EP0295716A2 - Verfahren zur Bildung eines Farbbildes und Verwendung eines Bandstopfilters dafür - Google Patents

Verfahren zur Bildung eines Farbbildes und Verwendung eines Bandstopfilters dafür Download PDF

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Publication number
EP0295716A2
EP0295716A2 EP88109778A EP88109778A EP0295716A2 EP 0295716 A2 EP0295716 A2 EP 0295716A2 EP 88109778 A EP88109778 A EP 88109778A EP 88109778 A EP88109778 A EP 88109778A EP 0295716 A2 EP0295716 A2 EP 0295716A2
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Prior art keywords
color
sensitive
light
nucleus
layer
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English (en)
French (fr)
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EP0295716A3 (en
EP0295716B1 (de
Inventor
Koji Takahashi
Keisuke Shiba
Yukio Muramatsu
Seiichi Taguchi
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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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
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation

Definitions

  • the present invention relates to a process for the formation of color images which comprises printing images on a color printing light-sensitive material from a color print original in a subtractive color exposure process, and then color-developing the color printing light-sensitive material. More particularly, the present invention relates to a process for the formation of color images which proves color reproducibility without deteriorating the conventional productivity, particularly without prolonged printing time.
  • color print originals such as transparent positive images obtained from photographing color reversal light-sensitive materials, color photographs obtained from instant photographic materials or color photographic papers, and color printed matters
  • color reproducibility faithful to color print originals has also been desired.
  • the spectral sensitivity distribution may be improved by the selection of a proper sensitizing dye or modification of crystal habit of particulate silver halide or process for the addition of particulate silver halide.
  • such approaches are not necessarily enough.
  • the modification of spectral sensitivity distribution can be also accomplished by a use of a suitable photographic dye as described in Japanese Patent Publication No. 1,419/76, and West German Patent No. 1,015,683.
  • a suitable photographic dye as described in Japanese Patent Publication No. 1,419/76, and West German Patent No. 1,015,683.
  • such an approach is disadvantageous, because only the overlapped portion of spectral sensitivity distribution of a specific layer and that of a layer other than the specific light-sensitive layer among a plurality of light-sensitive layers of a light-sensitive material is desensitized.
  • such a photographic dye lowers sensitivity itself or has a desensitizing effect.
  • Such a photographic dye is also disadvantageous in that it tends to leave color after the formation of images.
  • Improvements for color printing light-sensitive materials have been made to obtain faithful color reproducibility as well as excellent sharpness and graininess of images using an excellent print original obtained from an excellent photographing color light-sensitive material. Besides the improvement in photographing color light-sensitive materials, improvements have been made in color couplers and their color dyes and spectral sensitivity distribution in blue-sensitive, green sensitive and red-sensitive layers. Furthermore, efforts have been made to inhibit color mixture between various layers.
  • Japanese Patent Application (OPI) No. 113,627/76 discloses a process using a suitable light filter to cut a copying light in a wavelength band of 500 nm in which the blue sensitivity and the green sensitivity of a copying paper overlap each other, when an original is copied.
  • the object of the process if to decrease copy trials to obtain color balance of copy previously or to adjust deviation in color balance which is caused on getting color balance.
  • this approach effexcts on only copying conditions by cutting both blue and green light in a wavelength band in which the blue sensitivity and the green sensitivity of a copying paper overlapeach other. If a light filter having a wide absorption wavelength range is used, the blue sensitivity and green sensitivity of a copying paper are lowered. To compensate for this disadvantage, a stronger light for copy is required. This results in an increase in the remaining color mixture.
  • Japanese Patent Application (OPI) Nos. 64,037/78 and 113627/76 disclose a printer which is provided with filters such that the respective spectral sensitivities of a color paper are matched to that of blue light, green light and red light receivers in order to facilitate the adjustment of exposure time for the color paper when printing is made on a color paper from a negative film.
  • Processes for printing on a color printing light-sensitive material from a color print original include additive process and subtractive process.
  • subtractive exposure process particularly using a white light source has been commonly put into practical use.
  • this process provides a high processing capability per unit input, advantageous procedure for stabilization of photo- graphic properties, efficient use of a light source, high quality level of color images on a print, etc.
  • This process also enables a rapid or unmanned printing process.
  • the subtractive process such as white light subtractive process have been widely used in the form of an autoprinter because it can provide a high productivity and rapidity.
  • a process is disadvantageous to be improved in the finish quality and its stability. In order to eliminate these defects, many approaches have been suggested.
  • U.S. Patent No. 2,997,389 suggests the use of a filter having a spectral absorption band in a yellow region and between 465 nm and 490 nm during the printing of a color transparent image on a color printing light-sensitive material in the subtractive exposure process.
  • the above described U.S. Patent also suggests that a filter comprising a ZnS layer and an MgF 2 layer may be preferably used.
  • U.S. Patent No. 4,050,807 suggests the combined use of a subtractive color filter and a filter adapted to remove wavelengths in which spectral sensitivity curves of a copying photographic paper cross each other during enlarging and printing of photographic images or copy printing in the subtractive process.
  • an autoprinter for printing on a color paper from a color negative film may be provided with a filter adapted to cut light in a wavelength band of 460 to 540 nm and a filter adapted to cut light in a wavelength band of 570 to 640 nm to unite the spectral sensitivity of the receptor in the autoprinter with the spectral sensitivity distribution of the color paper increasing an accuracy of the exposure control in the autoprinter.
  • the latter two patents have no description about the constituting elements of such suitable filters.
  • the subtractive exposure process is also disadvantageous in that it is difficult to conform the spectral intensity distribution of the exposing light source to the spectral sensitivity distribution of three light-sensitive layers and to the spectral absorption characteristics of the corresponding color originals or materials to be copied.
  • a filter having a spectral absorption in a wavelength band out of an absorption wavelength band of 465 to 490 nm as described in U.S. Patent No. 2,997,389 or a filter having a spectral absorption in a wavelength band out of the wavelength in which the spectral sensitivity curves of a copying photographic paper cross each other as described in U.S. Patent No. 4,050.807 is often useful. Accordingly, it has been desired to develop a filter having sharp spectral absorption characteristics excellent in transparency and a transmission wavelength band which is not limited to these wavelength bands but can be freely selected.
  • Processes for image exposure such as photographing objects to be copied and copying or printing from a color original include three processes.
  • the first process the entire surface of a color light-sensitive material is imagewise exposed at the same time.
  • This process requires lens and a shutter.
  • An exposing machine to be used in this process may have a simple construction. In this process, the exposure can be effected only once or several times (sequential exposure process). This process can provide an excellent picture quality. Ordinary cameras and autoprinters employ this process.
  • the second process is a slit exposure process. In this exposure process, a slit moves across the light axis between the object to be copied or color original and the color light-sensitive material to effect image exposure.
  • the third process is a synchronous slit exposure process.
  • the object to be copied or color original and the color light-sensitive material are synchronously moved during image exposure.
  • the exposing machines according to these processes are relatively small but are susceptible to uneven scanning or image distortion due to unevenness in the speed of synchronous movement or insufficient accuracy of synchronous movement.
  • a wide radiation angle is obtained.
  • the filter used in this process is included in an interference filter of the kind which varies in spectral absorption characteristics depending on the angle of incidence of the light, causing unevenness in the finish quality of color prints. Therefore, it has been desired to develop a band stop filter which is particularly improved so as to provide a less radiation angle dependency of spectral absorption.
  • a process for the formation of color images which comprises printing on a color printing light-sensitive material comprising a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer provided on a support from a color print original in a subtractive exposure process, and then substantially subsequent color development, characterized in that the effective spectral light amount distribution of at least two light-sensitive layers in various light-sensitive layers in the color printing light-sensitive material are substantially independent from each other in a wavelength band of 400 to 750 nm and thereby an average color mixing degree in each color image forming layer of color print is 0.13 or less.
  • the inventors have found that an unprecedentedly excellent color reproducibility can be attained by printing with a filter interposed between the printing light source and the color printing light-sensitive material such that the distribution of the product of the spectral sensitivity distribution of the color printing light-sensitive material and the specteral transmittance distribution of the three primary colors, i.e., yellow, magenta and cyan in the color print original corresponding to the spectral sensitiavity distribution of each light-sensitive layer, i.e, blue-sensitive layer, green-sensitive layer and red-sensitive layer in the color printing light-sensitive material is independent while optimizing the spectral absorptivity of colored images obtained from main couplers for the formation of images, and the spectral absorptivity of colored images obtained from main couplers incorporated in a photographing color light-sensitive material as a color print original.
  • a filter interposed between the printing light source and the color printing light-sensitive material such that the distribution of the product of the spectral sensitivity distribution of the color printing light-
  • the inventors have worked out the concept of average color mixting degree as defined hereinafter and found that when the color mixturing degree is 0.13 or less, an unprecedentedly excellent color reproducibility can be attained in the transferred images from a color print original to a color printing light-sensitive material.
  • the color print original used in the present invention is a color light-sensitive material for use in photographing such as color negative light-sensitive material, color reversal light-sensitive material, and instant photographic light-sensitive material, negative film or transparent positive film obtained from dupe color light-sensitive material, or color photograph or printed matter comprising a transparent or reflective support.
  • These light-sensitive materials normally have an image comprising at least three primaries, i.e., yellow coloring material (Y), magenta coloring material (M) and cyan coloring material (C) on a support.
  • Examples of a color printing light-sensitive material of the present invention include color photographic paper, direct positive color light-sensitive material, and reversal color light-sensitive material.
  • the present invention may be preferably applied to the subtractive exposure process, particularly color image formation process comprising a printing process by means of an automatic printer using a white light source.
  • the color printing light-sensitive material it is necessary to receive image data such as color hue and graduation, independently, which each has different spectral absorption characteristics due to yellow, magenta and cyan coloring materials in a color print original.
  • image data such as color hue and graduation
  • the color printing light-sensitive material and blue sensitive layer may substantially have a spectral sensitivity in a wavelength band of 400 to 485 nm
  • the green-sensitive layer may substantially have a spectral sensitivity in a wavelength band of 485 to 570 nm
  • the red-sensitive layer may substantially have a spectral sensitivity in a wavelength band of 570 to 750 nm.
  • the blue-sensitive layer may have a maximum sensitivity wave-length ( ⁇ s max) of 400 to 470 nm
  • the green-sensitive layer may have a maximum sensitivity wavelength of 520 to 570 nm
  • the red-sensitive layer may have a maximum sensitivity wavelength of 600 to 740 nm.
  • the effective spectral light amount distribution of the present color printing light-sensitive material will be explained hereinafter.
  • T (X) the spectral transmittance distribution of coloring materials in a color print original such as color negative film
  • S(X) the spectral sensitivity distribution of a light-sensitive layer such as green-sensitive layer in a color printing light-sensitive material
  • P(X) the energy distribution of the printing light
  • E (X) in the light-sensitive layer is given by the equation (1-1):
  • E ( ⁇ ) S ( ⁇ )•T ( ⁇ )•P ( ⁇ ) (1-1)
  • the effective sensitive light amount of, for example, the green sensitive layer is given by the equation (1-2):
  • the effective spectral sensitive energy distribution given by the equation (1-1) is called effective spectral light amount distribution.
  • the present invention features that at least two of the effective spectral light amount distribution of a blue-sensitive layer (BL), a green-sensitive layer (GL) and a red-sensitive layer (RL) in a printing light-sensitive material, i.e., Eb ( ⁇ ), Eg ( ⁇ ) and Er (X), respectively, are substantially independent each other.
  • Eg ( ⁇ ) and Er ( ⁇ ) or Eg ( ⁇ ) and Eb (X), preferably Eb (X), Eg ( ⁇ ) and Er ( ⁇ ) each is substantially independent each other.
  • the effective spectral light amounts of the other light-sensitive layers or if within a range of only about 15% or less or preferably about 7% or less of the maximum value of the effective spectral light amount distribution (Eb (X), Eg ( ⁇ ) or Er (X)) of a light-sensitive layer, effective spectral light amount distributions of the other light-sensitive layers are contained, the color mixture is not substantially definitely observed, and this means that the effective spectral light amount distribution in these light-sensitive layers are substantially independent.
  • the green-sensitive layer (GL) in a color printing light-sensitive material if in a wavelength band of 485 to 570 nm Er ( ⁇ ) and Ef ( ⁇ ) are limited within a range of Eg ( ⁇ ) x 0.15 or less or there are no Er ( ⁇ ) and Eb (X), or if in a wavelength band of 485 to 570 nm Er and Eb are limited within a range of Eg x 0.10 or less or there are no Er and Eb, it can be said that the effective spectral sensitive light amount distribution Eg (X) of the green-sensitive layer is substantially independent from that of the other light-sensitive layers.
  • the coloring material to be used in the color pnnting light-sensitive material be particularly improved and the color development doesn't cause mixture on color images due to residual color, stain, poor desilvering, etc.
  • the spectral sensitivity of a photographing color light-sensitive material be predetermined as described in Japanese Patent Application (OPI) No. 89,850/88. More preferably, it is necessary that a coloring material comprising a yellow coupler or magenta coupler be improved so as to have a block type spectral transmittance.
  • the silver halide emulsion to be incorporated in the present color printing light-sensitive material, particularly in GL or RL preferably doesn't have an inherent sensitivity in the wavelength band for BL and a longer wavelength band.
  • the present color printing light-sensitive material is formed of such a silver halide emulsion and spectrally sensitized in such a manner that Eb ( ⁇ ), Eg ( ⁇ ) or Er (X) of each light-sensitive layer is independent.
  • the blue-sensitive layer (BL) is not always required to be spectally sensitized due to an inherent sensitivity of silver halide, but it may be preferably spectrally sensitized in such a manner that the maximum inherent sensitive wavelength thereof is set at 460 nm or less, preferably the wavelength band for BL or less, to provide a high rapidness in color development or inhibit mixture.
  • the maximum inherent sensitive wavelength thereof is set at 460 nm or less, preferably the wavelength band for BL or less, to provide a high rapidness in color development or inhibit mixture.
  • any suitable sensitizing dye selected from those represented by the general formula (I) explained later may be used.
  • a Macbeth chart comprising 18 chromatic colors and 6 achromatic colors may be commonly used. Examples of such a Macbeth chart are described in C.S.M. MaCamy, "J. Appl. Phot. Eng.”, Vol. 2, pp. 95-99, 1976.
  • such a Macbeth chart is used to define the average color mixing degree in a color printing light-sensitive material as described hereinafter.
  • the green-sensitive layer In the color printing light-sensitive material, the green-sensitive layer generally tends to deteriorate the color reproducibility among the three light-sensitive layers, i.e., blue-sensitive layer, green-sensitive layer and red-sensitive layer. Therefore, the green-sensitive layer in the color printing light-sensitive material will be further described hereinafter.
  • the spectral transmittance distribution of a color negative material obtained by photographing color chart i is Ti(X)
  • the spectral sensitivity distribution of the green-sensitive layer in a color printing light-sensitive material is S(X)
  • the energy distribution of a printing light source is P( ⁇ )
  • the exposure of the green-sensitive layer for color chart i is given by the equation (2-1).
  • a spectral sensitivity distribution in a delta function form having a 5 nm width in the center of the main maximum sensitive wavelength of the green-sensitive layer is the most preferable spectral sensitivity distribution, and Hi at the main maximum sensitive wavelength is defined as Hi * , ⁇ defined on the equation (2-3) represents the magnitude of the deviation of the exposure amount of color chart i from the ideal exposure amount.
