EP0351740A1 - Verfahren zur Herstellung eines Farbfilters und nach diesem Verfahren hergestellter Farbfilter - Google Patents

Verfahren zur Herstellung eines Farbfilters und nach diesem Verfahren hergestellter Farbfilter Download PDF

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Publication number
EP0351740A1
EP0351740A1 EP89112990A EP89112990A EP0351740A1 EP 0351740 A1 EP0351740 A1 EP 0351740A1 EP 89112990 A EP89112990 A EP 89112990A EP 89112990 A EP89112990 A EP 89112990A EP 0351740 A1 EP0351740 A1 EP 0351740A1
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EP
European Patent Office
Prior art keywords
color
dye
color filter
silver
compounds
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP89112990A
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English (en)
French (fr)
Inventor
Toshikazu C/O Konica Corporation Nishide
Ken C/O Konica Corporation Okauchi
Yoshiharu C/O Konica Corporation Mochizuki
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Konica Minolta Inc
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Konica Minolta Inc
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Publication date
Priority claimed from JP63179625A external-priority patent/JPH0229603A/ja
Priority claimed from JP63188632A external-priority patent/JPH0239002A/ja
Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Publication of EP0351740A1 publication Critical patent/EP0351740A1/de
Withdrawn legal-status Critical Current

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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/04Additive processes using colour screens; Materials therefor; Preparing or processing such materials
    • G03C7/06Manufacture of colour screens
    • G03C7/10Manufacture of colour screens with regular areas of colour, e.g. bands, lines, dots
    • G03C7/12Manufacture of colour screens with regular areas of colour, e.g. bands, lines, dots by photo-exposure
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/28Silver dye bleach processes; Materials therefor; Preparing or processing such materials

Definitions

  • This invention relates to a method for preparing a color filter, more particularly to a method for preparing a color filter which can control variance which may occur in fine lines of the color filter layer having picture ele­ments even in the case of, for example, preparing a color filter of large area, and also can give a color filter of good image quality by realizing excellent heat resistance, flatness and color purity, etc.
  • a color filter comprising a color filter layer having pic­ture elements of at least two colors on a transparent sub­strate has been used widely for liquid crystal color dis­play device, color camera tube, color solid image pickup element, etc.
  • the color filter layer having picture ele­ments must be formed on a light-transmissive substrate by effecting uniform exposure to form fine lines of the color filter layer (width about 10 to 20 ⁇ m) for respective col­ors accurately in mosaic shape or stripe shape, but since in the case of a color filter of large area (for example, 300 mm x 150 mm or larger), unevenness of exposure is liable to occur within the plane, it is difficult to real­ize uniform exposure dosage, whereby fluctuation in width of fine lines of the color filter layer occurs to cause such problems as color slippage, color irregularity, image slippage, etc.
  • the present inventors have proposed a method for preparing a color filter according to a combination of a dye having silver dye bleach action and a color forming dye from a coupler by performing silver dye bleach pro­cessing, but since the processing steps are entirely dif­ferent in the silver dye bleach method and external color developing processing method, when the preparation method which performs the external developing processing step is employed after the silver dye bleach processing step, there has been involved the problem that the dye density based on the nonincorporated-coupler type developing pro­cessing can not be sufficiently obtained.
  • the present inventors have further conducted studies to imporve heat resistance and light resistance.
  • the present invention has been accomplished on the basis of the state of the art as described above.
  • An object of the present invention is to provide a method for preparing a color filter which is free from variance in width of fine lines of the color filter layer even in the case of preparing a color filter of large area, and also which can obtain a color filter capable of realizing good image quality free from color irregularity, color slippage, image irregularity, etc. by realizing excellent heat resistance, flatness and color purity, etc. with good efficiency.
  • Another object of the present invention is to provide a method for preparing a color filter excellent in produc­tion efficiency which can prepare easily and stably a color filter which has excellent color reproducibility based on good spectral characteristics and can be used suitably particularly for color display or color pho­tographing tube, etc., and also can control the reaction and set the reaction conditions easily.
  • the present inventors have investigated intensively and consequently found that, when picture elements of two or more colors in the color filter layer to be formed on a transparent substrate are formed according to the silver dye bleaching method and the nonincorporated-coupler type color developing method, surprisingly, even when a color filter of large area may be prepared, variance occurring in width of fine lines of the color filter layer can be inhibited, and also a color filter realizing good image quality excellent in heat resistance, flatness and color purity, etc. without color slippage, image irregularity, etc. can be obtained with good efficiency to accomplish the present invention.
  • a method for preparing a color filter of the present invention comprises forming at least two color picture elements of at least two colors by effecting at least two pattern exposure to a photosensitive emulsion layer formed on a light-transmissive substrate and then developing said pattern exposed portions, characterized in that said pho­tosensitive emulsion layer contains a dye having a silver dye bleaching effect, at least one color picture element of a color is formed by steps of effecting development of said pattern exposed portions according to the silver dye bleaching method which performs the processing for forming a photosensitive emulsion layer containing a dye, the monochromatic developing processing, the silver dye bleaching processing and the silver bleaching processing in this order, and at least one color picture element of other colors is formed by the steps of effecting develop­ment of said pattern exposed portions according to the nonincorporated-coupler type color developing method which employs a developer containing a color forming coupler.
  • a color filter of the present invention comprises in a color filter having been formed at least two color picture elements of at least two colors by effecting at least two pattern exposure to a photosensitive emulsion layer formed on a light-transmissive substrate and then developing said pattern exposed portions, characterized in that said pho­tosensitive emulsion layer contains a dye having a silver dye bleaching effect, at least one color picture element of a color is formed by steps of effecting development of said pattern exposed portions according to the silver dye bleaching method which performs the processing for forming a photosensitive emulsion layer containing a dye, the monochromatic developing processing, the silver dye bleaching processing and the silver bleaching processing in this order, and at least one color picture element of other colors is formed by the steps of effecting develop­ment of said pattern exposed portions according to the nonincorporated-coupler type color developing method which employs a developer containing a color forming coupler.
