JP2006039157A - Electrochromic display apparatus and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrochromic display apparatus wherein problems of liquid leakage of a composition for display and peeling of a sealing wall are suppressed. <P>SOLUTION: In the electrochromic display apparatus wherein a working electrode side substrate having a transparent working electrode provided thereon and a counter electrode side substrate having a counter electrode provided thereon are opposed to each other so that the transparent working electrode and the counter electrode are opposed to each other, the composition for display containing a coloring substance capable of repetitively performing coloring and decoloring by oxidation and reduction and an aprotic polar solvent is disposed therebetween and coloring and decoloring the coloring substance by conducting electricity between the transparent working electrode and the counter electrode to perform display, the composition for display is sealed by a sealing wall adhering to inner peripheral parts of the working electrode side substrate and the counter electrode side substrate and consisting of a composition containing an olefinic resin having a polar group. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an electrochromic display device using a chromogenic substance capable of repeatedly performing color development and decoloration by oxidation and reduction.

  2. Description of the Related Art Conventionally, a display device called an electronic paper, a paper-like display, a digital paper, or the like has been proposed that displays an image by changing optical absorption or reflection by an electric field.

  As an element whose optical absorption and reflection change due to an electric field, a microcapsule containing rotating particles combined with hemispheres with different colors and electrical characteristics together with an insulating liquid, and a solvent in which electrophoretic particles are dispersed are used. There are microcapsules that are colored and encapsulate this solvent (see, for example, Patent Document 1), and a liquid crystal / polymer composite film containing a dichroic dye and a smectic liquid crystal. A display device using these technologies has a memory property, can hold image information even without a power source, and is a reflective display device, and thus is expected as a substitute for paper. As a substrate with electrodes, for example, a PET (polyethylene terephthalate) film or the like can be used. Therefore, the display device is thin, light, and can be bent.

  In recent years, an electro-deposition type display capable of realizing a paper-like contrast and whiteness has been proposed for an electrochromic display device using a color change of a substance due to a change in voltage. In these electrochromic display devices, for example, a working electrode side substrate provided with a transparent working electrode and a counter electrode side substrate provided with a counter electrode are opposed so that the transparent working electrode and the counter electrode face each other. A solid electrolyte containing silver halide and a supporting electrolyte containing halogen is disposed on the substrate, and silver is deposited on the transparent electrode by changing the potential to cause color development (see, for example, Patent Documents 2 and 3). In addition, the silver on the transparent electrode is re-dissolved by the reverse potential to cause the color to disappear.

  Many of these electrochromic display devices have a working electrode side substrate provided with a transparent working electrode and a counter electrode side substrate provided with a counter electrode facing each other so that the transparent working electrode and the counter electrode face each other, Thus, a device configuration is provided in which a display composition containing a color forming substance that develops and decolors by oxidation and reduction is enclosed. At that time, a seal wall made of an adhesive is adhered to the inner peripheral portion of the working electrode side substrate and the counter electrode side substrate, and the display composition is held in a space surrounded by the seal wall and the two substrates. . In general, there are wiring portions to the transparent working electrode and the counter electrode in the inner peripheral portion between the seal wall and the two substrates. Therefore, in such a case, the sealing wall adheres to the inner peripheral part and the wiring part of the two substrates, thereby preventing leakage of the display composition to the outside.

  As the adhesive used for this purpose, various materials such as acrylic, urethane, epoxy, polyester, and silicone, which are generally called adhesives and sealants, can be used.

With respect to this seal wall, the polar solvent contained in the display composition dissolves or swells the material constituting the seal wall, and enters the adhesive surface between the substrate and the seal wall or between the wiring portion and the seal wall. As a result, there is a problem in that the adhesive strength is remarkably lowered, causing liquid leakage and peeling of the seal wall. In order to cope with such a problem, a technique for sealing by using a combination of an ultraviolet curable adhesive and an epoxy adhesive has been introduced (for example, see Patent Document 4). In addition, it takes time to bond, and the material to be used is hardened and hardened. Therefore, there is a problem that it cannot be applied to a flexible display device using a resin film or the like.
Japanese Patent Laid-Open No. 01-086116 (Claims) US Pat. No. 4,240,716 (claims) US Pat. No. 4,240,717 (claims) Japanese Patent Laid-Open No. 06-250230 (Claims)

  The present invention eliminates such a decrease in adhesive strength on the bonding surface between the substrate and the sealing wall and the bonding surface between the wiring portion and the sealing wall, liquid leakage from the display panel of the electrochromic display device, peeling of the sealing wall, and the like. The goal is to provide technology that avoids the problems it causes. Still other objects and advantages of the present invention will become apparent from the following description.

  According to one aspect of the present invention, the working electrode side substrate provided with the transparent working electrode and the counter electrode side substrate provided with the counter electrode are opposed so that the transparent working electrode and the counter electrode face each other, A display composition comprising a chromogenic substance capable of repeatedly performing color development and decoloration by oxidation and reduction, and an aprotic polar solvent, and by energization between the transparent working electrode and the counter electrode In an electrochromic display device that performs display by coloring or decoloring a chromogenic substance, a polar group in which the display composition is bonded to the inner peripheral portion of the opposing working electrode side substrate and the counter electrode side substrate An electrochromic display device is provided which is sealed by a sealing wall made of a composition containing an olefin-based resin.