  • the color mixing degree on an exposure for printing or at the printing (hereinafter refer to the color mixing degree) ⁇ i of color chart i can be defined as shown by the equation (2-4).
  • an average color mixing degree on an exposure for printing (hereinafter refer to the average color mixing degree) r can be defined by averaging the color mixing degree 1 3 ; of color chart i over 18 Macbeth chromatic charts as shown in the equation (2-5).
  • the average color mixing degree of the blue-sensitive layer and the red-sensitive layer can be similarly defined and easily determined with the effective wavelength band set at 390 to 485 nm and 570 to 740 nm, respectively.
  • the color mixing degree of each chromatic chart has a close relathionship with the average color mixing degree.
  • the degree of color mixture can be represented by the color mixing degree or average color mixing degree on an exposure for printing (at the printing) in each of the light-sensitive layers.
  • the average color mixing degree is 0.13 or less, preferably 0.12 or less, particularly 0.10 or less in each of the light-sensitive layers, an excellent color reproducibility can be attained.
  • the color mixing degree is 0.0.
  • the average color mixing degree is 0.03 or less, it can be said that there is substantially no color mixing degree.
  • the blue-sensitive layer, the green-sensitive layer and the red-sensitive layer all have 0.13 or less of average color mixing degree thus defined above.
  • the silver halide light-sensitive emulsion generally absorbs light to provide a latent image or becomes light-sensitive in a wavelength band of less than about 540 nm for a silver bromoiodide emulsion, less than about 500 nm for a silver bromide emulsion, or less than about 420 nm for a silver chloride emulsion as described in T. H. James, "The Theory of the Photographic Process", 4th Ed., 1977, pp. 39-44. Therefore, the halogen composition of particulate silver halide and the process for the formation of crystalline particulate silver halide are important in the present invention.
  • the silver halide light-sensitive emulsion may or may not be subjected to spectral sensitization to obtain a blue-sensitive layer.
  • the inherent spectral sensitivity distribution of the silver halide is an important factor to improve the color mixing degree. The shorter the wavelength band of the inherent spectral sensitivity distribution is, the more advantageous is the effect.
  • a silver halide light-sensitive emulsion which has been spectrally sensitized may or may not be provided with a dye-containing layer such as a filter layer which is adapted to cut light in a blue-sensitive wave-length band.
  • a green-sensitive layer or red-sensitive layer may be provided on a support. Therefore, it is important to decrease the color mixing degree, especially, between the blue-sensitive layer and the green-sensitive layer or between the blue-sensitive layer and the red-sensitive layer is lowered.
  • a silver halide emulsion having a low silver iodide content or average silver bromide content is preferably incorporated in the silver halide emulsion layer, particularly in the blue-sensitive layer and/or green-sensitive layer.
  • a silver halide emulsion layer having 2 mol% or less of layer average silver iodide content, or being free of silver iodide is preferably used.
  • a silver halide emulsion layer having an average silver bromide content of 80 mol% or less is preferably used.
  • Eb ( ⁇ ) and Er (X) are made substantially independent from each other color reproducibility is remarkably improved when the distribution of proper spectral sensitivity of the photographing color light-sensitive material to the object of the photographing color light-sensitive material to the object is fully improved by a suitable method as described in Japanese Patent Application (OPI) Nos. 34,541 86, 201,245/86, 158.779 1 87 and 89850 ⁇ 88 or a coloring material to be used in the color printing light-sensitive material, especially coupler is fully improved.
  • OPI Japanese Patent Application
  • a suitable filter or a filter layer can be used.
  • a suitable filter or a filter lay can be used to restrict the main sensitive wavelength band of the blue-sensitive layer, the green-sensitive lauyer and the red-sensitive layer in the present color printing light-sensitive material to, for example, 400 to 485 nm, 485 to 570 nm, and 570 to 750 nm, respectively.
  • the spectral absorption distribution of the filter is broad or is not predetermined in a proper wavelength band, it may deteriorate color balance or color reproduction.
  • the average color mixing degree as defined above can be adjusted to 0.13 or less by providing a filter or a filter layer substantially between the light source and the light-sensitive layer in the color printing light-sensitive material when images are printed on the color printing light-sensitive material in a subtractive exposure process.
  • the average color mixing degree as defined above can be adjusted to 0.13 or less by providing in combination a color printing light-sensitive material comprising a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer as described above and the filter or filter layer as described above.
  • the filter which can be used in the present invention may be interposed between the light source for use in the subtractive exposure process and the concerned light-sensitive layer in the printing light-sensitive material.
  • Any optical filter otherwise prepared, filter layer incorporated in a color print original or filter layer provided on the light source side in the concerned light-sensitive layer in a color printing light-sensitive material may be preferably used so long as it gives 0.13 or less for the degree of color mixture in the color printing light-sensitive material.
  • a filter having a spectral. absorption band which substantially exists in a wavelength band excluding the band of ⁇ 20 nm, preferably ⁇ 15 nm of the maximum effective spectral light amount ⁇ E max of each light-sensitive layer is preferably interposed between the light source and the color printing light-sensitive material during the printing process.
  • the terminology "substantially exists” means half the width value or three-fourths the width value is used in the spectral transmittance curve.
  • a filter having an absorption band in a wavelength band e.g., of less than 400 nm, 485 to 525 nm, or 570 to 630 nm may be preferably used.
  • a filter layer previously provided on a color negative film or a filter layer provided on the top layer of a light-sensitive layer in a color printing light-sensitive material may be preferably used in combination with such a filter.
  • the green-sensitive layer is not sensitive to the light within a range of the wavelength ⁇ bsmax ⁇ 20 nm to which range the blue-sensitive layer is sensitive.
  • the green-sensitive layer may be subjected to a spectral sensitization process which gives a sharp spectral sensitivity distribution.
  • the green-sensitive layer may comprise a silver halide emulsion having substantially. no or low sensitivity in the above described wavelength band. This can apply to other light-sensitive layers.
  • a suitable filter there may be preferably used a band cut filter which comprises a multilayer dielectric-compound thin film as described hereinafter.
  • the band stop filter to be used in the present invention is a solid filter which has been prepared by repeatedly applying a silicon oxide layer and an aluminum oxide layer on a transparent substrate.
  • a substrate capable of withstanding a heat treatment such as hot coating.
  • a substrate include quartz, glass, ceramics, and plastic. Preferred among these materials are silicon oxide containing materials such as quartz and glass.
  • the thickness of the substrate is preferably in the range of 0.2 to 2 mm.
  • the silicon oxide or aluminum oxide layer has a thickness of 300 to 5,000 A.
  • the silicon oxide layer and the aluminum oxide layer are alternately provided on the substrate.
  • the present band stop filter having any spectral absorption characteristics in the visible band can be obtained by providing a multilayer structure of silicon oxide layer and aluminum oxide layer having different optical thicknesses (refractive index and thickness). Such a multilayer structure can provide a stabilized finish quality excellent in fastness to light, heat and scratch.
  • the filter has preferably 7 or more, more preferably 21 to 101, particularly 47 or more layers.
  • Such a multilayer structure can provide a less change in the spectral absorption characteristics due to a deviation of the angle of incidence from the axial direction in the band stop filter.
  • a protective layer having a thickness preferably greater than that of the other layers is provided at its top layer.
  • a protective layer can be provided by applying preferably a layer of silicon oxide or aluminum oxide, more preferably a layer of silicon oxide, to a thickness of 500 A to 1 um.
  • Such a protective layer having a greater thickness than the other layers can further improve the scratch resistance and chemically protect the multilayer film, providing a band stop filter excellent in strage ability.
  • a suitable filter according to the present invention is a band stop filter which has been prepared by applying 5 or more layers, preferably 21 to 101 layers, on a substrate and providing a protective layer having a greater thickness than the other layers thereon.
  • the present band stop filter can be obtained by alternately depositing silicon oxide and aluminum oxide on a substrate.
  • the deposition of the material can be accomplished by any common method such as vacuum deposition, PVD (Physical Vapor Deposition) process such as ion plating process , or CFD (Chemical Vapor Deposition) process such as plasma deposition process.
  • the degree of vacuum is preferably in the range of 10-11 to 10- 4 torr, particularly 10- 6 to 10- 4 torr with nitrogen gas or an inert gas such as argon and helium, optionally mixed with oxygen gas.
  • the layer structure, thickness and constituting material of the present stop filter can be determined by observing the section of the filter under an electron microscope or by ESCA.
  • the process for the formation of color images on a silver halide color light-sensitive material comprises photographing an object or image exposure such as copying or printing from a color original, and then color-developing the silver halide color light-sensitive material.
  • the image exposure can be effected by any suitable method selected from the three processes (collective simultaneous exposure process, slit exposure process, and simultaneous slit exposure process), additive exposure process, and subtractive exposure process.
  • the band stop filter according to the present invention can be effectively used in all these exposure processes, particularly in the subtractive exposure process.
  • a suitable silver halide color light-sensitive material for the present invention there can be preferably used a negativeipositive or positiveipositive working process printing color light-sensitive material such as color photographic paper, color reversal photographic paper, color reversal film, silver die bleach process color photographic paper, direct positive type color photographic paper, diffusion transfer type color photographic paper, heat-developable diffusion transfer type color photographic paper or film.
  • color light-sensitive materials can be used to directly photograph objects. Therefore, the present band stop filter can be used for an exposing machine, printer, mini-laboratory system printer and copying machine by which these color light-sensitive materials are processed.
  • the present band stop filter can be preferably used in place of a band stop filter or band cut filter as described in Japanese Patent Application Nos.
  • the present band stop filter can also be used for an exposing machine or autoprinter for printing on an ordinary color photographic paper in the white light subtractive process as described in Japanese Patent Application Nos. 146,542187, 200,508/87, 146,544/87, 191,18787, and 255,048/87.
  • the present band stop filter preferably has a maximum absorption wavelength, preferably an absorption wavelength band, in a wavelength band outside the maximum wavelength ⁇ 1 5 nm, preferably the maximum wavelength ⁇ 20 nm, in the maximum sensitiave wavelength or the effective spectral light amount distribution of the blue-sensitive layer, green-sensitive layer or red-sensitive layer in such a light-sensitive layer.
  • the present band stop filter preferably has a sharp spectral absorption.
  • the ratio of a width of 1 : 4 value of spectral transmittance (Wi/4) to a width of 3/4 value of spectral transmittance (W 3/4 ) is in the range of 0.50 or more, preferably 0.60 or more, more preferably 0.75 or more.
  • such spectral characteristics can be attained by properly arranging layer thicknesses and a multilayer structure of repeating layers.
  • a substrate material there may be commonly used glass, silicon, sapphire, quartz, or surface- treated plastic film or plate.
  • suitable dielectrics there may be used dielectrics as described in Japan Society for the Promotion of Science's No. 131 Thin Film Committee, Handbook of Thin Film, Ohm-sha, 1983, Chapter 2.2 on page 817 and Table 2.6 on page 820.
  • examples of such dielectrics include inorganic compounds such as silicon dioxide, aluminum oxide, tin oxide, zirconium oxide, titanium, zinc sulfide, silicon, germanium, and tellurium, metal such as silver, aluminum, neodymium, titanium, and thallium, and organic dielectrics, particularly high molecular dielectrics as described in Japan Society for the Promotion of Science's No.
  • a multilayer comprising 5 to 50 layers, optionally more layers, can be provided by repeatedly coating at least two dielectrics having different refractive indexes to a predetermined thickness.
  • the design of such a multilayer is described in Japan Society for the Promotion of Science's No. 131 Thin Film Committee, Handbook of Thin Film. Chapter 4 on page 823, and Shiro Fujiwara, Optical Thin Film, 2nd ,ed., 1986, Kyoritsu Shuppan Co.. Ltd., Chapter 6.
  • Such a multilayer thin film can be prepared by the sputtering process, CVD film-forming process or vacuum evaporation process.
  • a suitable band stop filter to be used in the present invention has a narrow absorption band having a half value width on the spectral transmittance curve (W 1iz ) of preferably less than 60 nm, more preferably 10 to 60 nm. Furthermore, the present band stop filter has a minimum transmittance of preferably 30% or less, more preferably 20% or less, particularly 10% or less.
  • a band stop filter preferably having a spectral transmittance of 70% or more and a lowest transmittance in spectral absorption band of preferably 20% or less, more preferably 10% or less, may be preferably has a shape coefficient W 1/4 /W 3/4 (W 1/4 represents 1/4 of spectral transmittance, and W 3/4 represents 3,4 of spectral transmittance) of 0.5 or more. Furthermore, a band stop filter having a spectral absorption in a wavelength band of 430 nm or less, 490 to 530 nm, or 570 to 630 nm.
  • the average color mixing degree in the present invention can widely vary depending on the sensitizing dye used, halogen composition, etc. However, since the average color mixing degree in each element can be adjusted to 0.13 or less in accordance with the present invention by providing a filter having a necessary spectral transmittance (calculated from the average color mixing degree), such a multilayer dielectric-deposited thin film is advantageous in that it can easily attain the present average color mixing degree.
  • a suitable layer is a filter layer to be incorporated in a color negative light-sensitive material.
  • This process is intended to provide the light-sensitive layer side or back side in the color negative light-sensitive material with a spectral absorption by a masking colored coupler.
  • a filter layer may be provided as a nondecolorizable dye-containing filter layer.
  • This process may also be intended to correct undesired absorption by color dyes incorporated in the color negative light-sensitive material.
  • Such a filter layer can be formed using, a colored coupler which has been prepared by optimizing the spectral absorptivity of conventional colored coupler so as to give 0.13 or less for the color mixing degree in a color printing light-sensitive material.
  • a filter layer there can be used a filter layer comprising a colored coupler as described in U.S. Patent Nos. 2,852,370, 2,860,975, 2,841,678, and 3,184,307, French Patent No. 73,826, West German Patent Application Disclosure No. 2,125,220, Japanese Patent Application (OPI) Nos. 45,732/72, 123,34175, and 130,024/79, Japanese Patent Publication Nos. 19,889/73, and 21,565 / 73. and British Patent No. 755,458. Particularly preferred are colored couplers as described in the patent application 129,143/87.
  • Such a filter layer may be provided by dyeing a hydrophilic light-sensitive layer (which may serve as an antihalation layer at the same time) disposed between a support and the nearest light-sensitive layer in a color negative light-sensitive material, dyeing the back layer of the support, or dyeing the support itself.
  • Particularly preferred dyes which can be used in such a dyeing can be selected from the group consisting of nondecolorizable dyes having a sharp spectral absorption in a wavelength band between the maximum spectral sensitivity of BL and GL in the color negative light-sensitive material, e.g., 485 to 530 nm, such as dyes described as specific examples in Japanese Patent Application (OPI) No. 45.237/85 (pages. 6 to 11).
  • a nondecolorizable dye having a sharp spectral absorption in a wavelength band between the maximum spectral sensitivity of GL and RL in the color negative light-sensitive material may be preferably used.
  • a nondecolorizable dye can be selected from the group consisting of anthraquinone dye, triphenylmethane dye, cyanine dye, melocyanine dye, pyrazolonexazole dye, azo dye, phthalocyanine dye, indoaniline dye, and indigo dye. If the above described two types of filter layers are provided in combination, the printing by the subtractive exposure process can be effected as easily as in the conventional process. This process can improve the color mixing degree without deteriorating the color reproducibility, sensitivity and sharpness of the color negative light-sensitive material.
  • a suitable filter layer is a filter layer incorporated in the color printing light-sensitive material.