  • the order of processing in the case of preparing the color filter having picture elements of the three colors of cyan, magenta and yellow it can be practiced in the order of, for exam­ple, (1) formation of picture elements according to the silver dye bleaching method ⁇ formation of picture ele­ments according to the nonincorporated-coupler type color developing method, or alternatively in the order of (2) formation of picture elements according to the nonincorpo­rated-coupler type color forming developing method ⁇ formation of picture elements according to the silver dye bleaching method.
  • picture elements of either one color of cyan, magenta and yellow are firstly formed according to the silver dye bleaching method, and thereafter picture elements of the remaining two colors are formed according to the nonincor­porated-coupler type color developing method.
  • picture elements of either two colors of cyan, magenta and yellow are firstly formed according to the nonincorporated-coupler type color developing method, and thereafter picture elements of the remaining one color are formed according to the silver dye bleaching method.
  • picture elements of either one color of cyan, magenta and yellow are firstly formed according to the nonincorporated-coupler type color developing method, and thereafter picture elements of either one color of the remaining two colors are formed according to the silver dye bleaching method and finally the remaining one color is formed according to the nonin­corporated-coupler type color developing method.
  • picture elements of cyan according to the silver dye bleaching method and picture elements of magenta and yellow accord­ing to the nonincorporated-coupler type color developing method.
  • One important point in the method of the present invention is to form at least one color of picture element of the picture elements of two or more colors in the color filter layer to be formed on a light-transmissive substrate by employment of the silver dye bleaching method.
  • a picture element is formed by performing the processing for forming a photosensitive emulsion layer containing a dye (hereinafter sometimes called as photo­sensitive emulsion layer (A)), the monochromatic develop­ing processing, the dye bleaching processing and the sil­ver bleaching processing are practiced in this order to form picture elements.
  • A photosensitive emulsion layer containing a dye
  • the photosensitive emulsion layer (A) is formed on a light-transmissive sub­strate by coating a photosensitive emulsion (hereinafter sometimes called as photosensitive emulsion (a)) containing a dye.
  • a photosensitive emulsion hereinafter sometimes called as photosensitive emulsion (a)
  • the above light-transmissive substrate provided to use may be either transparent or translucent, provided that it has light transmissivity. Further, since the color filter may be exposed to high temperature in the vapor deposition step of transparent electrodes etc., the material of the light-transmissive substrate should preferably have good heat resistance.
  • Examples of the material constituting such light-transmis­sive substrate may include polymeric compounds such as polyethylene terephthalate, polybutylene terephthalate, polystyrene, polycarbonate, polyether sulfone, polyvinyl alcohol and cellulose acetate; glasses such as soda glass, borosilicate glass, etc.; inorganic substances such as quartz and sapphire, etc.
  • polymeric compounds such as polyethylene terephthalate, polybutylene terephthalate, polystyrene, polycarbonate, polyether sulfone, polyvinyl alcohol and cellulose acetate
  • glasses such as soda glass, borosilicate glass, etc.
  • inorganic substances such as quartz and sapphire, etc.
  • the above light-transmissive substrate can be used in the form of plate, sheet or film by use of the above material.
  • the thickness of the above light-transmissive substrate can be set suitably depending on the use and the material, but is generally within the range of 0.5 ⁇ m to 10 mm.
  • the thickness should be preferably within the range of 0.3 to 2 mm.
  • the surface of the above light-transmissive substrate forming the above photosensitive emulsion layer (A) is not particularly limited, provided that it has surface precision to the same extent as the light-transmissive substrate which has been used in the prior art for a color filter, but for realizing further higher image quality, the surface precision of the light-transmissive substrate should be desirably ⁇ 0.1 ⁇ m.
  • a light-transmissive backing layer for antihalation On the surface of the above light-transmissive substrate opposite to the surface where the above photosensitive emulsion layer (A) is formed, a light-transmissive backing layer for antihalation may be also provided.
  • a dye or a pigment contained in the backing layer should be preferably a non-diffusible dye or pigment.
  • a carbon black dispersion can be suitably used.
  • the carbon black dispersion may be also one based on either preparation process of the furnace process and the channel process, and for example, "Diablack" (trade name; manufactured by Mitsubishi Kasei Corporation), etc. can be suitably used.
  • the above non-diffusible dye or pigment is contained in the backing layer under the state dispersed in hydrophilic colloid, but it must be one which will not be dissolved out into respective processing solutions even after devel­oping processing.
  • the light absorption characteristics of the above non-diffusible dye or pigment are different depending on the spectral absorption characteristics of the silver halide emulsion to be used in the method of the present invention, but for example, when a silver halide emulsion not spectrally sensitized with sensitizing dye is used, it should be preferably one capable of absorbing the light of 500 nm or less.
  • the backing layer may also contain a UV absorber.
  • the UV-ray absorber for example, "UVINULMS-40" (trade name; manufactured by BASF Co.), "TINUVIN P" (trade name; manufactured by Ciba Geigy AG) may be employed.
  • the above non-diffusible dye or pigment and the UV-ray absorber may be used by dissolving in a known high boiling organic solvent and a low boiling organic solvent as rep­resented by methyl acetate, ethyl acetate, propyl acetate, butyl acetate, cyclohexane, tetrahydrofuran, carbon tetra­chloride, chloroform, etc., then mixing the solution with an aqueous gelatin solution containing a surfactant, sub­sequently emulsifying the mixture by means of a dispersing means such as stirrer, homogenizer, colloid mill, flow jet mixer, ultrasonic homogenizer, etc., and then adding the emulsion into the coating composition for hydrophilic colloid backing layer.
