JP5284627B2 - 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 generally used as a device for displaying electronic information distributed on 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) 5)) have been proposed so far.

  By the way, in an electrochromic display device (electrochromic display device), as a display material, for example, an electrochromic composition containing, as an essential component, a dye precursor such as a leuco dye that develops color on the surface of an electrode is used. . A leuco dye is an excellent material as an electrochromic material because it is widely used as a recording material for heat-sensitive recording and can be easily obtained and procured and can display various colors. However, electrochromic display devices using leuco dyes, for example, when display and erasure are repeated, the display performance gradually deteriorates, and the background of the display is colored or the display density is reduced. Have

  In addition, electrochromic display devices using leuco dyes may be stored over time, such as when the display is colored for a long time or when it is left in a high temperature environment, the background color of the display may become colored or the display density may become thin. Deterioration of display performance occurs, which hinders the commercialization of electrochromic display devices using leuco dyes.

In addition, electrochromic display devices using leuco dyes, when used as passive matrix drive display devices that can be driven without using expensive materials such as TFT (Thin Film Transistor), provide sufficient display density when driven at high speed. In order to obtain a sufficient color density, a writing speed of several hundred milliseconds per line is required. That is, for example, when an electrochromic display device using a leuco dye is applied as an electronic book, even when the resolution is a relatively coarse QVGA (Quarter Video Graphics Array), the writing speed is set to 100 milliseconds per line. When calculated, it takes about 32 seconds to display one page. Therefore, in order to apply an electrochromic display device using a leuco dye as an electronic book, an active matrix drive using an expensive TFT has to be adopted, resulting in high cost and an electrochromic display device using a leuco dye. Is one of the obstacles to product development.
JP 2005-338356 A Japanese Patent Publication No. 07-037611 JP 2007-052236 A JP 2003-302659 A JP 2007-010975 A

  However, even in the techniques described in Patent Documents 1 to 5, in an electrochromic display device using a leuco dye, it is possible to eliminate display performance deterioration due to repeated display and erasure, and display performance deterioration due to storage over time. It is impossible to simultaneously solve the problem and obtain a sufficient display density even when driven at a high speed.

  An object of the present invention is to eliminate the deterioration of display performance due to repeated display and erasure and the deterioration of display performance due to storage over time, and to obtain a sufficient display density even when driven at high speed. An object of the present invention is to provide an electrochromic display device using a dye.

（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Ｒ１１、式中Ｒ９とＲ１２、式中Ｒ１０とＲ１１又は式中Ｒ１０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。）

（式中Ｒ１３は、炭素数１から１６の直鎖又は分岐したアルキル基、ハロゲン原子を表す。式中Ｒ１４、Ｒ１５、Ｒ１６は、水素原子、ハロゲン原子、アルキル基、アリール基、アルキルカルボニル基、アルコキシ基、カルボニルアルコキシ基又はジアルキルアミノ基を表す。式中Ｘは、ハロゲン原子、ＢＦ_４基、ＰＦ_６基、ＣＨ_３ＳＯ_３基、ＣＦ_３ＳＯ_３基、ｐ−トルエンスルホン酸基を表す。ただし、式中Ｒ１３とＸとが同時にハロゲン原子であることは無い。） 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; In an electrochromic display device comprising:
The electrochromic composition layer comprises an electrochromic composition comprising a leuco dye, a supporting electrolyte, and a polar solvent,
The electrochromic composition includes a compound represented by the following general formula (1) and / or a compound represented by the following general formula (2), a compound represented by the following general formula (3) and / or Alternatively, a compound represented by the following general formula (4) and a compound represented by the following general formula (5) are 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 R11, R9 and R12, R10 and R11 or R10 and R12 in the formula are bonded to each other. Represents a double bond.)

