JP2004258474A - Photochromic display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photochromic display element which is simple in structure of a display medium, is a energy-saving type, and can freely change the display owing to an internal light emitting pattern without using a pattern mask at the time of displaying. <P>SOLUTION: The element uses a light emitted from an electrochemical light emitting element as an excitation light. The element is specifically structured to have a polymer or a gel polymer solid electrolyte layer including a light emitting material between substrates having two pieces of electrodes, wherein a transparent substrate having transparent electrode of which the one side surface is provided with a photochromic layer is chosen as at least one substrate, or to have a laminated structure in which the polymer or the gel polymer solid electrolyte layer are laminated with a light emitting layer. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a photochromic display device in which light emitted from an electrochemical light emitting device (hereinafter, abbreviated as an ECL device) is used as excitation light.
[0002]
[Prior art]
Conventionally, a display element using a photochromic material has been known, and it is known that a display element using a photochromic material or a diarylethene compound which is a photochromic material in which a decoloring reaction due to heat is suppressed has a memory property. Since these photochromic display elements do not emit light by themselves, the display information is stored by writing from outside with light of the wavelength at which the photochromic material develops color, and display is performed by irradiating light of the wavelength at which the photochromic material decolorizes. Erase information. Therefore, although it is energy saving, it has a problem that the configuration of the display medium is complicated because an external light source for writing and erasing is required (for example, see Patent Document 1).
[0003]
On the other hand, an organic light emitting element has been developed in which a certain kind of organic thin film (organic light emitting body) is sandwiched between counter electrodes and emits light with energy generated by energization. The ECL device, which is one of the organic light-emitting devices, uses only the oxidation-reduction of the light-emitting material. Therefore, the applied voltage can be reduced, and it is necessary to control the energy levels of the light-emitting layer, the transport layer, and the electrodes. In recent years, it has attracted attention because of its lack. Among them, an ECL device using a gel polymer solid electrolyte in which an electrolyte solution is solidified into a gel state is particularly easy because sealing is easy at the time of device manufacture and the effect on the environment when the device is damaged is small. Attention has been paid.
[0004]
As an ECL device using a gel polymer solid electrolyte, an ECL device using a ruthenium (hereinafter abbreviated as Ru) (II) complex in a light emitting layer is known (for example, Non-Patent Document 1 and Non-Patent Document 2). reference.). The Ru (II) complex has high luminous efficiency in an electrolyte solution. Also, an ECL device using a π-conjugated polymer for the light emitting layer is known (for example, see Non-Patent Document 3). However, these ECL elements need to constantly supply a current to emit light in order to maintain display as a display medium, and as a result, there is a problem that the life is short or the power consumption is large.
[0005]
There has been proposed an optical memory in which a high-conductivity part and a low-conductivity part of a photochromic material are formed by pattern exposure from outside the element, and electroluminescence is emitted using the high-conductivity part (for example, see Patent Document 2). However, an external light source and a mask on which the pattern is recorded are required for pattern exposure, and the structure of the display medium is complicated, and continuous current is required because continuous light emission is required for pattern display. However, the problem of high power consumption has not been solved yet. Furthermore, since a mask having a pattern formed is required, the mask must be replaced each time the display is changed, which is not economical. Further, this method does not perform photochromic display using emission from electroluminescence as excitation light.
[0006]
[Non-patent document 1]
"Applied Physics Letters", 1996, No. 69, p. 1689
[Non-patent document 2]
"Journal of the American Chemical Society", 1997, No. 119, p. 3987
[Non-Patent Document 3]
"Science", 1995, No. 269, p. 1086
[Patent Document 1]
JP-A-9-313355
[Patent Document 2]
JP-A-10-152679
[0007]
[Problems to be solved by the invention]
An object of the present invention is to provide a photochromic display element in which the configuration of a display medium is simple and energy-saving, and at the time of display, a display can be freely changed by an internal light emitting pattern without using a pattern mask. It is to provide.
[0008]
[Means for Solving the Problems]
The present inventors have solved the above-described problem by incorporating a layer containing a photochromic material (hereinafter, abbreviated as a photochromic layer) inside or outside the ECL element and using the ECL element as an excitation light source of the photochromic display element. . Specifically, the photochromic display element of the present invention is:
[0009]
1. Since only the photochromic layer is incorporated inside or outside the ECL element, the configuration is simple.
[0010]
2. By simply changing the light emission pattern of the ECL element, a display corresponding to the pattern can be drawn on the photochromic layer. If a photochromic material in which the decoloring reaction due to heat is suppressed is used as the photochromic material, the display of the photochromic layer can be maintained for a certain period of time even when the light emission of the ECL element is stopped. The pattern can be arbitrarily displayed by displaying a dot pattern by a simple matrix drive or an active drive using a TFT in which the electrodes are rectangular and the rectangular electrodes are orthogonal to the display surface and the back surface. Further, when the color of the photochromic layer is red, green, blue, or a material showing a color such as cyan, magenta, and yellow, and is configured in a color filter-like pattern used for liquid crystal display, multicolor or full color Display is also possible.
[0011]
3. Since display can be maintained without continuously applying voltage, energy is saved.
[0012]
That is, the present invention provides a photochromic display element in which light emitted from an electrochemical light-emitting element is used as excitation light.
[0013]
BEST MODE FOR CARRYING OUT THE INVENTION
The photochromic display element of the present invention incorporates a photochromic layer inside or outside the ECL element. As a preferred embodiment, at least one of a transparent substrate having a transparent electrode, an ECL device having a polymer or gel polymer solid electrolyte layer containing a luminescent substance between substrates having two electrodes, or at least a high An ECL device having a laminated structure of a molecular or gel polymer solid electrolyte layer and a light emitting layer, having a photochromic layer on the side opposite to the transparent electrode side of the transparent substrate (that is, outside the ECL device); An embodiment in which a photochromic layer is provided on the transparent electrode (that is, inside the ECL element) or a photochromic layer is provided between the transparent substrate and the transparent electrode (that is, inside the ECL element) can be given. .
The photochromic layer may or may not be in contact with the transparent electrode surface or the transparent substrate surface.
[0014]
In the present invention, the ECL element is a polymer or gel polymer containing at least a luminescent substance between at least one of a transparent substrate having a transparent electrode and a substrate having two electrodes and in contact with the electrode. It refers to an ECL element having a solid electrolyte layer or an ECL element having at least a laminated structure of a polymer or gel polymer solid electrolyte layer and a light emitting layer in contact with an electrode.
[0015]
Further, in the present invention, the polymer or gel polymer solid electrolyte layer is a layer made of a polymer (hereinafter, abbreviated as a polymer solid electrolyte) solidified without containing a solvent, or contains a solvent. It refers to a layer made of a gel-like high molecular weight solidified in a solid state (hereinafter, abbreviated as a gel polymer solid electrolyte).
[0016]
When a voltage is applied to the ECL element, the value of a current flowing at a certain voltage or higher increases, and the light emitting layer of the ECL element emits light. This light becomes excitation light, and the photochromic material in the photochromic layer develops color. If the electrodes are formed in a strip shape and a simple matrix drive in which the strip electrodes are orthogonal to the display surface and the back surface or an active drive using a TFT is performed, the ECL element can emit light in an image-like manner, and the image is formed into a photochromic layer. Can be written to.
[0017]
At this time, a single color display can be performed by irradiating the photochromic layer with a light emitting pattern by the above-described driving method. In addition, the multi-color or full-color display, at the time of coloring, red, green, blue, or cyan, magenta, photochromic material showing a color such as yellow, constituting a color filter-like pattern used for liquid crystal display, the above It is possible by irradiating a light emitting pattern by a driving method or the like.
[0018]
When a photochromic material in which the decolorization reaction due to heat is suppressed is used as the photochromic material, the photochromic layer has a memory property. Therefore, the ECL element can maintain the display if it is driven for a short period of time until the photochromic layer develops a color, and can maintain the display for a long time by driving by applying a pulse voltage at regular time intervals.
In addition, although the memory property cannot be said unconditionally depending on the element configuration, generally, when a voltage of 5 V or more is applied and driven at 25 ° C., the voltage application is stopped and the display can be maintained for 1 minute or more. Point.
