JP5501587B2 - Electrochromic display device - Google Patents

Description

  The present invention relates to an electrochromic display device.

  With the spread of electronic information networks, publishing in the form of electronic books, that is, electronic publishing, has been actively performed in place of books by conventional printing technology. For example, a CRT (Cathode Ray Tube) display or a backlight type liquid crystal display is used as a device for displaying electronic information distributed through such a network. However, the display using these displays has a limited reading place and is inferior in terms of handling, weight, size, shape, and portability as compared with a conventional display printed on paper. In addition, since these displays consume a large amount of power, the display time is limited if driven by a battery. Further, these displays are all light-emitting displays, and there is a problem that high-level fatigue may be caused when staring for a long time.

  Therefore, a display device that can solve the above-described problems and a rewritable display device are desired. As such a display device, a so-called paper-like display or electronic paper has been proposed. Specifically, for example, a reflective liquid crystal display device, an electrophoretic display device, a display device that rotates dichroic particles with an electric field, an electrochromic display device (for example, Patent Documents 1 to 3) 3)) have been proposed so far.

  By the way, in an electrochromic display device (electrochromic display device), for example, an electrochromic composition containing, as an essential component, a dye that develops color on the surface of an electrode is used as a display material. Then, for example, (1) display by energization → (2) maintain the display by continuously energizing an energization amount smaller than the energization amount for display → (3) go through the process of erasing the display by interrupting energization The display operation is carried out. In the steps (1) and (2), desired display is quantitatively controlled by the energization amount. On the other hand, in the step (3), the image is erased by being left unattended, resulting in variations in the erase time and variations in the erase operation depending on the state of display coloration. There is a problem that an image remains and it takes time to completely erase the image.

As a method for solving this problem, for example, a method of performing erasing by energizing in the direction opposite to the energization for display can be considered (for example, see Patent Document 4).
JP 2006-119344 A JP 58-037872 A JP 05-098251 A JP-A-57-11323

  However, in the method of Patent Document 4, if the energization amount for energization for erasing is not strictly controlled, the dye moves to the electrode opposite to the display electrode to form a color display, and as a result, the display is There is a problem that it may not be erased.

  An object of the present invention is to provide an electrochromic display device capable of reliably erasing a display without strict control of the energization amount when erasing the display by energizing in a direction opposite to energization for display Is to provide.

In order to solve the above-mentioned problem, the invention described in claim 1
A first substrate; a first electrode provided on an upper surface of the first substrate; a second substrate provided above the first substrate so as to face the first substrate and formed of a transparent material; A second electrode provided on the lower surface of the second substrate, at least part of which is formed of a transparent electrode material, and an electrochromic composition layer provided between the first substrate and the second substrate; And performing display by energization between the first electrode and the second electrode, and by energization in a direction opposite to the energization for the display between the first electrode and the second electrode. In an electrochromic display device that erases the display,
The electrochromic composition layer comprises an electrochromic composition comprising a supporting electrolyte, a polar solvent, and an electron donating dye precursor,
The electrochromic composition does not adsorb the electron donating dye precursor when energized for display, but adsorbs the electron donating dye precursor when energized for erasing. It is characterized by adding aluminum oxide.

The invention described in claim 2
A first substrate; a first electrode provided on an upper surface of the first substrate; a second substrate provided above the first substrate so as to face the first substrate and formed of a transparent material; A second electrode provided on the lower surface of the second substrate, at least part of which is formed of a transparent electrode material, and an electrochromic composition layer provided between the first substrate and the second substrate; And performing display by energization between the first electrode and the second electrode, and by energization in a direction opposite to the energization for the display between the first electrode and the second electrode. In an electrochromic display device that erases the display,
The electrochromic composition layer comprises an electrochromic composition comprising a supporting electrolyte, a polar solvent, and an electron donating dye precursor,
The electron donating dye precursor is not adsorbed between the first electrode and the electrochromic composition layer when energizing for the display, but the electron donating dye precursor is not energized when energizing for the erasing. An adsorption layer containing adsorbed aluminum oxide and / or aluminum hydroxide is provided.

（式中Ｒ１、Ｒ２、Ｒ３、Ｒ４は、水素原子、アルキル基、アリル基、アルコキシ基、水酸基、ニトロ基、アルキルカルボニル基、ホルミル基、カルボキシル基又はアルコキシカルボニル基を表す。或いは、式中Ｒ１とＲ２及び／又は式中Ｒ３とＲ４は、互いに縮合して形成された５員又は６員の縮合環を表す。ただし、式中Ｒ１、Ｒ２、Ｒ３、Ｒ４のすべてが水素原子であることは無い。）

（式中Ｒ５、Ｒ６、Ｒ７、Ｒ８は、水素原子、アルキル基、アルコキシ基、アリル基、水酸基、ニトロ基、アルキルカルボニル基、ホルミル基、カルボキシル基又はアルコキシカルボニル基を表す。或いは、式中Ｒ５とＲ６、式中Ｒ６とＲ７及び／又は式中Ｒ７とＲ８は、互いに縮合して形成された５員又は６員の縮合環を表す。ただし、式中Ｒ５、Ｒ６、Ｒ７、Ｒ８のすべてが水素原子であることは無い。）

（式中Ｒ９、Ｒ１０、Ｒ１１、Ｒ１２は、水素原子を表す。或いは、式中Ｒ９とＲ１０又は式中Ｒ１１とＲ１２は、互いに結合して形成された二重結合を表す。）

（式中Ｚ及び点線は、環を形成している状態を表し、当該環が脂肪族の環の場合は、置換若しくは無置換のシクロヘキシル基を表し、当該環が芳香族の環の場合は、置換若しくは無置換のフェニル基又は置換若しくは無置換のナフチル基を表す。） The invention according to claim 3
The electrochromic display device according to claim 1 or 2,
The electrochromic composition includes a compound represented by the following general formula (1) and / or a compound represented by the following general formula (2) and a compound represented by the following general formula (3) and / or A compound represented by the following general formula (4) is added.

(Wherein R1, R2, R3 and R4 represent a hydrogen atom, an alkyl group, an allyl group, an alkoxy group, a hydroxyl group, a nitro group, an alkylcarbonyl group, a formyl group, a carboxyl group or an alkoxycarbonyl group. And R2 and / or R3 and R4 in the formula represent a 5-membered or 6-membered condensed ring formed by condensation with each other, provided that all of R1, R2, R3 and R4 are hydrogen atoms. No.)

(Wherein R5, R6, R7 and R8 represent a hydrogen atom, an alkyl group, an alkoxy group, an allyl group, a hydroxyl group, a nitro group, an alkylcarbonyl group, a formyl group, a carboxyl group or an alkoxycarbonyl group. And R6, wherein R6 and R7 and / or R7 and R8 are condensed with each other and represent a 5-membered or 6-membered condensed ring, provided that all of R5, R6, R7 and R8 are It is never a hydrogen atom.)

(Wherein R9, R10, R11 and R12 represent a hydrogen atom. Alternatively, R9 and R10 or R11 and R12 in the formula represent a double bond formed by bonding to each other.)

(In the formula, Z and a dotted line represent a state in which a ring is formed. When the ring is an aliphatic ring, it represents a substituted or unsubstituted cyclohexyl group, and when the ring is an aromatic ring, Represents a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group.)

The invention according to claim 4
In the electrochromic display device according to any one of claims 1 to 3,
The electron donating dye precursor is a leuco dye,
A hindered phenol is added to the electrochromic composition.

The invention described in claim 5
In the electrochromic display device according to any one of claims 1 to 4,
The polar solvent is at least one organic solvent that exhibits electrical conductivity using the supporting electrolyte.

（式中Ｍ_２は、Ｌｉ、Ｎａ、Ｋ、Ｒｂ、Ｃｓ又はＮＨ_４を表す。式中Ｘ_１は、ＣｌＯ_４、ＢＦ_４、ＣＦ_３ＳＯ_３又はＰＦ_６を表す。）

（式中Ｒ１３は、アルキル基又はアリール基を表す。式中Ｒ１４は、アルキル基を表す。式中Ｎは、窒素原子を表す。式中Ｘ_２は、Ｃｌ、Ｂｒ、Ｉ、ＣｌＯ_４、ＢＦ_４、ＣＦ_３ＳＯ_３又はＰＦ_６を表す。式中ｎは、０、１又は２を表し、式中ｍは、４−ｎを表す。） The invention described in claim 6
In the electrochromic display device according to any one of claims 1 to 5,
The supporting electrolyte is a compound represented by the following general formula (5) and / or a compound represented by the following general formula (6).

(In the formula, M ₂ represents Li, Na, K, Rb, Cs, or NH _{4. In the} formula, X ₁ represents ClO ₄ , BF ₄ , CF ₃ SO _3, or PF _6. )

(In the formula, R13 represents an alkyl group or an aryl group. In the formula, R14 represents an alkyl group. In the formula, N represents a nitrogen atom. In the formula, X ₂ represents Cl, Br, I, ClO ₄ , BF. ₄ represents CF ₃ SO ₃ or PF _{6. In the} formula, n represents 0, 1 or 2, and m represents 4-n.

The invention described in claim 7
In the electrochromic display device according to any one of claims 1 to 6,
A polymer compound is added to the electrochromic composition.

The invention according to claim 8 provides:
In the electrochromic display device according to any one of claims 1 to 7,
The first electrode is a plurality of electrodes extending in parallel,
The second electrode is a transparent display electrode composed of a plurality of transparent electrodes extending in parallel in a direction orthogonal to the first electrode,
A pixel is formed in a region where the first electrode and the second electrode intersect three-dimensionally.

The invention according to claim 9 is:
In the electrochromic display device according to any one of claims 1 to 7,
The first electrode is a plurality of electrodes extending in parallel,
The second electrode is composed of a transparent display electrode part and a line electrode part connected to the transparent display electrode part, and is a plurality of electrodes extending in parallel in a direction orthogonal to the first electrode. ,
A pixel is formed in a region where the first electrode and the transparent display electrode portion of the second electrode intersect three-dimensionally.

The invention according to claim 10 is:
In the electrochromic display device according to any one of claims 1 to 9,
The first electrode is a metal electrode.

The invention according to claim 11
In the electrochromic display device according to any one of claims 1 to 9,
The first electrode is a transparent electrode.

The invention according to claim 12
In the electrochromic display device according to any one of claims 1 to 7,
The first electrode is composed of a transparent display electrode part and a line electrode part connected to the transparent display electrode part, and is a plurality of electrodes extending in parallel.
The second electrode is composed of a transparent display electrode part and a line electrode part connected to the transparent display electrode part, and is a plurality of electrodes extending in parallel in a direction orthogonal to the first electrode. ,
A pixel is formed in a region where the transparent display electrode portion of the first electrode and the transparent display electrode portion of the second electrode cross each other in a three-dimensional manner.

The invention according to claim 13
In the electrochromic display device according to any one of claims 1 to 12,
The electrochromic composition layer includes a porous body having pores penetrating in a direction substantially perpendicular to the first substrate and the second substrate,
The electrochromic composition is introduced into pores of the porous body.

The invention according to claim 14
The electrochromic display device according to any one of claims 1 to 13,
The display is driven by passive matrix driving.

