WO2004049052A1 - 表示素子、表示装置及び表示装置の製造方法 - Google Patents
表示素子、表示装置及び表示装置の製造方法 Download PDFInfo
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- WO2004049052A1 WO2004049052A1 PCT/JP2003/014453 JP0314453W WO2004049052A1 WO 2004049052 A1 WO2004049052 A1 WO 2004049052A1 JP 0314453 W JP0314453 W JP 0314453W WO 2004049052 A1 WO2004049052 A1 WO 2004049052A1
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- display device
- forming
- solid electrolyte
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1506—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect caused by electrodeposition, e.g. electrolytic deposition of an inorganic material on or close to an electrode
- G02F1/1508—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect caused by electrodeposition, e.g. electrolytic deposition of an inorganic material on or close to an electrode using a solid electrolyte
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/153—Constructional details
- G02F1/157—Structural association of cells with optical devices, e.g. reflectors or illuminating devices
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F2001/164—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect the electrolyte is made of polymers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
- G02F2201/38—Anti-reflection arrangements
Definitions
- the present invention relates to a display element, a display device, and a method for manufacturing a display device, using a material that changes color by electrochemical oxidation and reduction as a display material.
- Display elements for viewing these include CRTs, liquid crystal displays, and organic EL displays.
- CTRs CRTs
- liquid crystal displays CTRs
- organic EL displays CTRs
- these display elements are of a light emitting type, and therefore are extremely fatigued for ergonomic reasons and cannot withstand long-time reading.
- the place to read is limited to the place where the computer is installed.
- electrochromic display elements that utilize the oxidation-reduction of metal ions have a white reflective plate on the back surface (see, for example, Patent Document 5) or a solid polymer electrolyte to achieve higher reflectivity.
- a colorant for increasing the whiteness has been proposed (for example, see Patent Document 6).
- the present invention has been made in view of the above-described problems, and an object of the present invention is to provide a material which has a sufficiently high whiteness of an underlayer as a visual characteristic and which changes color by electrochemical oxidation and reduction as a display material.
- an object of the present invention is to provide a material which has a sufficiently high whiteness of an underlayer as a visual characteristic and which changes color by electrochemical oxidation and reduction as a display material.
- the polymer A display element comprising: an antireflection layer provided on a surface of the first transparent electrode opposite to a surface on which a solid electrolyte layer is laminated.
- metal ions are each of bismuth, copper, silver, lithium, iron, chromium, nickel, force dome, or a combination thereof.
- the inorganic pigment comprises a powder of titanium dioxide, calcium carbonate, magnesium oxide, or anolemmium oxide.
- a first transparent electrode controlled by a driving element wherein a first transparent electrode controlled by a driving element, a polymer solid electrolyte layer containing a colorant and metal ions, and a second electrode are laminated in this order.
- the colorant is at least selected from titanium dioxide, calcium carbonate, magnesium oxide, and aluminum oxide, the surface of which has been treated with a hydrophobizing agent.
- a display element comprising a powder of one kind of inorganic compound.
- the hydrophobizing agent used in the surface-treated inorganic compound powder is a metal alkoxide, an organic metal compound having a bond between a metal and at least one halogen atom, or an organic metal having a metal-metal bond.
- the display element according to the item 8 wherein the display element is at least one compound selected from compounds.
- the polymer solid electrolyte constituting the polymer solid electrolyte layer has a skeleton unit of one (C-C-O) n -,-(CC (CH 3 ) -O) n -,-(CC -N) n- or one (C-C-S) n- represented by polyethylene oxide, polypropylene oxide, polyethyleneimine, polyethylene sulfide, or a polymer having a branched structure of these as a main chain structure.
- a first transparent electrode controlled by the driving element, a polymer solid electrolyte layer containing a colorant and a metal ion, and a second electrode are laminated in this order, and are opposite to the polymer solid electrolyte layer.
- a display device comprising a plurality of display elements having an antireflection layer on the surface of the first transparent electrode on the side of the first transparent electrode.
- a step of forming an antireflection layer on the transparent support a step of forming a transparent pixel electrode and a driving element on the surface of the transparent support opposite to the antireflection layer, and
- a method for manufacturing a display device comprising: a step of forming a polymer solid electrolyte layer containing a colorant and a metal ion; and a step of forming a common electrode facing the transparent pixel electrode.
- a step of forming a transparent pixel electrode and a driving element on a transparent support a step of forming a polymer solid electrolyte layer containing a colorant and a metal ion on the transparent support, and a step of forming the transparent pixel electrode
- Forming a common electrode facing the transparent pixel electrode and, after forming the common electrode facing the transparent pixel electrode, an anti-reflection layer on a surface of the transparent support opposite to the surface on which the transparent pixel electrode and the driving element are formed.
- FIG. 1 is a partial perspective view of a display device according to the present invention.
- FIG. 2 is a sectional view of the display device according to the present invention.
- FIGS. 3 (a) to (f) are cross-sectional views showing the steps of a method for manufacturing a display device according to the present invention.
- FIGS. 4 (a) to 4 (f) are cross-sectional views showing the steps of a method for manufacturing a display device according to the present invention.
- FIG. 6 is a block diagram of a display device according to the present invention. BEST MODE FOR CARRYING OUT THE INVENTION
- the display device of the present invention is a polymer solid containing a metal ion and a colorant on a transparent pixel electrode which is a first transparent electrode controlled by a TFT (Thin Film Transistor) which is a driving element.
- An electrolyte layer and a common electrode common to each pixel as a second electrode are laminated in this order, and a polymer solid electrolyte layer of a transparent pixel electrode as a first transparent electrode controlled by a TFT as a driving element.
- a plurality of display elements having an anti-reflection layer provided on the surface opposite to the surface on which the layers are laminated.
- FIG. 1 is a partial perspective view of the display device of the present invention.
