tとして分類されている顔料を挙げることができる。 For other specific compounds, see “New Edition Dye Handbook” (edited by the Society of Synthetic Organic Chemistry; Maruzen, 1970), “Color Index” (The Society of Dersandcolourists), “Color Material Engineering Handbook” (color materials) Association edition: Asakura Shoten, 1989), "Revised New Edition Pigment Handbook", etc. Further, specific examples of the blue pigment used in the present invention include pigments classified as CI Pigment B 1 ue in the “Color Index”. Similarly, the red pigment used in the present invention Examples of the pigment include CI Pigment Red, and examples of the purple pigment used in the present invention include pigments classified as CI Pigment Vio1et.
また、 本発明のハロゲン化銀カラ一写真感光材料においては、 本発明の目的 効果を損なわない範囲で、 当業者で従来公知の各種蛍光增白剤を用いることが でき、ベンゾォキサゾ一ル系、クマリン系、 ピラゾリン系を挙げることができ、 好ましくは、 ベンゾォキサゾリルナフタレン系及びべンゾォキサゾリルスチル ベン系の蛍光增白剤である。  In the silver halide color photographic light-sensitive material of the present invention, various fluorescent whitening agents conventionally known to those skilled in the art can be used as long as the effects of the present invention are not impaired, and benzoxazole and coumarin can be used. Benzoxazolyl naphthalene and benzoxazolyl stilbene based fluorescent whitening agents.
なお、 本発明のハロゲン化銀カラ一写真感光材料においては、 本発明の目的 効果である異種観察光源間での観察される白地特性の安定性を高める観点か ら、 上記蛍光增白剤は、 できる限り最小限の使用量とすることが好ましい。 次いで、 本発明のハロゲン化銀カラー写真感光材料について説明する。  In the silver halide color photographic light-sensitive material of the present invention, from the viewpoint of enhancing the stability of white background characteristics observed between different types of observation light sources, which is the object effect of the present invention, the fluorescent whitening agent is It is preferable to use the minimum amount possible. Next, the silver halide color photographic light-sensitive material of the present invention will be described.
本発明の感光材料で用いることのできる支持体としては、 基材の両面に樹脂 被覆層が塗設された紙支持体であることが好ましい。  The support that can be used in the light-sensitive material of the present invention is preferably a paper support in which a resin coating layer is provided on both surfaces of a substrate.
基紙の両面に樹脂被覆層が塗設された紙支持体としては、 基紙の両面をポリ ォレフィ ンでラミネートした紙支持体が好ましく、特に好ましくは、 ポリェチ レンでラミネ一トした紙支持体である。  As the paper support having a resin coating layer coated on both sides of the base paper, a paper support in which both sides of the base paper are laminated with a polyolefin is preferable, and a paper support laminated with polyethylene is particularly preferable. It is.
紙支持体に用いられる基紙は、 木材パルプを主原料とし、 必要に応じて、 木 材パルプに加えてポリプロピレンなどの合成パルプあるいはナイ口ンゃポリェ ステルなどの合成繊維を用いて抄紙される。 木材パルプとしては、 L BKP、 L B S P、 NBKP、 NB S P、 LDP、 NDP、 LUKP、 NUKPのいず れも用いることができるが、 短繊維分の多い L BKP、 NB S P、 L B S P、 NDP、 L D Pをより多く用いることが好ましい。 ただし、 L B S Pおよびま たは L DPの比率は 10質量％以上、 Ί 0質量％以下が好ましい。 The base paper used for the paper support is made of wood pulp as the main raw material, and if necessary, is made using synthetic pulp such as polypropylene or synthetic fibers such as Nyopen® polyester in addition to wood pulp. . Wood pulp can be any of L BKP, LBSP, NBKP, NB SP, LDP, NDP, LUKP and NUKP These can also be used, but it is preferable to use more LBKP, NBSP, LBSP, NDP, and LDP, which have a large amount of short fibers. However, the ratio of LBSP and / or LDP is preferably 10% by mass or more and 0% by mass or less.
上記パルプには、 不純物の少ない化学パルプ （硫酸塩パルプや亜硫酸塩パル プ） が好ましく用いられ、 また、 漂白処理を行って白色度を向上させたパルプ も有用である。 基紙中には、 高級脂肪酸、 アルキルケテンダイマー等のサイズ 剤、 炭酸カルシウム、 タルク、 酸化チタンなどの白色顔料、 スターチ、 ポリア クリルアミ ド、 ポリビニルアルコール等の紙力増強剤、 ポリエチレングリコ一 ル類等の水分保持剤、 分散剤、 四級アンモニゥム等の柔軟化剤などを適宜添加 することができる。 また、 本発明に係る前述の蛍光増白剤も用いることができ る  As the pulp, a chemical pulp (sulfate pulp or sulfite pulp) having a small amount of impurities is preferably used, and pulp having improved whiteness by a bleaching treatment is also useful. Base paper contains sizing agents such as higher fatty acids and alkyl ketene dimers, white pigments such as calcium carbonate, talc and titanium oxide, paper strength agents such as starch, polyacrylamide, and polyvinyl alcohol, polyethylene glycols, etc. A water retention agent, a dispersant, and a softening agent such as quaternary ammonium can be added as appropriate. Further, the above-described fluorescent whitening agent according to the present invention can also be used.
抄紙に使用するパルプの濾水度は、 C S Fの規定で 200〜500 m 1が好 ましく、 また、 叩解後の繊維長が J I S—P— 8207に規定される 24メッ シュ残分の質量％と 42メッシュ残分の質量％との和が 30〜70%が好まし い。なお、 4メッシュ残分の質量％は、 20質量％以下であることが好ましい。 基紙の坪量は、 30〜250 gZm2が好ましく、 特に 50〜200 g/m2が 好ましい。 基紙の厚さは 40〜 250 mが好ましい。 基紙は、 抄紙段階また は抄紙後にカレンダ一処理して、 高平滑性を与えることもできる。 基紙密度は 0. 7〜1. 2 gZc m3 ( J I S— P— 8 1 18 )が一般的である。 更に、 基 紙剛度は J I S -P-8 143に規定される条件で 20〜200 gが好まし い。 基紙表面には表面サイズ剤を塗布しても良く、 表面サイズ剤としては前記 基紙中添加できるサイズと同様のサイズ剤を使用できる。 基紙の p Hは、 J I S -P-81 13で規定された熱水抽出法により測定された場合、 5〜9であ ることが好ましい。 The freeness of pulp used for papermaking is preferably 200 to 500 m1 according to the CSF standard, and the fiber length after beating is 24 mass% by mass of the residual mesh specified in JIS-P-8207. It is preferable that the sum of the mass% and the residual amount of the 42 mesh is 30 to 70%. In addition, the mass% of the 4-mesh residue is preferably 20% by mass or less. The basis weight of the base paper is preferably 30 to 250 gZm 2 , particularly preferably 50 to 200 g / m 2 . The thickness of the base paper is preferably 40 to 250 m. The base paper can be calendered at the papermaking stage or after papermaking to provide high smoothness. Base paper density 0. 7~1. 2 gZc m 3 ( JIS- P- 8 1 18) are common. Further, the base paper stiffness is preferably 20 to 200 g under the conditions specified in JIS-P-8143. A surface sizing agent may be applied to the surface of the base paper. As the surface sizing agent, the same sizing agent as that which can be added to the base paper can be used. The pH of the base paper is 5 to 9 when measured by the hot water extraction method specified in JIS-P-8113. Preferably.
基紙表面および裏面を被覆するポリエチレンは、 主として低密度のポリェチ レン（ LDP E )および/または高密度のポリエチレン（HDP E )であるが、 他に L L D P E (リニァローデンシティ一ポリエチレン） ゃポリプロピレン等 も一部使用することができる。 特に、 感光性層側のポリエチレン層は、 写真用 印画紙で広く行われているように、 ルチルまたはアナタ一ゼ型の酸化チタンを ポリエチレン中に添加し、 不透明度および白色度を改良したものが好ましい。 酸化チタン含有量は、 ポリエチレンに対して通常 3〜 20質量％、 好ましくは 4〜13質量％である。  The polyethylene that covers the front and back of the base paper is mainly low-density polyethylene (LDPE) and / or high-density polyethylene (HDPE), but also LLDPE (linear low density polyethylene) 一 polypropylene, etc. Can also be used partially. In particular, as the polyethylene layer on the photosensitive layer side, as is widely used in photographic paper, rutile or anatase type titanium oxide is added to polyethylene to improve opacity and whiteness. preferable. The content of titanium oxide is usually from 3 to 20% by mass, preferably from 4 to 13% by mass, based on polyethylene.
ポリエチレン被覆紙は、 光沢紙として用いることも、 また、 ポリエチレンを 基紙表面上に溶融押し出してコ一ティングする際に、 いわゆる型付け処理を行 つて、 通常の写真印画紙で得られるようなマツ ト面ゃ絹目面を形成した物も本 発明で使用できる。  Polyethylene-coated paper can be used as glossy paper, or when polyethylene is melted and extruded onto the surface of a base paper and coated, so-called typed processing is performed to obtain matte that can be obtained with ordinary photographic printing paper. Those having a surface-to-silk surface can also be used in the present invention.
基紙の表裏のポリエチレンの使用量は、 通常、 感光性層を設ける側のポリェ チレン層が 20〜40〃 m、 バック層側が 10〜30 mの範囲である。 更に、 上記ポリエチレンで被覆紙支持体は、 以下の特性を有していることが 好ましい。  The amount of polyethylene used on the front and back of the base paper is usually 20 to 40 m on the side where the photosensitive layer is provided and 10 to 30 m on the back side. Further, the polyethylene-coated paper support preferably has the following properties.
1. 引っ張り強さ ： J I S— P— 81 13で規定される強度で、 縦方向が 2 0〜30 ON、 横方向が 10〜20 ONであることが好ましい  1. Tensile strength: The strength specified in JIS-P-8113, preferably 20-30 ON in the vertical direction and 10-20 ON in the horizontal direction.
2.引き裂き強度： J I S—P— 8 1 16に規定される方法で、縦方向が 0. 1〜20N、 横方向が 2〜 2 ONが好ましい  2.Tear strength: According to the method specified in JIS-P-816, preferably 0.1 to 20 N in the vertical direction and 2 to 2 ON in the horizontal direction
3. 圧縮弾性率≥ 98. IMP a  3. Compression modulus ≥ 98. IMP a
4. 表面ベック平滑度： J I S— P— 81 19に規定される条件で、 20秒 以上が光沢面としては好ましいが、 いわゆる型付け品ではこれ以下であっても 良い 4. Surface Beck smoothness: 20 seconds under the conditions specified in JIS-P-8119 The above is preferable for the glossy surface, but may be less for so-called molded products.