According to the present invention, the first substrate, the first electrode provided on the upper surface of the first substrate, the first electrode provided above the first substrate so as to face the first substrate, and formed of a transparent material. Two substrates, a second electrode provided on the lower surface of the second substrate, at least partially formed of a transparent electrode material, and an electrochromic composition layer provided between the first substrate and the second substrate, The display is performed by energization between the first electrode and the second electrode, and the display is energized in the direction opposite to the energization for the display between the first electrode and the second electrode. In an electrochromic display device that performs erasing, the electrochromic composition layer includes an electrochromic composition that includes a supporting electrolyte, a polar solvent, and an electron-donating dye precursor. Aluminum oxide and / or aluminum hydroxide to adsorb the dye is added during the energization for.
That is, during energization for erasing, since the dye is adsorbed to aluminum oxide and / or aluminum hydroxide, it is possible to prevent the dye from moving to the electrode opposite to the display electrode and forming a color display. Can do. Therefore, when the display is erased by energizing in the direction opposite to the energization for display, the display can be surely erased without strictly controlling the energization amount.

In addition, according to the present invention, the first substrate, the first electrode provided on the upper surface of the first substrate, and the first substrate provided above the first substrate so as to face the first substrate are formed of a transparent material. The second substrate, the second electrode provided on the lower surface of the second substrate, at least partially formed of a transparent electrode material, and the electrochromic composition provided between the first substrate and the second substrate A layer, and performing display by energization between the first electrode and the second electrode, and performing energization in a direction opposite to the energization for the display between the first electrode and the second electrode. In an electrochromic display device for performing display erasure, an electrochromic composition layer includes an electrochromic composition including a supporting electrolyte, a polar solvent, and an electron-donating dye precursor, and includes a first electrode and an electrochromic composition. Mi Between the composition layer, and a suction layer containing aluminum oxide and / or aluminum hydroxide to adsorb the electron-donating dye precursor when energized for erasure.
That is, during energization for erasing, since the dye is adsorbed to aluminum oxide and / or aluminum hydroxide, it is possible to prevent the dye from moving to the electrode opposite to the display electrode and forming a color display. Can do. Therefore, when the display is erased by energizing in the direction opposite to the energization for display, the display can be surely erased without strictly controlling the energization amount.

  Hereinafter, the best mode of an electrochromic display device according to the present invention will be described in detail with reference to the drawings. The scope of the invention is not limited to the illustrated example.

[First Embodiment]
First, the electrochromic display device 100 according to the first embodiment will be described.

<Configuration of electrochromic display device>
FIG. 1A is a plan view schematically showing an electrochromic display device 100 according to the first embodiment, and FIG.
The electrochromic display device 100 according to the first embodiment includes, for example, a first substrate 10, first electrodes 20 provided on the upper surface of the first substrate 10, and the first substrate 10 above the first substrate 10. The electrochromic composition provided between the first substrate 10 and the second substrate 20, the second electrode 30 provided on the lower surface of the second substrate 30, the second electrode 40. And a layer 50.
The electrochromic display device 100 performs display by energization between the first electrodes 20 and the second electrodes 40, and for the display between the first electrodes 20 and the second electrodes 40. The display is erased by energization in the opposite direction to energization.
The first electrodes 20 are, for example, a plurality of electrodes extending in parallel. The second electrodes 40 are, for example, transparent display electrodes made of a plurality of transparent electrodes extending in parallel with the direction orthogonal to the first electrodes 20. Pixels 60 are formed in a region where the first electrodes 20 and the second electrodes 40 intersect three-dimensionally.

  The first substrate 10 is formed in a planar shape, for example, and has a function as a base of the electrochromic display device 100.

  The material of the first substrate 10 is not particularly limited as long as it is electrically insulating, and for example, glass or plastic can be used. Examples of the glass include soda lime glass, low alkali / borosilicate glass, alkali-free / borosilicate glass, alkali-free / aminosilicate glass, and quartz glass. Examples of the plastic include polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyamides, polycarbonates, fluoropolymers such as polyvinylidene fluoride, polyethers, polyolefins such as polystyrene and polyethylene, and polyimides. Can be mentioned.

  The first substrate 10 preferably appears white. Therefore, when the material of the first substrate 10 is glass or plastic, for example, the first substrate 10 that looks white can be formed by blending a white pigment such as titanium dioxide, barium sulfate, or kaolin. Moreover, the 1st board | substrate 10 which looks white can be formed by apply | coating the said white pigment on the lower surface of a transparent substrate, or arrange | positioning white sheets, such as white paper and a white PET sheet.

The first electrodes 20 are formed, for example, in a line shape having a width, and are provided in stripes at equal intervals parallel to each other.
The first electrodes 20 are provided on the upper surface of the first substrate 10 so as to be in contact with the electrochromic composition layer 50 and to sandwich the electrochromic composition layer 50 facing the second electrodes 40. Yes.
The first electrodes 20 are paired with the second electrodes 40 and have a function of energizing the electrochromic composition layer 50.
The first electrodes 20 ... intersect with the second electrodes 40 ... three-dimensionally, that is, with an interval, and form a pixel 60 in the area of the intersection.

  The material of the first electrodes 20 is not particularly limited, and a material constituting a metal electrode or a material constituting a transparent electrode can be used. Examples of the material constituting the metal electrode include gold, platinum, silver, chromium, aluminum, cobalt, palladium, copper, nickel, and alloys thereof. Moreover, as a material which comprises a transparent electrode, ITO, ZnO, FTO etc. are mentioned, for example.

  The second substrate 30 is, for example, a transparent substrate formed in a planar shape, and has a function as a support for the second electrodes 40.

  The material of the second substrate 30 is not particularly limited as long as it is an electrically insulating transparent substrate. For example, glass or plastic can be used. Examples of the glass include soda lime glass, low alkali / borosilicate glass, alkali-free / borosilicate glass, alkali-free / aminosilicate glass, and quartz glass. Examples of the plastic include polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyamides, polycarbonates, fluoropolymers such as polyvinylidene fluoride, polyethers, polyolefins such as polystyrene and polyethylene, and polyimides. Can be mentioned.

The second electrodes 40 are transparent electrodes formed in a line shape having a width, for example, and are provided in stripes at equal intervals parallel to each other.
The second electrodes 40 are provided on the lower surface of the second substrate 30 so as to be in contact with the electrochromic composition layer 50 and to sandwich the electrochromic composition layer 50 facing the first electrodes 20. Yes.
The second electrodes 40 are paired with the first electrodes 20 and have a function of energizing the electrochromic composition layer 50.
The second electrodes 40 ... are three-dimensionally intersected with the first electrodes 20 ..., i.e. with a gap, and form a pixel 60 in the region of the intersection.

The material of the second electrodes 40 is not particularly limited as long as it is a material capable of forming a transparent electrode. Examples of the material capable of forming the transparent electrode include an ITO film and a thin film coated with SnO ₂ or InO ₂ . Further, an ITO film, a thin film coated with SnO ₂ or InO ₂ , or the like may be doped with Sn, Sb, or the like, or may be MgO, ZnO, FTO, or the like. Further, the second electrodes 40 can fulfill their functions as long as they are thin films, even if the material is gold, platinum or the like.

  The electrochromic composition layer 50 includes, for example, a porous body 51 having pores 51a penetrating in a substantially vertical direction with respect to the first substrate 10 and the second substrate 30, and inside the pores 51a of the porous body 51. And the electrochromic composition 52 introduced in FIG.

  The porous body 51 has a role of holding the electrochromic composition 52 in a certain volume between the first substrate 10 and the second substrate 30. That is, the porous body 51 includes the electrochromic composition 52 so that the electrochromic composition 52 is supported between the first substrate 10 and the second substrate 30, and the electrochromic composition 52 depends on the thickness of the porous body 51. It serves as a spacer for uniformly controlling the amount of the composition 52.

  The thickness of the porous body 51 is not particularly limited, but the display function of the electrochromic composition 52 can be effectively expressed by setting the thickness to preferably 10 μm to 500 μm, more preferably 30 μm to 200 μm. Can do.

The size of the pores 51a of the porous body 51 is not particularly limited, but is preferably smaller than the size of the pixel 60, for example, as shown in FIG. That is, for example, as shown in FIG. 2, when the shape of the pore 51a is circular and the shape of the image 60 (shown by a one-dot broken line in FIG. 2) is a square, the pores of the porous body 51 The diameter (hole diameter) of 51a is preferably smaller than the width of the pixel 60 (that is, the width of the first electrode 20 or the width of the second electrode 40).
Of course, the shape of the pore 51a is not limited to a circle, and may be a polygon such as a rectangle. The shape of the pixel 60 is not limited to a square, and may be another polygon or a circle.

  For example, when the size of the pore 51a of the porous body 51 is large (specifically, for example, when the pore diameter is 1/5 or more of the width of the pixel 60), or for example, the pore of the porous body 51 When the distance between 51a and 51a is short (specifically, for example, when the aperture ratio is 50% or more), the display image by the electrochromic display device 100 is an image having a high density and a high contrast. Become. On the other hand, when the size of the pore 51a of the porous body 51 is small (specifically, for example, when the pore diameter is 1/50 or less of the width of the pixel 60), or, for example, the pore of the porous body 51 When the distance between 51a and 51a is long (specifically, for example, when the hole area ratio is 20% or less), the display image by the electrochromic display device 100 has high resolving power and excellent sharpness. Clear image.

  The material of the porous body 51 is not particularly limited as long as it can have the thickness and shape described above, and any of inorganic materials and organic materials can be used.

Preferred materials include, for example, alumina (particularly anodized alumina) as an electrically insulating inorganic material, silica, zirconium oxide, SiC, glass, etc., an electrically insulating organic material, and a Teflon (US) as a polymer substance. DuPont registered trademark), nylon, polyester, polyimide, polycarbonate, etc., _{TiO 2,} SrTiO _{3, ZnO} as a metal oxide material comprising a _{semiconductor, SnO 2, InSnO X, Nb} 2 O 3, WO 3, CuO, CoO 2 , MnO ₂ , V ₂ O _5, etc., compound chalcogenides including compound semiconductors, and compound semiconductors represented by CdS, ZnS, GaP, GaAs, InP, FeS ₂ , PbS, CuInS ₂ , CuInSe, etc. Gold, such as a compound having a structure or a composite compound Examples of metal and metalloid materials include gold, platinum, silver, copper, chromium, zinc, tin, titanium, tungsten, aluminum, nickel, iron, silicon, and germanium, and carbon materials such as graphite, glassy carbon, and diamond. However, the present invention is not limited to this.

The porous body 51 may be composed of a single material or may be composed of a plurality of materials. In the case of being composed of a plurality of materials, the material may be varied for each part such as the wall part and other parts of the pores 51a, and the upper and lower parts of the pores 51a.
The material constituting at least a part of the pores 51a of the porous body 51 (walls of the pores 51a of the porous body 51) is preferably an insulator material or a semiconductor material. Specifically, metal chalcogenides (for example, oxides, sulfides, selenides, etc.) and silicon are preferable, metal oxides are more preferable, aluminum, alumina, predetermined fibers (for example, Teflon, nylon (DuPont, USA) And the like are most preferred.

  The production method of the porous body 51 is not particularly limited as long as it can have the above-described thickness and shape.