(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 formula, R13 represents a linear or branched alkyl group having 1 to 16 carbon atoms and a halogen atom. In the formula, R14, R15 and R16 represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkylcarbonyl group, Represents an alkoxy group, a carbonylalkoxy group or a dialkylamino group, wherein X represents a halogen atom, a BF ₄ group, a PF ₆ group, a CH ₃ SO ₃ group, a CF ₃ SO ₃ group or a p-toluenesulfonic acid group; However, in the formula, R13 and X are not simultaneously halogen atoms.)

The invention described in claim 2
The electrochromic display device according to claim 1.
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Ｒ１７は、アルキル基又はアリール基を表す。式中Ｒ１８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 according to claim 3
The electrochromic display device according to claim 1 or 2,
The supporting electrolyte is a compound represented by the following general formula (6) and / or a compound represented by the following general formula (7).

(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, R 17 represents an alkyl group or an aryl group. In the formula, R 18 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 according to claim 4
In the electrochromic display device according to any one of claims 1 to 3,
An electrochromic display device, wherein a polymer compound 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 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.

The invention described in claim 6
In the electrochromic display device according to any one of claims 1 to 5,
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.

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 electrochromic composition layer includes an electrochromic composition containing a leuco dye, a supporting electrolyte, and a polar solvent, and the electrochromic composition includes the general formula (1). ) And / or a compound represented by the above general formula (2), a compound represented by the above general formula (3) and / or a compound represented by the above general formula (4), And Compounds represented by the serial of formula (5) is added.
That is, the electrochromic composition includes a hydroquinone compound (a compound represented by the above general formula (1) and a compound represented by the above general formula (2)), a succinimide compound (the above A compound represented by the general formula (3) and a compound represented by the above general formula (4)) and a compound of a pyridinium salt (a compound represented by the above general formula (5)) are added.
Therefore, in an electrochromic display device using a leuco dye, since hydroquinone compounds and succinimides are added, deterioration of display performance due to repeated display and erasure can be eliminated. Since such a compound is added, deterioration of display performance due to storage over time can be eliminated. Further, since a pyridinium salt compound is added, a sufficient display density can be obtained even when driven at high speed.

  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.

<Configuration of electrochromic display device>
FIG. 1 is a plan view (a) and a cross-sectional view (b) schematically showing an electrochromic display device 100 of the present invention.
The electrochromic display device 100 of the present invention 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 facing the first substrate 10. A second substrate 30 provided, second electrodes 40 provided on the lower surface of the second substrate 30, an electrochromic composition layer 50 provided between the first substrate 10 and the second substrate 20, It is configured with.
The electrochromic display device 100 performs display by energization between the first electrodes 20 and the second electrodes 40. Further, the display is erased by energization in the direction opposite to the energization for the display or by cutting off the energization for the display.
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 in, for example, 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.
Examples of the material constituting 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. Furthermore, even if the material of the first electrodes 20 is, for example, gold or platinum, the function can be achieved as long as it is a thin film.

The first electrode 20 includes, for example, a metal electrode portion 21A formed in a line shape and a metal formed in a line shape having a width like the first electrode 20A of the electrochromic display device 100A shown in FIG. It may be constituted by a transparent electrode portion 22A covering the electrode portion 21A. Moreover, you may be comprised from the transparent electrode which covers the whole one surface of the 1st board | substrate 10 like the 1st electrode 20B of the electrochromic display device 100B shown in FIG.
The material of the metal electrode portion 21A is not particularly limited, and a material constituting the metal 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.
The material of the transparent electrode portion 22A ... and the first electrode 20B is not particularly limited, and a material constituting the transparent electrode can be used. Examples of the material constituting 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 electrode 22A, for example, can fulfill its function as long as it is a thin film even if the material is gold or platinum.

  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.

  In addition, the 2nd electrode 40 may be comprised from the transparent electrode which covers the whole one surface of the 2nd board | substrate 30 like the 2nd electrode 40B of the electrochromic display device 100B shown in FIG. 3, for example.