- the transparent pixel electrode 12 and the TFT 13 are formed so as to constitute one pixel by combining one by one, and each pixel is arranged in a matrix on the transparent support 11.
- a transparent glass substrate such as a quartz glass plate or a white plate glass plate can be used, but is not limited thereto, and a polyester such as polyethylene naphthalate or polyethylene terephthalate is used.
- cellulose ester resin such as cellulose acetate, polyvinylidene fluoride, polytetrafluoroethylene-co-hexaf Fluorine resins such as fluoropropylene, polyether resins such as polyoxymethylene, polyolefins such as polystyrene, polyethylene, polypropylene, polymethynolepentene, and nonolevonolene ring-opening polymers, and acrylyl resins such as polymethyl methacrylate And resin films of polyimide, polyamide-amide, polyetherimide, and the like, polyimide, polycarbonate, polyacetanol, polyarylate, polyetherenoate ketone, polysulfone, and polyethersulfone.
- these resin films When used as a support, they can be made into a rigid substrate shape that does not easily bend, and can be made into a film-like structure having a force and flexibility.
- a transparent glass substrate and a resin film, or a laminated support obtained by laminating a plurality of types of resin films can be appropriately selected and used for the purpose of achieving both flexibility and strength.
- An anti-reflection layer 18 is provided on the opposite side of the transparent support 11 where the transparent pixel electrode 12 and the TFT 13 are provided, that is, on the side to be observed, that is, on the side to be observed. It is provided for more clearly observing a material which changes color by electrochemical oxidation or reduction described above, and preferably has a smaller refractive index with respect to the transparent support 11.
- the antireflection layer is not particularly limited as lower refractive index than the transparent support 1 1, for example AIF 3, M g F 2, A l F 3 'M g F 2, Modification modified with a fluorine atom-containing homopolymer, copolymer, graft polymer, block polymer, or a fluorine atom-containing functional group such as metal fluoride such as C a F 2 , vinylidene fluoride, and Teflon (R) It is preferable that an organic fluoride such as a polymer has a lower refractive index than the transparent support described above.
- a support and a fluorine-based compound are provided.
- a known method such as a sol-gel method, a vacuum evaporation method, a sputtering method, a CVD method or a coating method, or a method disclosed in JP-A Nos. 7-27992 and 2001-123264.
- the methods described in JP-A-2001-264509 and the like can be appropriately selected and used.
- the transparent pixel electrode 12 is composed of a transparent conductive film formed in a substantially rectangular or square pattern, and the pixels are separated as shown in Fig. 1, and a TFT 13 for each pixel is installed in a part of it.
- the transparent pixel electrode 1 2 films used in can be used a film coated with I n 2 0 3 and mixtures of S N_ ⁇ 2, the so-called I TO film or S n0 2 or I n 2 ⁇ 3, these I tO film or S n0 2 or I n 2 0 3 may also to those Dobingu the S n and S b to Kotin grayed membrane, may be further used M g O and Z n O, and the like.
- TFT 13 a material used in a known semiconductor manufacturing technique used for a liquid crystal display or the like can be appropriately selected and used. Further, JP-A-10-125924, Organic TFTs comprising organic compounds described in, for example, Nos. 10 to 135481, 10 to 199000, and 2000 to 37171 may also be used.
- the TFT 13 formed for each pixel is selected by a wiring (not shown), and controls the corresponding transparent pixel electrode 12.
- TFT 13 is extremely effective in preventing crosstalk between pixels.
- the TFT 13 is formed so as to occupy one corner of the transparent pixel electrode.
- the transparent pixel electrode 12 may have a structure overlapping the TFT 13 in the laminating direction. Specifically, a gate line and a data line are connected to the TFT 13, a gate electrode of each TFT 13 is connected to each gate line, and one of the source 'drains of each TFT 13 is connected to the data line. Are connected to each other, and the other of the source and the drain is electrically connected to the transparent pixel electrode 12.
- Driving elements other than TFT 13 are flat type displays such as liquid crystal displays. Any other material may be used as long as it is a matrix drive circuit used for the display element and can be formed on a transparent substrate.
- the polymer solid electrolyte layer 14 contains metal ions, and the metal ions change color by electrical oxidation-reduction, electrochemical deposition, so-called electrolytic plating, and the like. Visualization can be achieved by reversible elution, which is a reverse reaction.
- the metal ions capable of developing and decoloring by such electrochemical deposition and elution are not particularly limited, but bismuth, copper, silver, lithium, iron , Chromium, nickel, and cadmium ions or an ion composed of a combination thereof. Of these, bismuth and silver ions are preferable because a reversible reaction can be easily performed.
- Polymer solid electrolyte layer 1 4 is formed by dissolving in addition to the supporting electrolyte and the matrix polymer.
- a lithium salt for example L i C 1, L i B r, L i I, L i BF 4 , L i C 1 0 4, L i PF 6, L i CF 3 S_ ⁇ 3 etc.
- Kariumu salts eg if KC 1, KI, and KB r, etc., Natoriumu salts, for example N a C 1, N a I , NaBr, or tetraalkylammonium salts, such as tetraethylammonium borofluoride, tetraethylammonium perchlorate, tetrabutylammonium borofluoride, tetrabutylammonium perchlorate And tetrabutylammonium halide.
- the alkyl chain lengths of the above quaternary ammonium salts may be the same or different, and if necessary, only one kind may be used, or two or more kinds may be used in combination.
- the polymer solid electrolyte layer 14 contains a colorant to improve the contrast, and provides a sufficient contrast with respect to the color developed by the redox of metal ions.
- a colorant to improve the contrast, and provides a sufficient contrast with respect to the color developed by the redox of metal ions.
- Known inorganic pigments, organic pigments or dyes can be appropriately selected and used as long as they can be used.