As an example of a preferable production method, for example, a method of producing a product while controlling the pore pitch over a large area for mass production, specifically, for example, self-organization involving diffusion and transport of ions and molecules in a chemical reaction. The method of creating the porous body 51 by controlling the conversion reaction is mentioned. As a method for producing the porous body 51 (porous nanostructure, porous film) having a regular pore arrangement by this self-assembly, the following known techniques can be applied.
Known techniques include, for example, (1) anodized alumina prepared by anodic electrolytic oxidation (for example, Science, 268, 1466 (1995)), and (2) plasma with a porous alumina film placed on a diamond film as a template. Diamond porous nanostructures (for example, Advanced Materials, 12,444 (2000)) created by etching and then melting the porous alumina film by soft etching (for example, soft etching with phosphoric acid), (3) Metal porous structure produced by transfer (for example, JP-A-6-200378), (4) An aluminum silicon mixed film is formed on a substrate by a sputtering method, and an aluminum region (including aluminum) in the mixed film is formed. Only the columnar structure region) is selectively etched (as an etching method, aluminum A porous silicon film prepared by wet etching using an acid or an alkali that selectively dissolves only (for example, JP-A-8-186245), (5) produced by self-organization. Using anodized alumina, the uneven structure of the pores is once transferred to a polymer such as polymethyl methacrylate, and then formed by forming an inorganic metal oxide layer on the transfer body by a sol-gel reaction or the like Porous nanostructures made of materials (for example, JP-A-6-32675), (6) Using a block copolymer, a microphase-separated structure oriented perpendicular to the membrane direction at intervals of several tens of nanometers A micro phase separation structure membrane is formed by forming, for example, a porous membrane created by dissolving a cylinder portion (for example, JP-A-2004-12) 4088, JP-A-2005-314526), (7) Porous film created by forming pores in polymer, metal, plastic, etc. by selective etching, or created porous film Is used as a template, and a porous film formed by transferring to another polymer, metal, plastic, etc., is not limited thereto.

  Moreover, as an example of a preferable production method, for example, a method of producing the porous body 51 appropriately formed in a lattice shape or the like using a screen printing method or a photolithography method can be given.

In the case of the screen printing method, the distance between the pores 51a and 51a is limited (approximately 30 μm or more) and the porosity is limited, but the porous body 51 having the above-described thickness and shape is created. can do.
As a preferable material, since the electrochromic composition 52 includes a polar solvent as a constituent component, the electrochromic composition 52 preferably has resistance to the polar solvent, such as glass paste and thermosetting resin resistant to polar solvent. Can be used. Examples of the glass paste include AP dielectric paste AP5346G and AP5695BD manufactured by Asahi Glass Co., Ltd., glass paste PLS-3124 manufactured by Nippon Electric Glass Co., Ltd., and powder glass LS-0241 manufactured by Nippon Electric Glass Co., Ltd. It is not limited. Examples of the thermosetting resin having polar solvent resistance include one-part epoxy resins (specifically, for example, 2217, 2217B, 2219D, etc. in the ThreeBond 2200 series manufactured by ThreeBond Co., Ltd.). However, the present invention is not limited to this.

In the case of photolithography, the porous body 51 having a fine structure can be created.
As described above, a material having resistance to a polar solvent is preferable as described above. Specifically, for example, Tokyo Ohka Kogyo Co., Ltd. can obtain a porous body 51 having a high aspect ratio by a single exposure. Examples thereof include, but are not limited to, a permanent resist TMMRS-2000 for MEMS.

The porous body 51 may be a commercially available product as long as it has the thickness and shape described above. As the commercially available porous body 51, for example, a membrane filter made of aluminum oxide (thickness: 60 μm, pore diameter: 0.2 μm, 0.1 μm, 0.02 μm) available as an Annodisc membrane filter manufactured by Whatman, Homme manufactured by Millipore Two-pore membrane (thickness: 80 μm, 100 μm, pore diameter: 0.1 μm, 0.2 μm, 0.45 μm, 1.0 μm, 5 μm, 10 μm), nylon net filter manufactured by Millipore (thickness: 55 μm, mesh opening (thread and thread) The size of the gap between the pores: 11 μm, 20 μm, 41 μm, 60 μm, 80 μm), Millipore isopore membrane (thickness: 10 μm, pore diameter: 0.05 μm, 0.1 μm, 0.22 μm, 0.4 μm, 0.6, 0.8, 1.2, 2, 3, 5, 5, 8, 10, and 12), Nitto Denko Corporation Ultra high molecular weight polyethylene porous film sunmap (thickness: 100 μm, 200 μm, pore size: 17 μm), NYTAL (nylon mesh cloth) NY-20HC (thickness 55 μm, opening: 20 μm), 21T-53 (thickness) manufactured by Sefar Inc. 100 μm, aperture: 53 μm), ASTM 270-53 (thickness 60 μm, aperture: 53 μm), NY5-HC (thickness 100 μm, aperture: 5 μm), NY1-HD (thickness 75 μm, aperture: 1 μm), Sefa Inc. PETEX (
Polyester mesh cloth) PET51HC (thickness 60 μm, opening: 51 μm), PET24 (thickness 70 μm, opening: 24 μm), PET11HC (thickness 60 μm, opening: 11 μm), and the like, but are not limited thereto. .

The electrochromic composition 52 includes a supporting electrolyte, a polar solvent, and a leuco dye 52a as an electron donating dye precursor.
The electrochromic composition 52 is added with an adsorbent 53 that adsorbs the leuco dye 52a when energized for erasing between the first electrode 20... And the second electrode 40.
Examples of the component that can be added to the electrochromic composition 52 include, for example, a compound for suppressing deterioration in display quality of the electrochromic display device 100 (a compound represented by the above formula (1) and / or a compound represented by the above formula (1)). Or the compound represented by the above formula (2) and the compound represented by the above formula (3) and / or the compound represented by the above formula (4)) and the physical properties of the electrochromic composition 52 (for example, And polymer compounds for adjusting the thickening, hindered phenols for promoting the color development of the leuco dye 52a, and the like.

The electrochromic composition 52 has a function of coloring and decoloring related to the display of the electrochromic display device 100.
Specifically, the electrochromic composition 52 develops color by energization between the first electrode 20 ... and the second electrode 40 ..., or by energization in the direction opposite to the energization for color development or for color development. The color is erased by shutting off the power supply.
The electrochromic composition 52 only needs to have fluidity, and may be, for example, a low-viscosity liquid, a high-viscosity paste, or a gel with a low fluidity. good.

The leuco dye 52a, which is a constituent component of the electrochromic composition 52, is a colorless or light-colored electron-donating dye precursor, and is a compound that develops color with a developer such as a phenolic compound, an acidic substance, or an electron-accepting substance. .
Examples of the leuco dye 52a include compounds that have a lactone, lactam, sultone, spiropyran, ester, or amide structure in the partial skeleton and can be practically colorless. Specific examples include triallylmethane compounds, bisphenylmethane compounds, xanthene compounds, fluorane compounds, thiazine compounds, and spiropyran compounds, but are not limited thereto.

  The leuco dye 52a can perform various colors by appropriately selecting from the above compounds. Therefore, the display color of the electrochromic display device 100 using the leuco dye 52a can be appropriately selected depending on the leuco dye 52a. Specifically, for example, when the leuco dye 52a that develops black is used, black and white and gray display are possible.

Since the blending amount of the leuco dye 52a depends on the solubility of the leuco dye 52a, it is difficult to express it generally. However, the leuco dye 52a needs to be blended in a sufficient amount for color development. In the case of the leuco dye 52a having a low solubility, the leuco dye is increased, for example, by increasing the volume of the electrochromic composition layer 50 (porous body 51) corresponding to each pixel 60 so that the necessary amount is included. The blending amount of 52a may be adjusted.
For example, if the leuco dye 52a is a compound represented by the following formula (17), a compound represented by the following formula (18), and a compound represented by the following formula (20), the blending amount is electro It can be 3 to 40 weight% with respect to the chromic composition 52 whole.

  Although the example of the leuco dye 52a is classified and shown below according to the color development, these are illustrations and do not limit the leuco dye 52a.

The following formulas (7) and (8) are leuco dyes 52a that develop yellow.

The following formulas (9) to (11) are leuco dyes 52a that develop magenta.

The following formulas (12) to (15) are leuco dyes 52a that develop cyan.

The following formulas (16) and (17) are leuco dyes 52a that develop red.

The following formula (18) is a leuco dye 52a that develops blue color.

The following formulas (19) and (20) are leuco dyes 52a that develop black.

The supporting electrolyte which is a constituent component of the electrochromic composition 52 has a function for facilitating the flow of current through the electrochromic composition 52. The supporting electrolyte contains a compound generally called a molten salt. As the supporting electrolyte, each compound may be used alone, or a plurality thereof may be mixed and used.
The supporting electrolyte is preferably added in an amount of 0.01 to 20% by weight with respect to the total weight of the electrochromic composition 52, and 0.1 to 20% by weight for sufficient expression of the function. It is more preferable to add so that it may become%.

  Specifically, the supporting electrolyte is not particularly limited as long as it is a compound having the above function. For example, the compound represented by the above formula (5) and / or the above formula (6) ).

Examples of the compound represented by the above formula (5) and the compound represented by the above formula (6) are shown below, but these are examples and limit the supporting electrolyte. is not.
Specific examples of the compound having the general formula represented by the above formula (5) include, for example, NaClO ₄ , LiClO ₄ , KClO ₄ , RbClO ₄ , CsClO ₄ , NH ₄ ClO ₄ , LiBF ₄ , and LiPF _6. It is done.
Specific examples of compounds of the general formula expressed by formula (6), for _{example, (CH 3) 4 NClO 4} , (C 2 H 5) 4 NClO 4, (n-C 4 H 9) ₄ NClO ₄ , (CH ₃ ) ₄ NBF ₄ , (C ₂ H ₅ ) ₄ NBF ₄ , (n-C ₄ H ₉ ) ₄ NBF ₄ , (CH ₃ ) ₄ NCl, (C ₂ H ₅ ) ₄ NCl, (CH ₃ ) ₄ NBr, (C ₂ H ₅ ) ₄ NBr, (nC ₄ H ₉ ) ₄ NBr, (n-C ₄ H ₉ ) ₄ NI, C ₆ H ₅ (CH ₃ ) ₃ NClO ₄ , C ₆ H ₅ (C ₂ H ₅ ) ₃ NClO ₄ , C ₈ H ₁₇ (CH ₃ ) ₃ NClO ₄ , (C ₂ H ₅ ) ₄ NPF ₆ , (n-C ₄ H ₉ ) ₄ NPF ₆ , (CH _{3) 4} NCF ₃ SO _3, and _{(C 2 H 5) 4 NCF} 3 SO 3 It is below.

  The polar solvent, which is a constituent component of the electrochromic composition 52, is at least one organic solvent that exhibits electrical conductivity using a supporting electrolyte, and the leuco dye 52a is colored and decolored by blocking voltage and / or current. It has a function to promote energization so that The polar solvent also serves as a solvent for the polymer compound when the polymer compound is added to the electrochromic composition 52. Various polar solvents may be used alone, or two or more polar solvents may be appropriately used in combination.

Although the example of a suitable polar solvent is shown below, these are illustrations and do not limit a polar solvent.
Specific examples of the polar solvent include N-methylpyrrolidone, dimethylformamide, diethylformamide, N, N-dimethylacetamide, propylene carbonate, dimethyl sulfoxide, γ-butyrolactone, acetonitrile, propionitrile, butyronitrile and the like. It is done. Any of the exemplified polar solvents is preferable as the polar solvent used as a constituent of the electrochromic composition 52, and particularly preferable is N, N-dimethylacetamide.

The adsorbent 53 added to the electrochromic composition 52 is, for example, aluminum oxide and / or aluminum hydroxide.
The mode of addition of the adsorbent 53 (aluminum oxide and / or aluminum hydroxide) is not particularly limited, but it is added as a powder to the electrochromic composition 52 and is used as a homogenizer such as an ultrasonic wave, a ball mill, or a homomixer. Is preferably dispersed as a dispersion of the electrochromic composition 52 solution.