5.表面粗さ ： J I S— B— 060 1に規定される表面粗さが、基準長さ 2. 5 mm当たり、 最大高さは 10〃 m以下であることが好ましい  5.Surface roughness: The surface roughness specified in JIS-B-0601 is preferably less than 10〃m per 2.5mm of reference length.
6. 不透明度： J I S—P— 8138に規定された方法で測定したとき、 8 0%以上、 特に 85〜 98 %が好ましい  6. Opacity: 80% or more, preferably 85-98%, as measured by the method specified in JIS-P-8138
7. 白さ ： J I S— Z— 8729で規定される L*、 a *ヽ b *が、 L*= 80 〜95、 a* =— 3〜十 5、 b* =— 6〜+ 2であることが好ましい  7. Whiteness: L *, a * ヽ b * specified by JIS-Z-8729 are L * = 80-95, a * = 3- 3-5, b * =-6- + 2 Preferably
8. 表面光沢度： J I S _ Z— 8741に規定される 60度鏡面光沢度が、 10〜95 %であることが好ましい  8. Surface glossiness: The 60-degree specular glossiness specified in JIS_Z—8741 is preferably 10 to 95%.
9. クラーク剛直度：記録媒体の搬送方向のクラーク剛直度が 50〜300 c mVl 00である支持体が好ましい  9. Clark stiffness: A support having a Clark stiffness of 50 to 300 cmVl00 in the recording medium conveyance direction is preferable.
10. 中紙の含水率： 中紙に対して、 通常 2〜100質量％、 好ましくは 2 〜6質量％  10. Moisture content of middle paper: usually 2 to 100% by mass, preferably 2 to 6% by mass based on the middle paper
本発明のハロゲン化銀カラー写真感光材料においては、 感光性乳剤層中には ハ口ゲン化銀乳剤が含有される。  In the silver halide color photographic light-sensitive material of the present invention, the photosensitive emulsion layer contains a silver halide emulsion.
本発明で用いるハロゲン化銀乳剤としては、 塩化銀含有率が少なくとも 9〇 モル％以上である高塩化銀乳剤が好ましい。 残りは実質的に沃化銀を含まない 臭化銀からなることが好ましい。 臭化銀含有率は 0. 03〜3モル％であるこ とがより好ましく、 特に好ましくは 0. 05〜2モル％である。  The silver halide emulsion used in the present invention is preferably a high silver chloride emulsion having a silver chloride content of at least 9 mol% or more. The balance is preferably made of silver bromide containing substantially no silver iodide. The silver bromide content is more preferably from 0.03 to 3 mol%, particularly preferably from 0.05 to 2 mol%.
ハロゲン化銀粒子の形状は任意のものを用いることができる。（ 100 )面を 結晶表面として有する立方体の他に、 米国特許 4， 183, 756号、 同 4， 225, 666号、特開昭 55— 26589号、特公昭 55— 42737号や、 ザ ' ジャーナル 'ォブ .フォ トグラフィ ック ·サイエンス ( J . P h 0 t o g r . S c i . ) 21巻， 39頁（ 1973年）等の文献に記載された方法等によ り、 八面体、 十四面体、 十二面体等の形状を有する粒子を造り、 これを用いる こともできる。 更に、 双晶面を有する粒子、 平板状ハロゲン化銀粒子を用いて もよいが、 本発明においては、 生産性、 製造安定性に優れる （ 100 ) 面を結 晶表面として有する立方体ハロゲン化銀粒子であることが好ましい。 Any shape can be used for the silver halide grains. In addition to cubes having a (100) plane as a crystal surface, U.S. Pat. Nos. 4,183,756 and 4,225,666, JP-A-55-26589, JP-B-55-42737, The 'Journal' of Photographic Science (J.Ph0 togr.Sci.), Vol. 21, p. 39 (1973), etc. Particles having a shape such as a dodecahedron or a dodecahedron can be produced and used. Further, grains having twin planes and tabular silver halide grains may be used. In the present invention, cubic silver halide grains having a (100) plane as a crystal surface, which is excellent in productivity and production stability, may be used. It is preferable that
ハロゲン化銀粒子は、 単一の形状からなる粒子が好ましく用いられるが、 単 分散のハ口ゲン化銀乳剤を 2種以上同一層に添加することもできる。  As the silver halide grains, grains having a single shape are preferably used, but two or more monodisperse silver halide emulsions can be added to the same layer.
ハロゲン化銀粒子の粒径は特に制限はないが、 迅速処理性及び感度等、 他の 写真性能などを考慮すると、 好ましくは 0. 1〜5. O jwm、 更に好ましくは 0. 2〜3. 0〃 m、 特に立方体を用いる場合には、 好ましくは 0. 1〜1. 2〃m、 更に好ましくは 0. 2〜1. 0〃 mの範囲であるが、 本発明において は、 青感光性層に用いるハロゲン化銀乳剤の平均粒径が、 0. 7 m以下であ ることが 1つの特徴であるが、 より好ましくは 0. 35〜0. 65〃mであり、 更に好ましくは 0. 35〜0. 60〃mである。 青感光性層に用いるハロゲン 化銀乳剤の平均粒径を、 本発明で規定する条件とすることにより、 本発明の目 的効果、 特に白地性の向上あるいは白地のバラツキを低減することができ好ま しい。  The grain size of the silver halide grains is not particularly limited, but is preferably 0.1 to 5.O jwm, more preferably 0.2 to 3.3 in consideration of other photographic properties such as rapid processing property and sensitivity. 0〃m, especially when using a cube, preferably in the range of 0.1 to 1.2〃m, more preferably in the range of 0.2 to 1.0〃m. One feature is that the average grain size of the silver halide emulsion used for the layer is 0.7 m or less, more preferably 0.35 to 0.65 μm, and still more preferably 0.3 to 0.6 μm. 35 to 0.60 m. By setting the average particle size of the silver halide emulsion used in the blue-sensitive layer under the conditions specified in the present invention, it is possible to improve the object effect of the present invention, particularly, to improve the white background property or to reduce the variation in the white background. New
この粒径は、 粒子の投影面積か直径近似値を使ってこれを測定することがで きる。 粒子が実質的に均一形状である場合は、 粒径分布は直径か投影面積とし て可成り正確にこれを表すことができる。  This particle size can be measured using the projected area of the particle or its approximate diameter. If the particles are substantially uniform in shape, the particle size distribution can represent this quite accurately as diameter or projected area.
ハロゲン化銀粒子の粒径の分布は、 好ましくは変動係数が 0. 05〜0. 2 2、 更に好ましくは 0. 05〜0. 15の単分散ハ口ゲン化銀粒子であり、 特 に好ましくは 0 . 0 5〜0 . 1 5の単分散乳剤を 2種以上同一層に添加するこ とである。 ここで変動係数は、 粒径分布の広さを表す係数であり、 次式によつ 変動係数 = S / R ( Sは粒径分布の標準偏差、 Rは平均粒径を表す。） 5 ここでいう粒径とは、 球状のハロゲン化銀粒子の場合は、 その直径、 また、 立方体や球状以外の形状の粒子の場合は、 その投影像を同面積の円像に換算し た時の直径を表す。 The particle size distribution of the silver halide grains is preferably monodisperse silver halide grains having a coefficient of variation of 0.05 to 0.22, more preferably 0.05 to 0.15. More preferably, two or more monodispersed emulsions of 0.05 to 0.15 are added to the same layer. Here, the coefficient of variation is a coefficient representing the breadth of the particle size distribution, and is represented by the following equation: coefficient of variation = S / R (where S is the standard deviation of the particle size distribution, and R is the average particle size). In the case of spherical silver halide grains, the diameter is defined as the diameter, and in the case of cubic or non-spherical shaped grains, the projected image is converted to a circular image of the same area. Represents
ハロゲン化銀乳剤の調製装置、 方法としては、 当業界において公知の種々の 方法を用いることができる。  Various methods known in the art can be used as a device and method for preparing a silver halide emulsion.
10 ハロゲン化銀乳剤は、 酸性法、 中性法、 アンモニア法の何れで得られたもの であってもよい。 該粒子は一時に成長させたものであってもよいし、 種粒子を 造った後で成長させてもよい。 種粒子を造る方法と成長させる方法は、 同じで あっても異なってもよい。 The silver halide emulsion may be obtained by any of the acidic method, the neutral method, and the ammonia method. The particles may be grown at one time or may be grown after seed particles have been produced. The method of producing the seed particles and the method of growing them may be the same or different.
また、 可溶性銀塩と可溶性ハロゲン化物を反応させる形式としては、 順混合 法、 逆混合法、 同時混合法、 それらの組合せなど何れでもよいが、 同時混合法 で得られたものが好ましい。 更に同時混合法の一形式として、 特開昭 5 4— 4 8 5 2 1号等に記載されている p A gコントロールド ·ダブルジヱッ ト法を用 いることもできる。  The form in which the soluble silver salt is reacted with the soluble halide may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like, but a method obtained by the simultaneous mixing method is preferable. Further, as one form of the double jet method, a pAg controlled double jet method described in JP-A-54-48521 can be used.
また、 特開昭 5 7— 9 2 5 2 3号、 同 5 7— 9 2 5 2 4号等に記載の反応母 20液中に配置された添加装置から水溶性銀塩及び水溶性ハロゲン化物水溶液を供 給する装置、 独国公開特許 2 , 9 2 1， 1 6 4号等に記載された水溶性銀塩及 び水溶性ハロゲン化物水溶液を連続的に濃度変化して添加する装置、 特表昭 5 6 - 5 0 1 7 7 6号等に記載の反応器外に反応母液を取り出し、 限外濾過法で 濃縮することによりハロゲン化銀粒子間の距離を一定に保ちながら粒子形成を 行う装置などを用いてもよい。 更に、 必要で有ればチォエーテル等のハロゲン 化銀溶剤を用いてもよい。 In addition, water-soluble silver salts and water-soluble halides were added from an addition device disposed in the reaction mother liquid described in JP-A-57-92523 and JP-A-57-92525. A device for supplying an aqueous solution, a device for continuously changing the concentration of an aqueous solution of a water-soluble silver salt and a water-soluble halide described in German Patent No. 2,921,164, etc. The reaction mother liquor was taken out of the reactor described in Table 5, No. 56-501, 776, etc. An apparatus for forming grains while keeping the distance between silver halide grains constant by concentration may be used. Further, if necessary, a silver halide solvent such as thioether may be used.
本発明のハロゲン化銀粒子は、 その粒子形成もしくは物理熟成の過程におい て種々の多価金属イオンを単独もしくは併用して含有させることができる。 例 えば力 ドミゥム、 亜鉛、 銅、 タリウム、 ガリウムなどの塩、 あるいは鉄、 ルテ 二ゥム、 ロジウム、 パラジウム、 オスミウム、 イ リジウム、 白金などの第 VI II 族遷移金属イオンの塩もしくは錯塩を挙げることができる。  The silver halide grains of the present invention can contain various polyvalent metal ions alone or in combination during the grain formation or physical ripening. For example, salts such as potassium, zinc, copper, thallium, and gallium, or salts or complex salts of Group VIII transition metal ions such as iron, ruthenium, rhodium, palladium, osmium, iridium, and platinum. Can be.