[0019]
On the other hand, when erasing an image written on the photochromic layer, light having a wavelength corresponding to the absorption of the photochromic material may be applied, and specifically, visible light, typically, sunlight or fluorescent light, etc. The room light may be irradiated for a certain period of time. Further, a front light used for a spotlight or a liquid crystal display can also be used.
[0020]
Embodiments of the photochromic display device of the present invention are shown in schematic sectional views in FIGS.
FIGS. 1 to 3 show an example of the photochromic display element of the present invention having a photochromic layer on the side opposite to the transparent electrode side of the transparent substrate of the ECL element (that is, outside the ECL element). Can be
[0021]
A polymer having a photochromic layer 1 on a surface of a transparent substrate 2 opposite to the transparent electrode 3 shown in FIG. 1 and including a luminescent substance between the transparent electrode 3 and the electrode 5 in contact with each electrode. Alternatively, a photochromic display device having the gel polymer solid electrolyte layer 4.
[0022]
As shown in FIG. 2, a photochromic layer 9 is provided on the surface of the transparent substrate 10 opposite to the transparent electrode 11, and a polymer or gel polymer solid is provided between the transparent electrode 11 and the electrode 14 in contact with each electrode. A photochromic display device having an electrolyte layer 12 and a light emitting layer 13 in this order.
[0023]
As shown in FIG. 3, a photochromic layer 18 is provided on the surface of the transparent substrate 19 opposite to the transparent electrode 20, and a polymer or gel polymer solid is provided between the transparent electrode 20 and the electrode 24 in contact with each electrode. A photochromic display device having an electrolyte layer 21, a light emitting layer 22, and a polymer or gel polymer solid electrolyte layer 23 in this order.
[0024]
FIGS. 4 to 9 show examples of a photochromic display element having a photochromic layer on a transparent electrode of an ECL element according to the present invention.
[0025]
A photochromic display element having a polymer or gel polymer solid electrolyte layer 30 containing a photochromic material and a luminescent material between transparent electrodes 29 and 31 shown in FIG.
[0026]
A photochromic display element having a photochromic layer 37 and a polymer or gel polymer solid electrolyte layer 38 containing a luminescent substance in contact with each electrode between a transparent electrode 36 and an electrode 39 shown in FIG.
[0027]
6, a photochromic display element having a polymer or gel polymer solid electrolyte layer 45 containing a photochromic material and a light emitting layer 46 in this order between a transparent electrode 44 and an electrode 47 in contact with each electrode.
[0028]
A photochromic display element having a photochromic layer 53, a polymer or gel polymer solid electrolyte layer 54, and a light emitting layer 55 in this order between a transparent electrode 52 and an electrode 56 shown in FIG.
[0029]
8, between a transparent electrode 61 and an electrode 65, a polymer or gel polymer solid electrolyte layer 62 containing a photochromic material in contact with each electrode, a light emitting layer 63, a polymer or gel polymer solid electrolyte A photochromic display element having a layer 64 in this order.
[0030]
As shown in FIG. 9, between the transparent electrode 70 and the electrode 75, a photochromic layer 71, a polymer or gel polymer solid electrolyte layer 72, a light emitting layer 73, a polymer or gel polymer solid electrolyte layer is in contact with each electrode. 74 in this order. Alternatively, a stacked structure of these and the like can be given.
[0031]
Above all, a photochromic display element having a photochromic layer on a transparent electrode of an ECL element (that is, inside the ECL element) as shown in FIGS. 4 to 9 is preferable because it has no parallax and has excellent display characteristics.
[0032]
Of the layers constituting the photochromic display element of the present invention, the photochromic layer is a layer containing a photochromic material and having an image display function. The polymer or gel polymer solid electrolyte layer is a solid layer containing an electrolyte and having a cation (or hole) or anion (or electron) transport function. The light-emitting layer is a layer that contains a light-emitting substance and has a light-emitting function.
The photochromic display element of the present invention may have a structure in which these layers are formed by laminating single layers having independent functions (for example, the photochromic display shown in FIGS. 2, 3, 7, and 9). Element), a single-layer structure having all three functions (for example, a photochromic display element shown in FIG. 4), or a structure in which a layer having two functions and a layer having one function are stacked. (For example, the photochromic display elements shown in FIGS. 1, 5, 6, and 8), and the image forming function derived from the photochromic material and the cation (or positive It suffices if it has a function of transporting pores or anions (or electrons) and a light emitting function derived from a light emitting substance.
[0033]
Further, a layer having a normal image display function is provided on the front surface of the element. Therefore, in the case of a photochromic display element having a structure in which a single layer in which each function is independent or a structure in which a layer having two functions and a layer having one function are stacked, a layer having an image display function is It is preferably provided on the surface of a transparent substrate or on a transparent electrode.
[0034]
All the layers constituting the photochromic display element of the present invention, such as a photochromic layer, a polymer or gel polymer solid electrolyte layer, and a light emitting layer, can be formed by a printing or coating method. For example, when manufacturing the photochromic display element shown in FIG. 9, a liquid composition in which a photochromic material is dissolved or dispersed in a solvent (hereinafter referred to as a photochromic composition (A)) is formed on a transparent electrode of a transparent substrate having a transparent electrode. Is printed or coated, dried to form a photochromic layer, and then an active energy ray-curable composition (hereinafter, referred to as polymer or gel height) containing an electrolyte and an active energy ray-polymerizable compound. After printing or coating the composition for a molecular solid electrolyte layer (B), the coated surface is irradiated with active energy rays to cure the coated film and form a polymer or gel polymer solid electrolyte layer. I do. Further, a composition containing a luminescent substance (hereinafter, abbreviated as composition (C) for a luminescent layer) is printed or applied thereon, followed by drying to form a luminescent layer. After printing or applying the polymer or gel polymer solid electrolyte composition (B) again on the light emitting layer, a substrate having electrodes is attached thereto, and irradiated with active energy rays to polymer or gel polymer solid. An electrolyte layer is formed, and then the two substrates are sealed with a sealant to produce the substrate.
[0035]
The present invention will be described using the photochromic display element of the present invention shown in FIG. 9 as an example.
The transparent substrate used as the transparent substrate 69 may be a substrate having transparency, and glass, plastic, or the like that does not deteriorate when an electrode or a light-emitting layer is formed can be used. , A film or a sheet is referred to as a film or the like). Examples of the plastic substrate include polyethylene terephthalate, polycarbonate, polycycloolefin, polyether sulfone, polyarylate, polyamide and the like. When using such a plastic film, it is preferable to use a film whose surface is gas-barrier-coated with silicon oxide, silicon nitride, or the like, in order to suppress the permeation of moisture and oxygen.
[0036]
Further, since the other substrate 76 is not necessarily required to be transparent, a plastic film such as polyimide or polytetrafluoroethylene or a metal foil such as aluminum, copper or stainless steel can be used in addition to the above-mentioned substrates. Further, a film or the like obtained by laminating glass or metal and plastic may be used. These substrates are preferably plastic substrates from the viewpoint of flexibility and light weight.
[0037]
The thickness of the substrate varies depending on the method of use and the material, but is preferably in the range of 10 μm to 10 mm. In the case of glass, the range is preferably 0.1 to 3 mm, and in the case of a plastic substrate or a metal substrate, the range is preferably 10 μm to 0.5 mm.
[0038]
Further, the transparent electrode used as the transparent electrode 70 may be any electrode material having transparency, such as tin oxide (hereinafter abbreviated as NESA), zinc oxide, indium oxide, and indium tin oxide (hereinafter abbreviated as ITO). And transparent electrodes of indium oxide / zinc oxide compounds, tin oxide / antimony compounds, gallium oxide / zinc oxide compounds, and translucent electrodes of gold, silver, copper, palladium, platinum and the like. The electrode is obtained, for example, by sputtering or vacuum depositing the above electrode material on a substrate, applying a suspension of the electrode material fine particles, and sintering the fine particles. When the thickness of the electrode is in the range of 10 nm to 5 μm, light is easily transmitted. Among them, the thickness is preferably in the range of 20 nm to 1 μm.