The amount of adsorbent 53 to be added varies depending on the activity and particle size of the aluminum oxide and / or aluminum hydroxide used.
Aluminum oxide having a small surface area such as α-alumina, large aluminum oxide having a particle size of 10 μm or more, aluminum hydroxide having a small surface area, and aluminum hydroxide having a particle size of 10 μm or more have a small adsorption effect on the leuco dye 52a. In order to develop a sufficient adsorption action, 0.5 gram to 5 grams, preferably 1 gram to 3 grams, is preferably added to 1 gram of leuco dye 52a.
In addition, aluminum oxide having a large surface area such as γ-alumina, small aluminum oxide having a particle size of 1 μm or less, aluminum hydroxide having a large surface area, and small aluminum oxide having a particle size of 1 μm or less have an effect of adsorbing the leuco dye 52a. Due to the large size, a sufficient adsorption action is exhibited by addition of 0.1 gram to 0.5 gram with respect to 1 gram of leuco dye 52a.
Further, activated aluminas used for thin layer chromatography and the like are added in an amount of 0.1 gram to 0.5 gram with respect to 1 gram of leuco dye 52a even if they are large particles having a particle size of several tens of micrometers. With this, sufficient adsorption operation is exhibited.

The adsorbent 53 (aluminum oxide and / or aluminum hydroxide) that adsorbs the leuco dye 52a can be easily obtained as a chemical product.
Although the example of the suitable commercially available adsorption agent 53 (aluminum oxide and / or aluminum hydroxide) is shown below, these are illustrations and do not limit adsorbent 53.
Specific examples of the commercially available adsorbent 53 include, for example, aluminum oxide 60GN neutral for thin layer chromatography (particle size: 4 μm to 50 μm) manufactured by Merck & Co., Ltd., Nippon Light Metal's low soda alumina LS235 (particle size: 0.47 μm), activated alumina C200 ( Particle diameter 4.4 μm), aluminum hydroxide B1403 (particle diameter 1.5 μm), and γ-alumina KC501 (particle diameter 1 μm) manufactured by Sumitomo Chemical.

Compound added to the electrochromic composition 52 (a compound represented by the above formula (1) and / or a compound represented by the above formula (2) and the above formula (3) The compound and / or the compound represented by the above formula (4) has a function of suppressing deterioration in display quality of the electrochromic display device 100 due to repeated operations of color development and decoloration of the leuco dye 52a. A compound.
The addition amount of these compounds is preferably 1 to 20% by weight with respect to the content of the leuco dye 52a, and 5 to 20% by weight for sufficient expression of the above functions. It is preferable to add so that it becomes.

  Although the example of these compounds is shown below, these are illustrations and do not limit these compounds.

The following formulas (21) to (35) are examples of compounds whose general formula is represented by the above formula (1).

The following formulas (36) to (51) are examples of compounds whose general formula is represented by the above formula (2).

The following formulas (52) and (53) are examples of compounds whose general formula is represented by the above formula (3).

The following formulas (54) to (56) are examples of compounds whose general formula is represented by the above (4).

The electrochromic composition 52 includes a compound represented by the above formula (1) and / or a compound represented by the above formula (2) and a compound represented by the above formula (3) and / or Alternatively, in place of the compound represented by the above formula (4), the compound represented by the following formula (57), the compound represented by the following formula (58) and / or the following formula (59): ) May be added.
The compound represented by the following formula (57) and the compound represented by the following formula (58) and / or the compound represented by the following formula (59) is a leuco dye 52a coloring and decoloring. It is a compound which has a function which suppresses the deterioration of the display quality of the electrochromic display device 100 accompanying the repetition operation | movement.

Here, M ₃ in the formula (57) is an element belonging to Group 15 of the periodic table and does not contain nitrogen. R15, R16 and R17 in the formula (57) are allyl groups having a substituent or allyl groups having no substituent, and may be the same or different from each other.
R18, R19, R20 and R21 in the formula (58) represent a group selected from a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group and an alkoxycarbonyl group. However, R18, R19, R20 and R21 are not all hydrogen atoms at the same time. Adjacent R18 and R19 may be condensed with each other to form a 5-membered or 6-membered condensed ring. Adjacent R20 and R21 may be condensed with each other to form a 5-membered or 6-membered condensed ring.
R22, R23, R24 and R25 in the formula (59) represent a group selected from a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group and an alkoxycarbonyl group. However, R22, R23, R24 and R25 are not all hydrogen atoms at the same time. One or both of adjacent R22 and R23 and adjacent R24 and R25 form a 5-membered or 6-membered condensed ring. When one of adjacent R22 and R23 and adjacent R24 and R25 forms a condensed ring, the other two groups are both hydrogen atoms.

The amount of the compound represented by the general formula (57) is preferably 1 to 50% by weight with respect to the content of the leuco dye 52a, and sufficient expression of the above functions is achieved. Therefore, it is more preferable to add so that it may become 10 to 50 weight%.
The amount of the compound represented by the above formula (58) and / or the compound represented by the above formula (59) is 1 to 20% by weight based on the content of the leuco dye 52a. It is preferable to use 5 to 20% by weight for sufficient expression of the above functions.

  Although the example of these compounds is shown below, these are illustrations and do not limit these compounds.

The following formulas (60) to (66) are examples of compounds in which the general formula is represented by the above formula (57).

The following formulas (67) to (72) are examples of compounds whose general formula is represented by the above formula (58).

The following formulas (73) to (77) are examples of compounds whose general formula is represented by the above formula (59).

The polymer compound added to the electrochromic composition 52 has a function of increasing the viscosity of the electrochromic composition 52 and facilitating the handling thereof. Various polymer compounds may be used alone, or two or more polymer compounds may be appropriately used in combination.
The polymer compound is used to increase the viscosity of the electrochromic composition 52. In this case, the properties of the electrochromic composition 52 include a low-viscosity liquid, a high-viscosity paste, and a low fluidity gel. can do.
It is preferable that the compounding quantity of a polymer compound shall be 0.1 to 80 weight% with respect to the weight of the electrochromic composition 52 whole.

Although the example of a suitable polymer compound is shown below, these are illustrations and do not limit a polymer compound.
Specific examples of the polymer compound include, for example, a polyalkylene oxide such as polyvinylidene fluoride, polyvinylidene chloride, and polyethylene oxide, or a polymer having a repeating unit of polyalkyleneimine and polyalkylene sulfide, polymethyl methacrylate, polyacrylonitrile, Polyvinyl formal, such as polycarbonate and polyvinyl butyral, may be mentioned. Particularly preferred are polyvinyl butyral and polyvinylidene fluoride.

  The hindered phenols added to the electrochromic composition 52 have a function of effectively promoting display color development. Various types of hindered phenols may be used alone, or two or more types may be used in combination as appropriate.

Although the example of suitable hindered phenols is shown below, these are illustrations and do not limit hindered phenols.
Specific examples of hindered phenols include, for example, 4-tert-butylphenol, 4-phenylphenol, 2,2′-dihydroxybiphenyl, 4,4′-sec-butylidene diphenol, bisphenol A, 4,4′- Cyclohexylidene diphenol, bis (3-allyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-3 ′, 4′-dimethylphenylsulfone, 4- (4′-isopropoxyphenylsulfonyl) phenol, 4,4 '-Dihydroxydiphenyl sulfide, 1,4-bis- (4'-hydroxycumyl) benzene, 1,3-bis- (4'-hydroxycumyl) benzene, 4,4'-thiobis (6-tert-butyl-3) -Methylphenol), 4,4'-dihydroxydiphenylsulfone, 2-te rt-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl), 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4- Methyl phenyl acrylate, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 2,2′-methylenebis (6-tert -Butyl-4-methylphenol), 4,4'-butylidenebis (6-tert-butyl-4-methylphenol), 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy ] -2,4,8,10-tetra-tert-butylbenz [d, f] [1,3,2] dioxaphospene.

Moreover, although the example of a suitable commercially available hindered phenol is shown below, these are illustrations and do not limit a hindered phenol.
Specific examples of commercially available hindered phenols (antioxidants) include, for example, Sumitizer GP, Sumitizer MDP, Smither WXR, Smither GA80 manufactured by Sumitomo Chemical Co., Ltd., Irganox 245, Irganox 1222, Irganox 1222, Irganox 10235, Irganox 10235 Irganox 1098 and the like can be mentioned.

  Any of the exemplified hindered phenols is preferable as the hindered phenol to be added to the electrochromic composition 52, and particularly preferable is 2,2′-methylenebis (6-tert-butyl-4- Methylphenol), 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butylbenz [d, f] [1,3 , 2] Dioxaphospene (Sumilyzer GP).

  The electrochromic composition 52 described above is only an example, and if the composition is capable of electrochemical color development, the electrochromic composition layer 50 is obtained by including this in the porous body 51. Can be used.

<Method of manufacturing electrochromic display device>
The manufacturing method of the electrochromic display device 100 includes the following steps [1] to [6].

[1] First Substrate Preparation Step The first substrate preparation step is a step of preparing the first substrate 10.

[2] First vapor deposition step The first vapor deposition step is a step of providing the first electrodes 20 on one surface of the first substrate 10. The first electrodes 20 are formed by a known vapor deposition method, plating method, sputtering method or the like, then patterned by a photolithography method, and then formed in a stripe shape by an etching method.

[3] Second substrate preparation step The second substrate preparation step is a step of preparing the second substrate 30.

[4] Second Deposition Step The second deposition step is a step of providing the second electrodes 40 on one surface of the second substrate 30. The second electrodes 40 are formed by a known vapor deposition method, plating method, sputtering method, or the like, then patterned by a photolithography method, and then formed in a stripe shape by an etching method.

[5] Porous body installation process The porous body installation process is performed between the first substrate 10 on which the first electrodes 20 are formed and the second substrate 20 on which the second substrates 40 are formed. This is a step of installing the body 51.
Specifically, for example, between the first substrate 10 on which the first electrodes 20... Are formed and the second substrate 20 on which the second electrodes 40. A porous body 51 is formed by sandwiching a nylon net filter (thickness: 55 μm, opening: 11 μm).
Alternatively, for example, a glass paste (for example, Nippon Electric Glass) is formed on the surface of the first substrate 10 on which the first electrodes 20... And / or the second substrate 20 on which the second electrodes 40. The porous body 51 is installed by screen-printing glass paste PLS-3124) manufactured by Co., Ltd.
Alternatively, for example, the surface of the first substrate 10 on which the first electrodes 20... And / or the second substrate 20 on which the second electrodes 40. The MEMS permanent resist TMMRS-2000 is applied by a spinner or the like, and then the porous body 51 is formed and installed by three-dimensional molding into a pattern by a photolithography method using a predetermined mask.

[6] Bonding process The bonding process includes bonding the first substrate 10 on which the first electrodes 20 are formed and the second substrate 20 on which the second electrodes 40 are formed with the electrodes on the inside. Predetermined additives (adsorbent 53, compound (a compound represented by the above formula (1) and / or a compound represented by the above formula (2) and the above formula (3)) This is a step of encapsulating the electrochromic composition 52 to which a compound and / or a compound represented by the above formula (4)), a polymer compound, hindered phenols, and the like are added. The electrochromic composition 52 includes a compound represented by the general formula (1) and / or a compound represented by the above formula (2) and a compound represented by the above formula (3). In place of the compound represented by the above formula (4), and / or the compound represented by the following formula (57) and the compound represented by the following formula (58) and / or the following formula: A compound represented by (59) may be added.
Specifically, for example, the electrochromic composition 52 to which a predetermined additive is added is immersed in the porous body 51 to form the electrochromic composition layer 50, and both surfaces of the electrochromic composition layer 50 are formed. Are bonded together to the first substrate 10 on which the first electrodes 20 are formed and the second substrate 30 on which the second electrodes 40 are formed.
Alternatively, for example, the electrochromic composition 52 to which a predetermined additive is added is immersed in the porous body 51 installed on one substrate (for example, the first substrate 10 on which the first electrodes 20... Are formed). Then, the electrochromic composition layer 50 is formed, and the other substrate (for example, the second substrate 30 on which the second electrodes 40... Are formed) is bonded to the electrochromic composition layer 50.
Or, for example, the first substrate 10 on which the first electrodes 20... Are formed and the second substrate 30 on which the second electrodes 40. An electrochromic composition 52 to which a predetermined additive is added is injected into a gap between the two substrates on which the body 51 is installed using a pipette or the like.
Or, for example, the first substrate 10 on which the first electrodes 20... Are formed and the second substrate 30 on which the second electrodes 40. A glass capillary or the like is separately formed in advance in a gap between the two substrates on which the body 51 is installed, and an electrochromic composition 52 to which a predetermined additive is added is porous using the glass capillary or the like. It encloses by sucking into the body 51.