  According to the aspect of the present invention, an electrochromic display device in which the liquid leakage of the display composition and the problem of peeling of the seal wall are suppressed is provided.

  According to another aspect of the present invention, the working electrode side substrate provided with the transparent working electrode and the counter electrode side substrate provided with the counter electrode are opposed so that the transparent working electrode and the counter electrode face each other, In the meantime, a display composition containing a chromogenic substance capable of repeatedly performing color development and decoloration by oxidation and reduction and an aprotic polar solvent is disposed, and between the transparent working electrode and the counter electrode. In a method of manufacturing an electrochromic display device that performs display by coloring or decoloring a chromogenic substance by energization, the display composition is bonded to the inner peripheral portion of the opposing working electrode side substrate and the counter electrode side substrate. There is provided a method for producing an electrochromic display device which is sealed by a sealing wall made of a composition containing an olefin resin having a polar group.

  According to the aspect of the present invention, there is provided a method for producing an electrochromic display device in which liquid leakage of a display composition and problems of peeling of a seal wall are suppressed.

  In any aspect, the effect of the present invention is particularly easily exhibited when the seal wall is bonded to the wiring portion to at least one of the transparent working electrode and the counter electrode.

  In addition, the olefin-based resin having a polar group contains at least one of a silane coupling agent and a titanium coupling agent, and the opposing working electrode side substrate to which the seal wall is bonded The adhesive surface of the inner peripheral part of the counter electrode side substrate and / or the adhesive surface of the wiring part are treated with at least one of a silane coupling agent and a titanium coupling agent, and polar groups It is preferable that the olefin-based resin has at least one group selected from the group consisting of a carboxy group, an amino group, an isocyanate group, a glycidyl group, and a mercapto group in order to further enhance the adhesion of the seal wall.

  The silane coupling agent or titanium coupling agent preferably has at least one group selected from the group consisting of a carboxy group, an amino group, an isocyanate group, a glycidyl group, and a mercapto group. The side substrate and the counter electrode side substrate are each preferably a substrate made of a material selected from the group consisting of glass, thermoplastic polyester resin, and cycloolefin resin.

  According to the present invention, there is provided an electrochromic display device in which the liquid leakage of the display composition and the problem of peeling of the seal wall are suppressed.

  Embodiments of the present invention will be described below with reference to the drawings, examples and the like. In addition, these figures, Examples, etc. and description illustrate the present invention, and do not limit the scope of the present invention. It goes without saying that other embodiments may belong to the category of the present invention as long as they match the gist of the present invention. In the drawings, the same reference numeral represents the same element.

  In the electrochromic display device according to the present invention, the working electrode side substrate provided with the transparent working electrode and the counter electrode side substrate provided with the counter electrode are opposed so that the transparent working electrode and the counter electrode face each other, In addition, a display composition containing a chromogenic substance capable of repeatedly performing color development and decoloration by oxidation and reduction and an aprotic polar solvent is arranged, and current is passed between the transparent working electrode and the counter electrode. Thus, an electrochromic display device that displays by developing or decoloring the chromogenic substance, the display composition is bonded to the inner peripheral portion of the opposing working electrode side substrate and the counter electrode side substrate, Sealed by a sealing wall made of a composition containing an olefin resin having a polar group (hereinafter, “olefin resin having a polar group” is also referred to as “modified olefin resin”). .

  This is shown in FIG. FIG. 1 is a schematic cross-sectional view of a display panel of an electrochromic display device according to the present invention. In FIG. 1, a display panel 1 is colored and decolored by oxidation and reduction between a transparent working electrode 2 and a counter electrode 4 provided on a facing working electrode side substrate 3 and a counter electrode side substrate 5, respectively. The display composition 6 containing a color-developing substance capable of repeating the above and an aprotic polar solvent is disposed. The arrow represents the direction in which a person views the display on the display panel 1. The transparent working electrode 2 and the counter electrode 4 are each in a stripe shape, and the stripe shapes are arranged so as to be orthogonal to each other when viewed from the direction of the arrow. A sealing wall 7 that surrounds and seals the display composition 6 is provided on the inner periphery of the substrates 3 and 5. In this example, the inner peripheral portion of the working electrode side substrate and the counter electrode side substrate facing the seal wall 7 and the wiring portion (not shown) for electrically connecting the transparent working electrode and the counter electrode to the outside of the display panel. This prevents the display composition from leaking outside.

  The transparent working electrode and the counter electrode are usually arranged directly on the substrate or via a layer provided for the purpose of improving the adhesion between the transparent working electrode and the substrate. The working electrode side substrate needs to be transparent, and transparent glass such as quartz glass, soda glass, borosilicate glass, etc. can be used, but is not limited thereto, polyethylene naphthalate, polyethylene Thermoplastic polyester resins such as terephthalate, cellulose esters such as polyamide, polycarbonate and cellulose acetate, fluoropolymers such as polyvinylidene fluoride, polytetrafluoroethylene and hexafluoropropylene, polyethers such as polyoxymethylene, polyacetal, Polyolefins such as polystyrene, polyethylene, polypropylene, polyolefins such as methylpentene polymer, cycloolefin trees represented by product brands such as ZEONOR, ZEONEX (manufactured by Nippon Zeon) and ARTON (manufactured by JSR) It can be cited as examples of polyimides such as classes and polyimide amides and polyetherimides.