  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. 4, when the shape of the pore 51a is circular and the shape of the pixel 60 (shown by a one-dot chain line in FIG. 4) is square, the pore 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 above-described thickness and shape.
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. Although the method etc. which create the porous body 51 by controlling a conversion reaction are mentioned, It is not limited to this.

  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, a porous body 51 having a fine structure can be produced.
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), manufactured by Sefa Inc Examples include, but are not limited to, 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), etc. is not.

  The electrochromic composition layer 50 includes a porous body 51 as long as it can hold the electrochromic composition 52 like the electrochromic composition layer 50B of the electrochromic display device 100B shown in FIG. It does not have to be.

The electrochromic composition 52 includes a leuco dye 52a, a supporting electrolyte, and a polar solvent.
The electrochromic composition 52 includes, for example, a compound 53 (a compound represented by the above formula (1) and / or a compound represented by the above formula (2), the above formula (3)). And / or the compound represented by the above formula (4) and the compound represented by the above formula (5) are added.
In addition, for example, a polymer compound 54 for adjusting the physical properties (for example, viscosity) of the electrochromic composition 52 is added to the electrochromic composition 52.

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 (18), a compound represented by the following formula (19), and a compound represented by the following formula (21), the blending amount is electro It can be 3 to 40 weight% with respect to the chromic composition 52 whole.

  Hereinafter, examples of the leuco dye 52a are classified and shown according to the color of the leuco dye 52a. However, since these are examples, the leuco dye 52a is not limited.

The following formulas (8) and (9) are leuco dyes 52a that develop yellow.

The following formulas (10) to (12) are leuco dyes 52a that develop magenta.

The following formulas (13) to (16) are leuco dyes 52a that develop cyan.

The following formulas (17) and (18) are leuco dyes 52a that develop red.

The following formula (19) is a leuco dye 52a that develops a blue color.

The following formulas (20) and (21) 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 two or more kinds of compounds may be appropriately used in combination.
The supporting electrolyte is preferably added in an amount of 0.01 to 2% by weight with respect to the total weight of the electrochromic composition 52, and 0.1 to 2% 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 (6) and / or the above formula (7) ).

Examples of the compound represented by the above formula (6) and the compound represented by the above formula (7) are shown below, but these are exemplifications and limit the supporting electrolyte. is not.
Specific examples of the compound whose general formula is represented by the above formula (6) include, for example, NaClO ₄ , LiClO ₄ , KClO ₄ , RbClO ₄ , CsClO ₄ , NH ₄ ClO ₄ , LiBF ₄ , LiPF _{6 and the} like. It is done.
Specific examples of compounds of the general formula expressed by formula (7), 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 54 when the polymer compound 54 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, for example, 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.

Of the compounds 53 added to the electrochromic composition 52, the compound represented by the above formula (1) and / or the compound represented by the above formula (2), and the general formula Is a compound represented by the above formula (3) and / or a compound represented by the above formula (4) is a compound of the electrochromic display device 100 that accompanies repeated operations of coloring and decoloring of the leuco dye 52a. It has a function of further suppressing deterioration of display quality.
Of the compounds 53 added to the electrochromic composition 52, the compound represented by the above formula (3) and / or the compound represented by the above general formula (4) is an electrochromic display device. 100 has a function of improving storage stability over time.
The amount of the compound represented by the general formulas (1) to (4) is preferably 1 to 20% by weight based on the content of the leuco dye 52a. For sufficient expression, it is preferable to add 5 to 20% by weight.

In addition, among the compounds 53 added to the electrochromic composition 52, the compound represented by the above formula (5) has a function of enhancing the color developability of the leuco dye 52a and enabling display at high speed. Have
The amount of the compound represented by the general formula (5) is preferably 3 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 preferable to add so that it may become 20 to 40 weight%.

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

The following formulas (22) to (36) are examples of compounds whose general formula is represented by the above formula (1). As for the compound represented by the above formula (1), various types may be used alone, or two or more types may be used in combination as appropriate.