[0039]
Further, since the other electrode 75 does not necessarily need to be transparent, in addition to the above electrode materials, magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, ytterbium, ruthenium, manganese, aluminum, gold And metals such as silver, copper, palladium, platinum, tin, lead, iron and nickel, and alloys containing these metals can be used. Further, conductive polymers such as carbon, polyaniline, polypyrrole, and polythiophene can also be used. Also, covering the electrode surface with an electrically conductive porous material such as platinum black increases the substantial surface area, which facilitates charge injection into the light emitting layer, which is more preferable. Further, a metal foil may be laminated on a plastic film as an electrode. When the above electrode material is used, the thickness of the electrode is preferably in the range of 10 nm to 1 mm, and more preferably in the range of 20 nm to 100 μm.
[0040]
A photochromic layer 71 is formed on the surface of the transparent electrode 70 of the transparent substrate 69 having the transparent electrode 70 on one side. As the photochromic material used for the photochromic layer 71, a photochromic material that emits color when excited by light emitted from the ECL element is used. As photochromic materials, "Chemistry of Organic Photochromism" (edited by The Chemical Society of Japan) (Quarterly Review of Chemistry, No. 28, 1996, published by Gakkai Shuppan Center), and "Chemical Reviews", 2000 No. 100, p. 1685-1890, and specific examples thereof include stilbene derivatives, spiropyrans, spirooxazines, diarylethenes, fulgides, cyclophanes, chalcone derivatives and the like, and mixtures thereof. Can be
[0041]
Among them, spirooxazines, diarylethenes, and fulgides are preferable because the photochromic material has high repetition stability at the time of coloring and decoloring by light, and hardly causes a decoloring reaction by heat. Further, from the viewpoint of display characteristics, a material which is excited by light in the range of 350 to 500 nm, which is the emission wavelength of the ECL element, and emits color from a colorless or pale color is particularly preferable. These materials are described in Chemical Reviews, 2000, No. 100, p. 1685-1716, and the like can be appropriately selected from these.
[0042]
As the diarylethenes, specifically, 1,2-bis (2,4-dimethyl-3-thienyl) perfluorocyclopentane, 2,3-bis (2,4,5-trimethyl-3-thienyl) -anhydride Maleic acid, 2- (1,2-dimethyl-3-indolyl) -3- (2,4,5-trimethyl-3-thienyl) maleic anhydride, 2,3-bis (1,2-dimethyl-3- Indolyl) maleic anhydride, 2,3-bis (1,2-dimethyl-5-methoxy-3-indolyl) maleic anhydride, 2- (1,2-dimethyl-3-indolyl) -3- (2,4 -Dimethyl-5-cyano-3-thienyl) maleic anhydride, 1- (1,2-dimethyl-methoxy-3-indolyl) -2- (2,4-dimethyl-5-cyano-3-thienyl) perfluoro Cyclopentane, 1 2- bis (2-hexyl-3-thienyl) perfluoro cyclopentane dithieno (thiophene) derivatives, and the like.
[0043]
In order to form the photochromic layer 71 on the surface of the transparent electrode 70 of the transparent substrate 69 having the transparent electrode 70 on one side, after applying or printing the photochromic composition (A) on the surface of the transparent electrode 70, It is formed by drying, or the photochromic material is deposited on the surface of the transparent electrode 70. Above all, it is preferable to form by a coating or printing method from the viewpoint of productivity.
[0044]
Examples of the solvent used in the coating or printing method include, for example, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as dichloromethane, chloroform and 1,1,2-trichloroethane, methanol and ethanol. Alcohols, ketones such as cyclohexanone, ethers such as 1,2-dimethoxyethane, tetrahydrofuran, diethylene glycol dimethyl ether, carbonates such as ethylene carbonate and propylene carbonate, esters such as methyl formate and ethyl acetate, acetonitrile, benzonitrile And aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, and the like. These solvents may be used alone or as a mixture.
[0045]
Further, a polymer material such as polystyrene, poly (methyl) methacrylate, polyvinyl acetate, polyvinyl chloride, polyvinyl carbazole, or nylon is added to the photochromic composition (A) as a binder resin or a dispersion resin. Is also good. Further, a compound having an active energy ray-polymerizable functional group such as a (meth) acryloyl group and a maleimide group, which will be described later, can also be added. In addition, oligomers and various known and commonly used additives used in inks and paints may be added within a range that does not impair the coloring characteristics and the temporal stability of the photochromic material.
[0046]
When the photochromic material has a high solvent solubility and is likely to be dissolved in the polymer or gel polymer solid electrolyte composition (B) to be laminated next, the polymer or gel polymer solid electrolyte composition is preliminarily prepared. The layer may be formed by mixing the object (B) and the photochromic material. Such a photochromic display element having a layer having both an image display function derived from a photochromic material and a cation (or hole) or anion (or electron) transport function derived from an electrolyte is shown in FIGS. , FIG. 6, FIG. 7, FIG. 8, and FIG.
[0047]
Since the photochromic layer preferably contains a photochromic material in an amount of 10% by mass or more in order to obtain a high color development state, it is preferable that the binder resin and the dispersion resin are appropriately added within this range. More preferably, the photochromic material in the photochromic layer contains 50% by mass or more.
[0048]
When the photochromic layer is formed to a thickness such that the absorbance of the photochromic material at the time of coloring becomes 1 or more, a clear display can be obtained. Since the extinction coefficient of the photochromic material at the time of coloring varies depending on the photochromic material, the film thickness cannot be specified unconditionally. You can get the display. The photochromic composition (A) is used by appropriately adjusting the nonvolatile content so that the film thickness after drying is in the range of 10 nm to 100 μm.
[0049]
Examples of the method of applying or printing the photochromic layer 71 on the surface of the electrode 70 include coating methods such as die coating, (micro) gravure coating, spin coating, and applicator method, inkjet printing, planographic printing, gravure printing, and screen. Known coating and printing methods, such as printing, can be applied. There is no limitation on the method for drying the coating film. For example, the coating film may be dried using a hot plate, an oven, an infrared oven, or the like.
[0050]
When a compound having an active energy ray-polymerizable functional group such as a (meth) acryloyl group or a maleimide group is added, it can be cured by a method for curing a polymer or gel polymer solid electrolyte layer described later.
[0051]
On the other hand, when the photochromic layer 71 is formed by vapor deposition, a general-purpose vacuum vapor deposition device is used.^-3It can be formed by vacuum deposition from a tungsten or molybdenum boat, a ceramic crucible, a Knudsen cell, or the like under a vacuum higher than Pa. The film thickness may be the same as in the above printing and coating methods.
[0052]
On the surface of the photochromic layer 71, a polymer or gel polymer solid electrolyte layer 72 is formed. In order to form the polymer or gel polymer solid electrolyte layer 72, after printing or applying the polymer or gel polymer solid electrolyte composition (B), the coating surface is irradiated with active energy rays to apply the composition. The film may be cured.
The composition for a polymer or gel polymer solid electrolyte (B) contains at least an active energy ray polymerizable compound (hereinafter abbreviated as monomer (D)) and an electrolyte. In addition, a solvent, a luminescent substance, a synthetic resin, an oligomer, and various known and commonly used additives used in inks and paints may be added within a range that does not impair the luminescent properties and the stability over time of the ECL element.
[0053]
The monomer (D) is not particularly limited as long as it has an active energy ray-polymerizable functional group such as a (meth) acryloyl group and a maleimide group, and is disclosed in JP-A-10-251318 and the like. Such (meth) acrylate compounds and maleimide compounds as disclosed in WO 02/35636 and the like can be used. In particular, as the monomer (D), an active energy ray polymerizable compound having a (poly) oxyalkylene chain, (poly) ester chain, (poly) carbonate chain, or (poly) amine chain having an ion transfer function is used. Then, an ECL element having higher luminous efficiency can be obtained.