  • a dispersing means such as stirrer, homogenizer, colloid mill, flow jet mixer, ultrasonic homogenizer, etc.
  • the amount of the above non-diffusible dye or pigment used may be preferably 0.1 mg or more, particularly 1 mg or more per 100 cm2 of the above light-transmissive sub­strate.
  • the above photosensitive emulsion layer (A) On the surface of the above light-transmissive substrate, the above photosensitive emulsion layer (A) is formed, and it is preferred to provide a subbing layer for reinforcing the adhesive force between the above photosensitive emul­sion layer (A) and the above light-transmissive substrate as well as for making the rough surface, if it is, of the above light-transmissive substrate a smooth surface.
  • the material for forming the subbing layer there may be included, for example, gelatin, albumin, casein, cellu­lose derivatives, starch derivatives, sodium alginate, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid (or polyacrylate) copolymer, polyvinylidene chloride copolymer and polyacrylamide.
  • the thickness of the above subbing layer may be preferably thin in view of the spectral characteristics of the color filter layer, generally 1 ⁇ m or less, preferably within the range of 0.05 to 0.5 ⁇ m.
  • the above photosensitive emulsion (a) provided for use contains at least a silver halide, a water-soluble binder and a dye.
  • silver halide for example, silver chloride, silver iodide, silver bromide, silver chloroiodide, silver chlorobromide, silver iodobromide etc. may be included. These may be used either singly or as a combination of two or more kinds. Among them, preferred are silver bromide and silver iodobromide.
  • the above silver halide it is desired to use one having a small average grain size, particularly preferably the so-called Lippmann emulsion having an average grain size of 0.1 ⁇ m or less.
  • the sharpness of the color filter obtained may be sometimes lowered.
  • water-soluble binder may include gelatin, albumin, casein, cellulose derivatives, starch derivatives, sodium alginate, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid (or polyacrylate) copolymer, polyacrylamide, etc. These may be used either singly or as a combination of two or more kinds. Among them, gelatin is preferred.
  • the above dye contains a dye exhibiting silver dye bleaching action.
  • phthalocyanine dyes for example, phthalocyanine dyes, azo dyes, etc, can be suitably used.
  • azo dyes particu­larly preferred are bisazo dyes.
  • the above photosensitive emulsion (a) should be preferably one containing the silver halide, water-soluble binder and dye as described above at a weight ratio of (silver halide) : (water-soluble binder) of 1 : 0.5 to 1 : 100, a weight ratio of (silver halide) : (dye) of 1 : 0.1 to 1 : 50 and a weight ratio of (water-soluble binder) : (dye) of 1 : 0.01 to 1:2.
  • the above photosensitive emulsion layer (A) can be formed by coating the above photosensitive agent on the above light-transmissive substrate by employing the coating method known in the art such as spinner coating, spray coating, etc.
  • the thickness of the above photosensitive emulsion layer (A) thus formed is generally within the range of 0.3 to 10 ⁇ m, preferably 0.5 to 3 ⁇ m as dry thickness.
  • the methods used for conventional pattern exposure e.g. contact exposure, proxymity expo­sure, step exposure, etc.
  • conventional pattern exposure e.g. contact exposure, proxymity expo­sure, step exposure, etc.
  • the above photosensitive emulsion layer can be applied with mask exposure for formation of picture elements, and then subjected to developing processing with a developer containing color forming couplers to form col­ored portions.
  • the exposure method which can be employed in the method of the present invention, for example, the methods used for conventional pattern exposure such as contact expo­sure, proximity exposure, step exposure, etc. may be included.
  • Pattern exposure may be practiced by arranging a photomask 14 on a photosensitive emulsion layer 13 having a photo­sensitive emulsion layer 12 containing the above dye exhibiting silver dye bleaching action laminated on a light-transmissive substrate 11 as shown in Fig. 1, an irradiating light from above the photomask 14.
  • the portion to be exposed 16 of the photosensi­tive emulsion layer corresponding to the opening 15 pro­vided in the photomask 14 can be selectively exposed.
  • the size of the portion to be exposed 16, namely the size of the opening 15 can be suitably set depending on the use of the color filter.
  • the width of the opening 15 is narrower than the wavelength of the light source used for exposure, no effective exposure can be done and therefore the width of the opening 15 is made wider than the wavelength. Since a silver halide has effective sen­sitivity to the light within the range of 340 to 420 nm, the width of the opening 15 is generally 340 nm or more, and further in view of the use as the color filter, it should be preferably made 1 ⁇ m or more. In the case of a color filter for liquid crystal display, for effective color reproduction by addition color mixing of the respec­tive colored portions of red, blue and green, it is desired that the width of the opening 15 should be set at 1000 ⁇ m or less (particularly desirably 500 ⁇ m or less).
  • the processing steps according to the silver dye bleaching method perform at least monochromatic developing process­ing, dye bleaching processing and silver bleaching pro­cessing in this order.
  • the above photo­sensitive emulsion layer subjected to image exposure to the same pattern as the pattern of the desired colored portion of the patterns of the respective colored portions formed according to the above nonincorporated-coupler type color developing method is applied with monochromatic developing processing by use of the monochromatic devel­oper to form a reduced silver image on the above photosen­sitive emulsion layer.
  • the above monochromatic developer provided for use con­tains, for example, a developing agent (hereinafter called as developing agent (D)), a developing aid, a preservative, a so-called developing antifoggant and an alkali buffering agent, and further a solvent for the above developing agent (D) and the developing aid as men­tioned above, if necessary.
  • developing agent (D) a developing agent
  • preservative a so-called developing antifoggant and an alkali buffering agent
  • solvent for the above developing agent (D) and the developing aid as men­tioned above, if necessary.