The following formulas (37) to (52) are examples of compounds whose general formula is represented by the above formula (2). As for the compound represented by the above formula (2), various kinds of compounds may be used alone, or two or more kinds may be appropriately used in combination.

The following formulas (53) and (54) are examples of compounds whose general formula is represented by the above formula (3). As the compound represented by the above formula (3), various compounds may be used alone, or two or more compounds may be appropriately used in combination.

The following formulas (55) to (57) are examples of compounds having a general formula represented by the above formula (4). As for the compound represented by the above formula (4), various types may be used alone, or two or more types may be appropriately used in combination.

The following formulas (58) to (83) are examples of compounds whose general formula is represented by the above formula (5). The compound represented by the general formula (5) may be used alone or in combination of two or more as appropriate.

The polymer compound 54 added to the electrochromic composition 52 has a function of increasing the viscosity of the electrochromic composition 52 and facilitating its handling. The polymer compound 54 may be used alone or in combination of two or more as appropriate.
The polymer compound 54 is used to increase the viscosity of the electrochromic composition 52. In this case, the properties of the electrochromic composition 52 are a low viscosity liquid, a high viscosity paste, a low fluidity gel, It can be.
A preferable blending amount of the polymer compound 54 is preferably 0.1 to 80% by weight with respect to the total weight of the electrochromic composition 52.

Although the example of the suitable polymer compound 54 is shown below, these are illustrations and do not limit the polymer compound 54.
Specific examples of the polymer compound 54 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. And polyvinyl formal such as polycarbonate and polyvinyl butyral. Particularly preferred are polyvinyl butyral and polyvinylidene fluoride.

  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 striped 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 striped 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 30 on which the second electrodes 40 are formed. This is a process 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 substrates 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 applied to the surface of the first substrate 10 on which the first electrodes 20... And / or the second substrate 30 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 30 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 Step The bonding step is to bond 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, with the electrodes inside, This is a step of encapsulating the electrochromic composition 52 to which predetermined additives (compound 53, polymer compound 54, etc.) are 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 in which a predetermined additive is added is immersed in the porous body 51 placed 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 has been 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 between the two substrates on which the body 51 is installed, and an electrochromic composition 52 to which a predetermined additive is added is made 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 configured 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. 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 color development of the electrochromic display device 100 can be maintained, for example, by supplying a current smaller than the current supplied for display. 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 a memory performance of display. Will have.
Specifically, when the electrochromic composition 52 is impregnated in the porous body 51 and the electrochromic composition 52 is introduced into the pores 51 a of the porous body 51, the leuco dye in the electrochromic composition 52 For example, as shown in FIG. 5, 52 a moves from the inside of the pores 51 a of the porous body 51 to the display area at the interface between the electrochromic composition layer 50 and the second electrode 40 as shown in FIG. 5. Color is generated and the current is interrupted, or the current is applied in the direction opposite to that for color development, so that the inside of the pores 51 a of the porous body 51 from the interface between the electrochromic composition layer 50 and the second electrode 40. Move to and erase. 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. As a result, in the electrochromic display device 100 of the present invention, the leuco dye 52a remains on the surface of the second electrode 40 for a certain period even after display and after interruption of energization. Will be maintained.

Therefore, in the present invention, energization for maintaining the display is performed only when it is desired to maintain the display for a long period of time, and when it is desired to erase the display immediately after the energization is cut off, This can be achieved by energizing in the opposite direction to the energization.
In order to further improve the memory performance, a technique of reducing the pore diameter of the pores 51a of the porous body 51 is effective, but the specification of the porous body 51 is that of the image displayed as described above. It is preferable to determine according to the target display performance such as contrast and resolution, and according to the necessity of energization for maintaining the display.

<Example>
Hereinafter, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited thereto.