[0054]
Specifically, for example, ethylene glycol monomethyl ether (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and diethylene glycol having a number average molecular weight (hereinafter abbreviated as Mn) of 400 (Meth) acrylates, (meth) acrylates such as di (meth) acrylate of polytetramethylene glycol having Mn of 250, and ethylene oxide-modified trimethylolpropane tri (meth) acrylate;
[0055]
Ethoxy- (3-maleimidopropoxy) ethane, ethoxy- (3-maleimidopropoxy) butane, diethylene glycol (3-maleimidopropyl) methyl ether, methyl (3-maleimidopropyl) ether of polyethylene glycol having Mn of 400, trimethylol Ether compounds such as propane tri (3-maleimidopropyl ether), bis (3-maleimidopropyl) ether of polyethylene glycol having Mn of 400, and mono (3-maleimidopropyl) vinyl ether of polyethylene glycol having Mn of 400; methylmaleimido acetate , Ethyl maleimide capronate, ethylene glycol monomethyl ether maleimide acetate, polyethylene glycol monomethyl ether maleimide amide having Mn of 400 Tate,
[0056]
Tetrahydrofurfurylmaleimide acetate, diethylene glycol bismaleimide acetate, diethylene glycol monomaleimide acetate acrylate, bismaleimide acetate of polyethylene glycol with Mn of 400, bismaleimide acetate of polytetramethylene glycol with Mn of 250, polyethylene glycol monomaleimide with Mn of 400 Capronate acrylate, trimethylolpropane trimaleimide acetate, ethylene oxide-modified trimethylolpropane trimaleimide acetate, ethylene oxide-modified trimethylolpropane dimaleimide acetate monoacrylate,
[0057]
Maleimide ester compounds such as pentaerythritol tetramaleimide acetate, ethylene oxide-modified pentaerythritol tetramaleimide acetate, ethylene oxide-modified pentaerythritol dimaleimide acetate diacrylate, N-ethyl- (2-maleimidoethyl) carbamate, isophorone diisocyanate and (poly) Urethane compounds such as reaction products of an equivalent mixture with an alkylene polyol with 2-maleimidoethanol; 2-maleimidoethyl-ethyl carbonate, 2-maleimidoethyl-isopropyl carbonate, tetraethylene glycol bis (3-maleimidopropyl carbonate) And maleimide compounds such as maleimide carbonate.
[0058]
Among them, an active energy ray polymerizable compound having a (poly) oxyalkylene chain such as polyethylene glycol is preferable. In particular, when a maleimide compound having a (poly) oxyalkylene chain is used, since the maleimide group has an active energy ray-polymerizable property and also has a polymerization initiation function, the composition for a polymer or gel polymer solid electrolyte is used. There is no need to add a polymerization initiator to (B). When a polymerization initiator is added, unreacted substances or decomposition products may remain as impurities in the obtained polymer or gel polymer solid electrolyte layer.
[0059]
When the active energy ray-polymerizable compound having the (poly) oxyalkylene chain or the like is used as the monomer (D), if the amount is too large, the strength of the obtained polymer or gel polymer solid electrolyte layer is increased. Therefore, the content is preferably 60% by mass or less, and most preferably 50% by mass or less, based on the total mass of the polymer or gel polymer solid electrolyte composition (B).
[0060]
When a maleimide compound is used, the amount of the maleimide compound used is preferably 10% by mass or more based on the total mass of the monomer (D), in order to obtain a practical polymerization rate. % Or more is most preferable. In addition, a polymerization initiator is not particularly required, but a polymerization initiator may be added for the purpose of improving the polymerization rate within a range that does not impair the light emission characteristics and the temporal stability of the ECL element.
[0061]
In order to obtain a cured coating film of the polymer or gel polymer solid electrolyte composition (B) by polymerization, a polyfunctional monomer having two or more active energy ray-polymerizable functional groups in the monomer (D) is required. It is preferred to incorporate the body. The blending amount of the polyfunctional monomer may be appropriately determined so as to obtain a desired gel fraction.
[0062]
As the electrolyte contained in the polymer or gel polymer solid electrolyte composition (B), various salts can be used. The salt may be an electrolyte containing an ion to be used as a carrier with a charge, but desirably has a large dissociation constant in a polymer or gel polymer solid electrolyte layer. Specifically, LiCF₃SO₃, NaCF₃SO₃, KCF₃SO₃Alkali metal salts of trifluoromethanesulfonic acid such as LiN (CF₃SO₂)₂, LiN (CF₃CF₂SO₂)₂Alkali metal salts of perfluoroalkanesulfonimides such as LiPF₆, NaPF₆, KPF₆Alkali metal salts of hexafluorophosphoric acid such as LiClO₄, NaClO₄Alkali metal perchlorates, such as
[0063]
LiBF₄, NaBF₄Tetrafluoroborate, LiSCN, LiAsF₆, LiI, NaI, NaAsF₆, KI, etc., quaternary ammonium salts of perchloric acid, such as tetraethylammonium perchlorate, [(C₂H₅)₄N]⁺[BF₄]⁻Quaternary ammonium salts of tetrafluoroboric acid such as [(C₂H₅)₄N]⁺[PF₆]⁻Quaternary ammonium salts such as [(CH₃)₄P]⁺[BF₄]⁻, [(C₂H₅)₄P]⁺[BF₄]⁻And the like. Further, a room temperature molten salt (also referred to as an ionic liquid) having a polymer electrolyte or a polymerizable group in which the cationic group or anionic group of the electrolyte is present on the main chain or side chain of the polymer is used. You can also. Among them, LiPF which is excellent in solubility in an organic solvent and ion conductivity.₆, LiBF₄, LiAsF₆It is preferable to use an alkali metal salt or quaternary ammonium salt of perfluoroalkanesulfonic acid imide.
[0064]
In order to maximize the ionic conductivity of the polymer or gel polymer solid electrolyte layer, the electrolyte should be as far as possible within a range in which the polymer or gel polymer solid electrolyte composition (B) does not cause layer separation. It is good to mix it in a large amount. In the present invention, it is preferably used in a solubility limit amount, and is preferably used in the range of 0.1 to 70% by mass in the composition (B) for a polymer or gel polymer solid electrolyte, and 1 to 60% by mass. % Is particularly preferred. When a solvent is used, it is preferably a solvent that dissolves the electrolyte.
[0065]
As the solvent, an organic solvent is preferable, and a solvent having a large dielectric constant, a high solubility of the electrolyte, a boiling point of 60 ° C. or higher, and an electrochemically stable solvent is suitable. Specifically, ethers such as 1,2-dimethoxyethane, 2-methyltetrahydrofuran, crown ether, triethylene glycol methyl ether, tetraethylene glycol dimethyl ether, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate , Carbonates such as vinylene carbonate, aliphatic esters such as methyl propionate and methyl formate, aromatic nitriles such as benzonitrile and tolunitrile, amides such as dimethylformamide, sulfoxides such as dimethyl sulfoxide, and butyrolactone. Examples thereof include lactones, sulfur compounds such as sulfolane, N-methylpyrrolidone, N-vinylpyrrolidone, and phosphate esters. Among them, carbonates, aliphatic esters, and ethers are preferable, and carbonates are particularly preferable. These may be used alone or as a mixed solvent in which two or more kinds are mixed.
[0066]
The polymer or gel polymer solid electrolyte layer 72 may be a polymer solid electrolyte layer or a gel polymer solid electrolyte layer, and the gel polymer solid electrolyte layer containing an organic solvent is a polymer solid electrolyte layer. It has a higher ionic conductivity than the electrolyte layer and can be suitably used. When a gel polymer solid electrolyte layer is used, a high boiling point organic solvent is selected from the above-mentioned organic solvents to prepare a composition (B) for a gel polymer solid electrolyte. After applying or printing the composition for gel polymer solid electrolyte (B) on the surface of the photochromic layer 71, the composition is irradiated with active energy rays.
[0067]
The ionic conductivity increases as the content of the organic solvent increases, but if the content is too large, the mechanical strength of the gel polymer solid electrolyte layer may decrease. The amount is preferably 0.5 to 12 times, and particularly preferably 1 to 8 times, the total mass of the monomer (D) constituting the composition for solid electrolyte (B).
[0068]
When the polymer or gel polymer solid electrolyte layer 72 is used as a polymer solid electrolyte layer, one having a low boiling point among the organic solvents is selected, or the polymer solid electrolyte layer is used without using an organic solvent. A composition (B) is prepared. After the composition (B) for a polymer solid electrolyte is applied or printed on the surface of the photochromic layer 71, if an organic solvent is used, it is dried and irradiated with active energy rays. In this case, it is necessary to adjust the concentration of the electrolyte so that the electrolyte does not precipitate when the solvent is distilled off from the coating film of the composition for a solid polymer electrolyte (B).