  • a filter layer may be a filter layer capable of being decolored after development, provided on the light source side in a predetermined light-sensitive layer.
  • Suitable dyes which can be incorporated in such a filter layer can be selected from the group consisting of dyes described in Japanese Patent Publication Nos. consisting of dyes described in Japanese Patent Publication Nos. 1,419/76, and 10,187/80, Japanese Patent Application (OPI) Nos. 154,439/84 and 64,346/85, French Patent Nos. 1,108,788, 2,182,329 and 3,514,450, and West German Patent No. 2,429,228.
  • a suitable filter layer is used while the spectral sensitivity distribution in the silver halide emulsion to be incorporated in the blue-sensitive layer and/or green-sensitive layer is shifted to a shorter wavelength band by reducing the average silver iodide content and average silver bromide content and the mutual color separation in the spectral sensitivity distribution in the blue-sensitive layer, green-sensitive layer and red-sensitive layer is improved by properly selecting sensitizing dyes.
  • Another method to obtain the objects of the present invention includes using a light-sensitive material comprising a blue-sensitive layer containing a yellow coupler, a green-sensitive layer containing a magenta coupler and a red-sensitive layer containing a cyan coupler provided on a support and satisfying the following conditions A), B) and C)
  • the heterocycle formed by Z 1 , Z 2 and Z 21 may contain a substituent such as halogen atom, e.g., F. CI and Br, lower alkyl group, e.g., methyl group, ethyl group, trifluoromethyl group, benzyl group, phenethyl group, hydroxyl group, and alkoxy group, acetyl group e.g., phenyl group, chlorophenyl group, carboxyl group and estrified carboxyl group, carbamoyl group, and sulfamoyl group.
  • a group which particularly forms a J-band, halogen atom, trifluoromethyl group, aryl group, and estrified carboxyl group may be preferably used.
  • R 1 , R 2 , R 21 , R 22 or R 23 there can be used a group commonly used for cyanine dye, such as C 1-6 lower alkyl group, alkoxyalkyl group, acetoxyalkyl group, alkylureidoalkyl group, hydroxyalkyl group, chloroalkyl group, sulfoalkyl group, carboxyalkyl group, allyl group, benzyl group, and phenethyl group.
  • a combination of a compound represented by the general formula (I) and a compound represented by the general formula (II) may be used.
  • the amount of the compound of the general formula (I) and/or (II) to be incorporated in the blue-sensitive layer is not specifically limited but is normally in the range of 10- 6 to 1 x 10- 2 mol, preferably 5 x 10- 5 to 2 x 10- 3 mol per 1 mol of silver halide.
  • a sensitizing dye which is strongly spectrally sensitized in a wavelength band of 485 to 570 nm, preferably about 520 nm, to 570 nm, particularly 530 nm to 570 nm may be' preferably incorporated in the green-sensitive layer.
  • a silver halide emulsion wherein inherent sensitivity of silver halide has been shifted to a short wavelength band shorter than 420 nm by using low silver iodide and silver bromide content silver halide particles may be preferably incorporated in the green-sensitive layer.
  • a silver halide emulsion which is sensitized in a J-band may be preferably incorporated in the green-sensitive layer.
  • Preferred examples of such a compound include those represented by the general formula (III): wherein Z 31 has represents benzimidazole nucleus, benzooxazole nucleus, naphthoimidazole nucleus or naphthooxazole nucleus; Z 32 represents benzimidazole nucleus, naphthoimidazole nucleus benzooxazole nucleus, naphthooxazole nucleus, benzothiazole nucleus or benzoselenazole nucleus which may be substituted; R 31 and R 32 each has the same meaning as R 1 and R 2 in the general formula (I); R 33 represents a hydrogen atom, lower alkyl group or aralkyl group; j 3 and k 3 have the same meaning as j 1 in the general formula (I); n 3 has the same meaning as n 1 in the general fromula (I); and X 3 - represents an acid anion.
  • Z 31 has represents benzimidazole nucleus
  • Suitable substituents which can be contained in the heterocycle formed by Z 31 and Z 32 in the general formula (III) include those described a suitable substituents for heterocycle formed by Z 1 , Z 2 and Z 21 with reference to the general formulae (I) and (II).
  • the amount of the compound of the general formula (III) to be incorporated in the green-sensitive layer is not specifically limited but is normally in the range of 1 x 10- 6 to 1 x 10- 2 mol, preferably 5 x 10- 5 to 2 x 10- 3 mol per 1 mol of silver halide.
  • Two or more sensitizing dyes of the general formula (III) may be incorporated in combination in the green-sensitive layer.
  • a silver halide emulsion having a low silver iodide content or low silver a bromide content may be advantageously incorporated in the green-sensitive layer to inhibit color mixture with the blue-sensitive layer.
  • the red-sensitive layer is spectrally sensitized with a sensitizing dye which gives a strong spectral sensitization in a wavelength band where the spectral absorption by a magenta dye is not observed, e.g., wavelength band of longer than 600 nm, preferably 630 nm, depending on the spectral absorption by a cyan dye in the color negative original.
  • a sensitizing dye which gives a strong spectral sensitization in a wavelength band where the spectral absorption by a magenta dye is not observed, e.g., wavelength band of longer than 600 nm, preferably 630 nm, depending on the spectral absorption by a cyan dye in the color negative original.
  • a silver halide emulsion as described above may be preferably incorporated in the red-sensitive layer to inhibit overlapping with the blue-sensitive layer.
  • Spectral sensitization preferably carried out so that an average color mixing degree with blue sensitive layer and a color mixing degree with green sensitive layer is each less than 0.13.
  • the red-sensitive layer to be used in the present invention may be preferably spectrally sensitized with a sensitizing dye represented by the general formula (IV), (V), or (VI).
  • Z 41 and Z 42 each represents a 5- or 6-membered heterocyclic nucleus such as thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, oxazole nucleus, benzooxazole nucleus, naphthooxazole nucleus, imidazole nucleus, benzimidazole nucleus, naphthoimidazole nucleus, 4-quinoline nucleus, pyrroline nucleus, pyridine nucleus, tetrazole nucleus, indolenine nucleus, benzindolenine nucleus, indole nucleus,
  • R 3 represents a hydrogen atom, lower alkyl group, aralkyl group or aryl group and R 44 represents a hydrogen atom, when m 41 is 2 or 3, R 43 represents a hydrogen atom and R44 represents a hydrogen atom, lower alkyl group or aralkyl group, and R 4 . 3 may be connected to other R 43 's to form a hydrocarbon ring or a heterocyclic ring.
  • Z 51 and Z 52 each has the same meaning as Z 41 or Z 42 ;
  • R 51 and Z 52 each has the same meaning as R41 or R 42 :
  • R 53 represents an alkyl group, alkenyl group, alkynyl group or aryl group such as substituted or unsubstituted phenyl group;
  • m 5 represents an integer of 0, 1 or 2;
  • R 54 represents a hydrogen atom, lower alkyl group or aryl;
  • Q 5 represents a sulfur atom, oxygen atom, selenium atom or >N-R ss in which R 55 has the same meaning as Rs 3 ;
  • Js, R 51 , X 5 ⁇ and n 5 have the same meaning as J 4 , K 4 , X 4 ⁇ and n 4 , respectively, with the proviso that when m 5 represents 2,
  • R 54 may be connceted to other R 54 's to form a hydrocarbon ring or a heterocyclic ring which is preferably a 5-
  • Z 6 represents an atomic garoup required to form a heterocyclic ring (e.g. those as described with reference to Z 41 and Z 42 , such as thiazolidine, thiazoline, benzothiazoline, naphthothiazoline, selenazolidine, selenazoline, benzoselenazoline, naphthoselenazoline, benzooxazoline, naphthooxazoline, dihydropyridine, dihydroquinoline, benzimidazoline, and haphthoimidazoline);
  • Q 6 has the same meansing as Q 5 ;
  • R 61 has the same meaning as R 51 or R 52 , Rs2 has the same meaning as R 53 ;
  • m 6 has the same meaning as ms;
  • R 63 has the same meansing as R 54 ; and
  • j 6 has the same meaning as js, with the proviso that when m 6 is 2 or 3;
  • Rs 3 may be connceted to other R
  • the sensitizing dyes of the presenht invention represented by the general formulae (IV), (V) and (VI) mkay be used in an amount of 1 x 10- 6 to 5 x 10- 6 to 1 x 10- 3 mol per 1 mol of silver halide, singly or in combination with other susper sensitizers.
  • the spectral transmittance distriubiton Ti(X) of a dye image obtained by the coupling reaction of a yellow, magenta or cyan coupler in a photographic color light-sensitaive material with a color developing agent affects the color mixing degree or the layer average color mixing degree r as shown in Equation (2-1) or (2-5).
  • a couler which provides an excellent color separation between dye images, particularly yellow andl magenta may be preferably used.
  • an average color mixing degree of color forming layer of a color printing light-sensitive material may be 0.13 or less by a process for the formation of color images which comprises printing on a color printing light-sensitive material from a color print original in a substactive exposure process, and subsequently color-developing said color pinting light-sensitive material, characterized in that said color printing light-sensitive material comprises at least one blue-sensitive layer, at least one green-sensitive layer and at least one red-sensitive layer provided on a support, said green-sensitive layer has an effective spectral sensitive light amount distribution which is substantially formed by a J-type sepctral sensitization, said red-sensitive layer has an effective spectral sensitive light amount distribution which is substnatially formed by an M-type or J-type spectral sensitization, the effective spectral sensitive light amount distribution of said green-sensitive layer and said red-sensitive layer, and/or the effective spectral sensitive light amount distribution of said green-sensitive layer and said blue-sensitive layer are substantially independent, and
  • the red-sensitive layer (RL) can be more easily provided depending on T ( ⁇ ) of the coloring material in the color print original on a wavelength band longer than the wavelength band for the green-sensitive layer. Therefore, in order to make E r( ⁇ ) independent from the other effective spectral sensitive energy distributions, any suitable sensitizing dye selected from those represented by the general formulas (IV), (V) and (VI) may be used to provide a maximum S ( ⁇ ) given by a J-type or M-type spectral sensitization. Sensitizing dyes represented by the general formula (IV) may be used to give a J-type spectral sensitivity. Sensitizing dyes represented by the general formulas (V) and (VI) may be used to give an M-type spectral sensitivity.
  • the spectral sensitization in the present color printing light-sensitive material essentially features a J-type spectral sensitization or M-type spectral sensitization.
  • the effective spectral sensitive light volume distribution in the green-sensitive layer (E g( ⁇ ) ) is given substantially by a J-type spectral sensitization
  • the effective spectral sensitive distribution in the red-sensitive layer (E r( ⁇ ) ) is given substantially by an M-type spectral sensitization or J-type spectral sensitization.
  • a J-type spectral sensitization is a sensitization by spectral absorption obtained by adsorption by J aggregates on a silver halide adsorbing substrate of a sensitizing dye.
  • An M-type spectral sensitization is a sensitization by spectral absorption obtained by molecular adsorption by a sensitizing dye. Examples of these types of spectral sensitizations are described in T. H. James, "The Theory of the Photographic Process", 4th ed., 1977, pp. 218-222.
  • Eg(h) is attributed to a J-type spectral sensitization, it means that E g ( ⁇ ) doesn't exhibit the maximum value of Eg(X) corresponding to an M-type spectral esnsitization. If Eg(h) is substantially attributed to a J-type spectral sensitization, it means that in the wavelength band for the green-sensitive layer the maximum value of Eg(X) corresponding to an M-type spectral sensitization does not exhibit a value over the value of about one-second, preferably one-third the maximum value of Eg( ⁇ ) corresponding to a J-type spectral esnsitization.
  • E ( ⁇ ) when S ( ⁇ ) is attributed to a J-type spectral sensitization, E ( ⁇ ) corresponding to the wavelength is normally attributed to a J-type spectral sensitization.
  • E ( ⁇ ) is attited to a J-type spectral sensitization or M-type spectral sensitization from. the structure of a sensitization dye used, the spectral absorption characteristics of the solution of the sensitizing dye, and the spectral absorption characteristics of the sensitizing dye adsorbed by silver halide.
  • the compound represented by the general formula (XI) has a strong effect of supersensitization for the M-type spectral sensitization of the present invention and thus tends to convert an H-type or J-type adsorption into an M-type adsorption.
  • a spectral sensitization belongs to M-type or noe from the spectral absorption characteristics of the sensitizing dye with respect to a silver halide adsorbing substrate which has been adjusted for a proper halogen composition by the use of, for example, Compound XI-(9) among compounds represented by the general formula (XI).
  • the present invention is advantageous in that S ( ⁇ ) , which is a factor of E( X ), is attributed to an M-type spectral sensitization, J-type spectral sensiitzation, or a spectral sensitization of a single structure such as inherent sensitivity of silver halide. Therefore, the gradation of images has a less fluctuation due to conditions of the object and printing conditions, and the gradation reproduction has a wide latitude. This is extremely advantageous to the present invention.
  • the use of a J-type spectral sensitization leaves to be desired in that it is difficult for aggregates of a sensitizing dye to be removed during the color development, causing color leaving and stain.
  • the use of a J-type spectral sensitization is disadvantageous in that it tends to retard the progress of color development, particularly the progress of blix of reduced silver. Therefore, such a defect can be eliminated by an improvement in the development process.
  • a coloring material in which T ( ⁇ ) of the coloring material in a photographing color light-sensitive material is reflected by E ( ⁇ ) is important in the present invention.
  • a coupler represented by the general formula (VIII) may by advantageously used in the present invention.
  • Such a coupler is advantageous in that it facilitates the use of a masking coloring material for the longer wavelength side in a yellow coloring material or filter coloring material which is adapted to improve E ( ⁇ ) of GL in a color printing light-sensitive material.
  • the use of such a coupler or a benzoylacetanilide type yellow coupler can provide a thin light-sensitive layer or improve image sharpness.
  • the sensitizing dye may be selected from those represented by formula (III) to provide a maximum S(X) given by a J-type spectral sensitization in order to make Eg(X) independent from Eb(x) or Er(X). Especially, it is preferred to carry out spectral sensitization so as to decrease a contribution by M-type spectral sensitization.
  • a use of CR-compounds disclosed in Japanese Patent Application Nos. 311131/86 and 47225/87 is preferred.
  • the color printing light-sensitive material according to the present invention may be printed from a color print original, particularly from a color genative film or color slide, in the above described white color exposure process.
  • a sharp band stop filter having a spectral absorption band in a wavelength band other than the range of ⁇ smax ⁇ 20 nm, ⁇ smax being a wavelength of the maximum S(X) of a light-sensitive layer of a color printing light-sensitive material may be preferably used in this exposure process.
  • a suitable sharp band stop filter there may be preferably used a band stop filter.
  • At least one of the color development bleach, fixing (or blix) and rinse and/or stabilization is effected in the presence of at least one of compounds represented by the general formula (XI).
  • the compound represented by the general formula (XI) may be incorporated in the light-sensitive material to be processed.
  • the pH value of the bleaching solution or blix solution is in the range of 3.5 to 6.0.
  • the replenishing amount of the solution for the subsequent rinse and / or stabilization step may be 3 to 50 times the amount of the solution carried over from the pre-bath.
  • the compound represented by the general formula (XI) may be used as a supersensitizing dye for an M-type spectral sensitization process as described above.
  • the compound represented by the general formula (XI) is advantageous in that it destroyes and puts H, D or J aggregates into a monomolecular adsorption state to intensify the M-type spectral sensitization, particularly when X and Y are not the same.