  Among these, when considering light transmittance and resistance to polar solvents, it is preferable to use a glass substrate, a thermoplastic polyester resin, or a substrate made of a cycloolefin resin.

  The material of the counter electrode side substrate does not necessarily need to be transparent. In addition to transparent glass such as quartz glass, soda glass, borosilicate glass, metal, ceramic, thermoplastic polyester resins such as polyethylene naphthalate and polyethylene terephthalate, polyamide , Cellulose esters such as polycarbonate and cellulose acetate, fluoropolymers such as polyvinylidene fluoride and tetrafluoroethylene-hexafluoropropylene copolymer, polyethers such as polyoxymethylene, polyacetal, polystyrene, polyethylene, polypropylene, methylpentene Polyolefins such as polymers, cycloolefin resins represented by product brands such as ZEONOR, ZEONEX (manufactured by ZEON CORPORATION) and ARTON (manufactured by JSR), and polyimide resins Polyimides such as de or polyetherimide and the like.

  Especially, when the tolerance with respect to a polar solvent is considered, it is preferable to use the board | substrate made from a glass substrate, a thermoplastic polyester resin, or a cycloolefin resin.

  In any case, the substrate can be a highly rigid substrate that does not easily bend, or can be a flexible film-like structure.

The transparent working electrode needs to have high transmittance for visible light for display, and the working electrode side substrate surface has conductivity such as ITO (indium tin oxide), FTO (fluorine-doped tin oxide), SnO ₂ . It is produced by depositing or applying a material. Further, an inorganic material layer such as silicon oxide or aluminum oxide or an organic material film such as polyamide may be formed between the conductive material layer and the working electrode side substrate. Thereby, the effect of improving the adhesiveness of the conductive material layer and improving the barrier property against gas or solvent can be obtained. The display of the image is performed by causing a color developing substance in the vicinity of the working electrode to be colored by electrochemical oxidation or reduction reaction by energization between the electrodes.

The material used for the counter electrode is not particularly limited as long as it is a conductive substance. For example, highly conductive metals such as silver, gold, platinum, aluminum, and copper, conductive polymers such as polyaniline and polypyrrole, metal oxide thin films such as ITO, FTO, and SnO ₂ , or vapor deposited films, or possible In some cases, it is preferable that the conductive layer is formed by a coating film using a paste of these powders.

  In particular, in an electrochromic display device that displays by precipitation and dissolution of silver, when a silver conductive layer is formed on the electrode surface of the counter electrode, silver ions are also eluted from the counter electrode side. Since silver ions are always replenished, the display speed is high and high contrast can be obtained, which is advantageous. More specifically, it is preferable to use a counter electrode having a silver surface thicker than 0.2 μm. It is sufficient to confirm that the thickness of the silver film is greater than 0.2 μm at any stage before or after the electrochromic display device is manufactured. This makes it easy to produce a device with high contrast and high whiteness while maintaining a high silver ion concentration in the display composition.

  A cell or panel of an electrochromic display device can be formed by sandwiching a spacer between the working electrode side substrate and the counter electrode side electrode or without sealing the display composition with a seal wall. The spacer used at this time is not particularly limited as long as a sufficient inter-electrode distance can be obtained without the working electrode and the counter electrode being in contact with each other. Non-woven fabric such as polypropylene and thermoplastic polyester, mesh types, particles Etc. can be used. The particles preferably have a sharp particle size distribution, and are known materials such as crosslinkable polymers (polystyrene, acrylic, etc.), wax-like substances, inorganic particles (zirconia, glass, etc.). Those that do not dissolve can be used. In the wax-like substance, the melting point of the wax needs to be higher than the temperature at the time of manufacturing the display panel of the electrochromic display device. In addition, the distance between electrodes in an electrochromic display device is generally about 10 μm to 1 mm.

  The display composition according to the present invention includes a chromogenic substance capable of repeatedly performing color development and decoloration by oxidation and reduction, and an aprotic polar solvent. A supporting electrolyte may be included. Other materials may be included as long as they are not contrary to the spirit of the present invention.

  A known material can be used as the color forming substance capable of repeatedly performing color development and decoloration by oxidation and reduction. Examples thereof include tungsten oxide, viologen and derivatives thereof, or compounds containing ions that can be electrodeposited, such as bismuth, copper, silver, lithium, iron, chromium, nickel, and cadmium. In particular, in an electroposition display device capable of high-contrast display by electrodeposition, it is preferable to use silver halide as the color developing material.

  As silver halide, silver fluoride (AgF), silver chloride (AgCl), silver bromide (AgBr), or silver iodide (AgI) can be used. Note that silver iodide is preferably used from the viewpoint of solubility. Further, the concentration of silver halide is preferably 0.05 to 8.0 moL / L.