<Example 1>
(Production of electrochromic display devices)
First, an electrochromic display device 100A (see FIG. 2) was created.

  Specifically, a 0.7 mm-thick rectangular non-alkali glass substrate was used as the first substrate 10. Then, chromium is deposited to a thickness of 10 nm on one surface (upper surface) of the first substrate 10, gold is deposited to a thickness of 120 nm on the chromium, and chromium is deposited to a thickness of 10 nm on the gold. A metal film was formed by vapor deposition. The formed metal film containing gold was patterned into a stripe pattern with a stripe width of 0.025 mm and a pitch of 0.45 mm by photolithography, thereby forming the metal electrode portions 21A of the first electrodes 20A. . Next, ITO having a film thickness of 150 nm was formed by sputtering on the formed stripe-patterned metal electrode portions 21A. The first electrode 20A is formed by patterning the sputtered ITO film in a stripe shape so as to cover the metal electrode portion 21A with a stripe width of 0.42 mm and a pitch of 0.45 mm by using a photolithography method. A transparent electrode portion 22A ... was formed.

As the second substrate 30, a 0.7 mm thick rectangular non-alkali glass substrate was used. Then, an ITO film having a thickness of 200 nm was formed on the second substrate 30 by sputtering. A second electrode 40 was formed by patterning the sputtered ITO film in a stripe shape with a stripe width of 0.42 mm and a pitch of 0.45 mm using a photolithography method.
The number of lines of the formed first electrode 20A and second electrode 40 was 128, respectively.

  Next, as a porous body 51, a PETEX (polyester mesh cloth) PET51HC made by Sefar Inc. is sandwiched between the first electrode 20A ... and the second electrode 40 ..., and the first electrode 20A ... is the second electrode 40. The first substrate 10 and the second substrate 30 were overlapped in a form orthogonal to the. And the orthogonal part of 1st electrode 20A ... and 2nd electrode 40 ... is adjusted so that it may become the pixel 60 ..., and three of four side surfaces (surface parallel to thickness direction) are adhesives (for example, It was adhesively sealed with a thermosetting epoxy).

  Next, an electrochromic composition 52 (hereinafter referred to as “electrochromic composition [A]”) to which a predetermined additive has been added using a pipette is injected from an unadhered portion of the adhesive, and four side surfaces ( The adhesive non-adhered portion of the surface parallel to the thickness direction was adhesively sealed with an adhesive. Then, a white pet having a thickness of 200 μm was attached to the lower surface of the first substrate 10 to produce an electrochromic display device 100A (hereinafter referred to as “display device [A-1]”).

  For comparison, electrochromic compositions [B] to [D] were prepared, and each was used to produce an electrochromic display device in the same manner as the display device [A-1].

The electrochromic composition [B] is an electrochromic composition 52 to which a compound represented by the above formula (5) is not added among predetermined additives.
Hereinafter, an electrochromic display device including the electrochromic composition [B] is referred to as “display device [B]”.

Among the predetermined additives, the electrochromic composition [C] is a compound represented by the above formula (3) and / or a compound represented by the above formula (4), and the general formula: The compound represented by the above formula (5) is not added, and the benzoquinone is substituted for the compound represented by the above formula (1) and / or the compound represented by the above formula (2). This is an electrochromic composition 52 to which triphenylantimony is added in order to suppress deterioration of display performance due to repeated display and erasing while adding a derivative.
Hereinafter, an electrochromic display device including the electrochromic composition [C] is referred to as “display device [C]”.

The electrochromic composition [D] is an electrochromic composition 52 to which only the polymer compound 54 is added among predetermined additives.
Hereinafter, an electrochromic display device including the electrochromic composition [D] is referred to as “display device [D]”.