本発明のハロゲン化銀粒子は、 化学增感をすることが好ましい。 化学增感法 としては金化合物による金増感法（例えば、米国特許第 2, 4 8, 060号、 同 3, 320, 069号） またはイ リジウム、 白金、 パラジウム等の金属によ る増感法 （例えば、 米国特許第 2， 448, 060号、 同 2， 566, 245 号、 同 2， 566, 263号） あるいは含硫黄化合物を用いる硫黄增感法 （例 えば、 米国特許第 2， 222， 264号）、 あるいはこれらの 2つ以上を組合せ て用いることができる。  The silver halide grains of the present invention preferably have a chemical sensation. Chemical sensitization methods include gold sensitization with gold compounds (for example, U.S. Pat. Nos. 2,48,060 and 3,320,069) or sensitization with metals such as iridium, platinum, and palladium. (For example, US Pat. Nos. 2,448,060, 2,566,245, and 2,566,263) or a sulfur sensitization method using a sulfur-containing compound (for example, US Pat. , No. 264), or a combination of two or more of these.
本発明において、 ハロゲン化銀乳剤は目的とする分光感度に対応する波長域 の光を吸収する色素 （分光増感色素） を添加して、 所望の波長領域に光学的に 分光増感できる。 この時用いられる分光増感色素としては、 例えば、 F. M. H a m e r ti e t e r o c y c l — i c c o mp o u n d s— C y a n i n e d y e s a n d r e l a t e d c o mp o u n d s ( J o h n W i l e y a n d S o n s ; N e w Y o r k, 1964年） に記載され ている化合物を挙げることができる。 本発明に用いられる分光増感色素として はシァニン色素、メロシアニン色素、複合メロシアニン色素等がある。 この他、 複合シァニン色素、 ホロポーラーシァニン色素、 へミシァニン色素、 スチリル 色素及びへミオキソノール色素がある。 シァニン色素としてはシンプルシァニ ン色素、 カルボシァニン色素、 ジカルボシァニン色素が好ましく用いられる。 本発明のハ口ゲン化銀力ラー写真感光材料においては、 上記説明した以外の 構成要素、 例えば、 その他のハロゲン化銀写真乳剤、 乳剤添加剤、 増感方法、 カプリ防止剤、 安定剤、 ィラジェーシヨン防止染料、 イエロ一カプラー、 マゼ ンタカプラー、 シアンカプラー、 分光増感色素、 乳化分散法、 界面活性剤、 色 濁りを防止剤、 バインダ一、 硬膜剤、 滑り剤やマツ ト剤、 塗布方法、 発色現像 主薬、 処理方法、 現像処理装置、 処理剤などは、 特開平 1 1一 347615号 公報明細書 9頁左 22行目の段落番号 0044〜14頁左 1 7行目の段落番号 0 106に記載の各化合物及び方法を用いることができる。 また、 リサーチ - ディスク口ジャー N o. 17643, 同 N o. 18716及び同 N o. 308 1 19 (それぞれ、 以下 RD 17643、 RD 18716及び RD 308 1 1 9と略す） に記載されている各構成要素を適宜選択して用いることもできる。 次いで、 本発明のハロゲン化銀カラー写真感光材料を用いたデジタル露光方 法について説明する。 In the present invention, a silver halide emulsion can be optically spectrally sensitized to a desired wavelength region by adding a dye (spectral sensitizing dye) that absorbs light in a wavelength region corresponding to a target spectral sensitivity. As the spectral sensitizing dye used at this time, for example, a compound described in FM Hamerti eterocycl—iccompounds—Cyaninedyesandrelatedcompounds (John Wileyand Sons; New York, 1964) Can be mentioned. Examples of the spectral sensitizing dye used in the present invention include a cyanine dye, a merocyanine dye, and a complex merocyanine dye. In addition, There are complex cyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. As the cyanine dye, simple cyanine dye, carbocyanine dye, and dicarbocyanine dye are preferably used. In the silver halide photographic light-sensitive material of the present invention, components other than those described above, for example, other silver halide photographic emulsions, emulsion additives, sensitization methods, anti-capri agents, stabilizers, and erasures Inhibiting dyes, yellow couplers, magenta couplers, cyan couplers, spectral sensitizing dyes, emulsifying dispersion methods, surfactants, color turbidity inhibitors, binders, hardeners, slip agents and matting agents, coating methods, coloring The developing agent, the processing method, the development processing device, the processing agent, etc. are described in JP-A-11-347615, paragraph 9 on page 9, left side, line 22, paragraph 0044 to page 14 left, line 17, paragraph number 0106. Can be used. In addition, each configuration described in Research-Disc Jar No. 17643, No. 18716 and No. 308 119 (hereinafter abbreviated as RD 17643, RD 18716 and RD 308 119), respectively. Elements can be appropriately selected and used. Next, a digital exposure method using the silver halide color photographic light-sensitive material of the present invention will be described.
本発明のハロゲン化銀カラ一写真感光材料を用いて、 写真画像を形成する又 は本発明のカラープリントを用いてコピー画像を形成するには、 ネガ上に記録 された画像を、 プリントしょうとするハロゲン化銀カラー写真感光材料上に光 学的に結像させて焼き付けてもよいし、 画像を一旦デジタル情報に変換した後 その画像を CRT (陰極線管） 上に結像させ、 この像をプリ ントしょうとする ハロゲン化銀カラ一写真感光材料上に結像させて焼き付けてもよいし、 デジタ ル情報に基づいてレーザ一光の強度を変化させて走査することによって焼き付 けてもよいが、 デジタル露光機で、 デジタル情報に基づき、 露光することが好 ましい。 To form a photographic image using the silver halide color photographic light-sensitive material of the present invention or to form a copy image using the color print of the present invention, the image recorded on the negative must be printed. The image may be formed optically on a silver halide color photographic light-sensitive material and printed. Alternatively, the image is once converted into digital information, and then the image is formed on a CRT (cathode ray tube). The image may be printed on a silver halide color photographic material to be printed and printed, or printed by changing the intensity of the laser beam based on digital information and scanning. However, it is preferable to use a digital exposure machine to perform exposure based on digital information.
レーザー光を用いて露光する場合には、 一画素あたりの露光時間は、 特に制 限はないが、 100ナノ秒〜 100マイクロ秒で露光されることが多い。 一画 素あたりの露光時間とは、 光束の強度の、 空間的な変化において、 光強度が最 大値の 1/2になるところをもつて光束の外縁とし、 走査線と平行でありかつ 光強度が最大となる点を通る線と光束の外縁の交わる 2点間の距離を光束の径 とした時、（光束の径） /(走査速度）をもって一画素あたりの露光時間とする。 こうしたシステムに適用可能と考えられるレーザープリ ンタ一装置として は、 例えば、 特開昭 55— 4071号、 同 59— 1 1062号、 同 63— 19 7947号、 同 2— 74942号、 同 2— 236538号、 特公昭 56— 14 963号、 特公昭 56— 40822号欧州広域特許 77410号、 電子通信学 科合技術研究報告 80巻 244号、 及び映画テレビ技術誌 1984Z6 ( 38 2 )、 34〜36ページなどに記載されているものがある。  When performing exposure using laser light, the exposure time per pixel is not particularly limited, but is often in the range of 100 nanoseconds to 100 microseconds. The exposure time per pixel is defined as the outer edge of the light beam where the light intensity becomes half of the maximum value in the spatial change of the light beam intensity. When the distance between two points where the line passing through the point where the intensity is maximum and the outer edge of the light beam intersect is defined as the light beam diameter, (light beam diameter) / (scanning speed) is defined as the exposure time per pixel. Examples of a laser printer device that can be applied to such a system include, for example, JP-A-55-4071, JP-A-59-11062, JP-A-63-197794, JP-A-74942, and JP-A-2-236538. No. 56-14963, Japanese Patent Publication No. 56-40822, European wide-area patent 77410, Department of Electronics and Communication Technology Technical Report 80, No. 244, and Cinema Television Engineering 1984Z6 (382), pp. 34-36 There are those described in such as.
本癸明のハロゲン化銀カラ一写真感光材料を露光するための光源としては、 X eフラッシュライ トの他に、発光ダイ才ード、ガスレーザ一、 固体レーザー、 半導体レーザ一、 H e N eレーザー、 A r レーザ一、 色素レーザ一等が挙げら れる。 更に縦シングル、 横マルチいずれのモードでも使用可能であり、 高周波 重畳による電気的変調及び S HG (第 2次高調波素子） により変調した光源を 使用してもよい。 特にコンパク トで安価、 更に寿命が長く安定性が高い装置を 設計するためには半導体レーザーの使用が好ましく、 露光光源の少なくとも一 つは半導体レーザ一を使用することが好ましい。  As a light source for exposing the silver halide photographic light-sensitive material of the present invention, in addition to the Xe flash light, a light emitting diode, a gas laser, a solid-state laser, a semiconductor laser, a HeNe Laser, Ar laser, dye laser and the like. Furthermore, it can be used in either vertical single mode or horizontal multi mode, and it is possible to use a light source modulated by electric modulation by superposition of high frequency and SHG (second harmonic element). In particular, a semiconductor laser is preferably used to design a compact, inexpensive device having a long life and high stability, and it is preferable to use a semiconductor laser as at least one of the exposure light sources.
このような走査露光における露光時間は、 画素密度 400 d p iとした場合 の画素サイズを露光する時間として定義すると、 好ましい露光時間としては 1 0一3秒以下、 より好ましくは 10—6秒以下である。 なお、 本発明でいう d p i とは、 2. 54 c m当たりのドッ ト数を表す。 The exposure time for such scanning exposure is assuming a pixel density of 400 dpi. Defined as the time necessary to expose the pixel size, the preferred exposure time 1 0 one 3 seconds or less, and more preferably not more than 10 6 seconds. In the present invention, dpi refers to the number of dots per 2.54 cm.
また、 本発明のハロゲン化銀カラ一写真感光材料においては、 高照度露光時 の濃度バラツキ、 濃度ムラを低減する観点から、 23で、 20%RHにおける カール度が、 + 15以下であることが好ましく、 より好ましくは 0〜十 15で める。  Further, in the silver halide color photographic light-sensitive material of the present invention, from the viewpoint of reducing the density variation and the density unevenness at the time of high illuminance exposure, the curl degree at 23 and 20% RH may be +15 or less. Preferably, it is more preferably 0 to 10.
次に、 実施例を挙げて本発明を具体的に説明するが、 本発明の実施態様はこ れらに限定されるものではない。  Next, the present invention will be described specifically with reference to examples, but embodiments of the present invention are not limited thereto.