  • Examples of the above developing agent may include hydro­quinone, chlorohydroquinone, catechol, etc.
  • Examples of the above developing aid may include pyrazone pyrazone derivatives, Metol, etc.
  • sulfites Ascorbic acids, etc. may be included.
  • Examples of the above developing antifoggant may include bromides, benzotriazole, etc.
  • Examples of the above alkali buffering agent may include carbonates, hydroxides, phosphates, borates and metabo­rates, etc.
  • antifoggant examples include bromides, benzotriazole, etc.
  • Examples of the solvents for the above developing agent (D) and developing aid may include ethylene glycol, tri­ethanol, diethanol, etc.
  • the above respective components in the above monochromatic developer there may be employed 1 to 20 g/liter of the above developing agent (D), 0.05 to 8 g/liter of the above developing aid, 1 to 120 g/liter of the above preservative, 0.001 to 5 g/liter of the above developing antifoggant, 0.1 to 50 g/liter of the above alkali buffering agent, and further when the solvent for the above developing agent and the above developing aid is to be employed, 1 to 20 ml/liter of the above solvent.
  • the monochromatic developing processing is generally car­ried out under the conditions of a temperature of 20 to 60 °C, for 10 to 200 seconds, by dipping the photosensitive emulsion layer (A) subjected to the above image-exposure in a developing bath housing the above monochromatic developer.
  • a reduced sil­ver image (silver negative image) is formed in the photo­sensitive emulsion layer (A) subjected to the above image exposure.
  • water washing processing is generally practiced before carrying out the dye bleaching processing described in detail below.
  • bleaching of the dye of the above dye contained in the above photosensitive emul­sion layer is effected by use of a dye bleaching solution.
  • the dye bleaching processing is a pro­cessing in which a positive-image of the above dye is formed by bleaching the dye at the portion containing more image silver among the dyes in the above dye contained in the photosensitive emulsion layer subjected to the above image exposure.
  • the above dye bleaching solution provided for use may con­tain, for example, a bleaching agent, a compound forming a silver salt or a silver complex and a dye bleaching pro­moting catalyst.
  • bleaching agent for example, mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, etc.; organic acids such as sulfamic acid, succinic acid, acetic acid, etc. may be included.
  • the compound forming the above silver salts or silver complex there may be included, for example, potassium bromide, potassium iodide, urea, thiourea, semicarbazide, thiosemicarbazide, etc.
  • Examples of the above dye bleaching promoting catalyst may include pyrazine, naphthazine, quinoline, quinoxalines, phenazines, anthraquinones, naphthoquinones, indophena­zines, N-substituted isoaroxazines, furoquinoxalines, thienoquinoxalines, diphenyl derivatives, triphenylmethane derivatives, lumazins, alloxazines, cinnolines, ortho­phenylenediamine derivatives, etc. (see U.S. Patents No. 2,270,118, No. 2,410,025, No. 2,541,884, No. 2,627,461 and No. 2,669,517, U.K. Patents No. 657,374 and No. 711,247, Japanese Patent Publication No. 22195/1970).
  • the dye bleaching solution there may be employed 1 to 20 g/liter of the above bleaching agent, 0.1 to 20 g/liter of the compound forming the above silver salt or silver complex, and 0.001 to 10 g/liter of the above dye bleaching promoting catalyst.
  • dye bleaching processing is practiced generally by dipping in a dye bleaching solution under the conditions of a temperature of 20 to 60 °C for 10 to 200 seconds.
  • water washing processing can be generally practiced before carrying out the silver bleaching processing which is described in detail below.
  • Silver bleaching processing is a processing in which all the black silver remaining in the photosensitive emulsion layer subjected to image exposure and the above dye bleaching processing is rehalogenated to be converted to silver chloride.
  • a silver bleaching solution is used for this silver bleaching processing.
  • the above silver bleaching solution may be one which has been known in the art, for example, a bleaching solution containing ferric chelate containing ethylenediamine-­tetraacetate can be preferably used.
  • the silver bleaching processing may be generally conducted under the condition of a tem­perature of 18 to 60 °C for 5 to 500 seconds.
  • the respective process­ings of water washing ⁇ fixing ⁇ water washing ⁇ stabilizing ⁇ drying can be performed in conventional manners to form a color filter layer having a picture ele­ment of either one color of cyan, magenta and yellow.
  • One of the important points in the method of the present invention is to form the remaining picture elements of other colors excluding the picture elements of at least one color formed according to the above silver dye bleach­ing method of the picture elements of two or more colors to be formed on a light-transmissive substrate by employ­ment of the nonincorporated-coupler type color developing method.
  • the photosensitive emulsion layer (A) formed by coating on the light-transmissive substrate is processed by the silver dye bleaching method to form pic­ture elements mask exposure for picture element formation is applied and developing processing with a developer con­taining a color forming coupler can be performed to form picture elements.
  • picture elements according to the nonincorporated-coupler type color developing method can be also formed on the photosensitive emulsion layer (A) by employment of the above method.
  • the exposure method there can be employed the method used for conventional pattern exposure similarly as in exposure in the case of the above silver dye bleaching method (e.g. contact exposure, proximity exposure, step exposure, etc.).
  • the method used for conventional pattern exposure similarly as in exposure in the case of the above silver dye bleaching method (e.g. contact exposure, proximity exposure, step exposure, etc.).
  • the nonincorporated-coupler type color developing method is a method in which developing is performed by use of a developer, thereby having the dye dyed or precipitated into the above photosensitive emulsion layer (A).
  • the above developer provided for use contains at least a color forming coupler and a developing agent (hereinafter called as developing agent (d)).
  • one kind of developing agent is selected and used. Selection of the developing agent is generally done in view of the kind and combination of the color forming coupler, etc.