The composition of the electrochromic composition [A] is:
[1] 400 mg of leuco dye 52a (the above formula (21)),
[2] 40 mg of a compound represented by the above formula (1) and / or a compound represented by the above formula (2) (the above formula (22); 2,5-ditertiary amylhydroquinone),
[3] A compound represented by the above formula (3) and / or a compound represented by the above formula (4) (the above formula (53); succinimide) 40 mg,
[4] 110 mg of a compound having the general formula represented by the above formula (5) (the above formula (63); 1-butylpyridinium hexafluorophosphate),
[5] supporting electrolyte _{((n-C 4 H 9} ) 4 NBF 4; tetra-n-butylammonium tetrafluoroborate) 40 mg,
[6] 1.0 g of polar solvent (N, N-dimethylacetamide),
[7] Polymer compound 54 (polyvinyl butyral; S-LEC BH3 manufactured by Sekisui Chemical Co., Ltd.) 50 mg,
It is.

The composition of the electrochromic composition [B] is:
[1] 400 mg of leuco dye 52a (the above formula (21)),
[2] 40 mg of a compound represented by the above formula (1) and / or a compound represented by the above formula (2) (the above formula (22); 2,5-ditertiary amylhydroquinone),
[3] A compound represented by the above formula (3) and / or a compound represented by the above formula (4) (the above formula (53); succinimide) 40 mg,
[4] supporting electrolyte _{((n-C 4 H 9} ) 4 NBF 4; tetra-n-butylammonium tetrafluoroborate) 40 mg,
[5] 1.0 g of polar solvent (N, N-dimethylacetamide),
[6] Polymer compound 54 (polyvinyl butyral; Swreck BH3 manufactured by Sekisui Chemical Co., Ltd.) 50 mg,
It is.

The composition of the electrochromic composition [C] is:
[1] 400 mg of leuco dye 52a (the above formula (21)),
[2] Benzoquinone derivative (2,5-ditertiary amylquinone) 40 mg
[3] Triphenylantimony 70mg
[4] supporting electrolyte _{((n-C 4 H 9} ) 4 NBF 4; tetra-n-butylammonium tetrafluoroborate) 40 mg,
[5] 1.0 g of polar solvent (N, N-dimethylacetamide),
[6] Polymer compound 54 (polyvinyl butyral; Swreck BH3 manufactured by Sekisui Chemical Co., Ltd.) 50 mg,
It is.

The composition of the electrochromic composition [D] is:
[1] 400 mg of leuco dye 52a (the above formula (21)),
[2] A compound represented by the above formula (6) and / or a compound represented by the above formula (7) ((nC ₄ H ₉ ) ₄ NBF ₄ ; tetra n butylammonium tetrafluoro Borate) 40mg,
[3] 1.0 g of polar solvent (N, N-dimethylacetamide),
[4] Polymer compound 54 (polyvinyl butyral; Sleksui BH3 manufactured by Sekisui Chemical Co., Ltd.) 50 mg,
It is.

(Evaluation of repeated stability)
First, a display operation was performed. Specifically, the pattern formation circuit was connected to each of the display device [A-1], the display device [B], the display device [C], and the display device [D]. Next, voltage application (energization) was performed at an operating voltage of 2.0 V and an operating speed of 100 ms / line, and a binary display pattern was formed by passive matrix drive display.
By this display operation, a black pigment was generated around the surface portion of the second electrode 40 at the portion where the first electrode 20A and the second electrode 40 intersect (pixel 60), and a black pattern was obtained.

Next, an erase operation was performed. Specifically, for example, the voltage application (energization) is stopped for each of the display device [A-1], the display device [B], the display device [C], and the display device [D] on which a black pattern is displayed. A voltage was applied in the direction opposite to the voltage application for display at an operating voltage of 1.5 V and an operating speed of 100 ms / line, and left as it was for 1 minute.
By this erasing operation, the black pattern displayed on the display device [A-1], the display device [B], the display device [C], and the display device [D] could be erased.
Subsequently, the display operation and the erasing operation were repeated.