<Driving method of electrochromic display device>
The electrochromic display device 100 is driven as follows by, for example, passive matrix driving.

Each pixel 60 of the electrochromic display device 100 is constituted by an electrochromic composition layer 50 sandwiched between first electrodes 20 and second electrodes 40.
When the electrochromic composition 52 is energized by energizing the electrochromic display device 100 between the first electrode 20 and the second electrode 40, the electrochromic composition layer 50 and the second electrode 40 are energized. The electrochromic composition 52 undergoes an electrochemical change at the interface (the surface of the second electrode 40). Further, the erasing of the electrochromic display device 100 is performed by energization in the direction opposite to the energization for color development or by leaving the energization for color development and leaving it to stand. In the reverse direction, the erasing operation can be carried out more quickly.
The color density of the electrochromic display device 100 can be arbitrarily adjusted by the amount of electricity to be energized (energization amount). Further, energization can be performed by continuous supply of current or intermittent supply of current. The intermittent supply of current refers to driving by a pulse, for example. On the other hand, the color of the electrochromic display device 100 is erased even when the current is cut off, but it is necessary to maintain the color when used as electronic paper. The display of the electrochromic display device 100 can be maintained by supplying a current smaller than the current supplied for display, for example. For example, in the case of supplying a continuous current, the color development can be maintained at a voltage or current that is less than half that during color development. In addition, in the case of intermittent current supply, that is, pulse driving, for example, maintenance of color development can be performed by, for example, shortening the energization period as compared to the time of color development or reducing the intensity, width, or interval of the pulse smaller than that during color development. Can be done.

Here, when the electrochromic composition 52 is introduced into the pores 51a of the porous body 51, the display device is prevented from being deteriorated in display performance due to crosstalk between the pixels 60 and 60, and has display memory properties. It will be.
Specifically, when the electrochromic composition 52 is impregnated in the porous body 51 and the electrochromic composition 52 is introduced into the pores 51a of the porous body 51, the leuco dye in the electrochromic composition 52 For example, as shown in FIG. 3, 52 a extends from the inside of the pores 51 a of the porous body 51 to the display region of the interface between the electrochromic composition layer 50 and the second electrode 40 (the surface of the second electrode 40). It moves and develops color, moves from the interface between the electrochromic composition layer 50 and the second electrode 40 (the surface of the second electrode 40) into the pores 51a of the porous body 51, and disappears. Accordingly, in the present invention, the leuco dye 52a can be detached from the surface of the second electrode 40 unless the leuco dye 52a moves into the pores 51a of the porous body 51. 52a takes time to detach | leave from the surface of the 2nd electrode 40 compared with the leuco dye 52a of the display device which does not utilize the porous body 51. FIG.
Therefore, in order to immediately remove the leuco dye 52a from the surface of the second electrode 40 and decolorize it, it is necessary to perform energization in the direction opposite to the energization for color development.

  In the conventional display device using the electrochromic composition 52 to which the adsorbent 53 (aluminum oxide and / or aluminum hydroxide) is not added, it is necessary to strictly control the energization amount for erasing. This is because the leuco dye 52a moves to the interface between the electrochromic composition layer 50 and the first electrode 20 (the surface of the first electrode 20) and develops color due to energization for erasing, resulting in a display. This is because it may not be erased.

On the other hand, in the electrochromic display device 100 according to the first embodiment, when the energization amount for erasing is not strictly controlled as in the conventional display device, the erasing is energized. Since the leuco dye 52a is adsorbed by the adsorbent 53 (aluminum oxide and / or aluminum hydroxide), the leuco dye 52a is the interface between the electrochromic composition layer 50 and the first electrode 20 (the surface of the first electrode 20). It is possible to prevent color development due to movement.
Specifically, the leuco dye 52a is polarized in the solution. The adsorbent 53 (aluminum oxide and / or aluminum hydroxide) has the characteristics that the specific surface area is large and the adsorption ability is high, and the surface is polarized. In the energization for the color display, the second electrode 40 is positively charged. Therefore, the leuco dye 52a having an electron donating property donates electrons to the second electrode 40 to generate a color and display. On the other hand, in the energization for erasing, since the energization is performed in the direction opposite to the display, the second electrode 40 is negatively charged. The leuco dye 52a accepts electrons from the negatively charged second electrode 40 and erases the color, and the color development is erased. The leuco dye 52a that has become colorless moves in the direction of the first electrode 20, but does not reach the first electrode 20 due to the presence of the adsorbent 53 having a high adsorption capability and a polarized surface, It moves to the adsorbent 53 and is captured and adsorbed. As a result, in the electrochromic display device 100 of the first embodiment, the leuco dye 52a is applied to the interface between the electrochromic composition layer 50 and the first electrode 20 (the surface of the first electrode 20) during energization for erasing. ) To prevent color development.

<Example 1>
Hereinafter, the present invention (first embodiment) will be described in more detail by way of specific examples, but the present invention is not limited to these examples.

(Creation of electrochromic display device)
A rectangular non-alkali glass substrate having a thickness of 0.7 mm was used as the second substrate 30, and ITO was sputtered as one of the second electrodes 40. The sputtered ITO had a film thickness of 200 nm and a surface resistance of 10Ω / □. The sputtered ITO was patterned into a stripe shape with a stripe width of 0.42 mm and a pitch of 0.45 mm using a photolithography method.
Similarly, a rectangular non-alkali glass substrate was used as the first substrate 10, and ITO was sputter-formed on the one surface (upper surface) as the first electrode 20. The sputtered ITO had a film thickness of 200 nm and a surface resistance of 10Ω / □. The sputtered ITO was patterned into a 128-line stripe using a photolithography method with a stripe width of 0.42 mm and a pitch of 0.45 mm.

  Subsequently, a rectangular Sefar Inc. PETEX (polyester mesh cloth) PET51HC is sandwiched between the first electrode 20 ... and the second electrode 40 ... as the porous body 51, and the first electrode 20 ... is the second electrode. Overlapping in a shape orthogonal to 40. Then, the orthogonal portions of the first electrodes 20 and the second electrodes 40 are adjusted so as to become the pixels 60, and three of the four side surfaces (surfaces parallel to the thickness direction) are adhesive (for example, And thermosetting epoxy).

  Next, a predetermined additive (adsorbent 53, compound (a compound represented by the above formula (1) and / or the above formula (2) is represented by a pipette) from an adhesive non-bonded portion. And a compound represented by the above formula (3) and / or a compound represented by the above formula (4)), a polymer compound, a hindered phenol, etc. , Referred to as “electrochromic composition A”), and the adhesive-unbonded portion of the four side surfaces (surfaces parallel to the thickness direction) was adhesively sealed with an adhesive. Then, a white pet having a thickness of 200 μm was pasted on the lower surface of the first substrate 10 to produce an electrochromic display device 100 (hereinafter referred to as “display device A”).

For comparison, two types of electrochromic compositions to which the adsorbent 53 was not added were prepared, and an electrochromic display device was prepared using each of them in the same manner as the display device A.
Hereinafter, the electrochromic composition to which the adsorbent 53 is not added is referred to as “electrochromic composition B” and “electrochromic composition C”. The electrochromic display device comprising the electrochromic composition C is referred to as “display device C”.

The composition of the electrochromic composition A is
Leuco dye (formula (20) above) 400 mg,
40 mg of the compound represented by the above general formula (1) (the above formula (21); 2,5-di-tert-amylhydroquinone),
40 mg of the compound represented by the above formula (3) (the above formula (52); succinimide),
20 mg of hindered phenols (Sumilyzer GP manufactured by Sumitomo Chemical Co., Ltd.)
General formula compounds represented by the formula (6) described above _{((n-C 4 H 9} ) 4 NBF 4) 40mg,
1.0 g of polar solvent (N, N-dimethylacetamide),
50 mg of a polymer compound (polyvinyl butyral; Sekisui Chemical's ESREC BH3),
It is 100 mg of adsorbent 53 (aluminum oxide; Nippon Light Metal activated alumina C200).

The composition of the electrochromic composition B is
Leuco dye (formula (20) above) 400 mg,
40 mg of the compound represented by the above general formula (1) (the above formula (21); 2,5-di-tert-amylhydroquinone),
40 mg of the compound represented by the above formula (3) (the above formula (52); succinimide),
20 mg of hindered phenols (Sumilyzer GP manufactured by Sumitomo Chemical Co., Ltd.)
General formula compounds represented by the formula (6) described above _{((n-C 4 H 9} ) 4 NBF 4) 40mg,
50 mg of a polymer compound (polyvinyl butyral; Sekisui Chemical's ESREC BH3),
1.0 g of polar solvent (N, N-dimethylacetamide).

The composition of the electrochromic composition C is
Leuco dye (formula (20) above) 400 mg,
General formula compounds represented by the formula (6) described above _{((n-C 4 H 9} ) 4 NBF 4) 40mg,
1.0 g of polar solvent (N, N-dimethylacetamide),
It is 50 mg of a polymer compound (polyvinyl butyral; Sekisui Chemical's ESREC BH3).

(Display operation)
A pattern forming circuit was connected to each of the display device A, the display device B, and the display device C. A voltage of 2.0 V was applied, and a binary display pattern was formed by passive matrix drive display. That is, for each of the display device A, the display device B, and the display device C, the surface portion of the second electrode 40 of the portion where the first electrode 20 and the second electrode 40 intersect (pixel 60) is driven by the passive matrix circuit. As a center, a black pigment was produced to obtain a black pattern.

(Erase operation)
The voltage application (energization) was stopped for each of the display device A, the display device B, and the display device C on which the black pattern was displayed, and the erase operation was performed.
At a predetermined timing, the maximum reflection density (OD value) was measured with a 2405 type microdensitometer (Sakata Inks engineering), and the result of FIG. 4 was obtained.

  Most of the displayed black pattern disappeared in the display device A, the display device B, and the display device C after being left for 3 minutes. I found out that It turned out that it was necessary to leave for 7 minutes or more to completely disappear.

(Display-erase operation)
A display operation is performed by applying a voltage of 2.0 V to each of display device A, display device B, and display device C, and then a voltage of 2.0 V is applied in the direction opposite to the voltage application for display to erase The operation was carried out. This display operation and erase operation were repeated 1000 times.
Each time a voltage was applied, the maximum reflection density (OD value) was measured with a 2405 type microdensitometer (Sakata Inks engineering), and the result of FIG. 5 was obtained.
In FIG. 5, “+2.0 V” indicates voltage application for display, and “−2.0 V” indicates voltage application for erasure.

In the display device A, it was found that the displayed black pattern was completely erased by applying a voltage for erasing at the first repetition. Further, it was found that the density of the displayed pattern was constant both at the 300th and 1000th repetitions, and the pattern was completely erased by applying a voltage for erasing.
That is, it has been found that the display device A can completely erase the display by applying a voltage for erasing (energization), and the performance does not deteriorate even if it is repeatedly used.