[0069]
When a polymerization initiator is used for the polymer or gel polymer solid electrolyte composition (B), a known and commonly used polymerization initiator can be used. Specifically, for example, a radical polymerization initiator such as 2,2'-azobisisobutyronitrile and benzoyl peroxide, CF₃Protonic acid such as COOH, BF₃, AlCl₃And cationic polymerization initiators such as Lewis acids, anionic polymerization initiators such as butyllithium, sodium naphthalene and lithium alkoxide, and photopolymerization initiators such as benzophenone and benzoin.
If necessary, a known and commonly used photosensitizer may be used within a range that does not impair the emission characteristics and stability over time of the ECL element.
[0070]
When a polymerization initiator is used, it is preferably used in the range of 0.1 to 3% by mass based on the monomer (D). When the amount of the polymerization initiator exceeds 3% by mass, the light-emitting characteristics and the temporal stability of the ECL element may be impaired.
[0071]
Examples of a method for applying or printing the polymer or gel polymer solid electrolyte composition (B) on the surface of the photochromic layer 71 include coating methods such as die coating, (micro) gravure coating, spin coating, and applicator method. Known and commonly used coating methods and printing methods such as ink jet printing, lithographic printing, gravure printing, and screen printing can be applied. When the coating film is dried and used as a polymer solid electrolyte, the method is not limited, and for example, it may be dried using a hot plate, an oven, an infrared oven, or the like.
[0072]
The thickness of the polymer or gel polymer solid electrolyte layer 72 is preferably in the range of 10 nm to 1 mm after drying. If the film thickness is less than 10 nm, a short circuit of the element may occur, and if it exceeds 1 mm, the driving voltage may increase. Particularly when the film thickness is 50 nm to 50 μm, higher luminous efficiency can be obtained.
[0073]
As the active energy ray for curing the coating film of the polymer or gel polymer solid electrolyte composition (B), infrared rays, visible rays, ultraviolet rays, electron rays, and the like can be used. When the polymer or gel polymer solid electrolyte layer 72 is a gel polymer solid electrolyte layer, it is preferable to use visible light, ultraviolet light, or an electron beam that does not cause evaporation of the solvent.
[0074]
As the infrared source, a general-purpose oven, a hot plate, an infrared furnace, or the like can be used. The heating temperature and the heating time can be appropriately selected depending on the type of the polymerization initiator to be used, and it is preferable to heat at 50 to 200 ° C. for 1 to 60 minutes. Examples of visible light sources and ultraviolet light sources include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, chemical lamps, black light lamps, mercury-xenon lamps, excimer lamps, short arc lamps, helium cadmium, Lasers, argon lasers, excimer lasers, sunlight and the like can be used. The light intensity is 500 J / m²~ 5000J / m²Is preferable. In the case of curing using an electron beam, a general-purpose electron beam irradiation device may be used.
[0075]
Next, after the composition (C) for a light emitting layer is applied or printed on the polymer or gel polymer solid electrolyte layer 72, it is dried to provide the light emitting layer 73.
As the light-emitting substance used for the light-emitting layer 73, a substance which emits fluorescence or phosphorescence in a visible light region or an ultraviolet light region when excited is used. Above all, those that emit fluorescence or phosphorescence within the range of 350 to 500 nm are preferable, and those that emit light within the range of 350 to 450 nm are preferable from the viewpoint of contrast and color tone before and after coloring of the photochromic material. A photochromic material that is excited by light having a wavelength longer than 500 nm may degrade display quality if the photochromic material is colored before coloring. At present, it is difficult to obtain light emission of 350 nm or less with an ECL element.
[0076]
Specific examples of the light-emitting substance include a π-conjugated polymer compound, a transition metal complex, nano-sized particles of an inorganic semiconductor and an organic pigment, and a mixture thereof.
Examples of the π-conjugated polymer compound include aromatic conjugated polymer compounds such as polyparaphenylene and polyfluorene, aliphatic conjugated polymer compounds such as polyacetylene, and heterocyclic conjugated polymer compounds such as polypyrrole and polythiophene. Examples include heteroatom-containing conjugated polymer compounds such as polyaniline, and complex conjugated polymer compounds such as polyphenylenevinylene and polyarylenevinylene. Many of these π-conjugated polymer compounds have poor solubility in organic solvents, but have an alkyl group having 1 to 10 carbon atoms such as a butyl group, an alkoxy group having 1 to 10 carbon atoms such as a butoxy group, and a cyano group. When a substituent such as an alkyl group having the formula (1) is introduced, the solubility is improved. The molecular weight of the π-conjugated polymer compound is preferably such that the mass average molecular weight (hereinafter abbreviated as Mw) is in the range of 1,000 to 500,000, more preferably 2,000 to 300,000.
[0077]
In the transition metal complex, as the metal ion, for example, chromium ion, molybdenum ion, tungsten ion, rhenium ion, ruthenium ion, osmium ion, cobalt ion, rhodium ion, iridium ion, platinum ion, copper ion, silver ion or gold ion And so on. Especially, a ruthenium ion, an iridium ion, or a platinum ion is preferable.
[0078]
Examples of the ligand include “Comprehensive Coordination Chemistry”, 1987, Pergamon Press, and “Photochemistry and Photophysics of Coordination Chemistry”. Nitrogen containing halogen ligands, pyridine, phenylpyridine, benzoquinoline, quinolinol, bipyridyl, terpyridine, phenanthroline, etc., described in Springer-Verlag and 1987, and Photophysics of Coordination Compounds. Aromatic ligand, acetylaceto Diketone ligands such as carboxylic acid ligands such as acetic acid, triphenylphosphine, phosphorus ligands such as phosphites, carbon monoxide ligands, isonitrile ligands, and cyano ligands, Examples include porphyrin, phthalocyanine, and derivatives thereof. Above all, nitrogen-containing aromatic ligands, porphyrins, phthalocyanines and derivatives thereof have high ability to form complexes with transition metal ions. Also, pyridine, bipyridyl, quinoline, quinoxaline, and their derivatives form stable complexes with transition metal ions.
[0079]
Examples of the counter ion of the transition metal complex include an alkali metal ion such as a lithium ion, a sodium ion, a potassium ion, a rubidium ion and a cesium ion; an alkaline earth metal ion such as a calcium ion, a magnesium ion and a barium ion;⁻, Cl⁻, Br⁻, I⁻Halogen ion, perchlorate ion, PF₆ ⁻, BF₄ ⁻, Borate ions such as tetraphenylborate ion, ammonium ions such as ammonium ion, tetramethylammonium ion, tetrabutylammonium ion and trimethylbenzylammonium ion, polystyrenesulfonic acid ion, trifluoromentanesulfonate ion, toluenesulfonate ion and the like. And carboxylate ions such as sulfonic acid ions, acetate ions, trifluoroacetate ions, and benzoate ions. Among them, perchlorate ion, PF₆ ⁻Or BF₄ ⁻Is preferred.
[0080]
The transition metal complex may form a mononuclear complex or a dinuclear complex. Further, it may contain a plurality of types of ligands. Further, the transition metal complex may be a low molecular compound, an oligomer or a polymer. As the molecular weight, Mw is preferably in the range of 300 to 500,000, and particularly preferably in the range of 500 to 100,000.
[0081]
Examples of the inorganic semiconductor or organic pigment nano-sized particles include inorganic semiconductor nano-sized particles such as cadmium selenide and organic pigment nano-sized particles having a fluorescent color such as quinacridone. These exhibit a quantum size effect in a particle size range of several nm, and have different fluorescent emission colors depending on the particle system. Therefore, light emission of various colors can be obtained by simply changing the particle size in the same material.
[0082]
Among these luminescent substances, sesqui (p-phenylene), poly (p-phenylene), poly (2,4-dibutoxy-p-phenylene), poly (2,5-diheptyl-2 ′, 5′-dipentyloxy) Π-conjugated polymer compounds such as biphenylene), poly (p-phenyleneenylene), poly (9,9-di-n-hexylfluorene), poly (9,9-di-2- (ethylhexyl) fluorene), Iridium (III) bis (2- (4,6-difluorophenyl) pyridinate-N, C²) Transition metal complexes such as picolinate and bis (8-hydroxyquinolinato) zinc, and mixtures thereof.