- a white concealing 1 "raw colorant as a background color. Examples of such a colorant include titanium dioxide, Calcium carbonate, silica, magnesium oxide, and aluminum oxide can be used.
- the mixing ratio of the coloring agent is preferably about 1 to 20% by mass, more preferably about 1 to 10% by mass, and more preferably about 5 to 10% by mass when inorganic particles are used. / 0 . This is because inorganic white particles such as titanium oxide do not dissolve in the polymer but only disperse. If the mixing ratio increases, the inorganic particles aggregate and the optical density becomes non-uniform. is there. Further, since the inorganic particles do not have ionic conductivity, an increase in the mixing ratio causes a decrease in the conductivity of the polymer solid electrolyte layer 14. Considering both, the upper limit of the mixing ratio is about 20% by mass.
- titanium dioxide, calcium carbonate, magnesium oxide, or aluminum oxide may be added to the polymer solid electrolyte layer 14 as a coloring agent. This is because the dispersibility of the matrix polymer and the dispersibility when preparing the polymer solid electrolyte layer forming composition described later are taken into consideration, and the colorants may aggregate after forming the polymer solid electrolyte layer. It is preferable to prevent whitening, and the whiteness can be maintained even after long-term use.
- Examples of the surface hydrophobizing agent for hydrophobizing the colorant surface include a metal alkoxide, an organic metal compound having a bond between a metal and at least one halogen atom, or an organic metal having a metal-metal bond. Compounds and the like can be mentioned, and it is more preferable to perform a surface treatment with at least one compound selected from these.
- organometallic compound having a metal bond or an organometallic compound having a metal-metal bond include, for example, silicon, germanium, titanium, tin, zirconium, aluminum, antimony, arsenic, norm, bismuth, boron, calcium, cerium, and chromium.
- Metal copper, erbium, gallium, hafnium, indium, iron, lanthanum, magnesium, manganese, neodymium, niobium, praseodymium, samarium, strontium, tantalum, tezorel, tungsten, vanadium, yttrium, zinc, zirconium, etc.
- halide and organic metal compounds having a metal-metal bond.
- silicon, germanium, titanium, tin, dinoreconium, and aluminum are particularly preferable. Ri preferred.
- Alcohol-forming alcohol components generally include straight-chain or branched alcohols having about 1 to 12 carbon atoms.All metal alkoxide compounds may be alcohols, or at least one alkoxide may be used in the compound. And a ligand such as an unsubstituted or substituted alkyl, an unsubstituted or substituted aryl group, and acetyl aceton.
- the halogen forming the organometallic compound having a bond between the metal and at least one halogen atom is not particularly limited as long as it is at least one halogen atom selected from chlorine, bromine and iodine.
- organometallic compound a compound having at least one metal-halogen bond, an unsubstituted or substituted alkyl bond with a metal, an unsubstituted or substituted aryl group with a metal, and acetylacetone
- organometallic compound having a ligand such as, for example, may be used.
- the mixing ratio of titanium dioxide, calcium carbonate, magnesium oxide, and aluminum oxide whose surfaces have been surface-treated with a hydrophobizing agent is preferably about 1 to 20% by mass in the case of inorganic particles, and more preferably. About 1 to 10% by mass. It is preferably about 5 to 10% by mass.
- the average particle size of the colorant is preferably in the range of 0.1 to 1.0 ⁇ m from the viewpoint of hiding properties and whiteness.
- Matrix polymers used for the solid polymer electrolyte constituting the solid polymer electrolyte layer 14 containing metal ions include polyethylene oxide, polypropylene oxide, polyethylene imine, and polyethylene sulfide. A resin having a chain structure or a resin having a branched structure may be used. Further, resins such as polymethyl methacrylate, polyvinylidene fluoride, polyvinylidene chloride, polycarbonate, and polyacrylitol can also be suitably used as the matrix polymer used in the polymer solid electrolyte of the present invention.
- the thickness of the polymer solid electrolyte layer 14 is preferably 20 to 200 / m, more preferably 50 to 150 ⁇ , and still more preferably 70 to 150 ⁇ .
- a thinner one is preferable because the resistance between the electrodes becomes smaller, which leads to a reduction in the color development / decoloration time and a reduction in power consumption.
- it is less than 20 ⁇ , the mechanical strength is reduced, and pinholes and cracks are generated, which is not preferable.
- the thickness is too small, the mixing amount of the white particles becomes small, so that the hiding property and the whiteness (optical density) become insufficient.
- the polymer solid electrolyte layer 14 when the polymer solid electrolyte layer 14 is formed, if necessary, water, ethanol alcohol, isopropyl alcohol, propylene carbonate, dimethyl carbonate, ethylene carbonate, ⁇ -petit mouth ratatone, acetonitrile , Snorrefholane, dimethyloxetane, ethyl alcohol, isopropyl alcohol, dimethylformamide, dimethylsulfoxide, dimethylacetamide, ⁇ -methylpyrrolidone, etc. to prepare a polymer solid electrolyte layer forming composition May be.
- An ionic fluid represented by the formula Q + A— may be added for the purpose of efficiently conducting ion conduction or for reducing the amount of flammable liquid.
- L is preferably a salt which is present as a liquid at 00 ° C, preferably 20 to 80 ° C, more preferably 20 to 60 ° C, still more preferably 20 to 40 ° C, especially 20 ° C. ° C) is not particularly limited as long as it is a melt at room temperature, but is preferably 1 to 200 mPa ⁇ s.
- the cation component represented by Q + is preferably an anion cation, more preferably an ammonium cation, an imidazolium cation, a pyridinium cation, a sulfonium cation, and a phosphonium cation.
- ionic fluids include WO 95Z18456, JP-A-8-245828, JP-A-8-259543, JP-A-10-92467, JP-A-10-2665673, JP-A-2002-99001, and JP-A-2002-99001.