  • the above developing agent (d) in the developer is gener­ally used so that it may be contained in an amount within the range of 0.1 to 10 g in 1 liter of the developer.
  • the developing agent (d) in an amount within the range of 0.5 to 7 g in one liter of the developer, further it is particularly pre­ferred to use the developing agent (d) in an amount within the range of 1 to 5 g.
  • the developing time at an ordi­nary temperature can be made within an adequate range (for example, within 1 to 10 minutes) regardless of the kind of the color forming coupler used, whereby workability becomes extremely good. Further, by setting the amount within this range, color formability tends to become par­ticularly good.
  • color forming couplers can be classi­fied into magenta color forming coupler, cyan color form­ing coupler and yellow color forming coupler depending on the wavelength for color formation.
  • color forming couplers can be classi­fied into magenta color forming coupler, cyan color form­ing coupler and yellow color forming coupler depending on the wavelength for color formation.
  • two kinds of these or color forming cou­plers exhibiting two kinds of different color formations are used in combination.
  • the above color forming coupler is different from the incorprated coupler (ballast type coupler) used in conven­tional color photographic process, and is a non-incorpo­rated-coupler type coupler which is used by being added into a developer and under the state at least partially dissolved in the developer, and known nonincorporated-cou­pler type couplers can be used.
  • examples of yellow color forming couplers can include ring-opened ketomethy­lene compounds (e.g., acylacetanilide such as 2-(p-­carboxyphenoxy)-2-pyvaloyl-2′,4′-dichloroacetanilide, etc.), and further in the present invention, those dis­closed in U.S. Patents No. 3,510,306 and No. 3,619,189, Japanese Patent Publications No. 33775/1965 and No. 3664/1969 can be used.
  • ketomethy­lene compounds e.g., acylacetanilide such as 2-(p-­carboxyphenoxy)-2-pyvaloyl-2′,4′-dichloroacetanilide, etc.
  • magenta color forming couplers can include active methylene compounds (e.g. hydrazones and cyanoacet­anilides such as 1-(2,4,6-trichlorophenyl)-3-(p-nitro­anilino)-2-pyrazolino-5-one, etc.), and further in the present invention, those disclosed in West German OLS 2,016, 587, U.S. Patents No. 3,152,896 and No. 3,615,502, and Japanese Patent Publication No. 133111/1969 can be used.
  • active methylene compounds e.g. hydrazones and cyanoacet­anilides such as 1-(2,4,6-trichlorophenyl)-3-(p-nitro­anilino)-2-pyrazolino-5-one, etc.
  • examples of cyan color forming couplers can include phenol compounds (e.g., 2-acetamido-4,6-dichloro-­5-methyl-phenol) or naphthol compounds (e.g., N-(O-­acetamidephenoethyl)-2-hydroxy-2-naphthoamide), and also in the present invention, those disclosed in U.S. Patents No. 3,002,836 and No. 3,542,552 and U.K. Patent No. 1,062,190 can be used.
  • phenol compounds e.g., 2-acetamido-4,6-dichloro-­5-methyl-phenol
  • naphthol compounds e.g., N-(O-­acetamidephenoethyl)-2-hydroxy-2-naphthoamide
  • the total content of the color forming couplers in one liter of the developer should be preferably set within the range of 0.5 to 20 g. If it is less than 0.5 g, no sufficient color formation may be sometimes effected, while on the other hand, if it is used in an amount of more than 20 g, the so-called fog may be sometimes generated.
  • this special nonin­corporated-coupler type developing method by making the total content of the color forming couplers in one liter of the developer within the range of 1 to 10 g, a color filter layer with little color contamination and good spectral characteristics can be obtained.
  • the formation ratio of the color forming couplers exhibit­ing different color formations in the developer can be suitably set in view of the color forming characteristics of the color forming couplers used.
  • the weight ratio of the both is made generally within the range of 1 : 9 to 7 : 3, preferably 1 : 9 to 4 : 6.
  • the weight ratio of the both is made gen­erally with the range of 1 : 9 to 7 : 3, preferably 1 : 9 to 4 : 6.
  • the weight ratio of the both is made generally within the range of 9 : 1 to 2 : 8, preferably 8 : 2 to 6 : 4.
  • the three of a cyan color forming coupler, a magenta color forming coupler and a yellow color forming coupler are combined, it is preferred to formulate the three in substantially equal amounts.
  • the formulation weight ratio of the total amounts of the above color forming couplers to the above develop­ ing agent (d) in the developer which can be suitably used in the nonincorporated-coupler type color forming develop­ing method in the method of the present invention can be set suitably in view of the kinds and contents of the above color forming couplers and the developing agent (d), but usually the formulation weight ratio of the color forming couplers and the above developing agent (d) is made within the range of 1 : 9 to 9 : 1.
  • the above developer may also contain additives which are contained in conventional nonincorporated-cou­pler type developers such as preservatives (e.g., sodium sulfite, diethylhydroxylamine), accelerators (e.g., alkali agents such as sodium hydroxide), controlling agents (e.g., potassium bromide, potassium iodide), aids (e.g., water quality controllers such as polyethylene glycol, etc., tone controllers such as citrazinic acid, imidazole derivatives, etc.) etc
  • preservatives e.g., sodium sulfite, diethylhydroxylamine
  • accelerators e.g., alkali agents such as sodium hydroxide
  • controlling agents e.g., potassium bromide, potassium iodide
  • aids e.g., water quality controllers such as polyethylene glycol, etc., tone controllers such as citrazinic acid, imidazole derivatives, etc.
  • the above developer can be prepared by dissolving the above components in water.
  • the above developer may be controlled to a pH value of 9.0 to 13.0 at ordinary use temperature (e.g., 10 to 40 °C) with the use of sodium hydroxide, etc. before it is used.