  In addition to these chromogenic substances, the display composition may contain other supporting electrolytes in order to adjust the solubility and reactivity of the chromogenic substance. For example, the supporting electrolyte containing halogen for dissolving silver halide includes ammonium iodide, tetraethylammonium iodide, potassium iodide, potassium bromide, potassium chloride, sodium iodide, sodium bromide, sodium chloride, Known materials such as lithium iodide, lithium bromide, and lithium chloride can be used. In view of the display speed of the electrochromic display device and the solubility of silver halide, it is preferable to use an ammonium salt. Moreover, it is preferable that this supporting electrolyte exists in the range of 0.5-2 mol times with respect to the density | concentration of a silver halide. More preferably, it is in the range of 0.5 to 1 mole times the silver halide concentration.

  Other supporting electrolytes include perchlorate, thiocyanate, sulfate, oxalic acid, tetrabutylammonium perchlorate, tetraethylammonium perchlorate, isocyanate thiocyanate, ammonium thiocyanate, sodium sulfide, etc. Known materials such as maleic acid, malonic acid, fumaric acid, lactic acid, and salicylic acid can be used.

  As a solvent that dissolves the color-developing substance and the supporting electrolyte, an aprotic polar solvent is preferable in terms of suppressing gas generation due to the oxidation-reduction reaction. Specifically, dimethylformamide (DMF), dimethylsulfoxide (DMSO), diethylformamide (DEF), N, N-dimethylacetamide (DMAA), N-methylpropionic acid amide (MPA), N-methylpyrrolidone (NMP) , Propylene carbonate (PC), ethylene carbonate (EC), hexamethylphosphoric triamide, sulfolane, acetonitrile (AN), 2-ethoxyethanol (EEOH), 2-methoxyethanol (MEOH), dioxolane (DOL), ethyl acetate ( EA), tetrahydrofuran (THF), methyltetrahydrofuran (MeTHF), dimethoxyethane (DME), γ-butyrolactone (GBL) and the like may be used, and these may be used in combination.

  The display composition according to the present invention may contain a colorant in order to adjust the color of the non-display portion. In order to improve contrast, it is often preferable to add a white pigment. Examples of white pigments include titanium dioxide, silicon dioxide, calcium carbonate, aluminum oxide, barium titanate, and zirconium oxide. From the viewpoint of the concealment rate, titanium dioxide is preferably used. In addition, inorganic pigments such as iron oxide and organic pigments such as copper phthalocyanine pigment and quinacridone pigment can also be used.

  The display composition according to the present invention has a form ranging from liquid to gel or completely solid, and is generally an electrolyte. In order to make the liquid display composition into a gel or solid form, a known material such as polyvinyl pyrrolidone, polyvinylidene fluoride, polyacrylonitrile, or a gel polymer of polyethylene oxide may be included.

  The display composition according to the present invention is sealed by a seal wall made of a composition containing a modified olefin resin bonded to two opposing substrates. The composition containing the modified olefinic resin may be the modified olefinic resin itself, but other resins, inorganic substances, and the like may be present unless it is contrary to the spirit of the present invention. When other resin, inorganic substance, etc. exist, the amount is preferably 30% by volume or less, and more preferably 10% by volume or less.

  As a method of adhering the composition containing the modified olefin resin to the inner peripheral part of the opposing working electrode side substrate and the counter electrode side substrate, or to the wiring part, the composition is softened by heating and applied to the part to be adhered. The method of crimping can be mentioned. In this case, the heating temperature and the degree of pressure bonding can be determined experimentally according to the physical properties of the composition used.

  Unmodified olefin resins that can be used for such purposes are olefin resins having an alkylene as the main skeleton, such as polyethylene and polypropylene. It may have a branched structure.

  The unmodified olefin resin has low polarity and low affinity with the solvent used in the display composition. Therefore, it is excellent in that it is difficult to dissolve and swell in the solvent used in the display composition.

  However, since the conductive material is formed in a line shape and various shapes on the substrate as a wiring portion for energizing the transparent working electrode and the counter electrode, the sealing wall is transparent. Usually, there is also a portion that is bonded to the wiring portion to at least one of the working electrode and the counter electrode, and adhesion at this portion becomes a problem. In other words, olefin-based materials themselves generally cannot secure sufficient adhesion to metals and metal oxides, so that a solvent enters the adhesion interface, peeling off the seal wall, and leakage of the display composition. May occur. This is because the surface of the wiring portion made of metal or metal oxide has a high polarity, and the characteristics are significantly different from those of the olefin-based material itself.

  Such a situation may also exist for the working electrode side substrate and the counter electrode side substrate. In other words, olefinic materials themselves often cannot ensure sufficient adhesion with glass or other plastics, and solvents may enter the adhesion interface, causing peeling of the seal wall and leakage of the display composition. May occur.

  In order to improve the adhesion in such a case, a modified olefin resin is employed in the present invention.

  Any known modified olefinic resin may be used as the modified olefinic resin. Examples thereof include a modified olefin resin having at least one group selected from the group consisting of a carboxy group, an amino group, an isocyanate group, a glycidyl group, and a mercapto group. By introducing such a polar group, the affinity for the surface of a metal surface or metal oxide can be increased. The amount of polar groups in the olefin resin can be determined according to the actual situation.