- a bluing agent or a fluorescent whitening agent may be added for the purpose of improving visual whiteness by fluorescence, bluish color, etc., and these may be appropriately selected from known ones. Can be.
- blueing agent examples include organic dyes and pigments that can be colored blue, and inorganic pigments. Specifically, ultramarine, cobalt blue, cobalt oxide phosphate, quinatalidone-based pigments and the like And mixtures thereof.
- fluorescent whitening agent examples include stilbene, pyrazoline, oxazole, coumarin, imidazole, distyryl-biphenyl, thiazole, and thiazole.
- fluorescent whitening agent examples include stilbene, pyrazoline, oxazole, coumarin, imidazole, distyryl-biphenyl, thiazole, and thiazole.
- examples thereof include liazole, oxadiazole, thiadiazole, naphthalimide, benzoimidazole, benzoxazonole, benzothiazonole, acenaphthene, and diaminostilbene.
- the above-mentioned bluing agent or optical brightener include, for example, JP-A-6-322697, JP-A-7-181626, JP-A-8-118824, JP-A-8-175033, and JP-A-10-44628.
- Those described in 1-518919 can be appropriately selected and used.
- the content is preferably 10 to: L00000ppm, particularly 50 to: LOOOOpm.
- the content of the bluing agent or the optical brightener is less than 10 ppm, the amount of fluorescent light is reduced and the bluish component of the reflected light is reduced, and as a result, the film becomes yellowish and has sufficient whiteness. Is not preferable because it tends to be difficult to obtain. Also, if the content of the bluing agent or fluorescent brightener exceeds l OOOOO ppm, the bluing agent or fluorescent brightener will be denatured when the display device is used under the condition of ultraviolet irradiation or high temperature and high humidity. This is not preferable because discoloration at the time of remarkable operation becomes remarkable and weather resistance as a display device may be deteriorated.
- a common electrode 15 is formed as a second electrode on the side facing the first transparent electrode.
- the common electrode 15 may be any metal that is electrochemically stable, but is preferably platinum, chromium, aluminum, cobalt, palladium, etc., and is formed as a metal film on a support by a known method. It can be manufactured by forming a film. Also, if sufficient conductivity can be obtained as the common electrode 15, If a conductive coating containing conductive particles such as conductive metal particles is coated on a support, the metal used for the main reaction can be further supplemented in advance or as needed, and carbon can be used as a common electrode. It can be used as As a method of supporting carbon on the electrode for that purpose, there is a method of forming an ink using a resin and printing the ink on a substrate surface. By using carbon, the cost of the electrode can be reduced. '
- the support used for providing the above-mentioned first transparent electrode can be appropriately used, but the second electrode does not necessarily need to be transparent, and may be a common electrode or a polymer solid.
- a substrate, a film, or the like that can securely hold the electrolyte layer can be appropriately selected and used.
- a sealing member 17 holding the transparent support 11 and the support 16 is formed around the first transparent electrode side and the second electrode so as to face each other. Is done.
- the transparent support 11 and the support 16 and the transparent pixel electrode 12 and the TFT 13, the polymer solid electrolyte layer 14, and the common electrode 15 disposed therebetween are formed by the sealing member 17. It will be securely held.
- the antireflection layer 18 is provided on the outermost layer of the support 16 on which the first transparent electrode is provided.
- matrix driving can be performed using a TFT, and the contrast and black density are increased by using metal ions contained in the polymer solid electrolyte layer.
- a display device having a visually higher reflectance can be manufactured.
- reflection is performed on one surface of a transparent support 11 such as a glass substrate by using a compound forming an antireflection layer 18 and a known method suitable for the transparent support.
- the prevention layer 18 is formed.
- the MgF 2 film and the AlF 3 'MgF 2 film are formed on the entire substrate by using a deposition method, a sputtering method, or the like.
- a transparent pixel electrode 12 made of an ITO film and a TFT 13 are formed for each pixel on the surface of the transparent support 11 opposite to the antireflection layer 18. .
- the TFT 13 is formed by using a known semiconductor manufacturing technique, and the ITO film is formed by a method such as evaporation or sputtering.
- the transparent pixel electrode 12 and the TFT 13 are formed for each pixel, and each pixel is arranged on the transparent support 11 in a matrix.
- the transparent pixel electrode 12 and the TFT 13 on the transparent support 11 are formed.
- the solid polymer electrolyte layer 14 is formed on the surface thus formed.
- the step of forming the polymer solid electrolyte layer 14 first, in forming the polymer solid electrolyte layer 14, the above-mentioned synthetic resin serving as the matrix polymer, a supporting electrolyte, a metal ion generator capable of generating metal ions, and If necessary, a solvent for dissolving these components is mixed, and white particles are dispersed as a colorant to prepare a polymer solid electrolyte layer forming composition.
- the polymer solid electrolyte layer-forming yarn is coated on a transparent support to form the polymer solid electrolyte layer 14.
- a support with a common electrode was formed by forming a common electrode 15 of a required thickness on a support 16 of a polyethylene terephthalate film or the like.
- the common electrode 15 side of the support with a common electrode is pressure-bonded to the polymer solid electrolyte layer 14 and bonded as shown in FIG. 3 (e).
- the polymer solid electrolyte layer 14 is formed by drying under reduced pressure between the support 16 and the transparent support 11.
- a sealing member 17 as shown in FIG. 3 (f) is attached to the bonded end, and a display device in which the antireflection layer 18 is provided on the display side is completed.
- FIG. 4 (a) to (f) show another method of manufacturing a display device according to the present invention.
- a transparent support 11 such as a glass substrate
- a transparent pixel electrode 12 composed of a TO film and a TFT 13 are formed for each pixel.
- the TFT 13 is formed by using a known semiconductor manufacturing technique, and the ITO film is formed by a method such as vapor deposition or sputtering.