  • R, and R3 are the same and R 2 and R 4 are the same at the same time. nor that R, and R 4 are the same and R 2 and R 3 are the same at the same time.
  • a compound represented by the general formula (I) wherein three or more sulfonic acid groups are incorporated in one molecule may be preferably used.
  • a particularly remarkable effect of inhibiting stain or eliminating fluctuation in photographic properties can be observed particularly by using the compound represented by formula (XI) other than the compound of formula (XI) wherein R 1 and R 3 are the same and R 2 and R 4 are the same at the same time, or R 1 and R 4 are the same and R 2 and R 3 are the same at the same time.
  • the process following the color development e.g. desilvering, rinse and stabilization
  • the replenishing amount of the solution to be used in the rinse or stabilization step is remarkably small, such an effect becomes remarkable.
  • the amount of water and time which has been conventionally required to reduce mixture or residual color on a light-sensitive material is not necessarily needed.
  • Ri, R 2 , R 3 and R 4 each represents a hydroxy group, C 1-4 alkoxy group such as methoxy group. ethoxy group, and methoxyethoxy group, amino group, C, - 6 alkylamino group such as methylamino group, ethylamino group, propylamino group, dimethylamino group, cyclohexylamino group, ⁇ -hydroxyethylamino group, di( ⁇ -hydroxyethyl)amino group, ⁇ -sulfoethylamino group, N-( ⁇ -sulfoethyl)-N-methylamino group, and ⁇ -carboxyethyl group, aryloxy group such as phenoxy group, and p-sulfophenyl group, or arylamino group such as anilino group, o-, m-, and p-sulfoanilino group, o-, m- and
  • M represents a monovalent cation such as Na and K .
  • diaminostylene brightening agent which can be used in the present invention represented by formula (XI) can be accomplished by any suitable conventional method as described in Kaseihin Kogyokai, "Fluorescent Brightening Agent", August 1976, page 8.
  • the amount of such a fluorescent brightening agent to be added to a processing solution such as color developing solution, blix solution and stabilizing solution is preferably in the range of 0.1 to 20 g/l, particularly 0.5 to 10 g/l.
  • the present silver halide emulsion particularly to be used in a color printing light-sensitive material is preferably a silver bromochloride emulsion substantially free of silver iodide and comprising silver chloride, silver bromide or mixed crystal thereof surrounded mainly by (100) plane as described in Japanese Patent Application Nos. 39,825I87 and 319,741/87.
  • the present silver halide emulsion is also preferably a silver bromochloride emulsion substantially free of silver iodide and comprising silver chloride, silver bromide or mixed crystal thereof surrounded mainly by (111) plane as described in Japanese Patent Application Nos. 47,225i87 and 150.320/87.
  • silver bromide, silver bromochloride or silver chloride having various compositions can be used.
  • silver bromochloride having a silver bromide content of 30 mol% or less or silver bromochloride or silver chloride emulsion having a silver iodide content of 0.4 moi% or less and a silver bromide content of 10 mol% or less is preferably used.
  • silver chloride having a silver bromide content of 3 mol% or less, preferably 1 mol% or less or substantially free of silver bromide is preferably used.
  • the halogen composition of the silver halide emulsion to be used in the present invention influences color leaving by dyes and desilvering during the color development.
  • a high silver iodide content gives a disadvantageous effect.
  • the present silver halide emulsion contains silver iodide in a appropriate amount of 2 mol% or less, preferably 1 mol% or less, more preferably 0.4 mol%, most preferably none, based on the total amount of silver halide.
  • the incorporation of silver iodide has many advantageous effects in light-sensitivity.
  • silver iodide increases light absorption or spectral sensitizing dyes or inhibits desensitization due to a spectral sensitizing dye.
  • a slow development speed causes a slow speed in development of the entire silver halide particles.
  • silver chloride having a silver bromide content of 3 mol% or less, preferably 1 mol% or less or substantially free of silver bromide may be preferably used.
  • a light-sensitive material which is insusceptible to fog and exhibits a stable gradation in accordance with the present technique
  • an emulsion having a higher silver bromide content, e.g. 50 mol% or more. If the silver bromide content exceeds 95 mol%, the rapidness in development is slightly lowered.
  • a development accelerator such as 3-pyrazolidone, thioether and hydrazine is used with the emulsion, the rapidness in development can be recovered, making it possible to provide a high sensitivity light-sensitive material stable in preservability and proccessability.
  • Particulate silver halide to be contained in the present photographic emulsion may have a regular crystal structure such as cube, octahedron, and tetradecahedron, an irregular crystal structure such as sphere, and plate, a crystal structure having crystal defect such as twinning plane, or a composite thereof.
  • Tabular particles having an aspect ratio of from about 2 or more, preferably about to about 10, more preferably about 5 to about 10 may be used in the present invention.
  • Such tabular particles can be easily prepared by any suitable method as described in Gutoff, "Photographic Science and Engineering”, as described in Gutoff. "Photographic Science and Engineering", Vol. 14, pp. 248-257, 1970, U.S. Patent Nos. 4,434,226, 4,414,310, 4,433,048, and 4,439,520, and British Patent No. 2,112,157.
  • the crystal structure of the present particulate silver halide may be uniform, or such that the halide composition varies between the inner portion and the outer portion thereof, or may be a layer.
  • silver halides having different compositions may be connected to each other by an epitaxial junction or by any suitable compound other than silver halide such as silver thiocyanate, and zinc oxide.
  • a mixture of particles having various crystal structures may be used in the present invention.
  • the silver halide emulsion of the present invention preferably has some distribution or structure concerning the halogen composition in the particles thereof.
  • a typical example of such a structure is a core/shell type or double structure type particle in which the internal portion thereof differs from the surface thereof in halogen composition.
  • the shape of the core may or may not be the same as that of the entire particle with the shell.
  • both the core and the entire particle with the shell may be cubic, or the core may be octahedron while the entire particle with the shell may be cubic.
  • the core may be in the form of a completely regular crystal while the entire particle with the shell may be slightly irregular.
  • the particulate silver halide may not be merely double-structured but may be triple-structured or may have a higher multistructure.
  • the surface of a core%shell double-structured particle may be provided with aq thin film of silver halide having a different halogen composition.
  • Preferable silver halide particles have maldistributed phases comprising layer structure or discontinuous isolated structure containing a different halide distribution on a surface or internal part of particles from in other phases.
  • silver chlorobromide particles having maldistributed phases have a cubic structure having (100) plane or tetradecahedron, and also have a structure of octahedron having (111) plane or tabular particles, especially having 2 to 10 of aspect ratio.
  • An emulsion containing particulate silver halide which has been adjusted for proper development starting points as described in Japanese Patent Application Nos. 319,741/87, 323,214/87 and 150,320/87 may be particularly preferably used in the present invention.
  • CR-compound as described in the above cited specification may be preferably sensitizing dyes.
  • the average size of particles to be used in the present silver halide emulsion is preferably in the range of 0.1 to 2 ⁇ rn, particularly 0.15 to 1.4 u.m as calculated in terms of diameter of sphere having the same volume.
  • the particle size distribution of the present particulate silver halide is preferably narrow.
  • a monodisperse emulsion is preferably used in the present invention.
  • a monodisperse emulsion of particles having a regular crystal shape may be preferably used in the present invention.
  • An emulsion of silver halide particles, preferably 90% or more, more preferably 95% or more by weight or number of particles of which fall within ⁇ 20% of the average particle size may be preferably used in the present invention.
  • Monodisperse emulsion is preferred as is disclosed in U.S. Patents 3,574,628 and 3,655,394, and Great Britain Patent 1,413,748, etc.
  • an emulsion comprising particulate silver halide having any suitable construction as described above may be preferably used in the present invention.
  • Two or more different kinds of monodisperse emulsions of cubic- or tetradecahedron particulate silver halide may be used in admixture or by coating in multilayer to provide an excellent result.
  • the mixing ratio as calculated in terms of amount of silver is preferably 5 to 95%.
  • the ratio of average particle size of emulsion particles to be mixed is 1:1.1 to 1:8, preferably 1:1.2 to 1:6 as calculated in terms of volume.
  • the mixing ratio is calculated in terms of amount of silver is preferably in the range of 0.05:0.95 to 0.95:0.05, particularly 0.1:0.9 to 0:9:0.1.
  • the preparation of a silver bromochloride emulsion to be used in the present invention can be accomplished by any one of acidic process, neutral, process, and ammonia process. Particularly preferred among these processes is acidic process.
  • the process for the reaction of the soluble silver salt with the soluble silver halide can be accomplished by separate mixing process, simultaneous mixing process, or combination thereof. In order to obtain monodisperse particles of the present invention, simultaneous mixing process may be preferably used.
  • the process for the reaction of the soluble silver salt with the soluble silver halide can be also accomplished by a process in which particles are formed in excess silver ions (so-called reversal mixing process).
  • One form of the simultaneous mixing process is a so-called controlled double jet-process in which the pAg of the liquid phase in which silver halide is formed is kept constant.
  • This process can provide a silver halide emulsion suitable for the present invention having a regular crystal structure and a narrow particle size distribution.
  • Such particles which can be preferably used in the present invention may be preferably prepared on the basis of the simultaneous mixing process.
  • cadmium salt zinc salt, lead salt.
  • thallium salt, iridium salt, or complex salt thereof, rhodium salt or complex thereof, or iron salt or complex salt thereof may be present.
  • iridium salt or complex salt thereof may be used in an amount of 10- 9 to 10- 4 mol/mol, preferably 10- 8 to 10-5 mol/mol.
  • a consideration is useful particularly when a rapid developability or stability is desired for a light-sensitive material which has been subjected to high intensity or low intensity exposure out of the proper exposure intensity range.
  • the removal of the soluble silver salts from the emulsion which has been subjected to physical ripening can be accomplished by any suitable method such as noodle rinsing process, flocculation sedimentation process, and ultrafiltration process.
  • the silver halide emulsion to be used in the present invention can be subjected to chemical sensitization such as selenium sensitization, reduction sensitization, noble metal sensitization, or combination thereof.
  • chemical sensitization such as selenium sensitization, reduction sensitization, noble metal sensitization, or combination thereof.
  • sulfur sensitization process using active gelatin or sulfur-containing compound capable of reacting with silver ion such as thiosulfate, thiourea compound, mercapto compound, and rhodanine compound
  • reduction sensitization process using a reducing substance such as stannous salt, amine salt, hydrazine derivative, formamidinesulfinic acid.
  • the present monodisperse silver bromochloride emulsion may be preferably subjected to sulfur sensitization or selenium sensitization. Such a senisitization process may be preferably effected in the presence of a hydroxylazaindene compound.
  • Preferred examples of a silver halide emulsion to be incorporated in the direct positive color printing light-sensitive material include an emulsion of internal latent type silver halide particles having the above described halogen composition and a multilayer construction as described in. Japanese Patent Application Nos. 25,737/87.
  • Preferred examples of a silver halide emulsion to be incorporated in the color reversal printing light-sensitive material include those described in European Patent No. 0217353A-2, and Japanese Patent Application (OPI) Nos. 39,043;86, and 61,156/86.
  • the blue-sensitive layer in the color printing light-sensitive material may preferably comprise a sensitizing dye such that it is not strongly sensitized to a long wavelength up to about 485 nm and is given a high spectral sensitivity in a shorter wavelength band less than about 485 nm. more preferalby less than about 460 nm, depending on the spectral absorption characterisitcs of dyes to be used in the color print original.
  • the silver halide may be preferably subjected to a spectral sensitization such that the inherent sensitivity thereof is limited in a short wavelength band and it is strongly sensitized on the long wavelength side, e.g., 450 to 470 nm while its sensitization is cut in a longer wavelength band, e.g., 485 nm or more.
  • the spectral absorption by a dye obtained by the coupling reaction of the respective yellow, magenta and cyan coupler in a color light-sensitive material for use in photographing with a color developing agent may preferably correspond to the spectral absorption by the corresponding blue-sensitive layer, green-sensitive layer or red-sensitive layer in a color printing light-sensitive material, and there is substantially no spectral absorption in the range of wavelength of spectral sensitivity of light-sensitive layers other than the corresponding light-sensitive layer.
  • the spectral absorption by a dye obtained in a color light-sensitive material for use in photographing is preferably out of the range of ⁇ E max t20 nm, XE max being the maximum spectral light amount of light-sensitive layers other than the corresponding light-sensitive layer of a color printing light-sensitive, preferably out of the range of XE max ⁇ 30 nm.
  • the present invention gives an unprecedentely remarkable improvement in color reproducibility. This is because that the disadvantageous effects by the spectral absorption by a dye in a cut wavelength range given by the present band cut filter is substantially completely eliminated.
  • the spectral absorption by a yellow, magenta or cyan dye obtained from a coupler to be used in a color printing light-sensitive material is only seen in the wavelength range of spectral absorption by a blue-sensitive layer, green-sensitive layer or red-sensitive layer in a color light-sensitive material for use in photographing.
  • Couplers which may be generally used in the present invention are described in patents cited in Research Disclosure No. 17,643, VII-C to G.
  • yellow couplers there can be used those described in U.S. Patent Nos. 3,933,501, 4,022,620, 4,326,024, and 4,401,752, Japanese Patent Publication No. 10.739/83, and British Patent Nos. 1,425,020, and 1,476,760.
  • magenta couplers there may be used 5-pyrazolone and pyrazoloazole compounds. Particularly preferred examples of such magenta couplers are described in U.S. Patent Nos. 4,310,619, 4,351,897, 3,061,432, 3,725,067, 4,500,630, and 4,540,654, European Patent No. 73,636, Research Disclosure Nos. 24,220 (June 1984) and 24,230 (June 1984), and Japanese Patent Application (OPI) Nos. 33,552/85, and 43,659/85.
  • cyan couplers there may be used phenolic and naphtholic couplers.
  • Preferred examples of such couplers are described in U.S. Patent Nos. 4,052,212, 4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162. 2,895,826, 3,772,002, 3,758,308, 4,334,011. 4,327,173, 3,446,622, 4,333,999, 4,451.559, and 4,427,767, West German Patent Disclosure No. 3,329,729, and European Patent Nos. 121.365A, and 161,626A.
  • colored couplers for correcting undesired absorption by color forming dye there may be used those described in Research Disclosure No. 17.643 (VII-G), U.S. Patent Nos. 4,163,670, 4,004,929, and 4,138,258, Japanese Patent Publication No. 39.413/82, and British Patent No. 1,146,368.
  • couplers which form a colored dye having a proper diffusibility there may be used those described in U.S. Patent No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,570, and West German Patent (Disclosure) No. 3,234,533.
  • Couplers which release a photographically useful residual group upon coupling can be preferably used in the present invention.
  • DIR couplers which release a development inhibitor there can be preferably used those described in patents cited in Research Disclosure No. 17,643 (VII-F), Japanese Patent Application (OPI) Nos. 151,944,82. 154,234.82, and 184,248/85, and U.S. Patent No. 4,248,962.
  • couplers which imagewise release a nucleating agent or development accelerator upon development there can be used those described in British Patent Nos. 2,097,140, and 2,131,188, and Japanese Patent Application (OPI) Nos. 157,638/84, and 170,840/84.
  • couplers which can be incorporated in the present light-sensitive material include competitive couplers as described in U.S. Patent No. 4,130,427, poly-equivalent couplers as described in U.S: Patent Nos. 4,283,472, 4,338,393, and 4,310,618, DIR redox compound-releasing couplers as described in Japanese Patent Application (OPI) No. 185,950/85, and couplers which release a dye which recovers its original color after being separated as described in European Patent No. 173,302A.