[0083]
The luminescent layer 73 is formed by applying or printing the luminescent layer composition (C) obtained by dissolving or dispersing the luminescent substance in a solvent on the surface of the polymer or gel polymer solid electrolyte layer 72 and then drying. I do. Examples of the solvent include aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane, chloroform and 1,1,2-trichloroethane; alcohols such as methanol and ethanol; ketones such as cyclohexanone; Ethers such as 2,2-dimethoxyethane, tetrahydrofuran and diethylene glycol dimethyl ether, carbonates such as ethylene carbonate and propylene carbonate,
[0084]
Esters such as methyl formate and ethyl acetate, nitriles such as acetonitrile and benzonitrile, and aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide and N-methylpyrrolidone can be used. These solvents may be used alone or as a mixture.
[0085]
In addition, a polymer material such as polystyrene, poly (methyl) methacrylate, polyvinyl acetate, polyvinyl chloride, polyvinyl carbazole, or nylon is added to the composition (C) for the light emitting layer as a binder resin or a dispersion resin. You may. In order to obtain high luminous efficiency, the luminescent layer preferably contains the luminescent substance in an amount of 10% by mass or more, and more preferably 50% by mass or more.
[0086]
The method for applying or printing the composition for a light emitting layer (C) on the surface of the polymer or gel polymer solid electrolyte layer 72 is the same as the method for producing the polymer or gel polymer solid electrolyte layer 72. Can be mentioned. The thickness of the light emitting layer 73 is preferably in the range of 10 nm to 100 μm after drying. If the film thickness is less than 10 nm, a short circuit of the device may be caused, and if it exceeds 100 μm, the driving voltage may be increased. Especially, when the film thickness is 50 nm to 1 μm, higher luminous efficiency is obtained, which is preferable. The non-volatile concentration of the light emitting layer composition (C) is different between a case where the coating method is printing and a case where the coating method is coating. Adjustment is preferred.
[0087]
After printing or coating the polymer or gel polymer solid electrolyte composition (B) on the surface of the light emitting layer 73, the electrode 75 of the substrate 76 having the electrode 75 on one side is adhered to the coating film surface, Next, the coating film is cured by irradiating active energy rays from the transparent substrate side to form a polymer or gel polymer solid electrolyte layer 74.
[0088]
When forming the polymer or gel polymer solid electrolyte layer 74, the coating film of the polymer or gel polymer solid electrolyte composition (B) is irradiated with an active energy ray to lose the tackiness of the coating film. After pre-curing to the extent that it does not occur, the electrode 75 of the substrate 76 having the electrode 75 on one side may be brought into close contact, and the active film may be again irradiated from the transparent substrate side to completely cure the coating film.
[0089]
The method for applying or printing the polymer or gel polymer solid electrolyte composition (B) on the surface of the light emitting layer 73 and the method for irradiating active energy rays to cure the coating film include the polymer or the polymer. The same method as in the case of producing the gel polymer solid electrolyte layer 72 can be used. The thickness of the polymer or gel polymer solid electrolyte layer 74 may be the same as that of the polymer or gel polymer solid electrolyte layer 72.
[0090]
The same electrolyte may be used for the polymer or gel polymer solid electrolyte layer 72 and the polymer or gel polymer solid electrolyte layer 74, but the polymer or gel polymer solid electrolyte formed on the anode may be used. When an electrolyte having a cation having a small atomic diameter or a small molecular diameter is used for the layer, the holes injected from the anode are easily transported as cations to the light-emitting layer 73, so that the luminous efficiency is further increased, which is preferable. Among them, LiI, NaI, KI, LiPF₆, LiBF₄, LiAsF₆, Alkali metal salts and quaternary ammonium salts of perfluoroalkanesulfonic acid imides, polymer electrolytes having cations in the main chain or side chain of the polymer, etc., have an adverse effect on solubility in organic solvents and ionic conductivity. It is particularly preferable because it is excellent.
[0091]
On the other hand, when an electrolyte having an anion having a small atomic diameter or a small molecular diameter is used for the polymer or gel polymer solid electrolyte layer formed on the cathode, electrons injected from the cathode are transported to the light emitting layer 73 as anions. This is preferable because the luminous efficiency is further increased because it is easy. Among them, LiI, NaI, KI, LiPF₆, LiBF₄, Tetramethylammonium iodide ([(CH₃)₄N]⁺[I]⁻), Tetraethylammonium fluoroborate ([(C₂H₅)₄N]⁺[BF₄]⁻), Tetramethylammonium hexafluorophosphate ([(CH₃)₄N]⁺[PF₆]⁻), A polymer electrolyte or the like having an anion in the main chain or side chain of the polymer is particularly preferable because of its excellent solubility in an organic solvent and excellent ionic conductivity.
[0092]
When the photochromic display element of the present invention has a plurality of light emitting layers, all the light emitting layers may contain the same light emitting substance or different light emitting substances.
[0093]
In addition, the photochromic display element of the present invention may have a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, and the like. The hole injection layer and the hole transport layer are formed on the anode, and the electron injection layer and the electron transport layer are formed on the cathode. As a material for these layers, a material usually used for an organic electroluminescence device or the like can be used.
[0094]
In the photochromic display element obtained by the above method, after the lead wire is taken out from the electrode, the periphery of the element is sealed with sealants 77 and 78. As the sealants 77 and 78, there can be used a well-known and commonly used thermosetting sealant or ultraviolet-curable sealant, or a sealant combining these, which is usually used in a liquid crystal display or the like. In particular, when the polymer or gel polymer solid electrolyte layer 72 or the polymer or gel polymer solid electrolyte layer 74 is a gel polymer solid electrolyte layer, an ultraviolet-curable sealant is used to prevent evaporation of the solvent. It is preferred to use.
[0095]
In the photochromic display element of the present invention, the outer surface excluding the transparent substrate surface may be covered with a water vapor barrier film. As the water vapor barrier film, a metal foil of aluminum or the like, a metal laminate film of aluminum and polyethylene terephthalate, or the like can be used.
[0096]
The photochromic display device of the present invention is a device which is excited by the emission of the ECL device and is colored to form a display pattern. Therefore, the short-wavelength light is blocked outside the photochromic layer so as to prevent the display pattern from being disturbed by the irradiation of daily light, thereby preventing coloring of the photochromic material in a portion not exposed by light emission of the ECL element. It is preferable to provide a short wavelength light blocking layer. For example, in the case of the photochromic display element shown in FIG. 9, a short-wavelength light blocking layer is provided outside the transparent substrate 69. As the short-wavelength light blocking layer, for example, L-39 or L-42 that cuts ultraviolet light, Y-44 or Y-52 that cuts light with a wavelength shorter than yellow in the visible light region, or light with a shorter wavelength than orange. There are O-54, O-58 and the like to be cut, which are appropriately selected depending on the excitation wavelength and the wavelength of the absorption edge of the photochromic material to be used.
[0097]
Various measures can be taken to increase the contrast of the display pattern of the photochromic layer and improve the visibility. For example, in the photochromic display element shown in FIG. 9, the electrode 75 on the back side is made a mirror surface, the electrode 75 is made transparent to make the substrate 76 white, and the polymer or gel polymer solid electrolyte layer 74 is made of titanium oxide or the like. It is possible to take measures such as mixing white fine particles such as zinc oxide to make the polymer or gel polymer solid electrolyte layer white. In addition, multi-color or full-color display can be performed by separately coating the photochromic layer with a material in which the color forming material of the photochromic material exhibits red, green, and blue or cyan, magenta, and yellow.
[0098]
Further, only by changing the light emission pattern of the ECL element, a display corresponding to the pattern can be drawn on the photochromic layer. The pattern can be arbitrarily displayed by displaying a dot pattern by a simple matrix drive or an active drive using a TFT in which the electrodes are rectangular and the rectangular electrodes are orthogonal to the display surface and the back surface. FIG. 10 shows an example in which information is displayed by a simple matrix drive in which the electrodes are rectangular and the rectangular electrodes are orthogonal to the display surface and the back surface.