実施例 1  Example 1
《ハロゲン化銀乳剤の調製》  << Preparation of silver halide emulsion >>
以下の方法により、 各ハロゲン化銀乳剤を調製した。  Each silver halide emulsion was prepared by the following method.
(赤感光性ハ口ゲン化銀乳剤の調製）  (Preparation of red-sensitive silver halide emulsion)
40°Cに保温した 2 %ゼラチン水溶液 1 リ ッ トル中に、下記（ A液）及び（ B 液）を、 p A gを 7. 3、 p Hを 3. 0に制御しつつ 30分かけて同時添加し、 更に、 下記 （ C液） 及び （ D液） を p A gを 8. 0、 pHを 5. 5に制御しつ つ 180分かけて同時添加した。 この時、 p A gの制御は、 特開昭 59— 45 437号記載の方法により行い、 p Hの制御は硫酸又は水酸化ナトリゥム水溶 液を用いて行つた。  In one liter of a 2% aqueous gelatin solution kept at 40 ° C, apply the following (Solution A) and (Solution B) for 30 minutes while controlling pAg to 7.3 and pH to 3.0. Then, the following (Solution C) and (Solution D) were simultaneously added over 180 minutes while controlling the pAg to 8.0 and the pH to 5.5. At this time, the pAg was controlled by the method described in JP-A-59-45437, and the pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.
( A液）  (A liquid)
塩化ナト リウム 3. 42 g 臭化カ リウム 0. 03 g 水を加えて 200m l ( B液） Sodium chloride 3.42 g potassium bromide 0.03 g 200 ml with water (Solution B)
硝酸銀 10 g 水を加えて 200m l Silver nitrate 10 g Add water 200ml
( C液） (C solution)
塩化ナト リウム 102. 7 g K2 I r C 16 4 X 10一9モル/モル A g K4F e ( CN ) 2 X 10— 6モル/モル A g 臭化力 リウム 1. 0 g 水を加えて 600m lSodium 102. 7 g K 2 I r C 16 4 X 10 one 9 mol / mol A g K 4 F e (CN ) 2 X 10- 6 mol / mol A g bromide force tumefaciens 1. 0 g Water chloride In addition 600ml
( D液） (D solution)
硝酸銀 300 g 水を加えて 600m l 上記各液の添加が終了した後、 花王ァトラス社製のデモール Nの 5 %水溶液 と硫酸マグネシウムの 20 %水溶液を用いて脱塩を行った後、 ゼラチン水溶液 と混合して、 平均粒径 0. 40 ^πι、 粒径分布の変動係数 0. 07、 塩化銀含 有率 99. 5モル％の単分散立方体乳剤である乳剤 ΕΜΡ— 1を得た。  After adding 300 g of silver nitrate water and adding 600 ml of the above solutions, desalting was performed using a 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate manufactured by Kao Atlas Co., Ltd. The mixture was mixed to obtain Emulsion II-1, which is a monodisperse cubic emulsion having an average particle size of 0.40 ^ πι, a coefficient of variation of the particle size distribution of 0.07, and a silver chloride content of 99.5 mol%.
次いで、 上記（Α液） と （ Β液） の添加時間及び（ C液） と （D液） の添加 時間を変更した以外は、 上記乳剤 ΕΜΡ_ 1と同様にして、 平均粒径 0. 38 m、 粒径分布の変動係数 0. 07、 塩化銀含有率 99. 5モル％の単分散立 方体乳剤である乳剤 E M P— 1 Bを得た。  Next, the average particle size was 0.38 m in the same manner as in the emulsion ΕΜΡ_1 except that the addition time of the above (Liquid) and (Liquid) and the addition time of (Liquid C) and (Dluid) were changed. Emulsion EMP-1B was obtained as a monodisperse cubic emulsion having a coefficient of variation of particle size distribution of 0.07 and a silver chloride content of 99.5 mol%.
上記乳剤 EMP— 1に対し、 下記化合物を用いて 60°Cにて最適に化学増感 を行った。 また、 乳剤 EMP— 1 Bに対しても同様に最適に化学増感した後、 増感された乳剤 EMP— 1と乳剤 EMP— 1 Bを銀量比で 1 ： 1の割合で混合 して、 赤感性ハロゲン化銀乳剤 （ Em— R ) を得た。 The above emulsion EMP-1 was optimally chemically sensitized at 60 ° C using the following compounds. Similarly, after optimal chemical sensitization of emulsion EMP-1B, sensitized emulsion EMP-1 and emulsion EMP-1B were mixed at a silver ratio of 1: 1. Thus, a red-sensitive silver halide emulsion (Em-R) was obtained.
チォ硫酸ナト リウム 1 X 1 0— 4モル/モル A 塩化金酸 1. 2 X 1 0— 4モル/モル A g X 安定剤： S T A B - 1 3 X 1 cr4モル/モル A g X 安定剤： S T A B - 2 3 X 1 0一4モル/モル A g X 安定剤： S T A B - 3 3 X 1 0— 4モル/モル A g 增感色素： R S - 1 1 X 1 0— 4モル/モル A g X 増感色素： R S— 2 1 X 1 0— 4モル/モル A g X S TAB— 1 ： 1一 ( 3 アセ トアミ ドフヱニル） 一 5 _メルカプトテトラ ゾール Chio isocyanatomethyl sulfate potassium 1 X 1 0- 4 mol / mol A chloroauric acid 1. 2 X 1 0- 4 mol / mol A g X Stabilizer: STAB - 1 3 X 1 cr 4 mol / mol A g X stabilizer : STAB - 2 3 X 1 0 one 4 mol / mol A g X stabilizer: STAB - 3 3 X 1 0- 4 mol / mol A g增感dye: RS - 1 1 X 1 0- 4 mol / mol A g X sensitizing dye: RS- 2 1 X 1 0- 4 mol / mol A g XS tAB- 1: 1 one (3 acetate Toami Dofuweniru) Single 5 _ mercaptotetrazole
S TAB— 2 ： 1一フエ ル一 5—メルカプトテトラゾール  S TAB—2: 1-Fer-5-Mercaptotetrazole
S TA B— 3 ： 1— ( ェ トキシフヱニル） 一 5—メルカプトテトラゾー ル  S TA B—3: 1— (Ethoxyphenyl) -1-5-mercaptotetrazole
また赤感光性乳剤には、 S S— 1をハロゲン化銀 1モル当り 2. 0 X 10一3 添加した。 Also the red-sensitive emulsion, SS- 1 was per mol of silver halide 2. 0 X 10 one 3 addition.
(緑感光性ハ口ゲン化銀乳剤の調製）  (Preparation of green photosensitive silver halide emulsion)
上記乳剤 EMP— 1の調製において、 （ A液） と （ B液）の添加時間及び（ C 液） と （D液） の添加時間を変更した以外は同様にして、 平均粒径 0. 40 m、 変動係数 0. 08、 塩化銀含有率 99. 5モル％の単分散立方体乳剤であ る乳剤 EMP— 2を得た。次いで、上記乳剤 EMP— 1の調製において、（ A液） と （ B液） の添加時間及び ( C液) と （ D液） の添加時間を変更した以外は同 様にして、 平均粒径 0. 50 m、 変動係数 0. 08、 塩化銀含有率 99. 5 モル％の単分散立方体乳剤である乳剤 EMP— 2 Bを得た。 上記調製した乳剤 EMP— 2に対し、 下記化合物を用い 5 5 °Cにて最適に化 学增感を行った。 また、 乳剤 EMP— 2 Bに対しても同様に最適に化学増感し た後、 増感された乳剤 EMP— 2と乳剤 EMP— 2 Bとを、 銀量比で 1 ： 1の 割合で混合し、 緑感光性ハロゲン化銀乳剤（ E m— G ) を得た。 In the preparation of emulsion EMP-1, the average particle size was 0.40 m in the same manner except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed. Emulsion EMP-2 was obtained as a monodisperse cubic emulsion having a coefficient of variation of 0.08 and a silver chloride content of 99.5 mol%. Next, in the preparation of the emulsion EMP-1, the average particle size was reduced in the same manner except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed. Emulsion EMP-2B was obtained as a monodisperse cubic emulsion having a particle diameter of 50 m, a coefficient of variation of 0.08 and a silver chloride content of 99.5 mol%. The emulsion EMP-2 prepared above was subjected to optimal chemical sensation at 55 ° C using the following compound. Similarly, after optimally chemical sensitizing emulsion EMP-2B, the sensitized emulsion EMP-2 and emulsion EMP-2B were mixed at a silver ratio of 1: 1. Thus, a green light-sensitive silver halide emulsion (Em-G) was obtained.
チォ硫酸ナトリウム 1 X 1 0—4モル/モル A g X 塩化金酸 1 2 X 1 0—4モル/モル A g X 安定剤： S T A B _ 1 2 5 X 1 0—4モル/モル A g X 安定剤： S T A B— 2 3 1 X 1 0一4モル/モル A g X 安定剤： S T A B _ 3 3 1 X 1 0— 4モル/モル A g X 増感色素： G S— 1 X 1 0— 4モル/モル A g XChio sodium sulfate 1 X 1 0- 4 mol / mol A g X chloroauric acid 1 2 X 1 0- 4 mol / mol A g X Stabilizer: STAB _ 1 2 5 X 1 0- 4 mol / mol A g X stabilizer: STAB- 2 3 1 X 1 0 one 4 mol / mol A g X stabilizer: STAB _ 3 3 1 X 1 0- 4 mol / mol A g X sensitizing dyes: GS- 1 X 1 0- 4 Mol / mol A g X
(青感光性ハ口ゲン化銀乳剤の調製） (Preparation of blue-sensitive silver halide silver halide emulsion)
前記乳剤 E PM— 1の調製において、（ A液） と （ B液）の添加時間及び（ C 液） と （D液） の添加時間を変更した以外は同様にして、 平均粒径 0. 7 1 m、 変動係数 0. 0 8、 塩化銀含有率 9 9. 5モル％の単分散立方体乳剤であ る乳剤 EMP— 3を得た。  In the preparation of the emulsion EPM-1, the average particle diameter was 0.7 in the same manner except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed. Emulsion EMP-3 was obtained as a monodisperse cubic emulsion having a length of 1 m, a coefficient of variation of 0.08 and a silver chloride content of 99.5 mol%.
上記 EMP— 3に対し、 下記化合物を用い 6 0 °Cにて最適に化学増感を行つ て、 青感光性ハロゲン化銀乳剤 （ E m— B ) を得た。  The above-mentioned EMP-3 was optimally chemically sensitized at 60 ° C using the following compound to obtain a blue-sensitive silver halide emulsion (Em-B).