- the transparent pixel electrode 12 and the TFT 13 are formed for each pixel, and each pixel is arranged in a matrix on the transparent support 11.
- the transparent pixel electrode 12 and the TFT 13 are formed on the surface of the formed transparent support 11 opposite to the surface on which the transparent pixel electrode 12 and the TFT 13 are formed.
- the anti-reflection layer 1 8 under conditions that do not deterioration and formed using known methods, Mg F 2 film and a 1 F 3 'Mg F 2 film is formed on the entire substrate by an evaporation or sputtering method, or the like You.
- the transparent pixel electrode 12 and the TFT 13 on the transparent support 11 are formed.
- the solid polymer electrolyte layer 14 is formed on the surface thus formed.
- the synthetic resin serving as the matrix polymer described above, a supporting electrolyte, a metal ion generator capable of generating metal ions, and, if necessary, a solvent dissolving these. are mixed, and white particles are further dispersed as a colorant to prepare a polymer solid electrolyte layer forming composition.
- the polymer solid electrolyte layer forming composition is applied to a transparent support to form the polymer solid electrolyte layer 14.
- a support with a common electrode was formed by forming a common electrode 15 of a required thickness on a support 16 of a polyethylene terephthalate film or the like. Then, the common electrode 15 side of the support with a common electrode is pressure-bonded to the polymer solid electrolyte layer 14 and bonded as shown in FIG. 4 (e). After this bonding, the polymer solid electrolyte layer 14 is dried under reduced pressure, and the polymer solid electrolyte layer 14 is placed between the support 16 and the transparent support 11. Formed. Then, a sealing member 17 as shown in FIG.
- FIGS. 5 (a) to (f) show a manufacturing method different from the manufacturing method shown in FIGS. 3 (a) to (f) and FIGS. 4 (a) to (f) of the display device of the embodiment.
- a transparent pixel electrode 12 made of an ITO film and a TFT (thin film transistor) 13 are formed for each pixel on a transparent support 11 such as a glass substrate.
- the TFT 13 is formed by using a known semiconductor manufacturing technique, and the ITO film is formed by a method such as vapor deposition and sputtering.
- the transparent pixel electrode 12 and the TFT 13 are formed for each pixel, and each pixel is arranged on the transparent support 11 in a matrix.
- the polymer solid electrolyte layer 14 is formed on the surface side.
- the polymer solid electrolyte layer forming composition is applied on a transparent support to form the polymer solid electrolyte layer 14.
- a support with a common electrode was formed by forming a common electrode 15 of a required thickness on a support 16 of a polyethylene terephthalate film or the like.
- the common electrode 15 side of the support with a common electrode is pressure-bonded to the polymer solid electrolyte layer 14 and bonded as shown in FIG. 5 (d).
- the polymer solid electrolyte layer 14 is dried under reduced pressure, and the polymer solid electrolyte layer 14 is placed between the support 16 and the transparent support 11. Formed.
- a sealing member 17 as shown in FIG. 5 (e) was attached to the bonded end, and finally, as shown in FIG. 5 (f), sealing was performed with the sealing member 17.
- An anti-reflection layer 18 is formed on the image display side of the transparent support 11 on the image display side under conditions that do not deteriorate the transparent pixel electrode 12, the TFT 13, and the polymer solid electrolyte layer 14 by using a known method. 2 films and a 1 F 3 'Mg F 2 film is formed on the entire substrate by an evaporation Ya sputtering, installed the display device is completed on the side to view the antireflection layer 18.
- FIG. 6 is a block diagram of a display device.
- a transparent pixel electrode 12 corresponding to each pixel and a TFT 13 corresponding to the transparent pixel electrode 12 are arranged in a matrix, and the counter electrode side of the capacitor is a common electrode.
- a gate line (scanning line wiring) 140 is connected to the gate electrode of TFT 13, and the other of the source and drain of TFT 13 is connected to a data line (signal line wiring) 150.
- the other of the source and the drain of the TFT 13 is connected to the transparent pixel electrode 12.
- the gate line 140 is connected to the gut line drive circuit 120, and the data line 150 is connected to the data line drive circuits 100 and 110.
- the gate line driving circuit 120 and the data and line driving circuits 110, 110 are connected to a signal control unit 130.
- the thickness 1.5111111 10 (: 111 10: 111 on a glass substrate of, depositing a M g F 2 from the deposition source consisting of 1 ⁇ ⁇ 2, forming a deposited film of M g F 2 having a thickness of 1600 A
- an ITO film and a TFT which are planarly arranged at a pitch of 15 ⁇ on the surface of the glass substrate opposite to the antireflection layer, were formed by a known method.
- 1 part by mass of polyvinylidene fluoride having a molecular weight of about 350,000 is mixed with 10 parts by mass of a 1: 1 mixed solvent of water and isopropyl alcohol, 1.7 parts by mass of lithium bromide, and 1.7 parts by mass of bismuth chloride at 120 ° C.
- a homogeneous solution 0.2 parts by mass of titanium dioxide having an average particle size of 0.5 ⁇ m was added thereto, and the mixture was uniformly dispersed with a homogenizer. This was applied on the above glass substrate with a doctor blade at a thickness of 60 ⁇ , and then a common electrode, which is the second electrode described below, was immediately bonded, and this was applied at 110 ° C and 0.05 MPa. After drying under reduced pressure for 1 hour, a solid polymer electrolyte was formed between the two electrodes. Next, a display device was manufactured by sealing the bonded end face with an adhesive.
- a palladium film having a thickness of 3000 A was formed on a polyethylene terephthalate film having a thickness of 0.5111111 and a size of 10 cm ⁇ 10 cm by sputtering. This was pressure-bonded immediately after the application of the solid polymer electrolyte.
- a known active matrix drive circuit oxidizes the display electrode with an amount of 5 / i C per pixel during color development, and reduces it with the same amount of electricity during decoloration, thereby providing a black display and a colorless (white) display. Switched.