  • magenta couplers as described in European Patent 226,849 A
  • cyan couplers as described in Japanese Patent Application (OPI) No. 105,229/83
  • color couplers as described in Japanese Patent Application No. 39,825/87.
  • Particularly preferred examples of such couplers inlcude color couplers represented by the general formulas (VII-a), (VII-b), (VIII), (IX) and (X).
  • R 71 , R 74 , and R 75 each represents an aliphatic group (the term "aliphatic group” as used herein means a straight-chain, branched or cyclic alkyl, alkenyl or alkynyl group), aromatic group, heterocyclic group, aliphatic amino group, aromatic amino group or heterocyclic amino group;
  • R 73 represents an aliphatic group;
  • R 72 and R 76 each represents a hydrogen atom, halogen atom, aliphatic group, aliphatic oxy group, or acylamino group;
  • Y 1 and Y 2 each represents a hydrogen atom or group which can be separated after coupling reaction with an oxidation product of a color developing agent (hereinafter including an atom, such as a halogen atom), with the proviso that R 72 and R 73 or R 75 and R 76 may be connected to each other to form 5-, 6- or 7-membered condensated carbostyryl or oxyindole
  • R 8 represents a hydrogen atom or substituent.
  • substituents include alkyl group such as methyl group, ethyl group, and butyl group; branched alkyl group such as isopropyl group, isobutyl group, and tertiary butyl group; substituted alkyl group (including branched groups); alkoxy group such as methoxy group, ethoxy group, and butoxy group; substituted alkoxy group such as ethoxyethoxy group, and phenoxyethoxy group, o-methoxyphenoxyethoxy group, o-butoxyphenoxyethoxy group, o-chlorophenoxyethoxy group; aryloxy group such as phenoxy group, o-methoxyphenoxy group, o-butoxyphenoxy group, o-chlorophenoxy group; and ureide group.
  • X represents a hydrogen atom or group which can be separated upon a coupling reaction with an oxidation product of an aromatic primary amine color developing agent.
  • halogen atom such as chlorine atom and bromine atom
  • arylthio group such as 2-butoxy-5-t-octylphenylthio group, and 2-propoxy-5-t-hexyphenylthio group
  • nitrogen-containing heterocyclic group such as imidazole group, and 4-chloroimidazole group
  • aryloxy group such as p-methylphenoxy group, 2,4-dimethylphenoxy group, and 2,4-dimethyl-t-phenoxy group.
  • Particularly preferred among these groups are halogen atom and arylthio group.
  • Za-Zb bond and Zb-Zc bond is a double bond, and the other is a single bond. If Za-Zb is a carbon-carbon double bond, it may be a part of an aromatic ring. Furthermore, R 81 or X may form a dimer or higher polymer. If Za, Zb or Za is a substituted methine, the substituted methine may form a dimer or higher polymer.
  • the substituent is preferably a substituted alkyl group, particularly a branched substituted alkyl group such as substituted isopropyl group, and substituted tertiary butyl group.
  • an aryl group such as a halogen substituted phenyl group is also preferable.
  • Y 3 represents a hydrogen atom or coupling-off group
  • R 91 and R 93 each represents a substituted or unsubstituted phenyl group
  • R 92 represents a hydrogen atom: aliphatic group or aromatic acyl or sulfonyl group.
  • Y 3 is a hydrogen atom or a coupling-off group containing sulfur atom as a coupling-off atom.
  • R 91 group is a substituted phenyl group and preferable R 93 group is a trichlorophenyl group.
  • Q represents a substituted or unsubstituted N-phenylcarbamoyl group
  • Y4 represents a halogen atom or the other group capable of released upon a coupling reaction with an oxidation product of a developing agent (preferable coupling-off atom contained in the coupling-off group is a nitrogen atom).
  • the couplers to be used in the present invention may be incorporated in a light-sensitive material by various known dispersion processes.
  • main couplers for the formation of dye which can be incorporated in a color light-sensitive material for use in photographing or color printing light-sensitive material will be shown hereinafter.
  • the printed color printing light-sensitive material according to the present invention may be preferably subjected to color development, blix, rinse and/or stabilization. Typical examples of processing steps will be described hereinafter, but the present invention should not be construed as being limited thereto.
  • blix as used herein means a so-called blix in which bleaching and fixing are simultaneously proceeded or a process in which bleaching and fixing are separately .proceeded
  • the step may be replaced by the stabilizing step.
  • the supply amount of the processing solution is 3 to 50 times the amount of the processing solution carried over from the pre-bath.
  • the color printing light-sensitive material according to the present invention may be susceptible to dye leaving, poor desilvering, and stain.
  • the color developing solution to be used in the present invention may comprise any suitable known aromatic primary amine color developing agent.
  • a preferred example of such an aromatic primary amine color developing agent is a p-phenylenediamine derivative. Typical examples of such a p-phenylenediamine derivative will be shown hereinafter, but the present invention should not be construed as being limited thereto.
  • p-phenylenediamine derivatives is 4-amino-3-methyl-N-ethyl-N-[ ⁇ -(methanesulfonamide)ethyl]-aniline (exemplary compound D-6).
  • These p-phenylenediamine derivatives may be salts such as sulfates, hydrochloride, sulfites, and p-toluenesulfonates.
  • the amount of such an aromatic primary amine developing agent to be used is preferably in the range of about 0.1 to about 20 g, particularly about 0.5 to about 10 g per 1 l of developing solution.
  • the present color developing solution may optionally comprise any suitable development accelerator.
  • the present color developing solution preferably doesn't contain benzyl alcohol in the light of pollution, facility in solution preparation, and fog inhibition.
  • the present color developing solution may contain benzyl alcohol in an amount of 5 ml or less, preferably 2 ml or less per 1 t thereof.
  • the present color developing solution is free of benzyl alcohol.
  • the present color developing solution may optionally comprise any other preservatives such as sulfite, e.g., sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metabisulfite, and potassium methasulfite, and carbonyl-sulfite addition product.
  • sulfite e.g., sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metabisulfite, and potassium methasulfite
  • carbonyl-sulfite addition product e.g., sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metabisulfite, and potassium methasulfite
  • carbonyl-sulfite addition product e.g., carbonyl-sulfite addition product.
  • the added amount of such a preservative is in the range of 0 to 20 g/l. preferably 0 to 5
  • the color developing solution contains a small amount of. sulfite ion
  • the colour developing capability thereof can be improved without increasing the used amount of silver halide or color couplers.
  • the reduction in the sulfite ion content increases color stain and deteriorates color reproducibility.
  • the present color image formation process using compounds represented by formula (XI) enables a processing which causes less color stain and provides an excellent color developing capability.
  • Sulfite ion may serve as a solvent for a silver halide emulsion having a high chlorine content (high silver chloride content emulsion), causing a remarkable reduction in the concentration of sulfite ion. If the sulfite ion concentration in the color developing solution varies due to the above described effect, the photographic properties, particularly printer conditions in the case of a printing light-sensitive material, show a continuous change.
  • the substantial absence of sulfite ion may be preferably compensated by the incorporation of an organic preservative as described hereinafter.
  • the incorporation of such an organic preservative can stabilize the color developing solution and improve color mixture inhibition without deteriorating the color developing capability.
  • An organic preservative can be used in the present invention is an organic compound which reduces the speed of deterioration of an aromatic primary amine color developing agent when incorporated in a solution for the processing of a color photographic light-sensitive material.
  • an organic compound serves to inhibit oxidation of a color developing agent by air.
  • Particularly useful examples of such an organic preservative include hydroxylamines, hydroxams, hydrazines, hydrazides, phenols, a-hydroxyketones, a-aminoketones, saccharides, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, and condensed ring amines.
  • Examples of Compounds which can be used in combination with these compounds include monoamines as described in Japanese Patent Application Nos. 147,823,86, 166,674/86, 165,621/86, 164,515/86, 170,789i86, and 168,159/86, diamines as described in Japanese Patent Application Nos. 173,595/86, 164,515/86, and 186,560/86, polyamines as described in Japanese Patent Application Nos. 165,621 86, 169,789/86, and 188,619/86, nitroxy radicals as described in Japanese Patent Application No. 197,760 / 86, alcohols as described in Japanese Patent Application Nos.
  • the present color developing solution may also contain an agent for restoring or capturing oxidation product of color developing agent as described in Japanese Patent Application No. 259,799/86.
  • preservatives which may be optionally incorporated in the present color developing solution include various metals as described in Japanese Patent Application (OPI) Nos. 44,148/82, and 53,749/82, salicylic acids as described in Japanese Patent Application (OPI) No. 180.588/84, alkanolamines as described in Japanese Patent Application (OPI No.
  • the color developing solution to be used in the present invention preferably has a pH value of 9 to 12, particularly 9 to 11.0.
  • the present color developing solution may contain compounds which constitute known developing solutions.
  • buffering agents may be preferably used.
  • buffering agents there may be used carbonates, phosphates, borates, tetraborates, hydroxybenzoates, glycine salts, N,N-dimethylglycine salts, leucine salts, norleucine salts, guanine salts, 3,4-dihydroxyphenyl- alanine salts, alanine salts, aminobutyrates, 2-amino-2-methyl-1,3-propanediolates, valine salts, proline salts, trishydroxyaminomethane salts, or lysine salts.
  • carbonates, phosphates, tetraborates, and hydroxybenzoates are excellent in solubility and buffering action at a high pH range of 9.0 or more.
  • these salts are inexpensive. In the light of such advantages, these salts may be particularly preferably used.
  • the amount of such a buffering agent to be incorporated in the color developing solution is preferably in the range of 0.1 mol/ or more, particularly 0.1 to 0.4 mol/ .
  • an organic phosphoric compound as described in Japanese Patent Application No. 37,350/87 may be preferably used.
  • the added amount of such an organic phosphonic compound is in the range of 0.1 to 40 g, preferably 0.2 to 10 g per I of color developing solution.
  • the present color developing solution may also contain various chelating agents other than organic phosphonic chelating agents.
  • chelating agents which can be used in combination with other additives include nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine tetraacetic acid, trancyclohexanediaminetetra-acetic acid, 1,2-diaminopropanetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediamineorthohydroxyphenylacetic acid, and N,N-bis(2-hydroxybenzyl)ethylenediamine-N,N -diacetic acid.
  • the present invention should not be construed as being limited to these chelating agents.
  • chelating agents may optionally be used in combination.
  • the present color developing solution may optionally comprise any suitable development accelerator.
  • the present color developing solution may preferably be substantially free of benzyl alcohol in the light of pollution, facility in solution preparation, fog inhibition, and stain inhibition.
  • development accelerators which can be optionally incorporated in the present color developing solution include thioether compounds as described in Japanese Patent Publication Nos. 16,088/62, 5,987/72. 7,826 / 63, 12,380/69, and 9,019/70, p-phenylenediamine compounds as described in Japanese Patent Application (OPI) Nos. 49,829/77, and 15,554/75, quaternary ammonium salts as described in Japanese Patent Application (OPI) Nos. 49,829/77, and 15,554/75, quaternary ammonium salts as described in Japanese Patent Application (OPI) Nos. 137,726175, 156,826/81, and 43,429/77, and Japanese Patent Publication No.
  • any suitable fog inhibitor may be optionally used.
  • a fog inhibitor there may be used a halide of an alkaline metal such as sodium chloride, potassium bromide, and potassium iodide, or an organic fog inhibitor.
  • an organic fog inhibitor include nitrogen-containing heterocyclic compounds such as benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole. 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolylbenzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolidine, and adenine.
  • the present color developing solution may optionally contain various active agents such as alkylsulfonic acid, arylphosphonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid.
  • the temperature at which the present color developing solution is used is in the range of 20 to 50° C, preferably 30 to 40 C.
  • the processinhg time is in the range of 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes.
  • the replenishing amount of the present color developing solution is preferably less and is in the range of 20 to 600 ml, preferably 50 to 300 ml, particularly 100 to 200 ml per 1 m 2 of light-sensitive material. The shorter the development time is, the more remarkable is the effect of the present invention.
  • the black-and-white developing solution may comprise known black-and-white developing agents such as dihydroxybenzene, e.g., hydroquinone, 3-pyrazolidone, e.g., 1-phenyl-3-pyrazolidone, and aminophenol, e.g., N-methyl-p-aminophenol, singly or in combination.
  • known black-and-white developing agents such as dihydroxybenzene, e.g., hydroquinone, 3-pyrazolidone, e.g., 1-phenyl-3-pyrazolidone, and aminophenol, e.g., N-methyl-p-aminophenol, singly or in combination.
  • These color developing solution and black-and-white developing solution normally have a pH value of 9 to 12.
  • the replenishing amount of these developing solutions depends on the type of the color photographic light-sensitive material to be processed but is normally in the range of 3 t per 1 m 2 of the light-sensitive material. If the replenishing liquid of the developing solution has a reduced concentration of bromide ion, the replenishing amount thereof can be 500 ml or less. If the replenishing amount of the developing solution is reduced, the area of the processing tank in contact with air is preferably reduced to prevent the solution from being evaporated or oxidized by air. A means of restricting the accumulation of bromide ion in the developing solution may be used to reduce the supply amount of the developing solution.
  • the photographic emulsion layer which has been subjected to color development is normally then subjected to bleaching.
  • the bleaching solution, blix solution and fixing solution to be used in the present invention will be further described hereinafter.
  • a bleaching solution or blix solution is unstable at a pH of 6 to 8.
  • the bleaching bath is more stable and more excellent in bleaching capability at a pH range of 3.5 to 5 than a pH value of 7.
  • a cyan die is converted to a leuco-compound in this pH range.
  • This approach also improves the bleaching capability. This approach further effectively eliminates stain which easily occurs after a processing with a two-equivalent coupler.
  • bleaching agent for the present bleaching solution or blix solution there can be used any suitable bleaching agent.
  • suitable bleaching agents include organic complex salts of iron (III) with organic acids such as aminopolycarboxylic acid, e.g., ethylenediaminetetraacetic acid, and diethylenetriaminepentaacetic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, tartaric acid, and malic acid, persulfate, and hydroperoxide.
  • organic complex salts of iron (III) are organic complex salts of iron (III) in the light of rapidness of the development and pollution prevention.
  • useful aminopolycarboxylic acid, aminopolyphosphonic acid, organic phosphonic acid, and salts thereof which can be used to form such organic complex salts of iron (III) include ethylenediaminetetraacetic acid, diethylenetraminepentaacetic acid, 1,3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, and glycoletherdiaminetetraacetic acid.
  • These compounds may be sodium salts, potassium salts, lithium salts or ammonium salts. Particularly preferred among these compounds are complex salts or iron (III) with ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, and methyliminodiacetic acid.
  • ferric iron complex salts may be used in the form of a complex salt or may be formed of a ferric salt such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, and ferric phosphate, and a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, and phosphonocarboxylic acid in a solution.
  • a chelating agent may be used in excess of the stoichiometric amount for the formation of the ferric ion complex salt.
  • Particularly preferred among these iron complexes are aminopolycarboxylic acid-iron complexes.
  • the amount of such an aminopolycarboxylic acid-iron complex to be added is in the range of 0.01 to 1.0 mot't, preferably 0.05 to 0.50 mol/l.