The display device [A-1], the display device [B], and the display device [C] do not change the ground color at all even when the display operation and the erasure operation are repeated 1000 times, and the display density deteriorates. The display performance was almost the same as that for the first repetition. Further, the display operation and the erasure operation were repeated 10,000 times. The display device [A-1], the display device [B], and the display device [C] were all changed in ground color and display density. There was no deterioration.
On the other hand, in the display device [D], as the display operation and the erasing operation are repeated 50 times or more, the yellow color of the ground color gradually progresses and the display density gradually deteriorates. As a result, the display device [D] repeats 100 times or more. It was found that the contrast ratio deteriorated significantly.
From the above results, a hydroquinone compound (a compound represented by the above formula (1) and / or a compound represented by the above formula (2)) and a succinimide compound (the general formula is It has been found that by adding the compound represented by the above formula (3) and / or the compound represented by the above formula (4), it is possible to eliminate the deterioration in display performance due to repeated display and erasure.

Moreover, in the display device [A-1] and the display device [B], since the electrochromic composition layer 50 is colorless and transparent, the ground color (non-display portion) is 200 μm thick pasted on the back side of the first substrate 10. The white color of the high-reflectance reflecting the whiteness of white pets, and as a result, a high contrast ratio of black on a white background was achieved.
However, since the electrochromic composition layer 50 is colored yellow in the display device [C], the ground color (non-display portion) is light yellow. As a result, the display device [A-1] and the display device [C] B] The contrast ratio as high as that was not obtained.
From the above results, instead of a benzoquinone derivative, a hydroquinone compound (a compound represented by the above formula (1) and / or a compound represented by the above formula (2)) is added. As a result, it was found that a display device having a substantially colorless and transparent ground color can be obtained.

(Evaluation of high-speed display)
First, a display operation was performed. Specifically, a pattern formation circuit was connected to each of the display device [A-1] and the display device [B]. Next, voltages were applied at an operating voltage of 2.0 V, an operating speed of 100 ms / line, an operating voltage of 3.5 V, and an operating speed of 10 ms / line, and a binary display pattern was formed by passive matrix drive display.
By this display operation, a black pigment was generated around the surface portion of the second electrode 40 at the portion where the first electrode 20A and the second electrode 40 intersect (pixel 60), and a black pattern was obtained.

  Next, the black pattern displayed on each of the display device [A-1] and the display device [B] was photographed using a digital camera, and the obtained photographing data was printed out using a laser printer. Then, the optical reflection density of the printed pattern was measured using a Macbeth densitometer. The result is shown in FIG.

As shown in FIG. 6, the display device [A-1] (the electrochromic display device 100A of the present invention) has a maximum display density of 1.33 at 100 ms / line and a maximum display density of 0.93 at 10 ms / line. The maximum display density is about 70% of the maximum display density at 100 ms / line even at a high-speed display such as 10 ms / line.
On the other hand, the display device [B] has a maximum display density of 1.20 at 100 ms / line, a maximum display density of 0.37 at 10 ms / line, and a maximum display density of 100 ms for high-speed display such as 10 ms / line. It was about 30% of the maximum display density in / line.
From the above results, it was found that by adding a pyridinium salt compound (a compound whose general formula is represented by the above formula (5)), a sufficient display density can be obtained even when driven at high speed.

<Example 2>
(Production of electrochromic display devices)
First, an electrochromic display device 100B (see FIG. 3) was created.

  Specifically, a 0.7 mm-thick rectangular non-alkali glass substrate was used as the first substrate 10. Then, on the one surface (upper surface) of the first substrate 10, ITO having a film thickness of 200 nm was formed by sputtering to form the first electrodes 20B.

  As the second substrate 30, a 0.7 mm thick rectangular non-alkali glass substrate was used. Then, a second electrode 40B was formed on the second substrate 30 by sputtering ITO having a thickness of 200 nm.