  Specific examples of such olefin resins include polyethylene-acrylic acid copolymer, polyethylene-methacrylic acid copolymer, polyethylene-acrylic acid ester copolymer, polyethylene-methacrylic acid ester copolymer, polyethylene-methacrylic acid. Examples include glycidyl copolymers, ethylene-vinyl acetate copolymers, polymethylene polyphenyl polyisocyanates, and copolymers of polyethylene and polypropylene with compounds having a polar group.

  Specific product brands of modified olefins include: Evaflex, Evaflex-EEA, Elvalloy AC, Nucrel (Mitsui DuPont Polychemical Co., Ltd.), NUC series (Nihon Unicar Co., Ltd.), Bondine, Bond First ( As mentioned above, Sumitomo Chemical Co., Ltd.), Novatec-EVA, Novatec-EAA (above, Nippon Polyethylene Co., Ltd.), etc. are mentioned.

  In the present invention, the seal wall is formed using the composition containing the modified olefin resin as described above, thereby reducing the adhesive strength between the seal wall and the wiring portion or the substrate, and the liquid for the display composition. Problems that cause leakage, peeling of the seal wall, etc. can be avoided. In addition, it is possible to maintain the property of being hardly dissolved or swollen in the solvent used in the display composition as an olefin resin. Furthermore, as in the case of the technique of sealing by using a combination of an ultraviolet curable adhesive and an epoxy adhesive, it is possible to obtain a flexible display device without losing flexibility.

  In order to further improve the adhesion to the wiring part and the substrate, the working electrode side substrate and the counter electrode to which the seal wall adheres are bonded using a compound having reactivity to both the modified olefin resin and the electrode substrate surface. It is effective to treat the adhesion surface of the inner peripheral portion with the side substrate and / or the adhesion surface of the wiring portion.

  Examples of such a compound include a silane coupling agent or a titanium coupling agent having at least one group selected from the group consisting of a carboxy group, an amino group, an isocyanate group, a glycidyl group, and a mercapto group.

  A silane coupling agent or a titanium coupling agent is a compound having a molecular structure in which an alkoxy group and an organic group are bonded to silicon or titanium, respectively, and can be firmly bonded to the wiring portion or the surface of the substrate by hydrolysis of the alkoxy group. In addition, the carboxy group, amino group, isocyanate group, glycidyl group and mercapto group contained in the organic group react with the polar group contained in the modified olefin resin and can be firmly bonded to the modified olefin resin.

  Specific examples of these silane coupling agents include γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (β -Aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- ( β-aminoethyl) -γ-aminopropylmethyldiethoxysilane and other aminosilane coupling agents, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane and other glycidylsilane coupling agents, isocyanatepropyl Trimethoxysilane, isocyanate Isocyanate silane coupling agents such as topropyltriethoxysilane, mercaptosilane coupling agents such as γ-mercaptopropyltrimethoxysilane, and titanium coupling agents include aminotitanium cups such as isopropyltri-N-ethylamino-ethylamino titanate. A ring agent etc. are mentioned. These silane coupling agents and titanium coupling agents may be used alone or in combination of two or more. In some cases, a silane coupling agent and a titanium coupling agent can be mixed and used.

  A well-known technique for treating the bonding surface of the inner peripheral portion of the working electrode side substrate and the counter electrode side substrate to which the seal wall is bonded or the bonding surface of the wiring portion with a silane coupling agent or a titanium coupling agent Can be used. For example, after applying a solution in which a silane coupling agent or a titanium coupling agent is dissolved in water or an organic solvent, to the substrate part and wiring part that should come into contact with the seal wall by means of dip coating, spin coating, spraying, etc. Then, the silane coupling agent or the titanium coupling agent is reacted and adhered to the substrate portion and the wiring portion, and the modified olefin resin is adhered thereto to form a seal wall. At this time, heat treatment may be performed to increase the reactivity.

  Furthermore, as another method, a silane coupling agent or a titanium coupling agent previously blended with a modified olefin resin may be used to adhere to the substrate portion and the wiring portion. In this case, the same effect can be obtained by improving the adhesive force. The silane coupling agent or titanium coupling agent and the modified olefin may be mixed by stirring and mixing using an extruder, a kneader, or a mixer heated to a temperature higher than the melting point of the modified olefin. A method of treating the bonding surface of the inner peripheral portion of the working electrode side substrate and the counter electrode side substrate to which the seal wall is bonded and the bonding surface of the wiring portion with a silane coupling agent or a titanium coupling agent; You may implement together two methods, the method of using what previously blended the coupling agent and the titanium coupling agent with the modified olefin resin.

  The electrochromic display device manufactured by the above method has a reduced adhesive strength on the adhesive surface between the substrate and the seal wall and the adhesive surface between the wiring portion and the seal wall, liquid leakage from the display panel of the electrochromic display device, and the seal wall. Therefore, it is possible to avoid a problem that causes peeling of the resin, and it becomes a highly reliable device that can be stably operated for a long time.

  Moreover, it is easy to select a composition having flexibility as a material used for the seal, and it can be suitably applied to a flexible display device using a resin film or the like.

  Hereinafter, the present invention will be described in more detail with reference to examples.