[0099]
On the other hand, the photochromic display element of the present invention can be manufactured continuously by a roll-to-roll method when the substrate is a flexible plastic film or the like having an electrode on one side.
[0100]
In the photochromic display element of the present invention, the ECL element portion is driven by applying a voltage of about 0.5 to 10 V, and is applied with a voltage of 0.1 to 1000 mA / cm.²Of 0.01 to 10000 cd / m²Light emission luminance of the order is obtained. Further, the luminescent color can be arbitrarily set by appropriately selecting the luminescent material.
[0101]
In the photochromic display element of the present invention, the ECL element portion may be driven for a short period until the photochromic material is colored, and may be driven by applying a pulse voltage at regular intervals. Further, such as under sunlight, when the photochromic display element of the present invention is continuously irradiated with strong light, the decolorization reaction of the colored photochromic material proceeds, and in this case, it is preferable to continuously apply a voltage, It is preferable to apply an AC voltage. When an AC voltage is applied to drive the ECL element portion, the polymer or gel polymer solid electrolyte layer is an electrolyte having a cation or anion having a small atomic or molecular diameter, such as LiI, NaI, KI, and LiPF.₆, LiBF₄, Tetramethylammonium iodide ([(CH₃)₄N]⁺[I]⁻) Is preferably used.
[0102]
The photochromic display element of the present invention is such that a photochromic layer, a polymer or gel polymer solid electrolyte layer and a light-emitting layer are sequentially formed on an electrode of one substrate, and a final polymer or gel polymer solid electrolyte layer is formed. Sometimes, the electrodes can be formed by a simple method in which the electrodes of another substrate are brought into close contact with each other, and then all layers are formed by irradiating active energy rays from the transparent substrate side. Further, if a plastic film having flexible electrodes is used as the substrate, it can be formed by a roll-to-roll method, and a large-area photochromic display element can be easily manufactured.
[0103]
The photochromic display element of the present invention is of an energy saving type in which a light emission pattern of an ECL element portion is converted into a display pattern of a photochromic layer, and display is maintained for a certain period of time without constantly emitting light in the ECL element portion. Therefore, the photochromic display element of the present invention can be suitably used for various display elements, displays, paper-like displays, electronic books, signs, signs, interiors, and the like.
[0104]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples. In the following examples, “%” is based on mass unless otherwise specified.
[0105]
<Example 1>
2- (1,2) was formed as a photochromic material on an ITO electrode of a Corning glass plate “1737” having a 100 nm-thick ITO electrode on one side and having a length and width of 20 mm and a thickness of 1.1 mm. -Dimethyl-3-indolyl) -3- (2,4,5-trimethyl-3-thienyl) mixture of maleic anhydride and bismaleimide acetic acid ester of polyethylene glycol with Mn of 400 (mass ratio 1: 1) was 1 μm. To a thickness of 1000 J / m using a high-pressure mercury lamp of 120 W / cm.²Was irradiated and cured to form a photochromic layer. Next, bismaleimide acetate of polyethylene glycol having Mn of 400 and LiPF₆0.5 mol / L ethylene carbonate / propylene carbonate solution (volume ratio of ethylene carbonate and propylene carbonate: 50:50) and the same mass of a composition (B) for a gel polymer solid electrolyte for a liquid crystal element having a diameter of 2 μm. A mixture of 2% of resin spherical spacers was applied using a spin coater to form a 20 μm thick coating film of the gel polymer solid electrolyte composition (B). 1000 J / m using a 120 W / cm high pressure mercury lamp²Was irradiated to form a gel polymer solid electrolyte layer having a thickness of 2 μm.
[0106]
On the gel polymer solid electrolyte layer, polyethylene glycol (Mn; 10,000), lithium trifluoromethanesulfonate and poly (2- (3,6-dioxaheptyloxy) -1,4-phenylene) (mass A ratio of 1: 0.18: 1) was dissolved in acetonitrile and spin-coated with a composition (C) for a light-emitting layer consisting of a solution having a concentration of 10.89 g / L, and then acetonitrile was removed in a vacuum dryer at 40 ° C. Thus, a light emitting layer having a thickness of 200 nm was formed. A mixture of the above-mentioned composition (B) for gel polymer solid electrolyte and 2% of a resin spherical spacer for a liquid crystal element having a diameter of 2 μm was applied on the light emitting layer using a spin coater, and a gel height of 2 μm was obtained. A coating film of the composition for molecular solid electrolyte (B) was formed. On this film, an aluminum electrode surface of a Corning glass plate “1737” having a length of 20 mm and a length of 1.1 mm each having an aluminum electrode having a thickness of 200 nm on one surface and a thickness of 1.1 mm was pressed from the transparent substrate side. 1000 J / m using a high-pressure mercury lamp of 120 W / cm²Was irradiated to form a gel polymer solid electrolyte layer having a thickness of 2 μm.
[0107]
After taking out the lead wire from the ITO electrode and the aluminum electrode, an ultraviolet-curing sealant was applied to the periphery of the element, and 1000 J / m using a 120 W / cm high-pressure mercury lamp.²Was irradiated to cure the sealant, and the element was sealed to obtain a photochromic display element.
Visible light having a center wavelength of 580 nm was irradiated from the ITO transparent electrode side of the device using a xenon lamp and an interference filter to guide the photochromic material into an open ring (light yellow). In this state, a sharp cut filter Y-48 was superimposed on a Corning glass plate “1737” having an ITO electrode and having a length and width of 20 mm and a thickness of 1.1 mm.
After applying a DC voltage of 5 V to the photochromic display element using the ITO electrode as an anode for 1 minute, the application was stopped. The photochromic layer was colored dark brown, and its color development was maintained for 10 minutes or more under room light.
[0108]
<Example 2>
2- (1,2) was formed as a photochromic material on an ITO electrode of a Corning glass plate “1737” having a 100 nm-thick ITO electrode on one side and having a length and width of 20 mm and a thickness of 1.1 mm. -Dimethyl-3-indolyl) -3- (2,4,5-trimethyl-3-thienyl) maleic anhydride, bismaleimide acetate of polyethylene glycol having Mn of 400, and LiPF₆Of a 0.5 mol / L ethylene carbonate / propylene carbonate solution (volume ratio of ethylene carbonate and propylene carbonate is 50:50) (mass ratio 1: 1: 1) was applied to a thickness of 1 μm, and 120 W / cm 1000 J / m using a high pressure mercury lamp²And then cured by irradiation with ultraviolet light to form a gel polymer solid electrolyte layer containing a photochromic material. Next, bismaleimide acetate of polyethylene glycol having Mn of 400 and LiPF₆0.5 mol / L ethylene carbonate / propylene carbonate solution (volume ratio of ethylene carbonate and propylene carbonate: 50:50) and the same mass of a composition (B) for a gel polymer solid electrolyte for a liquid crystal element having a diameter of 2 μm. A mixture of 2% of resin spherical spacers was applied using a spin coater to form a 20 μm thick coating film of the gel polymer solid electrolyte composition (B). 1000 J / m using a 120 W / cm high pressure mercury lamp²Was irradiated to form a gel polymer solid electrolyte layer having a thickness of 2 μm.
[0109]
On the gel polymer solid electrolyte layer, polyethylene glycol having Mn of 10,000, lithium trifluoromethanesulfonate, and poly (2- (3,6-dioxaheptyloxy) -1,4-phenylene) (mass ratio) , 1: 0.18: 1) in acetonitrile was spin-coated with a composition (C) for a light-emitting layer consisting of a solution having a concentration of 10.89 g / L, and then acetonitrile was removed in a vacuum dryer at 40 ° C. Thus, a light emitting layer having a thickness of 200 nm was formed. On the light-emitting layer, a mixture of the above-mentioned composition (B) for a polymer solid electrolyte and 2% of a resin spherical spacer for a liquid crystal element having a diameter of 2 μm was applied using a spin coater, and a polymer solid having a thickness of 2 μm was applied. A coating film of the composition for electrolyte (B) was formed. On this film, an aluminum electrode surface of a Corning glass plate “1737” having a length of 20 mm and a length of 1.1 mm each having an aluminum electrode having a thickness of 200 nm on one surface and a thickness of 1.1 mm was pressed from the transparent substrate side. 1000 J / m using a high-pressure mercury lamp of 120 W / cm²Was irradiated to form a gel polymer solid electrolyte layer having a thickness of 2 μm.