- the reflectance when colorless (white) was 68%, and the optical density (OD) of the display section when coloring (black) was about 0.8 (reflectance 8%). Therefore, the contrast of the reflectance was 1: 8.5.
- the circuit was opened and allowed to stand. One week later, the optical density of the display portion was not particularly changed, and had memory properties.
- a display device was produced under the same conditions as in Example 1 except that silver perchlorate was used instead of bismuth chloride used in Example 1.
- Example 2 After that, when driving and evaluation were performed in the same manner as in Example 1, the reflectance when colorless (white) was 70%, and the optical density (OD) of the display portion when coloring (black) was about 1.0 (reflectance 7 %). Therefore, a contrast of 1:10 was obtained for the reflectance. After placing the circuit in the color-developing state, the circuit was opened and left to stand. One week later, the optical density of the display portion did not change, and it had memory properties. In addition, as a sensory discrimination degree evaluation, when the display device manufactured in Example 2 and the display device manufactured in Comparative Example 2 shown below were evaluated by 50 persons, 94% of the persons installed the anti-reflection layer. The result is that the display device is easier to see.
- ITO films and TFTs arranged in a plane at a pitch of 150 ⁇ on a 10 (111: 111.111) glass substrate with a thickness of 5111111 were fabricated by a known method.
- an alloy in which metal magnesium was mixed with metal magnesium at an atomic composition ratio of 30% was used as a metal target.
- Sputtering was carried out using a% diluted F 2 gas to produce an A 1 F 3 ⁇ Mg F 2 antireflection film having a thickness of 300 nm.
- Example 2 After that, when driving and evaluation were performed in the same manner as in Example 1, the reflectance when colorless (white) was 70%, and the optical density (OD) of the display section when coloring (black) was about 1.0 (reflectance 6 %). Accordingly, a contrast of 1: 11.7 was obtained as the reflectance. After placing the circuit in the color-developing state, the circuit was opened and left to stand. One week later, there was no change in the optical density of the display section, and it had memory properties. In addition, as a sensory discrimination degree evaluation, when the display device manufactured in Example 3 and the display device manufactured in Comparative Example 2 shown below were evaluated by 50 people, 94% of the people installed the antireflection layer. The result is that the display device is easier to see.
- ITO films and TFTs arranged in a plane at a pitch of 150 ⁇ were formed by a known method.
- 1 part by mass of polyvinylidene fluoride having a molecular weight of about 350,000 is mixed with 10 parts by mass of a 1: 1 mixed solvent of water and isopropyl alcohol, 1.7 parts by mass of lithium bromide, and 1.7 parts by mass of silver perchlorate, The solution was heated to 120 ° C to prepare a homogeneous solution.
- 0.2 parts by mass of titanium dioxide having an average particle size of 0.2 was added thereto, and the mixture was uniformly dispersed with a homogenizer.
- Example 2 This was applied to a thickness of 60 ⁇ m on the glass substrate by a doctor blade, and then applied to Example 1.
- the common electrode which is the second electrode described in
- Example 1 Immediately bond the common electrode, which is the second electrode described in, and dry it under reduced pressure at 110 ° C and 0.05 MPa for 1 hour to form a solid polymer electrolyte between the two electrodes.
- the end face was sealed with an adhesive.
- the Mg F 2 was vapor deposited from the deposition source consisting of Mg F 2, thickness 160 OA of the deposited film of Mg F 2 Was formed and an antireflection layer was formed to produce a display device.
- Example 2 After that, when driving and evaluation were performed in the same manner as in Example 1, the reflectance when colorless (white) was 70%, and the optical density (OD) of the display portion when coloring (black) was about 1.0 (reflectance 7 %). Therefore, a contrast of 1:10 was obtained for the reflectance. After placing the circuit in the color-developing state, the circuit was opened and left to stand. One week later, the optical density of the display portion did not change, and it had memory properties. In addition, as a sensory discrimination degree evaluation, when the display device manufactured in Example 4 and the display device manufactured in Comparative Example 2 shown below were evaluated by 50 people, 94% of the people installed the antireflection layer. The result is that the display device is easier to see.
- a Mg F2 was vapor deposited from the deposition source consisting of Mg F2, forming a MgF2 deposited film of a thickness of 1600A L, to form an antireflection layer.
- an IT0 film and a TFT arranged in a plane at a pitch of 150 ⁇ on the surface of the glass substrate opposite to the antireflection layer were formed by a known method.
- 1 part by mass of polyvinylidene fluoride having a molecular weight of about 350,000 is mixed with 10 parts by mass of a 1: 1 mixed solvent of water and isopropyl alcohol, 1.7 parts by mass of lithium bromide, and 1.7 parts by mass of bismuth chloride.
- the solution was heated to 120 ° C. to prepare a homogeneous solution.
- the average particle size of the surface treated with dimethyldichlorosilane was 0. 0.2 parts by mass of 5 ⁇ titanium dioxide was added, and the mixture was uniformly dispersed with a homogenizer.
- Example 2 This was applied on the above glass substrate with a doctor blade at a thickness of 60 ⁇ , and then the common electrode as the second electrode described in Example 1 was immediately bonded, and this was applied at 110 ° C and 0.1 IMPa. After drying under reduced pressure for a period of time, a solid polymer electrolyte was formed between the two electrodes. Next, the end face of the bonding was sealed with an adhesive to form a display device. After that, when driving and evaluation were performed in the same manner as in Example 1, the reflectance when colorless (white) was 70%, and the optical density (0D) of the display section when coloring (black) was about 0.8 (reflectance) 8%). Therefore, the contrast of the reflectance was 1: 8.5.
- the circuit After placing the circuit in the color-developing state, the circuit was opened and left to stand. One week later, there was no change in the optical density of the color-developed portion, and the memory had a lifetime.