[Example 1]
(1) Production of display cell An ITO film (surface resistance 10Ω / □) is formed in a stripe shape (line width 290 μm, space width 30 μm) on a polyethylene naphthalate substrate (Q65, thickness 125 μm, manufactured by Teijin DuPont Films). A transparent working electrode and a wiring part were obtained. In addition, a silver film was formed in a striped shape (line width 290 μm, space width 30 μm) on a polyethylene naphthalate substrate (Q65, thickness 125 μm, manufactured by Teijin DuPont Films Ltd.) to form a counter electrode and a wiring part.

  Next, with respect to both substrates, the display surface is masked and a 1 wt% ethanol solution of aminosilane coupling agent SH6020 (manufactured by Toray Dow Corning Silicone) is applied to the surface to be bonded around the substrate at 120 ° C. Heat-dried. Next, Bondine TX8030 (manufactured by Sumitomo Chemical Co., Ltd.) processed into a sheet with a thickness of 100 μm is used for the seal wall, and bonded to the substrate by thermocompression bonding with the structure as shown in FIG. 2 to produce a display cell. did. In FIG. 2, the code | symbol 8 has shown the wiring part of a transparent working electrode and a counter electrode side.

(2) Preparation of composition for display Silver iodide (1.0 mol / L) and ammonium iodide (1.0 mol / L) are dissolved in propylene carbonate to obtain an electrolytic solution. Monomer (2-hydroxy-1,3-dimethacryloxypropane (manufactured by Shin-Nakamura Chemical, product number 701), 0.5 g, oligomer (1,6-hexanediol diglycidyl ether acrylate (manufactured by Shin-Nakamura Chemical, product number EA-5521) 0.1 g and 0.1 g of cyanoresin (manufactured by Shin-Etsu Chemical Co., Ltd., CR-S) were dissolved, and 500 μL of 2.5 wt% polymerization initiator V-65 (manufactured by Wako Pure Chemical Industries) was mixed in propylene carbonate. Then, 40% by weight of titanium dioxide (manufactured by Ishihara Sangyo Co., Ltd., CR-58) was dispersed in the mixture to prepare a raw material composition for a display composition.

  After inject | pouring the said display raw material composition (liquid state) into the said display cell, it was set as the display composition by heating, and the sheet type display panel was produced. When this display panel was allowed to stand in an oven at 80 ° C. for 24 hours, no penetration of the display composition into the adhesive surface was observed. This display panel could be easily bent by hand.

[Example 2]
A display panel was produced in the same manner as in Example 1 except that the silane coupling agent SH6020 was replaced with an isocyanate silane coupling agent Y-5187 (manufactured by Nihon Unicar). When this display panel was allowed to stand in an oven at 80 ° C. for 24 hours, no penetration of the display composition into the adhesive surface was observed.

[Example 3]
A display panel was produced in the same manner as in Example 1 except that the silane coupling agent SH6020 was replaced with a glycidyl silane coupling agent SH6040 (manufactured by Toray Dow Corning Silicone). When this display panel was allowed to stand in an oven at 80 ° C. for 24 hours, no penetration of the display composition into the adhesive surface was observed.

[Example 4]
A display panel was produced in the same manner as in Example 1 except that the silane coupling agent SH6020 was replaced with an aminotitanium coupling agent KR-44 (manufactured by Ajinomoto Fine Techno Co., Ltd.). When this display panel was allowed to stand in an oven at 80 ° C. for 24 hours, no penetration of the display composition into the adhesive surface was observed.

[Example 5]
A display panel was produced in the same manner as in Example 1 except that Bondin TX8030 was replaced with Nucrel N1207C (Mitsui DuPont Polychemical Co., Ltd.). When this display panel was allowed to stand in an oven at 80 ° C. for 24 hours, no penetration of the display composition into the adhesive surface was observed.

[Example 6]
A display panel was produced in the same manner as in Example 5 except that the silane coupling agent SH6020 was replaced with an isocyanate silane coupling agent Y-5187 (manufactured by Nihon Unicar). When this display panel was allowed to stand in an oven at 80 ° C. for 24 hours, no penetration of the display composition into the adhesive surface was observed.

[Example 7]
A display panel was produced in the same manner as in Example 1 except that Bondin TX8030 was replaced with Bond First 2B (manufactured by Sumitomo Chemical Co., Ltd.). When this display panel was allowed to stand in an oven at 80 ° C. for 24 hours, no penetration of the display composition into the adhesive surface was observed.

[Example 8]
A display panel was produced in the same manner as in Example 7 except that the silane coupling agent SH6020 was replaced with an isocyanate silane coupling agent Y-5187 (manufactured by Nihon Unicar). When this display panel was allowed to stand in an oven at 80 ° C. for 24 hours, no penetration of the display composition into the adhesive surface was observed.

[Example 9]
A display panel was produced in the same manner as in Example 7 except that the silane coupling agent SH6020 was replaced with mercaptosilane coupling agent A-189 (manufactured by Nihon Unicar). When this display panel was allowed to stand in an oven at 80 ° C. for 24 hours, no penetration of the display composition into the adhesive surface was observed.