  • formation of the color filter layers of the picture elements with other colors than one color formed by employment of the above silver dye bleaching method can be practiced by use of the above developer as described below.
  • the above photosensitive emulsion layer (b) is sub­jected to pattern exposure in conventional manner (the first exposure).
  • the first developing of the exposed portion is carried out by use of the developer containing the above color forming couplers.
  • the developer containing the above color forming couplers For example, by carrying out development by use of a developer containing a cyan color forming coupler and a magenta color forming coupler as the color forming cou­plers (blue developer), the exposed portion is developed to blue color.
  • a developer containing a cyan color forming coupler and a yellow color forming coupler green developer
  • the exposed portion is developed to green color.
  • a developer containing a magenta color forming coupler and a yellow color forming coupler red developer
  • the first exposed portion may be developed with either developer of the above blue developer, green developer and red developer.
  • cyan developer a developer containing a cyan color form­ing coupler
  • magenta developer a developer containing a magenta color forming coupler
  • yellow developer a developer containing a yellow color forming coupler
  • the reaction accompanied with development is generally stopped by dipping the above photosensitive emulsion layer (b) in a solution containing acetic acid and sodium sulfate, and subsequently the photosensitive emulsion layer (b) is washed with water and dried, thereby forming the first colored portion having picture elements of either red color, blue color and green color.
  • the unexposed portion adja­cent to the above first exposed portion is subjected to pattern exposure in the same manner as in the first expo­sure, and then developed by use of one kind of the devel­opers other than that used in the first step. Further, via the steps of dipping into a stopping solution, water washing and drying, etc., if desired, the second exposed portion can be formed.
  • the colored portions are generally fixed in the step of removing the silver component in the photosensi­tive emulsion layer (b) (bleaching step).
  • a color filter layer having picture elements of remaining colors excluding picture elements of at least one color formed by applying the above silver dye bleach­ing method of red color (R), blue color (B) and green color (G).
  • the gaps can be applied with pattern exposure and then subjected to devel­oping processing with the use of a developer containing a cyan color forming coupler, a magenta color forming cou­pler and a yellow color forming coupler, whereby light-­transmissive sections (black stripe) 33 can be also formed at the gaps between the colored portions 32 of red portion (R), blue portion (B) and green portion (G).
  • the silver dye bleaching process is conducted after completion of all the nonincorporated-coupler type developing process.
  • the color filter layer can be subjected to etching treatment to remove unnecessary por­tions of the color filter layer.
  • the formation mode of picture elements may be either one of mosaic shape and stripe shape.
  • the color filter thus obtained can be used suitably as the filter for liquid crystal color display as shown in Fig. 4. More specifically, as shown in Fig. 4, by arranging the color filter 43 so that the color filter 43 and the liquid crystal 47 controlled by the electrodes 48a and 48b may be sandwiched between the polarizing plates 46a and 46b, it can be used as the filter for liquid color dis­play.
  • a silver iodobromide emulsion containing 3 mole % of sil­ver iodide was prepared by adding an aqueous silver nitrate solution and an aqueous solution containing potas­sium bromide and potassium iodide at the same time into an aqueous 10 % gelatin solution.
  • the addition conditions were regulated so that Lippmann's emulsion having an aver­age grain size of 0.05 ⁇ m was obtained.
  • the emulsion was chemically aged with sodium thiosulfate under the condi­tion of a temperature of 60 °C for 100 minutes. The amount of silver per one liter of the emulsion was made 31.8 g.
  • the above emulsion coating solution was applied onto a transparent borosilicate glass substrate (30 cm x 30 cm) with a thickness of 1.1 mm to a dry film thickness of 2 ⁇ m to prepare a light-sensitive silver halide photographic material.
  • the amount of silver attached was 1.5 g/m2, and the cyan dye (Exemplary compound (g)) attached 0.15 g/m2.
  • the method for preparing a color filter having a mosaic pattern of the three colors of B (blue), G (green) and R (red) as shown in Fig. 5 is to be described below.
  • the size of each picture element is 150 ⁇ m x 150 ⁇ m.
  • the first exposure was effected by use of a tungsten lamp. Exposure was effected at the position corresponding to the part B in Fig 5.
  • the exposed photographic material was dipped in the fol­lowing magenta color developing solution shown below at 23 °C for 3 minutes.
  • the photographic material was dipped in a stopping solution (containing 32 ml of 28 % acetic acid and 45 g of sodium sulfate in one liter) for 30 seconds and washed with water for 5 minutes, and then bleached with a silver bleaching solution having the following composition (23 °C, 2 minutes), followed by washing with water for 2 min­utes and drying, to form a magenta dye on the substrate.
  • a stopping solution containing 32 ml of 28 % acetic acid and 45 g of sodium sulfate in one liter
  • a silver bleaching solution having the following composition (23 °C, 2 minutes)
  • Silver bleaching solution composition Ammonium bromide 160.0 g Aqueous ammonia (28 %) 25.0 ml Iron sodium ethylenediaminetetraacetate 130.0 g Glacial acetic acid 14.0 ml Water is added to make up the total amount to one liter.
  • the photographic material subjected to the second exposure was dipped in a yellow color developing solution having the following composition at 23 °C for 3 minutes, then dipped in the above stopping solution for 30 seconds and then washed with water for 5 minutes, followed by bleach­ing, water washing and drying similarly as the first time to form a yellow dye on the substrate.
  • the photographic material subjected to the third exposure was dipped in a red color developing solution having the following composition at 23 °C for 3 minutes, followed by stopping, bleaching, water washing and drying similarly as in the second time to form magenta and yellow dyes on the substrate.
  • a chromium mask for color filter was arranged so that the exposed portion became the part R in Fig. 5, and the fourth exposure was effected.