[0110]
After taking out the lead wire from the ITO electrode and the aluminum electrode, an ultraviolet-curing sealant was applied to the periphery of the element, and 1000 J / m using a 120 W / cm high-pressure mercury lamp.²Was irradiated to cure the sealant, and the element was sealed to obtain a photochromic display element.
Visible light having a center wavelength of 580 nm was irradiated from the ITO transparent electrode side of the device using a xenon lamp and an interference filter to guide the photochromic material into an open ring (light yellow). In this state, a sharp cut filter Y-48 was superimposed on a Corning glass plate “1737” having an ITO electrode and having a length and width of 20 mm and a thickness of 1.1 mm.
After applying a DC voltage of 5 V to the photochromic display element using the ITO electrode as an anode for 1 minute, the application was stopped. The photochromic layer was colored dark brown, and its color development was maintained for 10 minutes or more under room light.
[0111]
<Comparative Example 1>
In Example 1, a photochromic layer was formed on an ITO electrode of a Corning glass plate “1737” having a length of 20 mm and a length of 1.1 mm each having an ITO electrode having a thickness of 100 nm on one surface. Otherwise, the ECL element was formed in the same manner as in Example 1.
After applying a DC voltage of 5 V to the ECL element for 1 minute using the ITO electrode as an anode, the application was stopped. Although blue was exhibited during the application of the voltage, the blue display disappeared when the application of the voltage was stopped, and the display did not exhibit a memory property.
[0112]
【The invention's effect】
The photochromic display element of the present invention incorporates a photochromic layer inside or outside the ECL element, and uses the ECL element as an excitation light source of the photochromic display element. Since only the photochromic layer is incorporated inside or outside the ECL element, the configuration is simple.
[0113]
In addition, by simply changing the light emission pattern of the ECL element, a display corresponding to the pattern can be drawn on the photochromic layer, and even if the light emission of the ECL element is stopped, the photochromic layer maintains the display for a certain period of time. Can be. The pattern can be arbitrarily displayed by performing a dot pattern display by a simple matrix drive or an active drive using a TFT in which the electrodes are rectangular and the rectangular electrodes are orthogonal on the display surface and the back surface, and the like. Furthermore, if the pattern of the ECL element is configured as a color filter-like pattern using a material showing a color such as red, green, blue, or cyan, magenta, or yellow for a liquid crystal display, multicolor or full-color display is possible. It is.
[0114]
Furthermore, the ECL element portion of the photochromic display element of the present invention is such that the polymer or gel polymer solid electrolyte layer is composed of an electrolyte and a cured coating of an active energy ray-curable composition containing an active energy ray-polymerizable compound. . When an active energy ray polymerizable compound having a (poly) oxyalkylene chain having an ion transfer function is used as the active energy ray polymerizable compound, an ECL device having higher luminous efficiency can be obtained. In particular, when a maleimide compound having a (poly) oxyalkylene chain is used, the maleimide compound itself has polymerizability and also functions as a polymerization initiator. There is no need for a polymerization initiator in which substances or decomposition products cause impurities. Therefore, an ECL device having high luminous efficiency and excellent stability over time can be obtained. An ECL element with high luminous efficiency can be driven at a lower voltage, so that energy saving can be achieved and a photochromic display element with a long life can be obtained.
[0115]
In addition, when a flexible substrate such as a plastic film having electrodes is used, the substrate can be formed by a roll-to-roll method, and a large-area photochromic display element can be easily manufactured.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing one example of a photochromic display element of the present invention.
FIG. 2 is a cross-sectional view showing one example of the photochromic display element of the present invention.
FIG. 3 is a cross-sectional view showing one example of the photochromic display element of the present invention.
FIG. 4 is a cross-sectional view showing one example of the photochromic display element of the present invention.
FIG. 5 is a cross-sectional view showing one example of the photochromic display element of the present invention.
FIG. 6 is a sectional view showing an example of the photochromic display element of the present invention.
FIG. 7 is a cross-sectional view showing one example of the photochromic display element of the present invention.
FIG. 8 is a cross-sectional view showing one example of the photochromic display element of the present invention.
FIG. 9 is a cross-sectional view showing one example of the photochromic display element of the present invention.
FIG. 10 is a diagram showing an example in which the photochromic display element of the present invention is displayed by simple matrix driving.
[Explanation of symbols]
1 Photochromic layer
2 Transparent substrate
3 Transparent electrode
4. Polymer or gel polymer solid electrolyte layer containing luminescent substance
5 electrodes
6 substrate
7 Sealant
8 Sealant
9 Photochromic layer
10 Transparent substrate
11 Transparent electrode
12. Polymer or gel polymer solid electrolyte layer
13 Light-emitting layer
14 electrodes
15 Substrate
16 Sealant
17 Sealant
18 Photochromic layer
19 Transparent substrate
20 Transparent electrode
21 Polymer or gel polymer solid electrolyte layer
22 Emitting layer
23 Polymer or gel polymer solid electrolyte layer
24 electrodes
25 substrate
26 Sealant
27 Sealant
28 Transparent substrate
29 Transparent electrode
30 Polymer or gel polymer solid electrolyte layer containing photochromic material and luminescent material
31 electrodes
32 substrates
33 Sealant
34 Sealant
35 Transparent substrate
36 transparent electrode
37 Photochromic layer
38 Polymer or gel polymer solid electrolyte layer containing luminescent substance
39 electrodes
40 substrate
41 Sealant
42 Sealant
43 Transparent substrate
44 Transparent electrode
45 Polymer or gel polymer solid electrolyte layer containing photochromic material
46 light emitting layer
47 electrodes
48 substrates
49 Sealant
50 Sealant
51 Transparent substrate
52 transparent electrode
53 Photochromic layer
54 Polymer or gel polymer solid electrolyte layer
55 light emitting layer
56 electrodes
57 substrate
58 Sealant
59 Sealant
60 transparent substrate
61 Transparent electrode
62 Polymer or gel polymer solid electrolyte layer containing photochromic material
63 light emitting layer
64 Polymer or gel polymer solid electrolyte layer
65 electrodes
66 substrate
67 Sealant
68 Sealant
69 transparent substrate
70 Transparent electrode
71 Photochromic layer
72 Polymer or gel polymer solid electrolyte layer
73 Light-emitting layer
74 Polymer or gel polymer solid electrolyte layer
75 electrodes
76 substrate
77 Sealant
78 Sealant
79 Upper transparent substrate
80, 82, 83, 84, 85, 86, 87, 88 Lower substrate
89, 90, 91, 92, 93, 94, 95, 96 Upper transparent electrode

Claims (9)

A photochromic display device characterized in that light emitted from the electrochemical light-emitting device is used as excitation light. The photochromic display device according to claim 1, wherein a wavelength of light emitted by the electrochemical light-emitting device is in a range of 350 to 500 nm. The photochromic display device according to claim 1, wherein the photochromic display device has a memory property. A transparent substrate having a transparent electrode provided with a photochromic layer on one side, at least one, between the substrate having two electrodes, having a polymer or gel polymer solid electrolyte layer containing a luminescent substance, Alternatively, the photochromic display device according to any one of claims 1 to 3, having a laminated structure of a polymer or gel polymer solid electrolyte layer and a light emitting layer. The photochromic display device according to claim 4, wherein the photochromic layer contains a diarylethene-based compound. The photochromic display element according to claim 4, wherein the polymer or gel polymer solid electrolyte layer comprises a cured coating film of an active energy ray-curable composition containing an active energy ray-polymerizable compound and an electrolyte. The photochromic display device according to claim 6, wherein the active energy ray polymerizable compound is a compound having a (poly) oxyalkylene chain. The photochromic display element according to claim 6, wherein the active energy ray-curable compound is a maleimide compound having a (poly) oxyalkylene chain. 9. The photochromic display device according to claim 4, wherein at least one of the two substrates is a plastic substrate.

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