[Example 10]
An ITO film (surface resistance 10Ω / □) is formed in a stripe shape (line width 290 μm, space width 30 μm) on a polyethylene naphthalate substrate (Teijin DuPont Films Co., Ltd., Q65, thickness 125 μm). did. In addition, a silver film was formed in a stripe shape (line width 290 μm, space width 30 μm) on a polyethylene naphthalate substrate (Q65, thickness 125 μm, manufactured by Teijin DuPont Films, Inc.) to provide a counter electrode and a wiring part.

  Further, 5 parts by weight of aminosilane coupling agent SH6020 (manufactured by Toray Dow Corning Silicone) and 95 parts by weight of Bondine TX8030 (manufactured by Sumitomo Chemical Co., Ltd.) are kneaded using a kneader and processed into a sheet having a thickness of 100 μm. After that, this was used for a sealing wall and bonded by thermocompression bonding with the substrate to produce a display cell. Subsequently, after inject | pouring the liquid of the raw material composition for a display shown in Example 1 into this display cell, the sheet type display panel was produced by heating. When this display panel was allowed to stand in an oven at 80 ° C. for 24 hours, no penetration of the display composition into the adhesive surface was observed.

[Example 11]
The working electrode substrate and the counter electrode substrate provided with the transparent working electrode used in Example 1 were used without applying a coupling agent. Using a Bondine TX8030 (manufactured by Sumitomo Chemical Co., Ltd.) processed into a sheet having a thickness of 100 μm, a display cell was produced by thermocompression bonding with these substrates in the configuration as shown in FIG. Furthermore, after inject | pouring the raw material composition for display produced in Example 1 into this display cell, the sheet type display panel was produced by heating. Immediately after production, no penetration of the display composition into the adhesive surface was observed. Further, when this display panel was left in an oven at 80 ° C. for 24 hours, no penetration of the display composition into the adhesive surface was observed.

[Example 12]
A sheet type display panel was produced in the same manner as in Example 11 except that Bond First 2B (manufactured by Sumitomo Chemical Co., Ltd.) was used instead of Bondin TX8030 (manufactured by Sumitomo Chemical Co., Ltd.). Immediately after production, no penetration of the display composition into the adhesive surface was observed. Further, when this display panel was left in an oven at 80 ° C. for 24 hours, no penetration of the display composition into the adhesive surface was observed.

[Comparative Example 1]
A sheet type display panel was produced in the same manner as in Example 11 except that polyester resin Byron GA6400 (manufactured by Toyobo Co., Ltd.) was used instead of Bondin TX8030 (manufactured by Sumitomo Chemical Co., Ltd.). When this display panel was left in an oven at 80 ° C. for 24 hours, the adhesive layer became cloudy and the electrodes were easily peeled off.

[Comparative Example 2]
In the same manner as in Example 11 except that an epoxy adhesive Araldide (manufactured by Bantico) was used instead of Bondin TX8030 (manufactured by Sumitomo Chemical Co., Ltd.), the substrate was thermocompression bonded to the substrate as shown in FIG. In addition, the adhesive was cured by allowing it to stand at room temperature for 6 hours to produce a display cell. Furthermore, after inject | pouring the display raw material composition produced in the Example into this display cell, the sheet type display panel was produced by heating. When this display panel was left in an oven at 80 ° C. for 24 hours, the adhesive layer was softened and the electrodes were easily peeled off.

[Comparative Example 3]
In the same manner as in Example 11 except that acrylic adhesive Y600H (made by Cemedine) was used instead of Bondine TX8030 (made by Sumitomo Chemical Co., Ltd.), the substrate was thermocompression bonded to the substrate as shown in FIG. The display cell was produced by bonding and allowing to stand for 12 hours at room temperature to cure the adhesive. Furthermore, after inject | pouring the raw material composition for a display produced in the Example into this display cell, the sheet type display panel was produced by heating. When this display panel was left in an oven at 80 ° C. for 24 hours, the adhesive layer was softened and the electrodes were easily peeled off.

  In addition, the invention shown to the following additional remarks can be derived from the content disclosed above.

(Appendix 1)
The working electrode side substrate provided with the transparent working electrode and the counter electrode side substrate provided with the counter electrode are made to face each other so that the transparent working electrode and the counter electrode face each other. A coloring composition capable of repeatedly performing decoloring and decoloring, and a display composition comprising an aprotic polar solvent, and the chromogenic substance is energized between the transparent working electrode and the counter electrode. In an electrochromic display device that displays by developing or decoloring,
The display composition is sealed by a seal wall made of a composition containing an olefin-based resin having a polar group, which is bonded to the inner peripheral portion of the opposing working electrode side substrate and the counter electrode side substrate. Electrochromic display device.

(Appendix 2)
The electrochromic display device according to appendix 1, wherein the seal wall is adhered to a wiring portion to at least one of the transparent working electrode and the counter electrode.

(Appendix 3)
The electrochromic display device according to appendix 1 or appendix 2, wherein the olefin-based resin having a polar group includes at least one of a silane coupling agent and a titanium coupling agent.

(Appendix 4)
The adhesion surface of the inner peripheral portion of the opposing working electrode side substrate and the counter electrode side substrate to which the seal wall is bonded and / or the bonding surface of the wiring portion are at least of a silane coupling agent and a titanium coupling agent. The electrochromic display device according to any one of appendices 1 to 3, wherein the electrochromic display device is processed by either one of them.