  • the photographic material subjected to the fourth exposure was processed as follows under the condition of a tempera­ture of 33 °C. Monochromatic developing 1 minute Water washing 1 minute Dye bleaching 1 minute Water washing 1 minute Silver bleaching 1 minute Water washing 1 minute Fixing 1 minute Water washing 4 minutes Drying
  • the baths used for the respective processings have the following compositions.
  • ⁇ Monochromatic developer composition Sodium sulfite 20 g Hydroquinone 10 g Potassium hydroxide (48 % aqueous solution) 5 cc Diethylene glycol 20 cc Dimedone 0.7 g Sodium carbonate 20 g Potassium bromide 9 g Thiadiazole 0.05 g Water added to one liter
  • ⁇ Dye bleaching solution composition > 96 % Sulfuric acid 40 ml Potassium iodide 15 g 2 3,6-Trimethylquinoxaline 2 g Water added to one liter
  • the color filter thus obtained had square blue portion, green portion and red portion each with one side of 150 ⁇ m formed uniformly on the whole borosilicate glass sub­strate, and no color turbidity was recognized in each color.
  • Color filters were prepared in the same manner as in the above Example 1 except for replacing the cyan dye (Exemplary compound (g)) contained in the light-sensitive silver halide photographic material with Exemplary com­pounds (c), (e), (i) in the above Example 1.
  • a silver iodobromide emulsion containing 4 mole % of sil­ver iodide (average grain size: 0.05 ⁇ m, gelatin concen­tration: 9 % by weight) was prepared by adding an aqueous silver nitrate solution and an aqueous solution containing potassium bromide and potassium iodide at the same time into an aqueous solution containing 10 % by weight of gelatin.
  • the addition conditions were regulated so that Lippman emulsion could be obtained having an average grain size of 0.05 ⁇ m.
  • the above emulsion coating solution obtained was applied on a transparent borosilicate glass substrate (30 cm x 30 cm) with a thickness of 1.1 mm to a dry thickness of 3 ⁇ m to prepare a photosensitive emulsion layer having a photo­sensitive emulsion layer.
  • the amount of silver attached was 1.5 g/m2, and the amount of the dye attached 0.24 g/m2
  • This photosensitive emulsion layer has also a backing layer on the surface opposite to that having the above photosensitive emulsion layer in the above borosilicate glass substrate.
  • aqueous gelatin solution To an aqueous gelatin solution was added a dispersion of the compound Y-1 shown below, and also the above compounds H-1 and H-2 were added in amounts of 40 mg and 5 mg, respectively.
  • the gelatin amounts previously added were adjusted so that the gelatin in these aqueous gelatin solutions became 5 % by weight.
  • the amount of the com­pound shown below added into 100 cc of aqueous gelatin solution was 1.35 % by weight.
  • aqueous gelatin solution was coated on the above borosilicate glass substrate and then dried to form a backing layer.
  • the amount of the above compound Y-1 attached was 10 mg/dm2.
  • the above dispersion used was prepared by dissolving 1 g of tricresyl phosphate per 1 g of the compound Y-1 into 4.29 cc of ethyl acetate, then mixing the solution by adding into an aqueous solution containing 0.83 g of gelatin, 2.63 cc of an aqueous solution of 5 % by weight of sodium triisopropyl naphthalene sulfonate and 8.4 cc of water, dispersing by sonication the mixture under the con­dition of a temperature of 50 °C and removing ethyl acetate, followed further by addition of water to an amount of 17.6 cc.
  • the method for preparation of a color filter having the mosaic pattern of the three colors of B (blue), G (green) and R (red) as shown in Fig. 2 is to be described below.
  • the size of each picture element is 150 ⁇ m x 150 ⁇ m.
  • the first exposure was effected by use of a tungsten lamp exposure was effected at the position corresponding to the part B in Fig. 2.
  • magenta color developing solution composition Magenta coupler 2.0 g 1-(2.4,6-Trichlorophenyl)-3-(p-nitroanilino)-pyrazolin-5-one Developing agent 1.86 g 4-Amino-3-methyl-N-ethyl-N-(2-hydroxyethyl)aniline ⁇ sulfate Nitrotrimethylenesulfonic acid 3.00 ml Anhydrous sodium sulfate 6.66 g 0.1 % Aqueous potassium iodide solution 11.00 ml Anhydrous sodium bromide 0.86 g 6-Nitrobenzimidazole 0.02 g Sodium sulfite 20.00 g Hexylene glycol 5.00 ml Polyethylene glycol 0.60 ml Diethylhydroxylamine 0.27 ml Hydroquinone monosulfonic acid 0.10 g Tertiary butylaminoborane 0.07
  • the photographic material was dipped in a stopping solution (3 % by weight aqueous acetic acid solution) for one minute, then washed with water and bleached by dipping in the silver bleaching solution having the following com­position for one minute, followed by washing with water for one minute and drying, to form a blue color portion on the substrate (the first processing).
  • the photographic material subjected to the second exposure was dipped in the yellow color developing solution having the following composition at 25°C for 3 minutes, then dipped in the above stopping solution for one minute and washed with water, followed by bleaching, water washing and drying similarly as in the first time to form a green portion on the substrate (the second processing).
  • Yellow color developing solution composition Yellow coupler 1.5 g 2-(p-Carboxyphenoxy)-2-pyvaloyl-2′,4′-dichloroacetanilide Developing agent 1.86 g 4-Amino-3-methyl-N-ethyl-N-(2-hydroxyethyl)aniline ⁇ sulfate Nitrotrimethylenesulfonic acid 3.00 ml Anhydrous sodium sulfate 6.66 g 0.1 % Aqueous potassium iodide solution 11.00 ml Anhydrous sodium bromide 0.86 g 6-Nitrobenzimidazole 0.02 g Sodium sulfite 20.00 g Hexylene glycol 5.00 ml Polyethylene glycol 0.60 ml Diethylhydroxylamine 0.27 ml Hydroquinone monosulfonic acid 0.10 g Tertiary butylaminoborane 0.07 g Sodium thiocyanate 1.00 g Anhydrous sodium carbonate 16.67 g Anhydrous sodium hydrogen carbonate
  • the photographic material subjected to the third exposure was dipped in the red color developing solution having the following composition at 25 °C for 3 minutes, followed by stopping, water washing, bleaching, water washing and dry­ing similarly as in the second time to form a black por­tion on the substrate (the third processing).