  • the present bleaching solution, blix solution and;or pre-bath thereof may comprise various compounds as bleaching agents
  • suitable compounds excellent in bleaching capability include compounds containing a mercapto group or disulfide bound as described in U.S. Patent No. 3,893,858, West German Patent No. 1,290,812, Japanese Patent Application (OPI) No. 95,630/78, and Research Disclosure No. 17,129 (July 1978), thiourea compounds as described in Japanese Patent Publication No. 8,506/70, Japanese Patent Application (OPI) Nos. 20,832- r 77, and 32,735/78. and U.S. Patent No. 3,706,561, and compounds of halogen such as iodine, and bromine.
  • the present bleaching solution or blix solution may also contain a re-halogenating agent such as bromide, e.g.. potassium bromide, sodium bromide, and ammonium bromide, chloride, e.g., potassium chloride, sodium chloride, and ammonium chloride, and iodide, e.g., ammonium iodide.
  • a re-halogenating agent such as bromide, e.g.. potassium bromide, sodium bromide, and ammonium bromide
  • chloride e.g., potassium chloride, sodium chloride, and ammonium chloride
  • iodide e.g., ammonium iodide.
  • the present bleaching solution or blix solution may optionally contain one or more corrosion inhibitors having a pH buffering capability such as inorganic acid, e.g., boric acid, borax, phosphinic acid, and phosphonic acid, organic acid, e.g., acetic acid, and tartaric acid, alkaline metal or ammonium salt thereof, e.g., sodium metaborate, sodium acetate, sodium carbonate, potassium carbonate, sodium phosphate, and sodium citrate, ammonium nitrate, and guanidine.
  • inorganic acid e.g., boric acid, borax, phosphinic acid, and phosphonic acid
  • organic acid e.g., acetic acid, and tartaric acid
  • alkaline metal or ammonium salt thereof e.g., sodium metaborate, sodium acetate, sodium carbonate, potassium carbonate, sodium phosphate, and sodium citrate, ammonium nitrate, and guanidine.
  • the fixing agent to be used in the present blix solution or fixing solution may be a known fixing agent, i.e., a water-soluble silver halide solvent such as thiosulfate, e.g., sodium thiosulfate, and ammonium thiosulfate, thiocyanate, e.g., sodium thiocyanate, and ammonium thiocyanate, thioether compound, e.g., ethylenebisthioglycolic acid, and 3,6-dithia-1,8-octanediol, and thiourea.
  • thiosulfate e.g., sodium thiosulfate
  • ammonium thiosulfate e.g., sodium thiocyanate
  • thiocyanate e.g., sodium thiocyanate
  • ammonium thiocyanate e.g., thioether compound, e.g., ethylene
  • a special blix solution made of a combination of a fixing agent as described in Japanese Patent Application (OPI) No. 155,354/80 and a large amount of a halide such as potassium iodide may be used in the present invention.
  • a thiosulfate, particularly ammonium thiosulfate may be preferably used.
  • the amount of such a fixing agent to be incorporated in the fixing or blix solution is preferably in the range of 0.3 to 2 mol, particularly 0.5 to 1.0 mol/l.
  • the present fixing solution or blix solution may have a pH value of 3 to 10, preferably 5 to 9.
  • the present blix solution may contain a fluorescent brightening agent represented by the general formula (XI) in an amount of 0.1 to 10 g/l.
  • the present blix solution may further contain various antifoam agents, surface active agents or organic solvents such as polyvinyl pyrrolidone, and methanol.
  • the present fixing solution or blix solution may contain as a preservative a sulfite ion-releasing compound such as sulfite, e.g., sodium sulfite, potassium sulfite, and ammonium sulfite, bisulfite, e.g., ammonium bisulfite, sodium bisulfite, and potassium bisulfite, and metabisulfite, e.g., potassium metabisulfite, sodium metabisulfite, and ammonium metabisulfite.
  • a sulfite ion-releasing compound such as sulfite, e.g., sodium sulfite, potassium sulfite, and ammonium sulfite, bisulfite, e.g., ammonium bisulfite, sodium bisulfite, and potassium bisulfite, and metabisulfite, e.
  • a compound may be preferably used in an amount of 0.02 to 0.50 mol/
  • a preservative there may be commonly used a sulfite.
  • suitable preservatives include ascorbic acid, carbonyl-bisulfite addition product, and carbonyl compound.
  • the present fixing solution or blix solution may further contain a buffering agent, a chelating agent, an antifoam agent, and an antifungal agent as necessary.
  • the desilvering time is preferably 2 minutes or less, particularly 1 minute or less.
  • the rinsing solution or stabilizing bath may contain a fluorescent brightening agent represented by the general formula (XI) in an amount of 0.1 to 10 git.
  • the rinsing solution may further contain a surface active agent as a hydro-extracting agent or a chelating agent such as EDTA as a water softener.
  • a surface active agent as a hydro-extracting agent or a chelating agent such as EDTA as a water softener.
  • the rinse step may be followed by the stabilizing step.
  • the present light-sensitive material may be processed with aq stabilizing solution at first hand after being subjected to the fixing or blix step.
  • a stabilizing solution may contain a compound which serves to stabilize images. Examples of such a compound include aldehyde compound such as formalin, buffering agent for adjusing the film pH to a value suitable for the stabilization of dyes, and ammonium compound.
  • the stabilizing solution also may contain the above described various sterilizers or antifungal agents to inhibit proliferation of bacterial or render processed light-sensitive material fungi-resistant.
  • the stabilizing solution may further contain a surface active agent and a film hardener.
  • the amount of water to be used in the stabilizing step can drastically saved by employing the countercurrent process as in the rinse step by using 1 or less, preferably 0.5 or less.
  • the supply of the rinsing solution or stabilizing solution may be continuous or intermittent. In the latter case, the supply of the solution may be effected as necessary depending on the amount of the light-sensitive material to be processed or at predetermined time intervals.
  • the pH value of the solution to be used in the present rinse or stabilization step is in the range of 4 to 10, preferably 5 to 8.
  • the temperature of the solution to be used in the present rinse or stabilization step can be widely selected depending on the application, characteristics, etc. of the light-sensitive material to be processed but is normally in the range of 15 to 45 C, preferably 20 to 40 C.
  • the processing time can be freely selected. However, the shorter the processing time is, the more remarkable is the effect of the present invention. In the present invention, the processing time is preferably 30 seconds to 2 minutes, particularly 30 seconds to 1 minute and 30 seconds.
  • the supply amount of the processing solution is preferably small in the light or running cost, reduction in discharge and handleability. The less the supply amount of the processing solutions is, the more remarkable is the effect of the present invention.
  • the solution used in the rinse and/or stabilization step can be further used in the pre-baths.
  • the overflow of the rinsing water obtained by saving by the countercurrent process may be introduced into the pre-bath, e.g., blix bath whichis supplied with a concentrated solution to reduce the amount of waste liquid.
  • the overflow liquid produced with the supply of the above described rinsing solution and/or stabilizing solution can be re-used in the other steps such as desilvering step.
  • the present silver halide color light-sensitive material may comprise a color developing agent for the purpose of simplifying and expediting the processing.
  • a color developing agent can be incorporated in the light-sensitive material in the form of various precursors thereof.
  • precursors of color developing agent include indoaniline compounds as described in U.S. Patent 3,342,597, Schiff base compounds as described in U.S. Patent 3,342,599, and Research Disclosure Nos. 14,850 and 15,159, aldol compounds as described in Research Disclosure No. 13,913, metal complexes as described in U.S. Patent 3,719,492, and urethane compounds as described in Japanese Patent Application (OPI) No. 135,628178,.
  • the present silver halide color light-sensitive material may optionally comprise various 1-phenyl-3-pyrazolidones for the purpose of accelerating color development. Typical examples of such compounds are described in Japanese Patent Application (OPI) Nos. 64,339i81, 144.547/82. and 115,438/83.
  • the various processing solutions to be used in the present invention is used at a temperature of 10 to 50 C.
  • the standard temperature range is normally between 33 C and 38 C.
  • a higher temperature can be used to accelerate and shorten the'processing.
  • a lower temperature can be used to improve the picture quality or the stability of the processing solu-tion.
  • a processing using cobalt intensification or hydrogen peroxide intensification as described in West German Patent No. 2,226,770, and U.S. Patent 3,674,499 may be effected.
  • the sum of the time required for the blix step and the rinse or stabilization step is preferably 3 minutes or less.
  • the process of the present invention can be applied to any processing with a color developing solution.
  • the process of the present invention can be applied to the processing of color paper, color reversal paper, color direct positive light-sensitive material, color positive film, color negative film, color reversal film, or the like.
  • the process of the present invention is useful in the processing of color paper or color reversal paper which is susceptible to stain.
  • silver halide emulsion to be incorporated in the direct positive color printing light-sensitive material or color reversal printing light-sensitive material which is suitable for band stop filter of the present invention there may be preferably used a silver halide emulsion having the above described halogen composition comprising internal latent image type particulate silver halide having a multistructure as described in Japanese Patent Application No. 25,737/87.
  • the silver halide emulsion to be incorporated in the color reversal printing light-sensitive material there may be preferably used an emulsion as described in European Patent No. 0217353A-2, and Japanese Patent Application (OPI) Nos. 39,043/86, and 61,156/86.
  • a soluble coupler is used instead of a hydrophobic coupler.
  • a soluble coupler is incorporated in the color developing solution rather than the light-sensitive material.
  • Such an internal latent image type emulsion may be of the conversion type of the core/shell type, preferably of the core/shell type.
  • the direct positive color light-sensitive material which has been subjected to imagewise exposure is preferably then subjected to color development with a surface developing solution containing an aromatic primary amine color developing agent and preferably having a pH value of 12 or less subsequently after or simultaneously with a fogging process with light or a nucleating agent, and then to blix to provide a direct positive color image.
  • a surface developing solution containing an aromatic primary amine color developing agent and preferably having a pH value of 12 or less subsequently after or simultaneously with a fogging process with light or a nucleating agent More preferably, the developing solution has a pH value of 10.0 to 11.0.
  • the fogging process to be used in the present invention can be accomplished by a so-called “light fogging process” in which the second exposure is provided over the entire surface of the light-sensitive layer or a so-called “chemical fogging process” in which the development is effected in the presence of a nucleating agent.
  • the development may be effected in the presence of a nucleating agent and a fogging light.
  • a light-sensitive material containing a nucleating agent may be subjected to fog exposure.
  • nucleating accelerators which can be used in the present invention are described in the same Japanese Patent Application (OPI), left top to right bottom on page 15.
  • Specific examples of such nucleating accelerators which can be preferably used in the present invention include compounds (A-1) to (A-13) shown in the same Japanese Patent Application (OPI), page 15.
  • a multilayer color light-sensitive material specimen 101 was prepared by coating various layers of the undermentioned compositions on an undercoated cellulose triacetate film support.
  • the value of the coated amount of each component is represented in g/m 2.
  • the coated amount of silver halide is represented in terms of amount of silver.
  • the coated amount of sensitizing dye is represented by molar amount thereof per 1 mo t of silver halide contained in the same layer.
  • 3rd layer low sensitivity réd-sensitive emulsion layer
  • Silver bromoiodide emulsion (Agl content: 6.3 mot %; internal high Agl type; c/s ratio: 1/1; diameter in terms of sphere: 0.8 ⁇ m; coeffificent of fluctuation in diameter in terms of sphere: 25 %; tabular particles; diameter, thickness ratio: 2) 1.5 Gelatin 1.7 ExC-2 0.3 ExC-3 0.02 ExS-1 7.1 x 10 -5 ExS-2 1.9 x 10- 5 ExS-3 2.4 x 10 - 4 ExS-4 4.2 x 10 -5 Solv-2 0.03
  • Silver bromoiodide emulsion (Agl content: 4.8 mot %; internal high Agl type; c/s ratio: 1/4; diameter in terms of sphere: 0.9 ⁇ m; coefficient of fluctuation in diameter in terms of sphere: 50%; tabular particles; diameter/thickness ratio: 1.5) 1.4 Gelatin 2.1 ExC-2 0.4 ExC-3 0.002 ExS-1 5.2 x 10- 5 ExS-2 1.4 x 10 -5 ExS-3 1.8 x 10 -4 ExS-4 3.1 x 10- 5 Solv-2 0.5
  • 5th layer high sensitivity red-sensitive emulsion layer
  • Silver bromoiodide emulsion (Agl content: 10.2 mol %; internal high Agl type; c/s ratio: 1 / 2; diameter in terms of sphere: 1.2 ⁇ m; coefficient of fluctuation in diameter in terms of sphere: 35 %; tabular particles; diameter thickness ratio: 3.5) 2.1 Gelatin 2.0 ExC-1 0.06 ExC-4 0.04 ExC-5 0.2 ExS-1 6.5 x 10 - 5 ExS-2 1.7 x 10- 5 ExS-3 2.2 x 10 - 4 ExS-4 3.8 x 10 -5 Solv-1 0.1 Solv-2 0.3
  • Silver bromoiodide emulsion (Agl content: 6.3 mol %; internal high Agl type; cis ratio: 1/1; diameter in terms of sphere: 0.8 ⁇ m; coefficient of fluctuation in diameter in terms of sphere: 25 %; tabular particles; diameter/thickness ratio: 2) 0.6 Gelatin 0.8 ExM-2 0.3 ExM-1 0.03 ExY-1 0.04 ExS-5 3.1 x 10 - 5 ExS-6 1.0 x 10 -4 ExS-7 3.8 x 10- 4 H-1 0.04 H-2 0.01 Solv-2 0.2
  • Silver bromoiodide emulsion (Agl content: 4.8 mol %; internal high Agl type; c/s ratio: 1/4; diameter in terms of sphere: 0.9 ⁇ m; coefficient of fluctuation in diameter in terms of sphere: 50 %; tabular particles; diameter/thickness ratio: 1.5) 1.1 Gelatin 1.4 ExM-4 0.2 ExM-5 0.05 ExM-1 0.01 ExM-3 0.01 ExY-1 0.02 ExS-5 2.0 x 10- 5 ExS-6 7.0 x 10- 5 ExS-7 2.6 x 10 - 4 H-1 0.07 H-2 0.02 Solv-1 0.06 Solv-2 0.4
  • Silver bromoiodide emulsion (Agl content: 10.2 mol %; internal high Agl type; c/s ratio: 1/2; diameter in terms of sphere: 1.2 ⁇ m; coefficient of fluctuation in diameter in terms of sphere: 38 %; tabular particles; diameter, thickness ratio: 4) 2.1 Gelatin 2.2 ExC-2 0.02 ExM-5 0.1 ExM-1 0.05 ExS-5 3.5 x 10- 5 ExS-6 8.0 x 10- 5 ExS-7 3.0 x 10- 4 Solv-1 0.08 Solv-2 0.7
  • Silver bromoiodide emulsion (Agl content: 9.0 mot %; internal high Agl type; c/s ratio: 1/2; diameter in terms of sphere: 0.75 ⁇ m; coefficient of fluctuation in diameter in terms of sphere: 21 %; octahedron particles; diameter/thickness ratio: 1) 0.3 Gelatin 1.3 ExY-2 0.7 ExY-1 0.03 H-1 0.03 H-2 0.01 Solv-2 0.3
  • Silver bromoiodide emulsion (Agl content: 10.2 mo %; internal high Agl type; c/s ratio: 1/2; diameter in terms of sphere; 1.0 ⁇ m; coefficient of fluctuation in diameter in terms of sphere: 30 %; tabular particles; diameter/thickness ratio: 3.5) 0.4 Gelatin 0.7 ExY-2 0.1 ExS-8 2.2 x 10- 4 H-1 0.01 H-2 0.005 Solv-2 0.05
  • Silver bromoiodide emulsion (Agl content: 9.8 mol %; internal high Agl type; c/s ratio: 1/2; diameter in terms of sphere: 1.8 ⁇ m; coefficient of fluctuation in diameter in terms of sphere: 55 %; tabular particles; diameter thickenss ratio: 4.5) 0.8 Gelatin 0.7 ExY-2 0.2 - ExS-8 2.3 x 10-4 Solv-2 0.07
  • Emulsion of finely divided particles of silver bromide (average particle diameter: 0.07 ⁇ m) 0.1 Gelatin 0.7 H-1 0.2 H-2 0.05
  • So 1 v - 1 Di-n-butylphthalate
  • So 1 v - 2 Tricresylphosphate
  • So I v - 3 Trihexylphosphate
  • Specimen 102 was prepared in the same manner as in Specimen 101 except in that 0.2 g of Compound C of the undermentioned general formula was added to the 10th layer in stead of the yellow colloidal silver, ExM-4 and ExM-5 were replaced by the above described ecemplary compound (VIII)-2 and ExY-2 was replaced by the above described exemplary compound (X)-(7).