(Appendix 5)
The electro according to any one of appendices 1 to 4, wherein the olefin-based resin having a polar group has at least one group selected from the group consisting of a carboxy group, an amino group, an isocyanate group, a glycidyl group, and a mercapto group. Chromic display device.

(Appendix 6)
The said silane coupling agent or the said titanium coupling agent has any one group selected from the group which consists of a carboxy group, an amino group, an isocyanate group, a glycidyl group, and a mercapto group in any one of additional remarks 1-5. Electrochromic display device.

(Appendix 7)
Any one of appendices 1-6, wherein the opposing working electrode side substrate and the counter electrode side substrate are each independently a substrate made of a material selected from the group consisting of glass, a thermoplastic polyester resin, and a cycloolefin resin. A display device according to any one of the above.

(Appendix 8)
The working electrode side substrate provided with the transparent working electrode and the counter electrode side substrate provided with the counter electrode are made to face each other so that the transparent working electrode and the counter electrode face each other. A coloring composition capable of repeatedly performing decoloring and decoloring, and a display composition comprising an aprotic polar solvent, and the chromogenic substance is energized between the transparent working electrode and the counter electrode. In the manufacturing method of the electrochromic display device that displays by coloring or decoloring,
The display composition is sealed by a seal wall made of a composition containing an olefin-based resin having a polar group, which is adhered to the inner periphery of the opposing working electrode side substrate and the counter electrode side substrate. Manufacturing method of display device.

(Appendix 9)
9. The method of manufacturing an electrochromic display device according to appendix 8, wherein the seal wall is adhered to a wiring portion to at least one of the transparent working electrode and the counter electrode.

(Appendix 10)
The method for producing an electrochromic display device according to appendix 8 or appendix 9, wherein the composition containing the olefinic resin having a polar group contains at least one of a silane coupling agent and a titanium coupling agent. .

(Appendix 11)
The adhesion surface of the inner peripheral portion of the opposing working electrode side substrate and the counter electrode side substrate to which the seal wall is bonded and / or the bonding surface of the wiring portion are both at least of a silane coupling agent and a titanium coupling agent. The method for manufacturing an electrochromic display device according to any one of appendices 8 to 10, which is processed either.

(Appendix 12)
The electro according to any one of appendices 8 to 11, wherein the olefin-based resin having a polar group has at least one group selected from the group consisting of a carboxy group, an amino group, an isocyanate group, a glycidyl group, and a mercapto group. Method for manufacturing chromic display device.

(Appendix 13)
The supplementary note 8 to 12, wherein the silane coupling agent or the titanium coupling agent has at least one group selected from the group consisting of a carboxy group, an amino group, an isocyanate group, a glycidyl group, and a mercapto group. Manufacturing method of electrochromic display device.

(Appendix 14)
Supplementary notes 8 to 13, wherein the opposing working electrode side substrate and the counter electrode side substrate are each independently a substrate made of a material selected from the group consisting of glass, a thermoplastic polyester resin, and a cycloolefin resin. Manufacturing method of electrochromic display device.

1 is a schematic cross-sectional view of a display panel of an electrochromic display device according to the present invention. It is a perspective exploded view which shows the structure of a display cell.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Display panel 2 Transparent working electrode 3 Working electrode side board | substrate 4 Counter electrode 5 Counter electrode side board | substrate 6 Display composition 7 Seal wall 8 Wiring part

Claims (5)

The working electrode side substrate provided with the transparent working electrode and the counter electrode side substrate provided with the counter electrode are made to face each other so that the transparent working electrode and the counter electrode face each other. A coloring composition capable of repeatedly performing decoloring and decoloring, and a display composition comprising an aprotic polar solvent, and the chromogenic substance is energized between the transparent working electrode and the counter electrode. In an electrochromic display device that displays by developing or decoloring,
The display composition is sealed by a seal wall made of a composition containing an olefin-based resin having a polar group, which is bonded to the inner peripheral portion of the opposing working electrode side substrate and the counter electrode side substrate. Electrochromic display device.   The electrochromic display device according to claim 1, wherein the seal wall is adhered to a wiring portion to at least one of the transparent working electrode and the counter electrode.   The electrochromic display device according to claim 1, wherein the olefin resin having a polar group includes at least one of a silane coupling agent and a titanium coupling agent.   The adhesion surface of the inner peripheral portion of the opposing working electrode side substrate and the counter electrode side substrate to which the seal wall is bonded and / or the bonding surface of the wiring portion are at least of a silane coupling agent and a titanium coupling agent. The electrochromic display device according to claim 1, wherein the electrochromic display device is processed by any one of the above. The working electrode side substrate provided with the transparent working electrode and the counter electrode side substrate provided with the counter electrode are made to face each other so that the transparent working electrode and the counter electrode face each other. A coloring composition capable of repeatedly performing decoloring and decoloring, and a display composition comprising an aprotic polar solvent, and the chromogenic substance is energized between the transparent working electrode and the counter electrode. In the manufacturing method of the electrochromic display device that displays by coloring or decoloring,
The display composition is sealed by a seal wall made of a composition containing an olefin-based resin having a polar group, which is adhered to the inner periphery of the opposing working electrode side substrate and the counter electrode side substrate. Manufacturing method of display device.

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