  • Red color developing solution composition Magenta coupler 3.00 g 1-(2,4,6-Trichlorophenyl)-3-(p-nitroanilino)-pyrazolin-5-one Yellow coupler 1.00 g 2-(p-Carboxyphenoxy)-2-pyvaloyl-2′,4′-dichloroacetanilide Developing agent 1.86 g 4-Amino-3-methyl-N-ethyl-N-(2-hydroxyethyl)aniline ⁇ sulfate Nitrotrimethylenesulfonic acid 3.00 ml Anhydrous sodium sulfate 6.66 g 0.1 % Aqueous potassium iodide solution 11.00 ml Anhydrous sodium bromide 0.86 g 6-Nitrobenzimidazole 0.02 g Sodium sulfite 20.00 g Hexylene glycol 5.00 ml Polyethylene glycol 0.60 ml Diethylhydroxylamine 0.27 ml Hydroquinone monosulfonic acid 0.10 g Ter
  • a chromium mask for color filter was arranged so that the exposed portion became the part R in Fig. 2 to effect the fourth exposure.
  • the photographic material subjected to the fourth exposure was processed as described below under the condition of a temperature of 33 °C (the fourth processing), whereby the color filter having the mosaic pattern of the three colors of B (blue), G (green) and R (red) was obtained.
  • the baths used for the respective processings had the following compositions.
  • ⁇ Monochromatic developer composition Sodium sulfite 10 g Hydroquinone 10 g Potassium hydroxide (48 % aqueous solution) 5 cc Diethylene glycol 20 cc Dimedone 0.7 g Sodium carbonate 20 g Potassium bromide 2 g Thiadiazole 0.05 g Water added to one liter
  • ⁇ Dye bleaching solution composition > 96 % Sulfuric acid 40 cc Potassium iodide 15 g 2,3,6-Trimethylquinoxaline 2 g Water added to one liter
  • the photographic material was dipped in the fixing solution having the composition shown below of a liquid temperature of 25 °C or lower for one minute, washed with water for 4 minutes and then dried.
  • Table 1 Green light transmissive picture element Red light transmissitve picture element Example 3 1.80 1.60
  • Table 2 Blue light transmissive picture element Green light transmissitve picture element Example 3 1.00 2.00
  • Example 3 As is apparent from Table 1 and Table 2, the color filter obtained in Example 3 was confirmed to be excellent in color forming density.
  • an industrially useful method for prepar­ing a color filter having the following advantages:

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  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
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  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP89112990A 1988-07-19 1989-07-14 Verfahren zur Herstellung eines Farbfilters und nach diesem Verfahren hergestellter Farbfilter Withdrawn EP0351740A1 (de)

Applications Claiming Priority (4)

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JP63179625A JPH0229603A (ja) 1988-07-19 1988-07-19 カラーフィルターの製造方法
JP179625/88 1988-07-19
JP63188632A JPH0239002A (ja) 1988-07-28 1988-07-28 カラーフィルターの製造方法
JP188632/88 1988-07-28

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH506094A (fr) * 1969-05-28 1971-04-15 Mitsubishi Paper Mills Ltd Procédé pour colorer de façon non diffusible des couches photographiques au moyen d'un mordant à poids moléculaire élevé
FR2251840A1 (de) * 1973-11-16 1975-06-13 Eastman Kodak Co
US4294900A (en) * 1979-02-23 1981-10-13 Fuji Photo Film Co., Ltd. Process of producing multicolor optical filters
DE3133164A1 (de) * 1980-08-23 1982-05-06 Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa Verfahren zur herstellung von optischen mehrfarbenfiltern
EP0131970A1 (de) * 1980-02-22 1985-01-23 Ciba-Geigy Ag Verfahren zur Herstellung von Schwefelsäureaddukten des Harnstoffs
US4678740A (en) * 1985-04-29 1987-07-07 Catania James N Method for making photographic mattes
EP0233152A2 (de) * 1986-02-11 1987-08-19 Ilford Ag Photographisches Material für das Silberfarbbleichverfahren

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH506094A (fr) * 1969-05-28 1971-04-15 Mitsubishi Paper Mills Ltd Procédé pour colorer de façon non diffusible des couches photographiques au moyen d'un mordant à poids moléculaire élevé
FR2251840A1 (de) * 1973-11-16 1975-06-13 Eastman Kodak Co
US4294900A (en) * 1979-02-23 1981-10-13 Fuji Photo Film Co., Ltd. Process of producing multicolor optical filters
EP0131970A1 (de) * 1980-02-22 1985-01-23 Ciba-Geigy Ag Verfahren zur Herstellung von Schwefelsäureaddukten des Harnstoffs
DE3133164A1 (de) * 1980-08-23 1982-05-06 Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa Verfahren zur herstellung von optischen mehrfarbenfiltern
US4678740A (en) * 1985-04-29 1987-07-07 Catania James N Method for making photographic mattes
EP0233152A2 (de) * 1986-02-11 1987-08-19 Ilford Ag Photographisches Material für das Silberfarbbleichverfahren

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN, vol. 11, no. 378 (P-645)[2825], 10th December 1987; & JP-A-62 148 952 (KONISHIROKU PHOTO IND. CO., LTD) 02-07-1987 *

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