チォ硫酸ナト リウム 1 X 1 CI-4モル/モル A g X 塩化金酸 1. 2 X 1 0— 4モル/モル A g X 安定剤： S T A B— 1 2 X 1 0— 4モル/モル A g X 安定剤： S T A B— 2 2. 4- X 1 0— 4モル/モル A g X 安定剤： S T A B— 3 2. 1 X 1 0— 4モル/モル A g X 増感色素： B S— 1 4 X 1 0— 4モル Zモル A g X 増感色素： B S— 2 1 X 1 0— 4モル/モル A g X
Figure imgf000031_0001
Chio sodium sulfate 1 X 1 CI- 4 mol / mol A g X chloroauric acid 1. 2 X 1 0- 4 mol / mol A g X Stabilizer: STAB- 1 2 X 1 0- 4 mol / mol A g X stabilizer: STAB- 2 2. 4- X 1 0- 4 mol / mol A g X stabilizer: STAB- 3 2. 1 X 1 0- 4 mol / mol A g X sensitizing dyes: BS- 1 4 X 1 0- 4 mol Z moles A g X Sensitizing dye: BS- 2 1 X 1 0- 4 mol / mol A g X
Figure imgf000031_0001
Figure imgf000031_0002
Figure imgf000031_0002
GS— 1GS— 1
Figure imgf000031_0003
Figure imgf000031_0003
RS-1 RS-1
Figure imgf000031_0004
Figure imgf000031_0005
Figure imgf000032_0001
Figure imgf000031_0004
Figure imgf000031_0005
Figure imgf000032_0001
《ハ口ゲン化銀力ラ一写真感光材料の作製》 << Production of silver halide photographic light-sensitive material >>
〔試料 10 1の作製〕  [Preparation of Sample 101]
坪量 180 gZm2の紙パルプの両面に高密度ポリエチレンをラミネートし、 紙支持体を作製した。 但し、 乳剤層を塗布する側には、 表面処理を施したアナ ターゼ型酸化チタンを 15質量％の含有量で分散して含む溶融ポリエチレンを ラミネートし、 反射支持体を作製した。 この反射支持体をコロナ放電処理した 後、 ゼラチン下塗層を設け、 さらに以下に示す構成の各層を塗設して、 ハロゲ ン化銀写真感光材料である試料 101を作製した。 硬膜剤としては、 H— 1、High-density polyethylene was laminated on both sides of a paper pulp having a basis weight of 180 gZm 2 to produce a paper support. However, on the side to which the emulsion layer was applied, a reflective support was prepared by laminating a molten polyethylene containing a surface-treated anatase-type titanium oxide dispersed at a content of 15% by mass. After the reflective support was subjected to a corona discharge treatment, a gelatin undercoat layer was provided thereon, and each layer having the following constitution was further provided thereon, to prepare Sample 101 as a silver halide photographic light-sensitive material. As the hardener, H-1,
H— 2、 防腐剤としては、 F— 1を使用した。 H-2 and F-1 were used as preservatives.
[試料 10 1の層構成]  [Layer composition of sample 10 1]
第 7層 （保護層） g/  7th layer (protective layer) g /
ゼラチン 1. 00 Gelatin 1.00
D B P 0. 002D B P 0. 002
D I D P 0. 002 青味剤 （ W B— 1 ) 0. 0002 青味剤 （ W B— 2 ) 0. 002 二酸化珪素 0. 003 第 6層 （紫外線吸収層） ゼラチン 0 40DIDP 0.002 Blue tinting agent (WB-1) 0.0002 Blue tinting agent (WB-2) 0.002 Silicon dioxide 0.003 6th layer (UV absorbing layer) Gelatin 0 40
A I - 1 0 01 紫外線吸収剤（ u V - 1 ) 0 084 紫外線吸収剤（ U V— 2 ) 0 027 紫外線吸収剤（ U V— 3 ) 0 1 1 スティン防止剤（HQ— 5 ) 0 04 P V P 0 0 1 5 第 5層 （赤感光性層） AI-1 0 01 UV absorber (uV-1) 0 084 UV absorber (UV-2) 0 027 UV absorber (UV-3) 0 1 1 Sting inhibitor (HQ-5) 0 04 PVP 0 0 1 5 Fifth layer (Red-sensitive layer)
ゼラチン 30 赤感光性ハ口ゲン化銀乳剤（ E m 0. 21 シアンカプラー ( C一 1 ) 0. 25 シアンカプラー （ C一 2 ) 0. 08 色素画像安定化剤（ S T— 1 ) 0. 10 スティン防止剤（ HQ— 1 ) 0. 004 D B P 0. 10Gelatin 30 Red light sensitive silver halide emulsion (E m 0.21 Cyan coupler (C-1) 0.25 Cyan coupler (C-12) 0.08 Dye image stabilizer (ST-1) 0.10 Sting inhibitor (HQ-1) 0.004 DBP 0.10
D O P 0. 20 第 4層 （紫外線吸収層） D O P 0.20 4th layer (UV absorbing layer)
ゼラチン 0. 94 紫外線吸収剤（ U V - 1 ) 0. 196 紫外線吸収剤（ U V— 2 ) 0. 063 紫外線吸収剤 （ U V - 3 ) 0. 266 A I - 1 0. 02 スティン防止剤（HQ— 5 ) 0. 10 第 3層（緑感光性層） Gelatin 0.94 UV absorber (UV-1) 0.196 UV absorber (UV-2) 0.063 UV absorber (UV-3) 0.266 AI-1 0.02 Sting inhibitor (HQ-5) ) 0. 10 Third layer (green photosensitive layer)
ゼラチン 1 30Gelatin 1 30
A I— 2 0 01 緑感光性ハ口ゲン化銀乳剤（ E m— G ) 0 1 マゼンタカプラー （ M_ 1 ) 0 20 色素画像安定化剤 （ S T— 3 ) 0 20 色素画像安定化剤（ S T— 4 ) 0, 17 D I D P 0, 13 D B P 0, 13 第 2層 （中間層） AI—2001 Green photosensitive silver halide emulsion (Em—G) 0 1 Magenta coupler (M_1) 0 20 Dye image stabilizer (ST-3) 0 20 Dye image stabilizer (ST— 4) 0, 17 DIDP 0, 13 DBP 0, 13 Second layer (middle layer)
ゼラチン 1, 20 A I— 3 0. 0 1 スティ ン防止剤 （HQ— 2 ) 0. 03 スティ ン防止剤 （HQ— 3 ) 0. 03 スティ ン防止剤 （ H Q— 4 ) 0, 05 スティン防止剤 （HQ— 5 ) 0. 23 D I D P 0. 04 D B P 0. 02 蛍光増白剤 （W— 1 ) 0. 075 第 1層 （青感光性層） Gelatin 1, 20 AI—3 0.01 Stain inhibitor (HQ—2) 0.03 Stain inhibitor (HQ—3) 0.03 Stain inhibitor (HQ—4) 0,05 Stain inhibitor (HQ-5) 0.23 DIDP 0.04 DBP 0.02 Optical brightener (W-1) 0.075 First layer (blue-sensitive layer)
ゼラチン 20 青感光性ハ口ゲン化銀乳剤（ E m— B ) 0 26 イエロ一カプラー （ Y— 1 ) 0 70 色素画像安定化剤（ S T - 1 ) 0. 10 色素画像安定化剤（ S T - 2 ) 0. 10 スティン防止剤 （ HQ— 1 ) 0. 01 色素画像安定化剤（ S T— 5 ) 0. 10 画像安定剤 A 0. 15Gelatin 20 Blue light sensitive silver halide emulsion (Em-B) 0 26 Yellow coupler (Y-1) 0 70 Dye image stabilizer (ST-1) 0.10 Dye image stabilizer (ST-2) 0.10 Sting inhibitor (HQ-1) 0.01 Dye image stabilizer (ST-5) 0.10 Image stabilizer A 0.15
DN P 0. 05DN P 0.05
D B P 0. 15 支持体：ポリエチレンラミネート紙（微量の着色剤を含有） D B P 0.15 Support: Polyethylene laminated paper (contains a small amount of colorant)
なお、 上記の各ハロゲン化銀乳剤の添加量は、 銀に換算して表示した。 以下に、 上記試料 1 0 1の作製に用いた各添加剤の詳細を示す。  The amount of each of the above silver halide emulsions was expressed in terms of silver. The details of each additive used for producing the sample 101 are described below.
D B P ジブチルフタレ一ト  D B P Dibutyl phthalate
DN P ジノニルフタレート  DN P dinonyl phthalate
D 0 P ジォクチルフタレート  D 0 P Dioctyl phthalate
D I D P ジー i—デシルフタレート  D I D P G i-decyl phthalate
P V P ポリビニルピロリ ドン  P V P Polyvinylpyrrolidone
H— 1 テトラキス （ビニルスルホニ メタン  H— 1 tetrakis (vinylsulfonimethane
H— 2 2, 4—ジクロロ ー 6—ヒ ドロキシ s—トリアジン - ナトリウ ム  H—2 2,4-dichloro-6—hydroxy s—triazine-sodium
H Q - 1 2, 5—ジ一 tーォクチルハイ ドロキノン  H Q-1, 2, 5-dioctyl high droquinone
H Q - 2 2 , 5—ジ一 s e c—ドデシルノヽィ ドロキノン  H Q-2 2, 5-di sec-dodecylnody droquinone
H Q - 3 2 , 5—ジー s e cーテトラデシノレノヽィ ドロキノン  H Q-3 2, 5—Gee sec-tetradecinolenodidroquinone
H Q - 4 2— s e c―ドデシノレ一 5— s e cーテトラデシノレノヽィ ドロキノ ン HQ- 5 ： 2， 5—ジ〔（ 1, 1一ジメチルー 4一へキシルォキシカルボニル） ブチル〕 ハイ ドロキノン HQ-4 2—sec—Dodecinoleone 5—sec—Tetradecinolenodroquinone HQ-5: 2,5-di [(1,1-dimethyl-41-hexyloxycarbonyl) butyl] hydroquinone
画像安定剤 A ： P— tーォクチルフヱノール
Figure imgf000036_0001
Image stabilizer A: P-t-octylphenol
Figure imgf000036_0001
M-1
Figure imgf000036_0002
M-1
Figure imgf000036_0002
c一 1
Figure imgf000036_0003
c-1
Figure imgf000036_0003
Figure imgf000036_0004
ST— 1
Figure imgf000036_0004
ST— 1
Figure imgf000037_0001
Figure imgf000037_0001
ST— 2 ST— 2
CsHntt)
Figure imgf000037_0002
CsHntt)
Figure imgf000037_0002
ST— 3
Figure imgf000037_0003
ST— 3
Figure imgf000037_0003
ST— 4 ST— 4
Figure imgf000037_0004
Figure imgf000037_0004
ST— 5 ST— 5
Figure imgf000037_0005
Figure imgf000037_0005
Figure imgf000037_0006
UV-2
Figure imgf000038_0001
Figure imgf000037_0006
UV-2
Figure imgf000038_0001
UV-3UV-3
Figure imgf000038_0002
Figure imgf000038_0002
AI-1AI-1
Figure imgf000038_0003
Figure imgf000038_0003
AI-2 AI-2
Figure imgf000038_0004
Figure imgf000038_0005
W-1
Figure imgf000038_0004
Figure imgf000038_0005
W-1
Figure imgf000039_0001
Figure imgf000039_0001
F— 1
Figure imgf000039_0002
F— 1
Figure imgf000039_0002
(50%) (46%) (4%) モル比 (50%) (46%) (4%) molar ratio
WB-1
Figure imgf000039_0003
WB-1
Figure imgf000039_0003
WB-2 WB-2
Figure imgf000039_0004
Figure imgf000039_0004
〔試料 1 0 2〜； L 1 0の作製〕 上記試料 1 0 1の作製において、 下表に示す r a、 となるように、 下記 の各階調修正手段を、 適宜選択あるいは組み合わせて、 試料 1 0 2〜 1 1 0を 作製した。 なお、 下表には、 代表例として第 3層の各特性値を示す。 [Production of Samples 102 to L10] In the preparation of Sample 101, Samples 102 to 110 were prepared by appropriately selecting or combining the following gradation correcting means so that ra shown in the following table was obtained. The following table shows the characteristic values of the third layer as representative examples.