In the display device B, the black dye is centered on the surface portion of the second electrode 40 at the portion where the first electrode 20 and the second electrode 40 intersect (pixel 60) by applying a voltage for erasing at the first repetition. It was found that a black pattern was formed. Further, although the density of the displayed pattern was constant at the 300th and 1000th repetitions, the pattern was formed on the first electrode 20 side by applying the voltage for erasing, and as a result, display was performed. It turned out that it was not erased.
That is, it has been found that the display device B has a constant display density even after repeated use, but the display cannot be erased.

In the display device C, the black dye is centered on the surface portion of the second electrode 40 in the portion where the first electrode 20 and the second electrode 40 intersect (pixel 60) by applying a voltage for erasing at the first repetition. It was found that a black pattern was formed. It was also found that the density of the displayed pattern decreased as the number of repetitions increased, and that no pattern was displayed at the 1000th repetition. This is because the electrochromic composition C of the display device C has a compound represented by the above formula (1) and / or a compound represented by the above formula (2) and a general formula represented by the above formula (2). The cause is considered to be that the compound represented by the above formula (3) and / or the general formula does not contain the compound represented by the above formula (4).
That is, it has been found that the display device C cannot erase the display, and the display density decreases when it is repeatedly used.

According to the electrochromic display device 100 of the first embodiment described above, the first substrate 10, the first electrodes 20 provided on the upper surface of the first substrate 10, and the first substrate 10 above the first substrate 10. A second substrate 30 provided opposite to the substrate 10 and formed of a transparent material, and a second electrode 40 provided on the lower surface of the second substrate 30 and at least partially formed of a transparent electrode material. And an electrochromic composition layer 50 provided between the first substrate 10 and the second substrate 30, and display is performed by energization between the first electrode 20 ... and the second electrode 40 ... At the same time, the display is erased by energization in the direction opposite to the energization for the display between the first electrode 20... And the second electrode 40. The electrochromic composition layer 50 includes an electrochromic composition 52 including a supporting electrolyte, a polar solvent, and a leuco dye 52a as an electron donor dye precursor. An adsorbent 53 (aluminum oxide and / or aluminum hydroxide) that adsorbs the leuco dye 52a when energized is added.
That is, during energization for erasing, since the leuco dye 52a is adsorbed by the adsorbent 53, the leuco dye 52a moves to the electrode (first electrode 20) opposite to the display electrode (second electrode 40) and develops color. It is possible to prevent the display from being formed. Therefore, when the display is erased by energizing in the direction opposite to the energization for display, the display can be surely erased without strictly controlling the energization amount.

  In addition, according to the electrochromic display device 100 of the first embodiment, the electrochromic composition 52 includes the compound represented by the general formula (1) and / or the general formula (2). And a compound represented by the above general formula (3) and / or a compound represented by the above general formula (4) are added. That is, since the electrochromic composition 52 is added with a white compound having a function of suppressing deterioration of display quality of the electrochromic display device 100 due to repeated operations of color development and decoloration of the leuco dye 52a. Is preferred.

  In addition, according to the electrochromic display device 100 of the first embodiment, hindered phenols are added to the electrochromic composition 52. That is, the electrochromic composition 52 is suitable because a compound for promoting the color development of the leuco dye 52a is added.

  Moreover, according to the electrochromic display device 100 of 1st Embodiment, a polar solvent is at least 1 sort (s) of the organic solvent which shows electroconductivity using a supporting electrolyte. That is, the electrochromic composition 52 is preferable because it contains a compound having a function of promoting energization so that the leuco dye 52a can be colored and decolored by blocking voltage and / or current.

  Further, according to the electrochromic display device 100 of the first embodiment, the supporting electrolyte is a compound represented by the above general formula (5) and / or a compound represented by the above general formula (6). is there. That is, the electrochromic composition 52 is preferable because it contains a compound having a function for facilitating the flow of current in the electrochromic composition 52.

  In addition, according to the electrochromic display device 100 of the first embodiment, a polymer compound is added to the electrochromic composition 52. That is, the electrochromic composition 52 is preferable because a compound having a function of increasing the viscosity of the electrochromic composition 52 and facilitating the handling thereof is added.

Further, according to the electrochromic display device 100 of the first embodiment, the first electrodes 20 are a plurality of electrodes extending in parallel, and the second electrodes 40 are orthogonal to the first electrodes 20. A transparent display electrode composed of a plurality of transparent electrodes extending in parallel to the direction, pixels are formed in a region where the first electrode 20 ... and the second electrode 40 ... are three-dimensionally crossed, and the electrochromic composition layer 50 includes A porous body 51 having pores penetrating in a substantially vertical direction with respect to the first substrate 20 and the second substrate 40, and a predetermined additive (adsorbent 53, compound (general formula is the above formula (1) And / or a compound represented by the above formula (2) and a compound represented by the above formula (3) and / or a compound represented by the above formula (4)), a polymer compound, Hindered phenols) Electrochromic composition 52 is introduced into the pores of the porous body 51.
That is, the crosstalk between the pixels 60 and 60 can be caused only by introducing the electrochromic composition 52 into the pores 51a of the porous body 51 and without having a partition wall formed through a dense and complicated process. Can be suppressed. Further, since the pores 51a formed in the porous body 51 penetrate in a substantially vertical direction with respect to the first substrate 10 and the second substrate 30, the porous body in which the pores are randomly formed is used. Compared with the case of using, the resolution and contrast are increased, and high display performance can be achieved with a simple configuration.

  In addition, according to the electrochromic display device 100 of the first embodiment, driving for display is performed by passive matrix driving. Therefore, the structure is simple and suitable.

[Second Embodiment]
Next, the electrochromic display device 200 of the second embodiment will be described.

<Configuration of electrochromic display device>
In the electrochromic display device 200 of the second embodiment, the adsorbent 53 is not added (dispersed) to the electrochromic composition 52 constituting the electrochromic composition layer 50, and instead, the adsorbent is used. 53 is different from the electrochromic display device 100 of the first embodiment only in that the adsorption layer 70 including 53 is provided between the first electrode 20... And the electrochromic composition layer 50. Therefore, only different parts will be described, and other common parts will be described with the same reference numerals.

FIG. 6 is a plan view (a) and a cross-sectional view (b) schematically showing the electrochromic display device 200 of the second embodiment.
The electrochromic display device 200 according to the second embodiment includes, for example, a first substrate 10, a first electrode 20, a second substrate 30, a second electrode 40, an electrochromic composition layer 50, And an adsorption layer 70 provided between the first electrodes 20 and the electrochromic composition layer 50.

  The electrochromic composition layer 50 includes, for example, a porous body 51 having pores 51a, an electrochromic composition 52 introduced into the pores 51a, and the like.

The electrochromic composition 52 includes a supporting electrolyte, a polar solvent, and a leuco dye 52a as an electron donating dye precursor.
The component that can be added to the electrochromic composition 52 includes, for example, a compound for suppressing deterioration of display quality of the electrochromic display device 100 (a compound represented by the above formula (1) and / or a compound represented by the above formula (1)). Or the compound represented by the above formula (2) and the compound represented by the above formula (3) and / or the compound represented by the above formula (4)) and the physical properties of the electrochromic composition 52 (for example, And polymer compounds for adjusting the viscosity, hindered phenols for promoting the color development of the leuco dye 52a, and the like.

Here, in the electrochromic display device 200 of the second embodiment, the adsorbent 53 is not added to the electrochromic composition 52.
The electrochromic composition 52 includes a compound represented by the general formula (1) and / or a compound represented by the above formula (2) and a compound represented by the above formula (3). In place of the compound represented by the above formula (4), and / or the compound represented by the following formula (57) and the compound represented by the following formula (58) and / or the following formula: A compound represented by (59) may be added.

The adsorption layer 70 has a function of adsorbing the leuco dye 52a during energization for erasing between the first electrode 20 and the second electrode 40, for example.
For example, the adsorption layer 70 is deposited on the first electrodes 20 and is in contact with the electrochromic composition layer 50.

The adsorption layer 70 is composed of, for example, an adsorbent 53 (aluminum oxide and / or aluminum hydroxide), a water-soluble binder, and the like.
Specifically, the adsorption layer 70 is prepared by, for example, uniformly dispersing the adsorbent 53 or a water-soluble binder in a medium such as water to form a dispersion, and applying the dispersion onto the first electrodes 20. And then dried.

  The adsorbent 53 (aluminum oxide and / or aluminum hydroxide) is not particularly limited, but from the viewpoint of adsorption effect and the like, aluminum oxide having a large surface area such as γ-alumina, and having a particle size of 1 μm or less is small. Aluminum oxide, aluminum hydroxide having a large surface area, and small aluminum hydroxide having a particle size of 1 μm or less can be preferably used.

The water-soluble binder used as the binder is not particularly limited, and examples thereof include starch, gelatin, cellulose derivatives such as carboxymethylcellulose (CMC) and methylcellulose (MC), polyvinyl alcohol (PVA), and polyacrylic acid. A polymer, polyacrylamide (PAM), polyethylene oxide (PEO), etc. can be used. Among these, polyvinyl alcohol can be preferably used.
Although the addition amount of a water-soluble binder is not specifically limited, 0.1-30 weight% is preferable with respect to the adsorption agent 53, and 1-10 weight% is more preferable. If the amount of the water-soluble binder added is too small, the applied and formed adsorption layer 70 is likely to be physically damaged such as being easily peeled off by contact or the like. On the other hand, when there is too much addition amount of a water-soluble binder, the adsorption effect of the adsorption agent 53 (aluminum oxide and / or aluminum hydroxide) will be inhibited. Further, if the amount of the water-soluble binder added is too large, it causes an increase in electrical resistance, and adversely affects the color display operation and the erasing operation of the electrochromic display device 200, such as a decrease in the amount of energization.

Aluminum oxide and / or aluminum hydroxide can be easily obtained as a chemical product.
Although the example of the suitable commercially available aluminum oxide and aluminum hydroxide is shown below, these are illustrations and do not limit aluminum oxide and aluminum hydroxide.
Specific examples of the commercially available adsorbent 53 include, for example, aluminum oxide 60GN neutral for thin layer chromatography (particle size: 4 μm to 50 μm) manufactured by Merck & Co., Ltd., Nippon Light Metal's low soda alumina LS235 (particle size: 0.47 μm), activated alumina C200 ( Particle diameter 4.4 μm), aluminum hydroxide B1403 (particle diameter 1.5 μm), and γ-alumina KC501 (particle diameter 1 μm) manufactured by Sumitomo Chemical.

<Method of manufacturing electrochromic display device>
The manufacturing method of the electrochromic display device 200 includes the following steps [1] to [7].

[1] First Substrate Preparation Step The first substrate preparation step is a step of preparing the first substrate 10.

[2] First vapor deposition step The first vapor deposition step is a step of providing the first electrodes 20 on one surface of the first substrate 10.

[3] Second substrate preparation step The second substrate preparation step is a step of preparing the second substrate 30.

[4] Second Deposition Step The second deposition step is a step of providing the second electrodes 40 on one surface of the second substrate 30.

[5] Adsorption layer installation process The adsorption layer installation process is a process of installing the adsorption layer 70 on the surface of the first electrodes 20 formed on the first substrate.
Specifically, for example, adsorbent 53 (aluminum oxide and / or aluminum hydroxide) is mixed with a water-soluble binder such as polyvinyl alcohol, water, etc. using ball milling, a homogenizer, a homomixer, an ultrasonic disperser, or the like. A dispersion is prepared by dispersing in a medium. And the adsorption layer 70 is formed by apply | coating the dispersion liquid to the surface of the 1st electrode 20 ... using a Mayer bar, an applicator, etc. FIG.