  • composition of various processing solutions used in the above processing steps were as follows:
  • Tap water was passed through a mixed bed type column filled with a strongly acidic H type exchange resin (Rome & Herse Corp's Amberlite IR-120B) and an OH type anionic exchange resin (Amberlite IR-400) so that the calcium and magnesium concentration was adjusted to 3 mg/t or less.
  • a strongly acidic H type exchange resin Rosulfate
  • Amberlite IR-400 an OH type anionic exchange resin
  • Sodium dichlorinated isocyanurate and sodium sulfate were added to the water thus treated in amounts of 20 mg/l and 150 mg/l, respectively.
  • the pH value of the rinsing solution thus prepared was in the range of 6.5 to 7.5.
  • the color light-sensitive material specimen 101 thus prepared was then exposed to light from a standard light source for use in photographing (about 5,500 K) through a Macbeth chart.
  • the specimen thus exposed was then subjected to the above described color development to obtain a color negative film.
  • the spectral transmittance curve T ( ⁇ ) for the various coloring materials contained in the color negative film were then obtained.
  • the specimen 101 was exposed to light through a Macbeth chart No. 22 (achromatic chart; optical density: about 0.7).
  • the image on the film was then printed on a color printing paper (Fuji Photo Film Co., Ltd.'s Super HR) by means of a printer.
  • the printing paper was then subjected to processing with Fuji Photo Film Co., Ltd.'s standard developing solution CP-20 to obtain a grey color print.
  • the spectral sensitivity distribution S (X) (modified so as to give the same energy) of the color printing paper was obtained.
  • the energy distribution of a light source for printing p(X) was determined.
  • the image on the negative film was then printed on a color printing paper (Fuji Photo Film Co., Ltd.'s Super HR) with a multi-layer dielectric compound deposited film, having a spectral transparent curve as is shown in Fig. 3-(a), interposed between a light source and the negative film.
  • the color printing paper thus printed was then subjected to the above described processing with CP-20 to obtain a grey color print.
  • a multilayer color printing paper specimen 201 was prepared by coating various layers of the undermentioned compositions on a paper support laminated with polyethylene on the both sides thereof.
  • a blue-sensitive sensitizing dye was added to a silver bromochloride emulsion (containing 80.0 mo % of silver bromide and 70 g/kg of Ag) in an amount of 5.0 x 10- 4 mo per 1 mo of silver to prepare an emulsion.
  • the emulsion dispersion and the emulsion thus obtained were mixed to prepare a 1st layer coating solution having the undermentioned composition.
  • Coating solutions for the 2nd layer to the 7th layer were then prepared in the same manner as described above.
  • As a gelatin hardener for the various layers there was used sodium 1-oxy-3,5-dichloro-s-triazine.
  • a compound of the undermentioned general formula was incorporated in the red-sensitive emulsion layer in an amount of 2.6 x 10- 3 mol per 1 mol of silver halide.
  • 1-(5-Methylureidephenyl)-5-mercaptotetrazole was incorporated in the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer in amounts of 4.0 x 10- 6 mol, 3.3 x 10 -5 mo and 1.0 x 10- 5 mo per 1 mol of silver halide, respectively.
  • the undermentioned dyes were incorporated in the emulsion layer.
  • the composition of the various layers will be described hereinafter.
  • the value of the coated amount of each component is represented in g/m 2 .
  • the coated amount of silver halide emulsion is represented in terms of amount of silver.
  • Polyethylene laminated paper Polyethylene at the first layer side contains white pigment (Ti0 2 ) and blue dye (ultramarine)).
  • UV-1 Ultraviolet absorber
  • Cpd-5 Color mixing inhibitor
  • Solv-3 Solvent
  • UV-1 Ultraviolet absorber
  • the color printing light-sensitive material thus obtained was then subjected to the following color development.
  • the stabilizing step was effected in a countercurrent process in which water flows from the tank 4 to the tank 1 through the tank 3 and the tank 2).
  • composition of the various processing solutions were as follows:
  • Formalin (37 %) 0.1 g Formalin-sulfite addition product 0.7 g 5-Chloro-2-methyl-isothiazoline-3-one 0.02 g 2-Methyl-4-isothiazoline-3-one 0.01 g Copper sulfate 0.005 g Water to make 1,000 m l pH at 25 C 4.0
  • Specimen 202 was prepared in the same manner as in Specimen 201 except in that the silver halide emulsion (Br: 80 mol %) to be incorporated in the 1st layer was replaced by the silver halide emulsion A (Br: 0.5 mol %) shown below and the silver halide emulsion B (Br: 1.0 mpl %) shown below was incorporated in the 3rd layer.
  • the silver halide emulsion (Br: 80 mol %) to be incorporated in the 1st layer was replaced by the silver halide emulsion A (Br: 0.5 mol %) shown below and the silver halide emulsion B (Br: 1.0 mpl %) shown below was incorporated in the 3rd layer.
  • Solution 1 was heated to a temperature of 76 ° C.
  • Solution 2 and Solution 3 were then added to Solution 1.
  • Solution 4 and Solution 5 were then added to the mixture at the same time in 10 minutes.
  • Emulsion (A) was then halved.
  • 12.6 cc of a 0.6 % solution of a blue spectral sensitizing dye (general formula CR-1 shown below) as CR compound was added to one of the two halves of the emulsion.
  • An emulsion of ultrafine particulate AgBr having a particle size of 0.05 ⁇ m was added to the emulsion in a proportion of 0.5 mot % based on the host AgCt emulsion.
  • the emulsion was then subjected to mixing and ripening at a temperature of 58 °C for 10 minutes.
  • the emulsion was then subjected to optimum chemical sensitization with sodium thiosulfate.
  • a stabilizer of the undermentioned general formula B was added to the emulsion in an amount of 10 -4 mol/mol Ag to prepare Emulsion (A).
  • Solution 8 was heated to a temperature of 52 °C.
  • Solution 9 and Solution 10 were then added to Solution 8 thus heated.
  • Solution 11 and Solution 12 were then added to the mixture at the same time in 14 minutes.
  • Solution 13 and Solution 14 were then added to the mixture at the same time in 15 minutes.
  • the temperature of the emulsion was lowered. The emulsion was then desalted.
  • Water and dispersed gelatin were then added to the emulsion to adjust the pH value thereof to 6.2 to obtain a monodisperse emulsion of cubic particulate silver chloride having an average particle size of 0.48 ⁇ m and a particle size fluctuation coefficient (value obtained by dividing standard deviation by average particle size: s d) of 0.10.
  • a compound of the undermentioned general formula CR-2 was then added to the emulsion in an amount of 4.0 x 10- 4 mol per 1 mol of silver halide.
  • An emulsion of ultrafine particulate silver bromide having a particle size of 0.05 ⁇ m was then added to the emulsion in an amount of 1 mot % as calculated in terms of amount of silver bromide based on the silver silver chloride emulsion.
  • the emulsion was then ripened at a temperature of 58 C for 10 minutes.
  • the emulsion was then subjected to optimum chemical sensitization with sodium thiosulfate at a temperature of 58 C.
  • the emulsion was further subjected to spectral sensitization with Compound CR-2 added in an amount of 4 x 10 -4 mot per 1 mol of silver halide.
  • Compound CR-2 added in an amount of 4 x 10 -4 mot per 1 mol of silver halide.
  • Compound B as used in Emulsion A was added to the emulsion in an amount of 5 x 10 -4 mot per 1 mol of silver halide.
  • a Macbeth chart was then photographed on Specimen 102 in the same manner as in Example 1 to prepare a color negative film.
  • the images on the color negative film were then printed on the color printing light-sensitive material specimens 201 and 202 by means of a printer, and then subjected to the above described color development to obtain color prints.
  • E b ( ⁇ ), Eg ( ⁇ ) and E, ( ⁇ ) of these color prints were determined in the same manner as in Example 1.
  • the results show that Specimen 201 gives the similar characteristics as shown in Fig. 1-(a).
  • E b (X), Eg( ⁇ ) and E r -( ⁇ ) obtained from Specimen 202 are shown in Fig. 3-(a).
  • Fig. 5-(a) shows the representation of the color prints obtained from Specimens II and III and CIE (L “a” b) color specification system (as described in Nihon Shikisai Gakkai, “Shikisai Kagaku Handbook, 5th ed., 1985, pp. 140-141) (represented at points II and III, respectively).
  • Macbeth charts were photographed with Fuji Photo Film Co., Ltd.'s photographing color light-sensitiye material SUPER HR 100 under a photographing standard light source (about 5,500 K). The light-sensitive material was then subjected to development with Fuji Photo Film Co., Ltd.'s standard developing solution CN-16 (Fuji color negative process and chemicals) to obtain a color negative film.
  • the images on the color negative film were then printed on Fuji Photo Film Co., Ltd.'s color photographic paper SUPER HR Paper by means of a printer (see P curve in Fig. 1-(b)).
  • the color photographic paper thus printed was then subjected to development with Fuji Photo Film Co., Ltd.'s standard developing solution CP-20 (Fuji color negative process and chemicals) to obtain a color print.
  • the spectral sensitivity of GL in the color photographic paper used in the present example was determined by a conventional method. (See GL curve in Fig. 1-(b))
  • the average color mixing degree r of GL was determined by means of the equation (2-5) to obtain 0.14.
  • a multilayer dielectric-deposted filter was prepared.
  • the spectral transmittance F (X) curve of the filter thus obtained is shown in Fig. 1-(d).
  • X spectral transmittance F
  • the exposure is given by the following equation:
  • the value of color stain degree ⁇ -i F obtained with the filter interposed between the light source and GL in the printing light-sensitive material during the printing is shown in Table 4.
  • i 16 (Y)
  • the color mixing degree degree ⁇ -i F is 0.23
  • the average color mixing degree r of GL is 0.07.
  • the color mixing degree of a color printing light-sensitive material shows the greatest value in GL. Therefore, it can be said that the above described value is the color mixing degree of the color printing light-sensitive material.
  • a multilayer color photographic paper was prepared by coating various layers of the undermentioned composition on a paper support laminated with polyethylene on both sides thereof.
  • the coating solution used were prepared according to the procedure in Example 2, to prepare Specimen 401.
  • Specimen 402 was prepared in the same manner as in Specimen 301 except in that the compound of the general formula D-3 was further incorporated in the 4th layer.
  • Specimen 403 was prepared in the same manner as in Specimen 402 except in that Compound (D-3) to be incorporated in the 4th layer was replaced Compound (S-1) and a functional dye (F-1) as is shown in Table 5.
  • Compounds (S-1) and (F-1) were dispersed in the layer together with an ultraviolet absorber.
  • Compound (D-3) was incorporated in the layer in the form of an aqueous solution.
  • the color printing light-sensitive material thus obtained was subjected to the following color development.
  • the stabilizing step was effected in a countercurrent process in which water flows from the tank 4 to :he tank 1 through the tank 3 and the tank 2.
  • composition of the various processing solutions used were as follows:
  • Formalin (37 %) 0.1 g Formalin-sulfite addition product 0.7 g 5-Chloro-2-methyl-isothiazoline-3-one 0.02 g 2-Methyl-4-isothiazoline-3-one 0.01 g Copper sulfate 0.005 g Water to make 1,000 m l pH at 25°C 4.0
  • Specimen 404 was prepared in the same manner as in Specimen 403 except in that the silver halide emulsion (Br: 80 mol%) to be incorporated in the 1 st layer was replaced by the silver halide emulsion A (Br: 0.5 mol%) used in Example 2 and the silver halide emulsion B (Br: 1.0 mol%) used in Example 2 was incorporated in the 3rd layer.
  • a multilayer color light-sensitive material specimen 601 was prepared by coating various layers of Example 1 or an undercoated cellulose triacetate film support in the same manner as in Example 1.
  • Specimen 602 was prepared in the same manner as in Specimen 601 except in that the yellow colloidal silver to be incorporated in the 10th layer was replaced by Compound C shown below as a comparative compound in an amount of 0.2 g.
  • Color negative films were prepared in the same manner as in Example 3 except in that the color light-sensitive material for use in photographing was replaced by Specimens 601 and 602. These color negative films were then used as print originals.
  • a photographing multilayer color light-sensitive material specimen 701 was prepared by coating various layers of the undermentioned compositions on an under-coated cellulose triacetate film support.
  • the value of the coated amount of each component is represented in g/m 2
  • the coated amount of silver halide is represented in terms of amount of silver.
  • the coated amount of sensitizing dye is represented by molar amount thereof per 1 mo of silver halide contained in the same layer.
  • Emulsion of tabular particulate silver bromoiodide (Agl content: 10 mo l %; average particle diameter: 0.7 ⁇ m; average aspect ratio: 5.5; average thickness: 0.2 ⁇ m) 1.0 Sensitizing dye I 5.1 x 10 -5 Sensitizing dye II 1.4 x 10 -5 Sensitizing dye III 2.3 x 10 -4 Sensitizing dye IV 3.0 x 10 -5 EX-2 0.400 EX-3 0.050 EX-10 0.015 Gelatin 1.30
  • Silver bromoiodide emulsion (Agl content: 16 mol %; average particle diameter : 1.1 ⁇ m) 1.60 Sensitizing dye IX 5.4 x 10- 5 Sensitizing dye II 1.4 x 1 0- 5 Sensitizing dye III 2.4 x 10 -4 Sensitizing dye IV 3.1 x 10 -5 EX-3 0.240 EX-4 0.120 HBS-1 0.22 HBS-2 0.10 Gelatin 1.63
  • Emulsion of tabular particulate silver bromoiodide (Agl content: 6 mo l %; average particle diameter: 0.6 ⁇ m; average aspect ratio: 6.0; average thickness: 0.15) 0.40 Sensitizing dye V 3.0 x 10 -5 Sensitizing dye VI 1.0 x 10 -4 Sensitizing dye VII 3.8 x 10- 4 EX-6 0.260 EX-1 0.021 EX-7 0.030 EX-8 0.025 HBS-1 0.100 HBS-4 0.010 Gelatin 0.75
  • Silver bromoiodide emulsion (Agl content: 12 mot %; average particle diameter:1.0 ⁇ m) 0.77 Sensitizing dye V 3.5 x 10- 5 Sensitizing dye VI 8.0 x 10- 5 Sensitizing dye VII 3.0 x 10- 4 EX-6 0.065 EX-11 0.030 EX-1 0.025 HBS-1 0.25 HBS-2 0.10 Gelatin 1.74
  • Emulsion of tabular particulate silver bromoiodide (Agl content: 6 mol %; average particle diameter: 0.6 ⁇ m; average aspect ratio: 5.7; average thickness: 0.15 ⁇ m) 0.24 Sensitizing dye VIII 3.5 x 10 -4 EX-9 0.85 EX-8 0.12 HBS-1 0.28 Gelatin 1.28 12th layer (2nd blue-sensitive emulsion layer)
  • Monodisperse emulsion of silver bromoiodide (Agl content: 10 mo l %; average particle diameter : 0.8 ⁇ m; coefficient of fluctuation in particle diameter: 0.16) 0.45 Sensitizing dye VIII 2. 1 x 10 -4
  • Silver bromoiodide emulsion (Agl content: 14 mot %: average particle diameter: 1.3 ⁇ m) 0.77 Sensitizing dye VIII 2.2 x 10- 4 EX-9 0.20 HBS-1 0.07 Gelatin 0.69
  • Silver bromoiodide emulsion (Agl content: 1 mot l %; average particle diameter: 0.07 ⁇ m) 0.5 U-4 0.11 U-5 0.17 HBS-1 0.90 Gelatin 1.00
  • Particulate polymethyl acrylate (particle diameter: about 1.5 ⁇ m) 0.54 S-1 0.15 S-2 0.05 Gelatin 0.72
  • a gelatin hardener H-1 and a surface active agent were incorporated in each layer.