手段 1 ：第 1層、 第 3層及び第 5層で用いたハロゲン化銀乳剤の調製時にお いて、 C液に用いた K2 I r C 1 6及び K4F e ( C N ) 6の使用量を調整した。 手段 2 ：第 1層、 第 3層及び第 5層で用いたハロゲン化銀乳剤の化学増感条 件を調整した。 Means 1: the first layer, and have contact during the preparation of silver halide emulsions used in the third layer and the fifth layer, the use of K 2 I r C 1 6 and K 4 F e (CN) 6 was used in solution C The amount was adjusted. Means 2: The chemical sensitization conditions of the silver halide emulsions used in the first, third and fifth layers were adjusted.
手段 3 ：第 1層、 第 3層及び第 5層のハロゲン化銀乳剤及び各カプラーの添 加量を調整した。 試料番号 r a γ b 備考  Means 3: The amounts of the silver halide emulsions of the first, third and fifth layers and the amount of each coupler were adjusted. Sample number r a γ b Remarks
1 0 1 1， 67 1. 6 4 比較例 1 0 1 1, 67 1.64 Comparison example
1 0 2 1， 86 1. 9 5 比較例  1 0 2 1, 86 1.95 Comparison example
1 03 1， 9 2 2. 5 7 比較例  1 03 1, 9 2 2.5.7 Comparison example
1 04 1. 89 2. 5 0 比較例  1 04 1.89 2.50 Comparative example
1 05 1. 76 3. 7 2 比較例  1 05 1.76 3.7.2 Comparative example
1 0 6 2. 33 1. 8 8 本発明  1 0 6 2.33 1.88 8 The present invention
1 07 2. 49 1. 8 8 本発明  1 07 2.49 1.88 8 The present invention
1 08 3. 78 3. 1 1 本発明  1 08 3.78 3.1 1 The present invention
1 09 2. 38 3. 0 3 本発明  1 09 2.38 3.03 The present invention
1 1 0 2. 40 2. 2 5 本発明 更に、 上記試料 1 0 1の作製において、 下表に示す白色光照明及び単色光照 明における L*、 a *、 b 及び下表に示す W a、 Wb、 W cとなるように、 下 記の各階調修正手段を、 適宜選択あるいは組み合わせて、 試料 1 0 2〜1 1 0 を作製した。 なお、 下表には、 代表例として第 3層の各特性値を示す。 1 1 0 2.40 2.25 The present invention Further, in the preparation of the above sample 101, the following L *, a *, b in white light illumination and monochromatic light illumination shown in the table below and Wa, Wb, Wc shown in the table below were used. Samples 102 to 110 were prepared by appropriately selecting or combining the gradation correcting means. The following table shows the characteristic values of the third layer as representative examples.
5 手段 1 ： L*、 a \ b*、 W a、 W bの調整  5 Measure 1: Adjust L *, a \ b *, Wa, Wb
第 2層で用いた蛍光増白剤（W— 1 )の添加量及び第 7層で用いた青味剤（W B— 1 ) 及び青味剤 （ WB— 2 ) の添加量を適宜調整した。 料 白色光照明 単色光照明  The amount of the optical brightener (W-1) used in the second layer and the amount of the bluing agent (WB-1) and bluing agent (WB-2) used in the seventh layer were appropriately adjusted. Material White light illumination Monochromatic light illumination
10 番号 L a ' b L! a * b 10 number L a 'b L ! A * b
1 0 1 8 8. 8 - 0. 5 - 5. 2 8 8. 6 一 0. 1 - 3. 11 0 1 8 8.8-0.5-5.2 8 8.6 1 0.1-3.1
1 0 2 8 8. 5 0. 3 - 3. 9 8 7. 7 — 0. 3 一 2. 81 0 2 8 8.5 5 0.3-3.98 8 7. 7-0.3 1 2.8
1 03 8 9. 2 0. 3 一 3. 4 8 8. 8 - 0. 3 一 1. 41 03 8 9.2 0.3-1-1.3.4 88.8-0.3-1.1.4
15 1 04 8 8. 5 0. 3 一 3. 9 8 7. 7 一 0. 3 - 2. 815 1 04 8 8.5 5 0.3 1 3. 9 8 7. 7 1 0.3-2.8
1 05 8 8. 5 0. 3 -4. 3 8 7. 8 一 0. 2 一 3. 01 05 8 8. 5 0. 3 -4. 3 8 7. 8 1 0 2 1 3.0
1 06 8 9. 2 0. 5 -4. 4 8 8. 8 一 0. 3 一 1. 21 06 8 9.2 0. 5 -4. 4 8 8. 8 1 0 3 1 1.2
1 07 8 8. 8 0. 3 一 3. 8 8 7. 8 一 0. 3 - 2. 91 07 8 8.8 0 0.3 1 3.8 8 7.8 1 0.3-2.9
1 08 8 8. 5 0. 3 一 4. 3 8 7. 8 — 0. 2 - 3. 01 08 8 8.5 5 0.3 1 4. 3 8 7. 8 — 0.2-3.0
20 1 09 8 9. 2 0. 5 一 4. 4 8 8. 8 一 0. 3 一 1. 220 1 09 8 9.2 0 .5 1 4.4 8 8.8 1 0 .3 1 1.2
1 1 0 8 8. 7 0. 9 - 3. 8 8 8. 6 一 0. 2 一 2. 6 試料番号 W a W b W c 備考 1 1 0 8 8. 7 0.9-3.88 8 8.6 1 0.2 1 2.6 Sample number W a W b W c Remarks
101 97. 0 86. 7 1 0. 3 比較例 101 97. 0 86. 7 1 0.3 Comparative example
102 90. 3 83. 4 6. 9 比較例  102 90.3 83.46.9 Comparative example
103 89. 5 79. 0 1 0. 5 比較例  103 89. 5 79. 0 1 0.5 Comparative example
104 90. 3 83. 4 6. 9 比較例  104 90.3 83.46.9 Comparative example
105 92. 3 84. 5 7. 8 比較例  105 92.3 84.5 7.8 Comparative example
106 94. 4 78. 3 1 6. 1 本発明  106 94.4 78.3 16.1 The present invention
107 90. 2 84. 1 6. 1 本発明  107 90.2 84.16.1 The present invention
108 92. 3 84. 5 7. 8 本発明  108 92.3 84.57.8 The present invention
109 94. 4 78. 3 1 6. 1 本発明  109 94.4 78.3 16.1 The present invention
1 10 90. 4 84. 5 5. 9 本発明 なお、 上表に記載の各特性値は、 以下のようにして測定した。  1 10 90. 4 84. 5 5.9 The present invention Each characteristic value described in the above table was measured as follows.
く a、 の測定〉  A, measurement)
光学楔を介してキセノンフラッシュ光源により、 露光時間 1 X 10— 6秒で露 光を施した後、 自動現像機としてノーリツ （株） 製の C S R型シート自動現像 機を使用し、 下記の方法でランニング処理を行い、 処理液状態を安定させたプ 口セス名 CP K— 22 Q A (コニ力社製） を用いて処理を行った。 なお、 ラン 二ング処理は、 各感光材料に平均濃度からなるカラ一ネガティブフィルムで像 様露光を行い、 発色現像補充液の容量が発色現像タンク容量の 2倍量となるま で連続処理し、 処理液特性を収斂させた。 次いで、 得られた現像処理済み試料を、 光学濃度計 （X— R i t e社製 X - R i t e 3 1 O T R ) を用いて濃度測定して、 縦軸が発色濃度（ D )、 横軸が 露光量（ L o g E )からなる特性曲線を作成し、 この得られた特性曲線により、 r a及び γ b 求めた。 A xenon flash light source through an optical wedge, was subjected to exposure light in an exposure time 1 X 10- 6 seconds, using Noritsu Co., Ltd. CSR type sheet automatic processing machine as an automatic developing machine, by the following method A running process was performed, and the process was performed using a process name CP K-22 QA (manufactured by Koni Riki Co., Ltd.) that stabilized the state of the processing solution. In the running process, each photosensitive material is exposed imagewise with a color negative film having an average density, and is continuously processed until the volume of the color developing replenisher becomes twice the volume of the color developing tank. The properties of the processing solution were converged. Next, the obtained developed sample was measured for density using an optical densitometer (X-Rite 31 OTR manufactured by X-Rite), and the vertical axis was the color density (D) and the horizontal axis was the exposure. A characteristic curve composed of the quantities (Log E) was prepared, and ra and γ b were determined from the obtained characteristic curve.
く L *、 a *、 b *、 W a、 W bの測定〉  Measurement of L *, a *, b *, Wa, Wb>
上記ランニング処理後に得られた各試料の未露光部について、 日立製作所製 の C— 2 0 0 0カラ一アナライザーを用いて、 タングステン常用光源による測 定モードと、 単色光光源による測定モードにより測定し、 D 6 5を白色点とし て L a b色空間上の各 L *、 a b *を求めた。 また、 得られた測定値 L *、 b *値より白色度 W a、 白色度 W b及びその白色度差 W cを求めた。  The unexposed part of each sample obtained after the above-mentioned running process was measured using a C-2000 color analyzer manufactured by Hitachi, Ltd. in a measurement mode using a tungsten common light source and a measurement mode using a monochromatic light source. , D65 as white points, L * and ab * on the Lab color space were determined. Further, whiteness W a, whiteness Wb and a whiteness difference Wc thereof were determined from the obtained measured values L * and b *.