[6] Porous body installation process The porous body installation process includes the first substrate 10 on which the adsorption layer 70 and the first electrodes 20 are formed, and the second substrate 20 on which the second substrates 40 are formed. This is a step of installing the porous body 51 between them.

[7] Bonding Step In the bonding step, the first substrate 10 on which the adsorption layer 70 and the first electrodes 20... Are formed and the second substrate 20 on which the second electrodes 40. Additives (compounds (compounds represented by the above formula (1) and / or compounds represented by the above formula (2) and compounds represented by the above formula (3) and / or the above) In which the electrochromic composition 52 to which the compound represented by the formula (4)), the polymer compound, the hindered phenols, and the like are added is encapsulated. The electrochromic composition 52 includes a compound represented by the general formula (1) and / or a compound represented by the above formula (2) and a compound represented by the above formula (3). In place of the compound represented by the above formula (4), and / or the compound represented by the following formula (57) and the compound represented by the following formula (58) and / or the following formula: A compound represented by (59) may be added.

<Driving method of electrochromic display device>
The electrochromic display device 200 is driven by, for example, passive matrix driving.
Since the driving of the electrochromic display device 200 of the second embodiment is substantially the same as the driving of the electrochromic display device 100 of the first embodiment, detailed description thereof is omitted.

Here, in the electrochromic display device 200 according to the second embodiment, even when the energization amount for erasing is not strictly controlled as in the conventional display device, the leuco Since the dye 52a is adsorbed by the adsorbent 53 (aluminum oxide and / or aluminum hydroxide) contained in the adsorption layer 70, the leuco dye 52a is prevented from moving to the surface of the first electrode 20 and coloring. can do.
Specifically, the leuco dye 52a is polarized in the solution. The adsorbent 53 (aluminum oxide and / or aluminum hydroxide) has the characteristics that the specific surface area is large and the adsorption ability is high, and the surface is polarized. In the energization for the color display, the second electrode 40 is positively charged. Therefore, the leuco dye 52a having an electron donating property donates electrons to the second electrode 40 to generate a color and display. On the other hand, in the energization for erasing, since the energization is performed in the direction opposite to the display, the second electrode 40 is negatively charged. The leuco dye 52a accepts electrons from the negatively charged second electrode 40 and erases the color, and the color development is erased. The colorless leuco dye 52a moves in the direction of the first electrode 20. However, the leuco dye 52a moves to the adsorption layer 70 due to the presence of the adsorbent 53 having a high adsorption capability and a polarized surface, and is trapped and adsorbed. Is done. As a result, in the electrochromic display device 200 of the second embodiment, it is possible to prevent the leuco dye 52a from moving to the surface of the first electrode 20 and developing color during energization for erasing.

<Example 2>
Hereinafter, the present invention (second embodiment) will be described in more detail by way of specific examples, but the present invention is not limited to these examples.

(Creation of electrochromic display device)
A rectangular non-alkali glass substrate having a thickness of 0.7 mm was used as the second substrate 30, and ITO was sputtered as one of the second electrodes 40. The sputtered ITO had a film thickness of 200 nm and a surface resistance of 10Ω / □. The sputtered ITO was patterned into a stripe shape of 60 lines with a stripe width of 0.42 mm and a pitch of 0.45 mm using a photolithography method.
Similarly, a rectangular non-alkali glass substrate was used as the first substrate 10, and ITO was sputter-formed on the one surface (upper surface) as the first electrode 20. The sputtered ITO had a film thickness of 200 nm and a surface resistance of 10Ω / □. The sputtered ITO was patterned into a stripe shape of 60 lines with a stripe width of 0.42 mm and a pitch of 0.45 mm using a photolithography method.

  Next, 2 g of aluminum oxide (KC501, manufactured by Sumitomo Chemical Co., Ltd.) and 0.1 g of polyvinyl alcohol (special grade # 2000, manufactured by Kanto Chemical Co., Ltd.) are dispersed in 20 g of water using ball milling to prepare a dispersion. The dispersion liquid was applied to the surface (upper surface) of the first electrode 20... Using a 200 μm applicator and dried in an oven at 70 ° C. for 30 minutes to form the adsorption layer 70.

  Next, a PETEX (polyester mesh cloth) PET51HC made by Sefar Inc. is sandwiched between the adsorption layer 70 and the second electrodes 40 as the porous body 51, and the first electrodes 20 ... Was superimposed in a form orthogonal to the above. Then, the orthogonal portions of the first electrodes 20 and the second electrodes 40 are adjusted so as to become the pixels 60, and three of the four side surfaces (surfaces parallel to the thickness direction) are adhesive (for example, And thermosetting epoxy).

  Next, from a non-adhesive part of the adhesive, a predetermined additive (a compound (a compound represented by the following formula (57) and a compound represented by the following formula (58) and / or a compound represented by the following formula (58) is used) And an electrochromic composition 52 (hereinafter referred to as “electrochromic composition D”) to which a compound (such as a compound represented by the formula (59) of FIG. The adhesive non-adhered portion of the parallel surfaces was adhesively sealed with an adhesive. Then, a white pet having a thickness of 200 μm was pasted on the lower surface of the first substrate 10 to produce an electrochromic display device 200 (hereinafter referred to as “display device D-1”).

  For comparison, an electrochromic display device (hereinafter, “display device D-2”) that does not include the adsorption layer 70 was created using the electrochromic composition D.

The composition of the electrochromic composition D is
Leuco dye (formula (20) above) 400 mg,
40 mg of a compound represented by the above general formula (58) (the above formula (67); 2,5-di-tert-amylquinone),
35 mg of the compound represented by the above general formula (57) (the above formula (60); triphenylantimony),
General formula compounds represented by the formula (6) described above _{((n-C 4 H 9} ) 4 NBF 4) 40mg,
1.0 g of polar solvent (N, N-dimethylacetamide),
It is 50 mg of a polymer compound (polyvinyl butyral; Sekisui Chemical's ESREC BH3).

(Display by display device D-1-Erase operation by energization)
A pattern forming circuit was connected to the display device D-1. Then, energization for display was performed using a passive matrix driving method. Specifically, a voltage of 5.0 V was applied at a speed of 10 milliseconds per line, and a black pattern (checkered pattern) as shown in FIG. 7 was formed in 0.6 seconds. Thereafter, the applied voltage was 2.5 V, and a black pattern as shown in FIG. 7 was held for 60 seconds.
Next, the display device D-1 on which the black pattern as shown in FIG. 7 was displayed was energized in the direction opposite to the display (energization for erasure). Specifically, a voltage of 7.0 V was applied at a speed of 10 msec per line and energized for 1 sec.

  In the display device D-1, the black pattern disappeared completely by energization for erasing, and a quick erasing operation could be performed.

(Display by display device D-1-Erase operation by leaving)
A pattern forming circuit was connected to the display device D-1. Then, energization for display was performed using a passive matrix driving method. Specifically, a voltage of 5.0 V was applied at a speed of 10 milliseconds per line, and a black pattern as shown in FIG. 7 was formed in 0.6 seconds. Thereafter, the applied voltage was 2.5 V, and a black pattern as shown in FIG. 7 was held for 60 seconds.
Next, voltage application (energization) was stopped with respect to D-1 on which a black pattern as shown in FIG. 7 was displayed, and the erase operation was performed.

In the display device D-1, after the energization for display was stopped, the black pattern disappeared completely by leaving it for about 1 minute.
As a result, it has been found that the erasing operation by energization can perform the erasing operation faster than the erasing operation by neglecting.

(Display by display device D-2-Erase operation by energization)
A pattern forming circuit was connected to the display device D-2. Then, energization for display was performed using a passive matrix driving method. Specifically, a voltage of 5.0 V was applied at a speed of 10 milliseconds per line, and a black pattern as shown in FIG. 7 was formed in 0.6 seconds. Thereafter, the applied voltage was 2.5 V, and a black pattern as shown in FIG. 7 was held for 60 seconds.
Next, the display device D-2 on which the black pattern as shown in FIG. 7 was displayed was energized in the direction opposite to the display (energization for erasure). Specifically, a voltage of 7.0 V was applied at a speed of 10 msec per line, energized for 1 second, and further energized for 3 seconds.

In the display device D-2, a decrease in the display density of the black pattern was confirmed by energization for erasing for 1 second, but it did not completely disappear but remained slightly.
Further, in the display device D-2, the display density of the black pattern is increased by the subsequent energization for erasing for 3 seconds, and the leuco dye 52a is an electrode opposite to the display electrode (second electrode 40). It was confirmed to move to (first electrode 20).
Thereby, it was found that the display could not be erased without the adsorption layer 70.

According to the electrochromic display device 200 of the second embodiment described above, the adsorbent that adsorbs the leuco dye 52a between the first electrodes 20... And the electrochromic composition layer 50 during energization for erasing. An adsorption layer 70 containing 53 (aluminum oxide and / or aluminum hydroxide) is provided.
That is, during energization for erasing, since the dye is adsorbed to aluminum oxide and / or aluminum hydroxide, it is possible to prevent the dye from moving to the electrode opposite to the display electrode and forming a color display. Can do. Therefore, when the display is erased by energizing in the direction opposite to the energization for display, the display can be surely erased without strictly controlling the energization amount.

  The present invention is not limited to the above-described embodiment, and can be appropriately changed without departing from the gist thereof.

(Modification 1)
In the electrochromic display device 100 according to the first embodiment, a predetermined current introduced into the pores 51a of the porous body 51 is energized between the first electrodes 20 ... and the second electrodes 40 ... The electrochromic composition 52 to which the additive is added can be energized. For example, as in the electrochromic display device 100A shown in FIG. The member 54A may be provided.
The same applies to the electrochromic display device 200 of the second embodiment.

  Specifically, the electrochromic display device 100A includes, for example, a first substrate 10, a first electrode 20,..., A second substrate 30, a second electrode 40, the first substrate 10, and a second substrate 30. And an electrochromic composition layer 50 </ b> A provided therebetween.

  The electrochromic composition layer 50A includes, for example, a porous body 51, and an electrochromic composition 52 to which a predetermined additive (such as an adsorbent 53) introduced into the pores 51a of the porous body 51 is added. And a conductive member 54A that closes the bottom of the pore 51a of the porous body 51.

  The conductive member 54A is formed in a planar shape, for example, and the porous body 51 is laminated on the upper surface of the conductive member 54A.

  The material of the conductive member 54A is not particularly limited, and for example, a conductive metal or a carbon material can be used. Further, the conductive member 54A may be constituted by, for example, one layer made of a single material, or may be constituted by two or more layers made of different materials.

(Modification 2)
In the electrochromic display device 100 according to the first embodiment, a predetermined current introduced into the pores 51a of the porous body 51 is energized between the first electrodes 20 ... and the second electrodes 40 ... The electrochromic composition 52 to which the additive is added may be energized. The first electrode 20... And the second electrode 40... And the second electrodes 40B.
The same applies to the electrochromic display device 200 of the second embodiment.

  Specifically, the electrochromic display device 100B includes, for example, a first substrate 10, a first electrode 20B, a second substrate 30, a second electrode 40B, the first substrate 10, and a second substrate 30. And an electrochromic composition layer 50 provided therebetween.

The first electrodes 20B are formed in, for example, a line shape, and are provided in stripes at equal intervals parallel to each other.
The first electrodes 20B are provided on the upper surface of the first substrate 10 so as to be in contact with the electrochromic composition layer 50 and to sandwich the electrochromic composition layer 50 opposite to the second electrodes 40B. Yes.
The first electrodes 20B ... are paired with the second electrodes 40B ... and have a function of energizing the electrochromic composition layer 50.
The first electrodes 20B ... intersect with the transparent display electrode portions 41B of the second electrodes 40B ... at a three-dimensional intersection, that is, with an interval, and form a pixel 60 in the region of the intersection.