  • H B S - 1 Tricresyl phosphate
  • H B S - 2 Dibutyl phthalate
  • H B S - 3 Bis (2-ethylexyl)phthalate
  • Specimens 702 and 703 were prepared in the same manner as in Specimen 701 except in that EX-6 was replaced by VII-(2) and X-(7) was used as shown in Table 8. (EX-2, EX-4 and EX-7 are couplers according to the present invention.)
  • Color development of color light-sensitive material for use in photographing is carried out according to the same procedure as in Example 1.
  • a multilayer color photographic paper specimen 801 was prepared by coating various layers of the undermentioned compositions on a paper support laminated with polyethylene on both sides thereof.
  • a blue-sensitive sensitizing dye of the undermentioned general formula was added to a silver bromochloride emulsion (containing 80.0 mol% of silver bromide and 70 g/kg of Ag) in an amount of 5.0 x 10- 4 mo per 1 mo of silver.
  • the emulsion dispersion and the emulsion thus obtained were mixed to prepare the 1st layer coating solution having the undermentioned composition.
  • the coating solutions for the 2nd layer to the 7th layer were similarly prepared.
  • As a gelatin hardener for each layer there was used sodium 1-oxy-3,5-dichloro-s-triazine.
  • Compound 1-(9) was incorporated in the red-sensitive emulsion layer in an amount of 2.6 x 10- 3 mol per 1 moilof silver halide.
  • 1-(5-Methylureidephenyl)-5-mercaptotetrazole was incorporated in the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer in amounts of 4.0 x 10 -6 mot, 3.0 x 10- 5 mol and 1.0 x 10- 5 mot per 1 mol of silver halide, respectively.
  • Example 2 For the purpose of inhibiting irradiation, the dyes used in Example 2 were incorporated in the emulsion layer.
  • composition of the various layers is the same as in Example 2.
  • Specimen 802 was prepared in the same manner as in Specimen 801 except in that the silver halide emulsion (Br: 80 mol%) to be incorporated in the 1st layer was replaced by the silver halide emulsion A (Br: 0.5 mol%) used in Example 2 shown below and the undermentioned silver halide emulsion B used in Example 2 (Br: 1.0 mo%) was incorporated in the 3rd layer.
  • ExY. ExM or ExC as used in Example 8 is a suitable color coupler which can be used in the present invention.
  • Specimens 801 and 802 were then exposed to light by means of a spectral photographing machine which had been corrected so as to give the same spectral energy intensity of the light source. These specimens were then subjected to the same color development as in Example 2, except for adjusting pH value of blix being 5.5.
  • composition of the processing solutions used in the various steps were as follows:
  • Aqueous ammonia and water were used to give a pH as shown in Tables 9-1 and 9-2.
  • Eb( ⁇ ) The effective spectral sensitive energy distribution Eb( ⁇ ). Eg( ⁇ ) or Er( ⁇ ) obtained when a grey object was photographed on the color printing light-sensitive materials used in the previous example in combination with the color negative films used in the previous example as shown in Table 10 is shown in Figs. 2-(c), 3-(c), 4-(c) and 5-(c).
  • Fig. 2-(c) shows that in the combination of Specimen 701 and Specimen 701 Er( ⁇ ) is independent but Eg( ⁇ ) and Eb(x) are independent.
  • Figs. 3-(c) and 4-(c) show that Er( ⁇ ) and Eg( ⁇ ) are independent but Eb( ⁇ ) is not independent.
  • Fig. 5-(c) shows that Er( ⁇ ), Eg( ⁇ ) and Eb( ⁇ ) are all independent.
  • the use of the sharp and band cut-off filter II gives an improvement in the saturation, lightness and hue fidelity of yellow, green and violet color systems.
  • Specimen 703 obtained in Example 7 was used to replace Specimen 102 in Examples 10 and 11. As a result, an improvement in color reproducibility was observed similarly.
  • a polished white glass plate having a thickness of 3 mm was cleaned with soapy water. After being dried, the glass plate was then ultrasonically cleaned in a liquid fleon in an ultrasonic cleaner for 1 minute and 30 seconds. The glass plate thus treated was later used as a substrate for deposited film interference filter. The glass plate was then mounted on a substrate holder in an electron beam heating type evaporator.
  • One of two evaporation sources was provided with 20 g of pelletized silicon oxide and the other was provided with 20 g of aluminum oxide.
  • the evaporator was pre-evacuated for 10 minutes by a rotary pump, and then evacuated by an oil diffusion pump for 20 minutes so that the pressure therein reached 2 x 10- 5 torr. Then. silicon oxide and aluminum oxide were alternately evaporated.
  • the substrate was kept at a temperature of about 350 C by a halogen lamp in the tank during evaporation. Silicon oxide was heated by an electron beam of 5 KV and 30 mA for 6 minutes, and aluminum oxide was heated by an electron beam of 5 KV and 250 mA for 8 minutes. The thickness of the film thus deposited was controlled while being observed by an optical monitor.
  • Filter Specimens 1 and 2 having thicknesses as shown in Table 13 were prepared. These interference filters thus prepared were then measured for properties by Hitachi's Type 307 Spectrophotometer. The spectral transmittance curves thus determined are shown in Figs. 1-(d) and 2-(d).
  • a filter having a structure shown in Fig. 5 in U.S. Patent No. 2,997,389 was prepared in the vacuum evaporation process to obtain Filter Specimen A.
  • Filter Specimens A and 1 were then scratched on the surface thereof with the tip of an aluminum diecast of the same material as the insertion holder for band stop filter under substantially the same pressure. Furthermore, these filter specimens were rubbed on the surface thereof with a dust-covered cloth. As a result. Specimen A had scratches on the surface thereof while Specimen 1 had no scratched on the surface thereof. Thus. it is obvious that Specimen 1 is excellent in scratch resistance as compared to Specimen A.
  • a Macbeth's color chart, a man, and a natural flower were photographed as objects on a 135-size color negative light-sensitive material (Fuji Color SUPER HR 100) under a 5,500*K light source.
  • the color negative light-sensitive material was subjected to CN-16 standard color development to obtain a color negative film.
  • the images on the color negative film were then printed on Fuji Color Super HR Paper by means of Fuji Color Film Co., Ltd.'s Auto-printer Type 3500 with a band stop filter according to the present invention interposed between the filter source in the autoprinter and the negative filter.
  • printing was effected in the same manner as described above except in that no band stop filter was interposed between the light source and the color negative film.
  • the color prints obtained with Band Stop Filter Specimen 1 or 2 shows remarkable improvements in fidelity in color reproduction and saturation, particularly of green or yellow system as compared to the color prints obtained without such a filter.
  • Specimen 3 was prepared in the same manner as in Specimen 1 of Example 13 except in that the film thickness and the number of layers were changed (See Table 13). The spectral transmittance curve of Specimen 3 is shown in Fig. 3-(d).
  • Example 13 The same objects as used in Example 13 were photographed on Fuji Photo Film Co., Ltd.'s Fujichrome 100D (135-size).--The light-sensitive material was then subjected to CR-56P standard color reversal development to obtain a transparent positive film.
  • the images on the transparent positive film were then printed on Fuji Color Print by means of Fuji Photo Film Co., Ltd.'s Autoprinter Type 8C 6910 II with Filter Specimen 3 interposed between the light source and the film original and disposed close to the light source.
  • the light-sensitive material was then subjected to RP-303 standard color reversal development to obtain a color print.
  • printing was effected in the same manner as described above except in that Filter Specimen 3 was not used. Thus, a comparative color print was obtained.
  • the color print obtained with Band Stop Filter Specimen 3 according to the present invention showed an excellent color reproducibility, and remarkable improvement in the saturation of a red system as compared to the color print obtained without such a filter.
  • a color print was obtained in the same manner as described above except in that Filter Specimen 1 was used in combination with Specimen 3.
  • the color print thus prepared showed remarkable improvements in the fidelity in color reproduction of a green system and the saturation of a red system.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP88109778A 1987-06-18 1988-06-20 Verfahren zur Bildung eines Farbbildes und Verwendung eines Bandstopfilters dafür Expired - Lifetime EP0295716B1 (de)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
JP15032087 1987-06-18
JP150320/87 1987-06-18
JP19522287 1987-08-06
JP195222/87 1987-08-06
JP206589/87 1987-08-21
JP20658987 1987-08-21
JP112608/88 1988-05-11
JP11260888 1988-05-11

Publications (3)

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EP0295716A2 true EP0295716A2 (de) 1988-12-21
EP0295716A3 EP0295716A3 (en) 1989-11-23
EP0295716B1 EP0295716B1 (de) 1994-12-07

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EP88109778A Expired - Lifetime EP0295716B1 (de) 1987-06-18 1988-06-20 Verfahren zur Bildung eines Farbbildes und Verwendung eines Bandstopfilters dafür

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EP (1) EP0295716B1 (de)
CA (1) CA1339192C (de)
DE (1) DE3852342T2 (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0501464A1 (de) * 1991-03-01 1992-09-02 Konica Corporation Verfahren zur Herstellung farbphotographischer Bilder mit verbesserter Farbenreproduktion
EP0502491A1 (de) * 1991-03-04 1992-09-09 Konica Corporation Verfahren zur Herstellung eines farbphotographischen Silberhalogenidbildes
EP0581697A1 (de) * 1992-07-27 1994-02-02 Eastman Kodak Company Für die Unterwasserphotographie geeignete photographische Elemente

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1015683B (de) * 1955-06-15 1957-09-12 Agfa Ag Verfahren zur Verbesserung der Farbwiedergabe in farbenphotographischen Mehrschichtenmaterialien
FR1248376A (fr) * 1959-02-17 1960-12-09 Gevaert Photo Prod Nv Procédé pour copier des images photographiques en couleurs
US2997389A (en) * 1957-04-12 1961-08-22 Eastman Kodak Co Exposure control in color printing
US4045125A (en) * 1974-06-27 1977-08-30 Etat Francias Band filters for use in protective glasses
US4050807A (en) * 1975-03-06 1977-09-27 Durst Ag. Fabrik Fototechnischer Apparate Bozen Process and device for copying photographic color images
JPS5364037A (en) * 1976-11-19 1978-06-08 Fuji Photo Film Co Ltd Automatic color printer
EP0082649A1 (de) * 1981-12-19 1983-06-29 Konica Corporation Lichtempfindliches farbfotografisches Silberhalogenidmaterial
DE3333227A1 (de) * 1982-09-14 1984-03-15 Konishiroku Photo Industry Co., Ltd., Tokyo Verfahren zur behandlung bzw. entwicklung von lichtempfindlichen photographischen silberhalogenidmaterialien
EP0115304A2 (de) * 1983-01-19 1984-08-08 Fuji Photo Film Co., Ltd. Multigeschichtetes lichtempfindliches farbphotographisches Silberhalogenidmaterial
GB2165954A (en) * 1984-08-31 1986-04-23 Fuji Photo Film Co Ltd Method for processing of silver halide color photographic materials
EP0189191A2 (de) * 1985-01-24 1986-07-30 Konica Corporation Behandlungsverfahren eines farbphotoempfindlichen Silberhalogenidmaterials
EP0277644A2 (de) * 1987-02-05 1988-08-10 Konica Corporation Verfahren zum Belichten eines lichtempfindlichen farbphotographischen Materials

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1015683B (de) * 1955-06-15 1957-09-12 Agfa Ag Verfahren zur Verbesserung der Farbwiedergabe in farbenphotographischen Mehrschichtenmaterialien
US2997389A (en) * 1957-04-12 1961-08-22 Eastman Kodak Co Exposure control in color printing
FR1248376A (fr) * 1959-02-17 1960-12-09 Gevaert Photo Prod Nv Procédé pour copier des images photographiques en couleurs
US4045125A (en) * 1974-06-27 1977-08-30 Etat Francias Band filters for use in protective glasses
US4050807A (en) * 1975-03-06 1977-09-27 Durst Ag. Fabrik Fototechnischer Apparate Bozen Process and device for copying photographic color images
JPS5364037A (en) * 1976-11-19 1978-06-08 Fuji Photo Film Co Ltd Automatic color printer
EP0082649A1 (de) * 1981-12-19 1983-06-29 Konica Corporation Lichtempfindliches farbfotografisches Silberhalogenidmaterial
DE3333227A1 (de) * 1982-09-14 1984-03-15 Konishiroku Photo Industry Co., Ltd., Tokyo Verfahren zur behandlung bzw. entwicklung von lichtempfindlichen photographischen silberhalogenidmaterialien
EP0115304A2 (de) * 1983-01-19 1984-08-08 Fuji Photo Film Co., Ltd. Multigeschichtetes lichtempfindliches farbphotographisches Silberhalogenidmaterial
GB2165954A (en) * 1984-08-31 1986-04-23 Fuji Photo Film Co Ltd Method for processing of silver halide color photographic materials
EP0189191A2 (de) * 1985-01-24 1986-07-30 Konica Corporation Behandlungsverfahren eines farbphotoempfindlichen Silberhalogenidmaterials
EP0277644A2 (de) * 1987-02-05 1988-08-10 Konica Corporation Verfahren zum Belichten eines lichtempfindlichen farbphotographischen Materials

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0501464A1 (de) * 1991-03-01 1992-09-02 Konica Corporation Verfahren zur Herstellung farbphotographischer Bilder mit verbesserter Farbenreproduktion
US5389500A (en) * 1991-03-01 1995-02-14 Konica Corporation Method for forming color photographic images improved in color reproduction
EP0502491A1 (de) * 1991-03-04 1992-09-09 Konica Corporation Verfahren zur Herstellung eines farbphotographischen Silberhalogenidbildes
US5376508A (en) * 1991-03-04 1994-12-27 Konica Corporation Method for forming a silver halide color photographic image
EP0581697A1 (de) * 1992-07-27 1994-02-02 Eastman Kodak Company Für die Unterwasserphotographie geeignete photographische Elemente

Also Published As

Publication number Publication date
CA1339192C (en) 1997-08-05
DE3852342D1 (de) 1995-01-19
EP0295716A3 (en) 1989-11-23
DE3852342T2 (de) 1995-05-24
EP0295716B1 (de) 1994-12-07

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