《感光材料の特性評価》  << Characteristic evaluation of photosensitive material >>
(文字再現性の評価）  (Evaluation of character reproducibility)
上記各試料に、 1〜6ポイ ントのアルファベッ ト文字及び和文文字を、 D u r s t社製の 1 a m b d a 7 6 (ダースト社製 ラムダ 7 6 ) を用いてレーザ —露光を施した後、 上記ノーリツ （株） 製の C S R型シート自動現像機を使用 し、 プロセス名 C P K— 2 2 Q A (コニ力社製） に従って現像処理を行った。 以上のようにして得られた文字画像をプリントした各試料を、 観察光源とし て、タングステン光（観察光源 1 )、 5 0 0 0 ° Kの観察用蛍光灯（観察光源 2 ) 及び晴れた日の屋外昼光 （観察光源 3 ) の 3条件で、 2 0人の一般評価者によ る目視評価を行い、 下記の基準に則り文字再現性の評価を行い、 その平均値を 求めた。  Each sample was subjected to laser-exposure using 1 to 6 points of alphabetic characters and Japanese characters using a 1 ambda 76 manufactured by Durst (lambda 76 manufactured by Durst). Development was performed using a CSR type sheet automatic developing machine manufactured by Konica Corporation in accordance with the process name CPK-22 QA (manufactured by KONiki Co., Ltd.). Each sample on which the character image obtained as described above was printed was used as an observation light source, such as tungsten light (observation light source 1), a fluorescent lamp for observation at 500 ° K (observation light source 2), and a sunny day. Under the three conditions of outdoor daylight (observation light source 3), visual evaluation was performed by 20 general evaluators, character reproducibility was evaluated according to the following criteria, and the average value was obtained.
1 0 ：非常に好ましい白地を有し、 文字画像と白地とで明らかな濃度差があ り、 1ポイント以上の文字画像が明瞭に識別でき、 また文字のつぶれ、 色にじ みの発生が全く認められない 10: Very favorable white background, with a clear density difference between the character image and the white background, character images of 1 point or more can be clearly identified, and character collapse and color blur No occurrence
7 ：好ましい白地を有し、 文字画像と白地とで濃度差があり、 2ボイント以 上の文字画像が明瞭に識別でき、 また文字のつぶれ、 色にじみの発生がほぼ認 められない  7: Having a preferable white background, there is a density difference between the character image and the white background, character images of 2 points or more can be clearly distinguished, and almost no collapse of characters and no color fringing is observed.
5 ：ほぼ好ましい白地を有し、 文字画像と白地とでほぼ許容される濃度差が あり、 4ポイント以上の文字画像が識別でき、 また文字のつぶれ、 色にじみの 発生が僅かに認められるが実用上許容の範囲にある  5: Preferable white background, almost allowable difference in density between character image and white background, character image of 4 points or more can be identified, and occurrence of character collapse and color blurring is slightly observed, but practical Within acceptable range
3 ： 白地に色調差が認められ、 文字画像と白地との濃度差にやや乏しく、 6 ポイントの文字画像でもやや識別に難があり、 また文字のつぶれ、 色にじみの 発生が認められ、 実用上問題となる品質  3: Difference in color tone on white background, slight difference in density between character image and white background, difficulty in discrimination even with 6-point character image, collapse of characters, color blurring, and practical use Quality in question
1 ： 白地が明らかな色調があり、 文字画像と白地との濃度差に乏しく、 6ポ イ ントの文字画像でも識別に難があり、 また明らかな文字のつぶれ、 色にじみ の発生が認められ、 実用上極めて問題となる品質  1: The white background has a clear color tone, the density difference between the character image and the white background is poor, and it is difficult to identify even a 6-point character image. Also, clear character collapse and color blur are observed. Quality that is extremely problematic in practical use
また、 各ランク以外の中間に位置するランクに関しては、 それぞれの隣接す るランク間を等間隔で配分して評価を行った。  In addition, for intermediate ranks other than each rank, evaluation was performed by distributing them at equal intervals between adjacent ranks.
(調子再現性の評価）  (Evaluation of tone reproducibility)
肌色階調性が確認できるポートレートシーン （ゥエディングドレスの女性撮 影シーン） の画像データを C D— Rでメディア入力し、 この画像を用いて、 各 試料に D u r s t社製の 1 a m b d a 7 6 (ダースト社製 ラムダ 7 6 ) によ るレーザー露光を施した後、 上記ノーリツ （株） 製の C S R型シート自動現像 機を使用し、 プロセス名 C P K— 2 2 Q A (コニ力社製） に従って現像処理を 行つた。  Image data of a portrait scene (scene of a woman in an edging dress) where the skin color gradation can be confirmed is input to the media using a CD-R, and this image is used to apply a 1 ambda made by Durst to each sample. (Lastrda 76 manufactured by Durst Co., Ltd.), and then developed using the above-mentioned automatic CSR type sheet developing machine manufactured by Noritz Co., Ltd. according to the process name CPK-22 QA (manufactured by KONiki). Processing was performed.
得られた各ポ一トレ一ト画像について、 観察光源として、 5 0 0 0 ° Kの観 察用蛍光灯（観察光源 2 )下で、 一般評価者 2 0人による目視観察を行って、 下記の基準に則り、 調子再現性の評価を行い、 その平均値を求めた。 For each of the obtained portlet images, a view at 500 ° K was used as an observation light source. Under a fluorescent light for observation (observation light source 2), 20 general evaluators visually observed and evaluated the tone reproducibility according to the following criteria, and the average value was obtained.
◎：人物の顔、 髮の毛等で、 ハイライ ト部〜シャ ドー部にかけて、 メリハリ のある画像で、 非常に好ましい調子再現にあり、 また髪の毛等の鮮明度も高い 〇：人物の顔、 髪の毛等で、 ハイライ ト部〜シャド一部にかけて、 ほぼメリ ハリのある画像で、 好ましい調子再現にあり、 また髪の毛等の鮮明度も好まし い特性にある  ◎: The face, hair, etc. of the person, from highlight to shadow, sharp image, very good tone reproduction, and high clarity of hair, etc. 〇: Face, hair of the person In the highlight part to the part of the shadow, the image is almost sharp, with good tone reproduction, and also has favorable characteristics such as hair clarity
△ :人物の顔、 髪の毛等で、 ハイライ ト部〜シャド一部にかけて、 やや過度 に硬調、 あるいは軟調であるが、 ほぼ許容される調子再現にあり、 また髪の毛 等の鮮明度も許容の範囲にある  △: A person's face, hair, etc., which is slightly excessively hard or soft over the highlight area to part of the shadow, but reproduces almost acceptable tone, and the sharpness of hair etc. is also within the acceptable range. is there
X ：人物の顔、 髪の毛等で、 ハイライ ト部〜シャドー部にかけて、 過度に硬 調、 あるいは軟調すぎ、 好ましくない調子再現にあり、 また髪の毛等の鮮明度 も乏しい  X: A person's face, hair, etc., from highlights to shadows, where the tone is excessively hard or too soft, causing undesired tone reproduction, and poor clarity of hair etc.
X X ：明らかに人物の顔、髪の毛等で、ハイライ ト部〜シャ ドー部にかけて、 過度に硬調、 あるいは軟調すぎ、 非常に好ましくない調子再現にあり、 また髪 の毛等の鮮明度も極めて乏しい  XX: Obviously a person's face, hair, etc., from highlights to shadows, excessively hard or too soft, very poor tone reproduction, and very poor clarity of hair etc.
以上により得られた結果を、 下表に示す。 The results obtained above are shown in the table below.
感光材料 〔文字再現性〕 〔調子再現性〕 備考 観察光源 1 観察光源 2 観察光源 3 Photosensitive material [character reproducibility] [tone reproducibility] Remarks Observation light source 1 Observation light source 2 Observation light source 3
1 0 1 4 6 4 X 比較例1 0 1 4 6 4 X Comparative example
5 102 6 6 6 X 比較例5 102 6 6 6 X Comparative example
103 5 7 6 X 比較例103 5 7 6 X Comparative example
104 7 7 7 Δ 比較例104 7 7 7 Δ Comparative example
105 7 7 7 X 比較例105 7 7 7 X Comparative example
106 7 9 7 Δ 本発明106 7 9 7 Δ The present invention
10 107 9 9 8 Δ 本発明10 107 9 9 8 Δ The present invention
108 10 10 10 ◎ 比較例108 10 10 10 ◎ Comparative example
109 7 10 7 〇 本発明109 7 10 7 発 明 The present invention
110 10 10 10 ◎ 本発明 110 10 10 10 ◎ The present invention
15 以上のように、 本発明で規定する階調特性（ r a、 γ b ) にある本発明の試 料は、 比較例に対し、 光源の異なる環境下での文字画像の観察において、 いず れの照明条件でも文字再現性に優れ、 かつポ一トレート画像のシャド一部から ハイライ ト部にかけての調子再現性が好ましい範囲にあることが分かる。 ただ し、 上記結果の中でも、 r a値が 3. 8に近似の試料では、 露光制御がやや困15 As described above, the sample of the present invention having the gradation characteristics (ra, γ b) specified in the present invention was different from the comparative example in the observation of the character image under the environment of different light sources. It can be seen that the character reproducibility is excellent even under the illumination conditions of, and the tone reproducibility from the part of the shadow of the port image to the highlight part is in a preferable range. However, among the above results, exposure control was somewhat difficult for samples whose ra value was close to 3.8.
20難となり、 ハイライ ト部の階調再現がやや困難となった。 20 difficulties, and it became somewhat difficult to reproduce the gradation of the highlight part.
また、 白地特性として、 本発明で規定する L*、 a *、 h W a、 W b、 W c 値を有する試料は、 文字再現性及び調子再現性がより一層向上していることが 分かる。 実施例 2 In addition, it can be seen that the samples having the L *, a *, hWa, Wb, and Wc values defined in the present invention as white background characteristics have further improved character reproducibility and tone reproducibility. Example 2
実施例 1で作製した試料 101〜1 10について、 富士写真フィルム （株） 製のデジタルミニラボフロンティア 350を用いて、 特開 2003-4360 4号公報の段落番号〔 0243：]〜〔 0246〕 に記載の現像処理を行つた以 外は同様にして、 実施例 1と同様の方法で文字再現性及び調子再現性の評価を 行った結果、 実施例 1と同様に本発明の試料は、 光源の異なる環境下での文字 画像の観察において、 いずれの照明条件でも文字再現性に優れ、 かつポートレ ―ト画像のシャドー部からハイライ ト部にかけての調子再現性が好ましい範囲 にあることを確認することができた。 産業上の利用の可能性  The samples 101 to 110 prepared in Example 1 are described in paragraph numbers [0243:] to [0246] of JP-A-2003-43604 using a digital minilab frontier 350 manufactured by Fuji Photo Film Co., Ltd. Characteristic reproducibility and tone reproducibility were evaluated in the same manner as in Example 1 except that the development processing was performed.As a result, the samples of the present invention differed in light source as in Example 1. When observing character images in an environment, it was confirmed that the character reproducibility was excellent under any lighting conditions, and that the tone reproducibility from the shadow part to the highlight part of the portrait image was in a preferable range. Was. Industrial potential
以上のように、 本発明のハロゲン化銀カラ一写真感光材料により、 様々な照 明条件下の観察においも文字再現性に優れ、 かつ好ましい調子再現性を有する ハ口ゲン化銀力ラー写真感光材料を提供することができる。  As described above, the silver halide color photographic light-sensitive material of the present invention has excellent character reproducibility and favorable tone reproducibility in observation under various lighting conditions, and has excellent tone reproducibility. Material can be provided.