- an ITO film and TFTs arranged in a plane at a pitch of 150 ⁇ were prepared by a known method.
- an alloy in which metal magnesium was mixed with metal aluminum at an atomic composition ratio of 30% was used as a metal target.
- Sputtering was performed using 5% diluted F2 gas as the reaction gas, and an AIF3 • MgF2 antireflection film with a thickness of 300 nm was fabricated.
- 1 part by weight of polyvinylidene fluoride having a molecular weight of about 350,000 is mixed with 10 parts by weight of a 1: 1 mixed solvent of water and isopropyl alcohol, 1.7 parts by weight of lithium bromide, and tetrafluorobenzene.
- 1.7 parts by mass of silver borate were mixed and heated to 120 ° C. to prepare a homogeneous solution. to this! / — 0.2 parts by mass of titanium dioxide having an average particle size of 0.5 ⁇ , surface-treated with glycidoxypropyltrimethoxysilane, was added, and the mixture was uniformly dispersed with a homogenizer.
- titanium dioxide having an average particle diameter of 0.5 ⁇ which was surface-treated with y_daricidoxypropyltrimethoxysilane used in Example 6 was used.
- a display device was prepared under the same conditions as in Example 1 except that the display device was used. After that, when driving and evaluation were performed in the same manner as in Example 1, the reflectance in colorless (white) was 72%, and the optical density (0D) of the display portion in color (black) was about 1.0 (reflection). Rate 7%). Therefore, the contrast of the reflectance was 1: 7. After placing the circuit in the color-developing state, the circuit was left open and left.
- a display device was manufactured under the same conditions as in Example 1 except that the antireflection layer provided on the glass substrate was not provided in Example 1. Thereafter, when driving and evaluation were performed in the same manner as in Example 1, the reflectance when colorless (white) was 70%, and the optical density (OD) of the display section when color was developed (black) was about 0.8 (reflectance). 13%). Therefore, a contrast of 1: 5 was obtained for the reflectance. After placing the circuit in the color-developing state, the circuit was left open and left. One week later, there was no change in the optical density of the display unit, indicating that the memory was uniform.
- a display device was manufactured under the same conditions as in Example 1 except that the antireflection layer provided on the glass substrate was not provided in Example 4. After that, when driving and evaluation were performed in the same manner as in Example 1, the reflectance when colorless (white) was 72%, and the optical density (OD) of the display portion when color (black) was about 1.0 (reflectance) 10%). Therefore, a contrast of 1: 7 was obtained for the reflectance. After placing the circuit in the color-developing state, the circuit was left open and left. One week later, there was no change in the optical density of the display unit, indicating that the memory was uniform.
- Example 5 the anti-reflection layer provided on the glass substrate was not provided, and the surface was treated with dimethyldichlorosilane.
- the average particle diameter was 0.5 ⁇ instead of titanium dioxide.
- Example 5 The same conditions as in Example 5 except that 0.5 ⁇ of titanium diacid was used. Display device was created. After that, when driven and evaluated in the same manner as in Example 1, the reflectance when colorless (white) is 70%, and the optical density of the display unit when color (black) is developed
- Example 6 the surface treatment was performed in place of titanium dioxide having an average particle diameter of 0.5 ⁇ without providing the antireflection layer provided on the glass substrate and treating the surface with ⁇ _glycidoxypropyltrimethoxysilane.
- a display device was prepared under the same conditions as in Example 6, except that titanium dioxide having an average particle size of 0.5 ⁇ was used. After that, when driven and evaluated in the same manner as in Example 1, the reflectance when colorless (white) is 72%, and the optical density (0D) of the display section when color is developed (black) is approximately 1.0 (reflection). Rate 10%). Therefore, a contrast of 1: 7 was obtained. After placing the circuit in the color-developing state, the circuit was opened and left to stand. One week later, there was no particular change in the optical density of the display section, and the display had memory properties. The reflectance of the colorless part (white part) was slightly deteriorated at 67% after 1.5 months. Industrial applicability
- a display element it is possible to provide a display element, a display device, and a method of manufacturing a display device using a material whose discoloration is caused by electrochemical oxidation or reduction as a display material, with sufficiently high whiteness of a base as a visual characteristic. it can.