  The material of the first electrode 20B ... is not particularly limited, and the material constituting the metal electrode or the material constituting the transparent electrode can be used. Examples of the material constituting the metal electrode include gold, platinum, silver, chromium, aluminum, cobalt, palladium, copper, nickel, and alloys thereof. Moreover, as a material which comprises a transparent electrode, ITO, ZnO, FTO etc. are mentioned, for example.

The second electrodes 40B are formed in a line shape with, for example, the transparent display electrode portions 41B provided in positions corresponding to the pixels 60, and are formed in a line shape provided in stripes at equal intervals parallel to each other. And so on. The transparent display electrode portions 41B are connected to the line-shaped electrode portion 42B.
The second electrodes 40B are provided on the lower surface of the second substrate 30 so as to be in contact with the electrochromic composition layer 50 and to sandwich the electrochromic composition layer 50 so as to face the first electrodes 20B. Yes.
The second electrodes 40B ... are paired with the first electrodes 20B ... and have a function of energizing the electrochromic composition layer 50.
The transparent display electrodes 41B of the second electrodes 40B ... intersect with the first electrodes 20B ... at a three-dimensional intersection, that is, with a gap, and form a pixel 60 in the area of the intersection.

The material of the transparent display electrode portions 41B is not particularly limited as long as it is a material capable of constituting a transparent electrode. Examples of the material capable of forming the transparent electrode include an ITO film and a thin film coated with SnO ₂ or InO ₂ . Further, an ITO film, a thin film coated with SnO ₂ or InO ₂ , or the like may be doped with Sn, Sb, or the like, or may be MgO, ZnO, FTO, or the like. Further, the transparent display electrode portions 41B.

  The material of the line-shaped electrode portions 42B is not particularly limited, and a material constituting a metal electrode or a material constituting a transparent electrode can be used. Examples of the material constituting the metal electrode include gold, platinum, silver, chromium, aluminum, cobalt, palladium, copper, nickel, and alloys thereof. Moreover, as a material which comprises a transparent electrode, ITO, ZnO, FTO etc. are mentioned, for example.

  The second electrodes 40B are formed by a known vapor deposition method, plating method, sputtering method in the above-mentioned [4] second vapor deposition step (a step of providing the second electrodes 40B ... on one surface of the second substrate 30). The film is then formed by photolithography, patterned by photolithography, and then formed by etching. The transparent display electrode portion 41B and the line-shaped electrode portion 42B are formed by a single deposition method, plating method, sputtering, or the like. It may be formed simultaneously by film formation by the method, or may be formed separately by film formation by two vapor deposition methods, plating methods, and sputtering methods.

  According to the electrochromic display device 100B of Modification 2, the first electrodes 20B are a plurality of line-shaped electrodes extending in parallel, and the second electrodes 40B are transparent display electrode portions 41B and transparent display electrodes. It is comprised by the line-shaped electrode part 42B ... connected to the part 41B .... Accordingly, since the second electrodes 40B (transparent display electrode portions 41B) can be thinned, the degree of color development can be improved and the display brightness of the electrochromic display device can be improved. Further, since the electrochromic composition 52 can be energized by energizing the line-shaped electrodes (the line-shaped electrode portions 42B of the first electrode 20B... And the second electrode 40B. The potential difference between the two becomes small, and power can be saved.

  In the second modification, the first electrode 20B ... may also be composed of a transparent display electrode portion and a line electrode portion connected to the transparent display electrode portion. In this case, a pixel is formed in a region where the transparent display electrode portion of the first electrode 20B... And the transparent display electrode portion 41B of the second electrode 40B.

  In the above-described first and second embodiments and modifications 1 and 2, the dye constituting the electrochromic composition 52 is not limited to the leuco dye 52a, and may be any electron-donating dye precursor. is there.

It is the top view (a) and sectional drawing (b) which show typically the electrochromic display device of 1st Embodiment. It is a figure for demonstrating the relationship between the size of a pixel and the size of the pore of a porous body. It is a figure for demonstrating the color development of an electrochromic composition. In the electrochromic display device (display device A) for comparison with the electrochromic display device of the first embodiment (display devices B and C), the display density when the display is left after being turned off for display It is a figure which shows the change of. In the electrochromic display device (display devices B and C) for comparison with the electrochromic display device (display device A) of the first embodiment, energization for display and energization for display erasure are performed. It is a figure which shows the change of the display density at the time of repeating. It is the top view (a) and sectional drawing (b) which show typically the electrochromic display device of 2nd Embodiment. 6 is a diagram illustrating an example of a black pattern displayed on a display device of Example 2. FIG. It is a figure which shows the electrochromic display device of the modification 1 typically. It is a figure which shows the electrochromic display device of the modification 2 typically.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 1st board | substrate 20,20B 1st electrode 30 2nd board | substrate 40,40B 2nd electrode 50,50A Electrochromic composition layer 51 Porous body 51a Pore 52 Electrochromic composition 52a Leuco dye (electron-donating dye precursor) )
53 Adsorbent (aluminum oxide and / or aluminum hydroxide)
60 pixels 70 adsorption layer 100, 200, 100A, 100B electrochromic display device

Claims (14)

A first substrate; a first electrode provided on an upper surface of the first substrate; a second substrate provided above the first substrate so as to face the first substrate and formed of a transparent material; A second electrode provided on the lower surface of the second substrate, at least part of which is formed of a transparent electrode material, and an electrochromic composition layer provided between the first substrate and the second substrate; And performing display by energization between the first electrode and the second electrode, and by energization in a direction opposite to the energization for the display between the first electrode and the second electrode. In an electrochromic display device that erases the display,
The electrochromic composition layer comprises an electrochromic composition comprising a supporting electrolyte, a polar solvent, and an electron donating dye precursor,
The electrochromic composition does not adsorb the electron-donating dye precursor when energized for display, but adsorbs the electron-donating dye precursor when energized for erasing. An electrochromic display device characterized in that aluminum oxide is added. A first substrate; a first electrode provided on an upper surface of the first substrate; a second substrate provided above the first substrate so as to face the first substrate and formed of a transparent material; A second electrode provided on the lower surface of the second substrate, at least part of which is formed of a transparent electrode material, and an electrochromic composition layer provided between the first substrate and the second substrate; And performing display by energization between the first electrode and the second electrode, and by energization in a direction opposite to the energization for the display between the first electrode and the second electrode. In an electrochromic display device that erases the display,
The electrochromic composition layer comprises an electrochromic composition comprising a supporting electrolyte, a polar solvent, and an electron donating dye precursor,
The electron donating dye precursor is not adsorbed between the first electrode and the electrochromic composition layer when the display is energized, but the electron donating dye precursor is not adsorbed when the erase is energized. An electrochromic display device comprising an adsorbing layer containing adsorbing aluminum oxide and / or aluminum hydroxide. The electrochromic display device according to claim 1 or 2,
The electrochromic composition includes a compound represented by the following general formula (1) and / or a compound represented by the following general formula (2) and a compound represented by the following general formula (3) and / or An electrochromic display device, wherein a compound represented by the following general formula (4) is added.

(Wherein R1, R2, R3 and R4 represent a hydrogen atom, an alkyl group, an allyl group, an alkoxy group, a hydroxyl group, a nitro group, an alkylcarbonyl group, a formyl group, a carboxyl group or an alkoxycarbonyl group. And R2 and / or R3 and R4 in the formula represent a 5-membered or 6-membered condensed ring formed by condensation with each other, provided that all of R1, R2, R3 and R4 are hydrogen atoms. No.)

(Wherein R5, R6, R7 and R8 represent a hydrogen atom, an alkyl group, an alkoxy group, an allyl group, a hydroxyl group, a nitro group, an alkylcarbonyl group, a formyl group, a carboxyl group or an alkoxycarbonyl group. And R6, wherein R6 and R7 and / or R7 and R8 are condensed with each other and represent a 5-membered or 6-membered condensed ring, provided that all of R5, R6, R7 and R8 are It is never a hydrogen atom.)

(Wherein R9, R10, R11 and R12 represent a hydrogen atom. Alternatively, R9 and R10 or R11 and R12 in the formula represent a double bond formed by bonding to each other.)

(In the formula, Z and a dotted line represent a state in which a ring is formed. When the ring is an aliphatic ring, it represents a substituted or unsubstituted cyclohexyl group, and when the ring is an aromatic ring, Represents a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group.) In the electrochromic display device according to any one of claims 1 to 3,
The electron donating dye precursor is a leuco dye,
An electrochromic display device, wherein a hindered phenol is added to the electrochromic composition. In the electrochromic display device according to any one of claims 1 to 4,
The electrochromic display device, wherein the polar solvent is at least one organic solvent that exhibits electrical conductivity using the supporting electrolyte. In the electrochromic display device according to any one of claims 1 to 5,
The electrochromic display device, wherein the supporting electrolyte is a compound represented by the following general formula (5) and / or a compound represented by the following general formula (6).

(In the formula, M ₂ represents Li, Na, K, Rb, Cs, or NH _{4. In the} formula, X ₁ represents ClO ₄ , BF ₄ , CF ₃ SO _3, or PF _6. )

(In the formula, R13 represents an alkyl group or an aryl group. In the formula, R14 represents an alkyl group. In the formula, N represents a nitrogen atom. In the formula, X ₂ represents Cl, Br, I, ClO ₄ , BF. ₄ represents CF ₃ SO ₃ or PF _{6. In the} formula, n represents 0, 1 or 2, and m represents 4-n. In the electrochromic display device according to any one of claims 1 to 6,
The electrochromic display device, wherein a polymer compound is added to the electrochromic composition. In the electrochromic display device according to any one of claims 1 to 7,
The first electrode is a plurality of electrodes extending in parallel,
The second electrode is a transparent display electrode composed of a plurality of transparent electrodes extending in parallel in a direction orthogonal to the first electrode,
An electrochromic display device, wherein a pixel is formed in a region where the first electrode and the second electrode intersect three-dimensionally. In the electrochromic display device according to any one of claims 1 to 7,
The first electrode is a plurality of electrodes extending in parallel,
The second electrode is composed of a transparent display electrode part and a line electrode part connected to the transparent display electrode part, and is a plurality of electrodes extending in parallel in a direction orthogonal to the first electrode. ,
An electrochromic display device, wherein a pixel is formed in a region where the first electrode and the transparent display electrode portion of the second electrode intersect three-dimensionally. In the electrochromic display device according to any one of claims 1 to 9,
The electrochromic display device, wherein the first electrode is a metal electrode. In the electrochromic display device according to any one of claims 1 to 9,
The electrochromic display device, wherein the first electrode is a transparent electrode. In the electrochromic display device according to any one of claims 1 to 7,
The first electrode is composed of a transparent display electrode part and a line electrode part connected to the transparent display electrode part, and is a plurality of electrodes extending in parallel.
The second electrode is composed of a transparent display electrode part and a line electrode part connected to the transparent display electrode part, and is a plurality of electrodes extending in parallel in a direction orthogonal to the first electrode. ,
An electrochromic display device, wherein a pixel is formed in a region where the transparent display electrode portion of the first electrode and the transparent display electrode portion of the second electrode cross each other. In the electrochromic display device according to any one of claims 1 to 12,
The electrochromic composition layer includes a porous body having pores penetrating in a direction substantially perpendicular to the first substrate and the second substrate,
The electrochromic display device, wherein the electrochromic composition is introduced into pores of the porous body. The electrochromic display device according to any one of claims 1 to 13,
An electrochromic display device which is driven for display by passive matrix driving.

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