Claims

請求の範囲 The scope of the claims
1. 反射支持体上に、 それぞれ少なくとも一層のイェロー発色感光性ハロゲ ン化銀乳剤層、 マゼンタ発色感光性ハ口ゲン化銀乳剤層及びシァン発色感光性 ハロゲン化銀乳剤層と、 非感光性親水性コロイ ド層を有するハロゲン化銀カラ —写真感光材料において、 光学楔を介して露光時間 1 X 1 0— 6秒で露光を施し た後、 発色現像処理して形成された最小濃度 （未露光部） 及び最大濃度を含む ゥエッジ状画像より、 濃度 D (発色濃度） 一 L o g E (露光量） からなる特性 曲線を作成し、該特性曲線における少なくともマゼンタ発色濃度が、下式〔 1〕 の条件を満たすことを特徴とするハロゲン化銀カラ一写真感光材料。 1. At least one yellow-sensitive silver halide emulsion layer, magenta-sensitive silver halide emulsion layer and cyan cyanide-sensitive silver halide emulsion layer and at least one non-photosensitive hydrophilic layer the silver halide color having sex colloids layer - photographic in the photosensitive material, was subjected to exposure with an exposure time 1 X 1 0- 6 seconds through an optical wedge, color development processing to form the minimum concentration (unexposed from Uejji shaped image including parts) and maximum density, creates a characteristic curve composed of density D (color density) Single L o g E (exposure), at least the magenta color density in the characteristic curve, the following equation (1) A silver halide color photographic light-sensitive material, characterized by satisfying the following conditions:
式 〔 1〕  Equation (1)
2. 3≤ a ≤ 3. 8  2.3 ≤ a ≤ 3.8
〔式中、 r aは、最小濃度から + 0. 2 5の濃度を得るのに要する露光量点と、 最小濃度から + 0. 7 5の濃度を得るのに要する露光量点とを結んだ直線の傾 き （ t a n ） を表す。〕  (In the formula, ra is a straight line connecting the exposure point required to obtain a density of +0.25 from the minimum density and the exposure point required to obtain a density of +0.75 from the minimum density. Represents the inclination (tan) of ]
2. 前記特性曲線における少なくともマゼンタ発色濃度が、 下式 〔 2〕 の条 件を満たすことを特徴とする請求の範囲第 1項に記載のハロゲン化銀カラ一写 真感光材料。  2. The silver halide color photosensitive material according to claim 1, wherein at least the magenta color density in the characteristic curve satisfies the condition of the following formula [2].
式 〔 2〕  Equation (2)
2. 0≤ γ b≤ 3. 8  2.0≤γb≤3.8
〔式中、 r bは、最小濃度から + 0. 75の濃度を得るのに要する露光量点と、 最小濃度から + 1. 7 5の濃度を得るのに要する露光量点とを結んだ直線の傾 き （ t a n S ) を表す。〕 [Where rb is a straight line connecting the exposure point required to obtain a density of +0.75 from the minimum density and the exposure point required to obtain a density of +1.75 from the minimum density. It represents the inclination (tan S). ]
3. 前記発色現像処理後の最小濃度（未露光部） の下記で定義する白色光照 明時及び単色光照明時に得られる C I E 1 9 7 6 L* a * b *色空間における明度 指数 L*がそれぞれ 8 5 L* 9 6で、知覚色度指数 a *がそれぞれ— 1. 0≤ a *≤ 2. 0で、 かつ知覚色度指数 b *がそれぞれ— 8. 0≤ b *≤- 2. 2であ ることを特徴とする請求の範囲第 1項または第 2項に記載のハロゲン化銀力ラ 一写真感光材料。 3. The minimum density (unexposed area) of the CIE 1976 L * a * b * lightness index L * in color space obtained at the time of white light illumination and monochromatic light illumination defined below is the minimum density (unexposed area) after the color development processing. Each is 85 L * 96, and the perceived chromaticity index a * is — 1. 0 ≤ a * ≤ 2.0, and the perceived chromaticity index b * is each-8.0 ≤ b * ≤ 2. 3. The silver halide light-sensitive photographic material according to claim 1 or 2, wherein
白色光照明 ：照明光源を直接未露光部に照射する照明  White light illumination: Illumination that irradiates the illumination light source directly to unexposed areas
単色光照明 ：照明光源を、一旦グレーディングにより各単色光に分離した後、 未露光部に照射する照明  Monochromatic light illumination: Illumination that illuminates the unexposed part after the illumination light source is once separated into each monochromatic light by grading.
4. 前記発色現像処理後の最小濃度（未露光部） が、 下式 〔 3〕 で定義する 前記白色光照明により得られる C I E白色度 W aと、 下式〔 4〕 で定義する前 記単色光照明により得られる C I E白色度 W bとの差 W c ， 0以下である ことを特徵とする請求の範囲第 1項乃至第 3項のいずれか 1項に記載のハ口ゲ ン化銀カラー写真感光材料。 4. The minimum density (unexposed area) after the color development processing is the CIE whiteness Wa obtained by the white light illumination defined by the following equation [3] and the single color defined by the following equation [4]. The silver halide color according to any one of claims 1 to 3, wherein a difference Wc from CIE whiteness Wb obtained by light illumination is not more than 0. Photosensitive material.
式〔 3〕  Equation [3]
W a = 2. 1 L 1 * - 4. 4 5 b ι*{ 1 - 0. 0 09 0 X ( L i* - 9 6 )} - 1 1.  W a = 2. 1 L 1 *-4.45 b ι * {1-0.009 0 X (L i *-9 6)}-1 1.
〔式中、 L は白色光照明により得られる未露光部の C I E 1 9 7 6 L* a * b *色空間における明度指数であり、 b は白色光照明により得られる C I E L* a * b *色空間における知覚色度指数を表す。〕  (Where L is the lightness index in the CIE 197 L * a * b * color space of the unexposed area obtained by white light illumination, and b is the CIEL * a * b * color obtained by white light illumination. Represents the perceived chromaticity index in space. ]
式〔4〕  Equation [4]
W b = 2. 1 L 3*- 4. 4 5 b 2*{ 1 - 0. 0 0 9 0 X ( L 2* - 9 6 )} - 1 1. 〔式中、 L 2 *は単色光照明により得られる未露光部の C I E 1976 L*a*b *色空間における明度指数であり、 b2*は単色光照明により得られる C I EL* a * b *色空間における知覚色度指数を表す。〕 W b = 2. 1 L 3 *-4.45 b 2 * {1-0.0.0 9 0 X (L 2 *-9 6)}-1 1. (Where L 2 * is the lightness index in the CIE 1976 L * a * b * color space of the unexposed portion obtained by monochromatic illumination, and b 2 * is the CIEL * a * b obtained by monochromatic illumination. * Represents the perceived chromaticity index in the color space. ]
5. 前記発色現像処理後の未露光部の前記白色光照明により得られる C I E L* a* b*色空間における色度 L が 80 < L !*< 91であって、 かつ前記式 5. The chromaticity L in the CIE L * a * b * color space obtained by the white light illumination of the unexposed portion after the color development processing is 80 <L! * <91, and the formula
〔 3〕 で求められる C I E白色度 W aが 85 <W a < 91であることを特徴と する請求の範囲第 4項に記載のハロゲン化銀カラー写真感光材料。 5. The silver halide color photographic light-sensitive material according to claim 4, wherein the CIE whiteness Wa determined in [3] is 85 <Wa <91.
6. 前記特性曲線における各色画像濃度 0. 75を得るのに要する露光量の 4倍の露光量点におけるそれぞれの濃度が、 2. 0以上であることを特徴とす る請求の範囲第 1項乃至第 5項のいずれか 1項に記載のハ口ゲン化銀力ラー写 真感光材料。  6. The method according to claim 1, wherein each density at an exposure point four times the exposure required to obtain 0.75 of each color image density in the characteristic curve is 2.0 or more. 6. The photosensitive material according to any one of claims 1 to 5, wherein the photosensitive material is silver halide.
PCT/JP2003/009980 2003-08-06 2003-08-06 Silver halide color photography sensitive material WO2005015307A1 (en)

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JPH10254108A (en) * 1997-03-13 1998-09-25 Konica Corp Silver halide photographic sensitive material
JP2000010224A (en) * 1998-06-19 2000-01-14 Konica Corp Silver halide color photographic sensitive material and method for forming images
JP2000098518A (en) * 1998-09-28 2000-04-07 Konica Corp Silver halide photographic sensitive material, preparation of silver halide emulsion and image forming method
JP2001042481A (en) * 1999-08-03 2001-02-16 Fuji Photo Film Co Ltd Silver halide color photographic sensitive material and image forming method
JP2001281816A (en) * 2000-03-29 2001-10-10 Fuji Photo Film Co Ltd Silver halide color photographic sensitive material
JP2002107879A (en) * 2000-09-29 2002-04-10 Fuji Photo Film Co Ltd Silver halide color photographic sensitive material
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JP2002296737A (en) * 2001-03-30 2002-10-09 Fuji Photo Film Co Ltd Silver halide color photographic sensitive material, processing method and color proof image forming method
JP2002311540A (en) * 2001-02-07 2002-10-23 Konica Corp Photographic element and silver halide photographic sensitive material
JP2002351026A (en) * 2001-05-23 2002-12-04 Fuji Photo Film Co Ltd Silver halide color photographic sensitive material
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07306505A (en) * 1994-05-12 1995-11-21 Fuji Photo Film Co Ltd Method for forming color photographic image
JPH08339056A (en) * 1995-06-13 1996-12-24 Konica Corp Method for forming color proof by using silver halide color photographic sensitive material
JPH10254108A (en) * 1997-03-13 1998-09-25 Konica Corp Silver halide photographic sensitive material
JP2000010224A (en) * 1998-06-19 2000-01-14 Konica Corp Silver halide color photographic sensitive material and method for forming images
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JP2001042481A (en) * 1999-08-03 2001-02-16 Fuji Photo Film Co Ltd Silver halide color photographic sensitive material and image forming method
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JP2002351025A (en) * 2001-05-23 2002-12-04 Fuji Photo Film Co Ltd Silver halide color photographic sensitive material and color image forming method

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