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Abstract
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Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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AU2003280766A AU2003280766A1 (en) | 2002-11-28 | 2003-11-13 | Display element, display and method for manufacturing display |
EP03772734A EP1582914A4 (en) | 2002-11-28 | 2003-11-13 | DISPLAY ELEMENT, DISPLAY AND MANUFACTURING PROCESS FOR DISPLAY |
US10/536,430 US7397594B2 (en) | 2002-11-28 | 2003-11-13 | Display element, display and method for manufacturing display |
Applications Claiming Priority (8)
Application Number | Priority Date | Filing Date | Title |
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JP2002345360A JP2004177756A (ja) | 2002-11-28 | 2002-11-28 | 表示素子、表示装置及び表示装置の製造方法 |
JP2002-345361 | 2002-11-28 | ||
JP2002345361 | 2002-11-28 | ||
JP2002345359A JP2004177755A (ja) | 2002-11-28 | 2002-11-28 | 表示素子、表示装置および表示装置の製造方法 |
JP2002-345360 | 2002-11-28 | ||
JP2002-345359 | 2002-11-28 | ||
JP2002356614A JP2004191473A (ja) | 2002-12-09 | 2002-12-09 | 表示素子、表示装置および表示装置の製造方法 |
JP2002-356614 | 2002-12-09 |
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WO2004049052A1 true WO2004049052A1 (ja) | 2004-06-10 |
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PCT/JP2003/014453 WO2004049052A1 (ja) | 2002-11-28 | 2003-11-13 | 表示素子、表示装置及び表示装置の製造方法 |
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US (1) | US7397594B2 (ja) |
EP (1) | EP1582914A4 (ja) |
KR (1) | KR100973395B1 (ja) |
AU (1) | AU2003280766A1 (ja) |
WO (1) | WO2004049052A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006129429A1 (ja) | 2005-06-02 | 2006-12-07 | Konica Minolta Holdings, Inc. | 表示素子 |
WO2007032117A1 (ja) * | 2005-09-14 | 2007-03-22 | Konica Minolta Holdings, Inc. | 表示素子の駆動方法 |
US8107116B2 (en) | 2006-05-18 | 2012-01-31 | Konica Minolta Business Technologies, Inc. | Image forming apparatus |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
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US20070166472A1 (en) * | 2004-02-18 | 2007-07-19 | Kawamura Institute Of Chemical Research | Organic-inorganic hybrid nanofiber, organic-inorganic hybrid structure, and method for producing the same |
JP4666531B2 (ja) * | 2005-03-25 | 2011-04-06 | シャープ株式会社 | 画像表示装置 |
JP4300203B2 (ja) * | 2005-06-30 | 2009-07-22 | Tdk株式会社 | 透明導電フィルム製造方法およびタッチパネル製造方法 |
KR100673765B1 (ko) | 2006-01-20 | 2007-01-24 | 삼성에스디아이 주식회사 | 유기전계발광 표시장치 및 그 제조방법 |
KR100671646B1 (ko) * | 2006-01-25 | 2007-01-19 | 삼성에스디아이 주식회사 | 유기 전계 발광 표시장치 및 그 제조 방법 |
KR100685853B1 (ko) | 2006-01-25 | 2007-02-22 | 삼성에스디아이 주식회사 | 유기전계발광표시장치 및 그 제조방법 |
TW201215980A (en) * | 2010-10-05 | 2012-04-16 | J Touch Corp | Electrochromic module and stereoscopic image display device having the same |
CN103760730B (zh) * | 2014-01-08 | 2017-03-22 | 京东方科技集团股份有限公司 | 一种黑矩阵及其制造方法、显示面板及显示装置 |
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JP2002014381A (ja) * | 2000-04-25 | 2002-01-18 | Fuji Xerox Co Ltd | 画像表示媒体 |
WO2002052339A1 (fr) * | 2000-12-27 | 2002-07-04 | Sony Corporation | Dispositif d'affichage electrochromique et dispositif d'affichage forme par electrodeposition |
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JPS57144530A (en) | 1981-03-04 | 1982-09-07 | Toppan Printing Co Ltd | Display element |
JP2844405B2 (ja) * | 1992-02-17 | 1999-01-06 | 信越化学工業株式会社 | 疎水性酸化チタン微粒子の製造方法 |
JP2686022B2 (ja) * | 1992-07-01 | 1997-12-08 | キヤノン株式会社 | 光起電力素子の製造方法 |
US6178034B1 (en) * | 1996-04-10 | 2001-01-23 | Donnelly Corporation | Electrochromic devices |
WO1998037964A1 (en) * | 1997-02-26 | 1998-09-03 | Integument Technologies, Inc. | Polymer composites and methods for making and using same |
JP5081345B2 (ja) * | 2000-06-13 | 2012-11-28 | 富士フイルム株式会社 | 光電変換素子の製造方法 |
JP2003021848A (ja) * | 2001-07-06 | 2003-01-24 | Sony Corp | 表示素子 |
US7431903B2 (en) * | 2001-10-30 | 2008-10-07 | Catalysts & Chemicals Industries Co., Ltd. | Tubular titanium oxide particles and process for preparing same |
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2003
- 2003-11-13 EP EP03772734A patent/EP1582914A4/en not_active Ceased
- 2003-11-13 KR KR1020057009451A patent/KR100973395B1/ko not_active IP Right Cessation
- 2003-11-13 WO PCT/JP2003/014453 patent/WO2004049052A1/ja active Application Filing
- 2003-11-13 AU AU2003280766A patent/AU2003280766A1/en not_active Abandoned
- 2003-11-13 US US10/536,430 patent/US7397594B2/en not_active Expired - Fee Related
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JP2002014381A (ja) * | 2000-04-25 | 2002-01-18 | Fuji Xerox Co Ltd | 画像表示媒体 |
WO2002052339A1 (fr) * | 2000-12-27 | 2002-07-04 | Sony Corporation | Dispositif d'affichage electrochromique et dispositif d'affichage forme par electrodeposition |
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006129429A1 (ja) | 2005-06-02 | 2006-12-07 | Konica Minolta Holdings, Inc. | 表示素子 |
EP1887419A1 (en) * | 2005-06-02 | 2008-02-13 | Konica Minolta Holdings, Inc. | Display element |
EP1887419A4 (en) * | 2005-06-02 | 2008-09-17 | Konica Minolta Holdings Inc | DISPLAY ELEMENT |
US7751111B2 (en) | 2005-06-02 | 2010-07-06 | Konica Minolta Holdings, Inc. | Display element |
WO2007032117A1 (ja) * | 2005-09-14 | 2007-03-22 | Konica Minolta Holdings, Inc. | 表示素子の駆動方法 |
JP4905353B2 (ja) * | 2005-09-14 | 2012-03-28 | コニカミノルタホールディングス株式会社 | 表示素子の駆動方法 |
US8107116B2 (en) | 2006-05-18 | 2012-01-31 | Konica Minolta Business Technologies, Inc. | Image forming apparatus |
Also Published As
Publication number | Publication date |
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US7397594B2 (en) | 2008-07-08 |
KR100973395B1 (ko) | 2010-07-30 |
EP1582914A4 (en) | 2007-01-17 |
US20060050359A1 (en) | 2006-03-09 |
KR20050086836A (ko) | 2005-08-30 |
AU2003280766A1 (en) | 2004-06-18 |
EP1582914A1 (en) | 2005-10-05 |
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