  Next, a holding body 51B such as a pet film is sandwiched between end portions of the first electrode 20B and the second electrode 40B between the first electrode 20B and the second electrode 40B, and the first substrate 10 and the second substrate 30 are overlapped. Combined. Then, three of the four side surfaces (surfaces parallel to the thickness direction) were adhesively sealed with an adhesive (for example, thermosetting epoxy).

  Next, the above-described electrochromic composition [A] is injected from the adhesive non-adhered portion using a pipette, and the adhesive non-adhered portion of the four side surfaces (surface parallel to the thickness direction) is adhesive. And sealed. 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 100B (hereinafter referred to as “display device A-2”).

For comparison, an electrochromic composition [E] was prepared, and an electrochromic display device (hereinafter referred to as “display device [E]”) was prepared in the same manner as the display device [A-2].
Further, the electrochromic composition [A] is sealed in a glass tube, heat sealed, and left in an oven at 60 ° C. for 10 days to prepare an electrochromic composition in the same manner as the display device [A-2]. A chromic display device (hereinafter referred to as display device [A-2-10]) is prepared, and the electrochromic composition [E] is sealed in a glass tube, heat-sealed, and then heated in a 60 ° C. oven. What was left to stand for 10 days was prepared and the electrochromic display device (henceforth a display device [E-10]) was produced like display device [A-2].

  In the electrochromic composition [E], among the predetermined additives, a compound represented by the above formula (3) and / or a compound represented by the above formula (4) is added. The electrochromic composition 52 is not.

The composition of the electrochromic composition [E] is:
[1] 400 mg of leuco dye 52a (the above formula (21)),
[2] 40 mg of a compound represented by the above formula (1) and / or a compound represented by the above formula (2) (the above formula (22); 2,5-ditertiary amylhydroquinone),
[3] 110 mg of a compound having the general formula represented by the above formula (5) (the above formula (63); 1-butylpyridinium hexafluorophosphate),
[4] supporting electrolyte _{((n-C 4 H 9} ) 4 NBF 4; tetra-n-butylammonium tetrafluoroborate) 40 mg,
[5] 1.0 g of polar solvent (N, N-dimethylacetamide),
[6] Polymer compound 54 (polyvinyl butyral; Swreck BH3 manufactured by Sekisui Chemical Co., Ltd.) 50 mg,
It is.

(Evaluation of stability over time)
A direct current power source was connected to each of the display device [A-2], the display device [A-2-10], the display device [E], and the display device [E-10]. Next, through the electrodes (first electrode 20B, second electrode 40B), the current amount is 3 mA, the energization time is changed in the order of 10 seconds, 15 seconds, and 20 seconds, and the current is displayed on the second electrode 40B. The color development state (absorbance) during that time was measured using a spectrophotometer (U-3310 manufactured by Hitachi, Ltd.). The results are shown in FIGS.

7 and 8, the horizontal axis represents time, and the vertical axis represents absorbance detected at a wavelength of 585 nm. 7 is the result of the display device [A-2], the broken line is the result of the display device [A-2-10], the solid line of FIG. 8 is the result of the display device [E], and the broken line is the display device. It is a result of [E-10].
As shown in FIG. 7, the display device [A-2-10] had substantially the same absorbance value as the display device [A-2] even when the energization time was increased. Accordingly, the color development characteristics of the display devices [A-2] and [A-2-10] (the electrochromic display device 100B of the present invention) may not change even after storage at 60 ° C. for 10 days. I understood.
On the other hand, the absorbance value of the display device [E-10] became smaller than that of the display device [E] as the energization time increased. Further, the display device [E] returns to the colorless state before the color development after the power supply is cut off, whereas the display device [E-10] remains colorless before the color development even when the power supply is cut off. As a result, it was found that the ground color was colored and the contrast ratio was lowered. Accordingly, it was found that when the display devices [E] and [E-10] were stored at 60 ° C. for 10 days, the color development characteristics changed and the display performance before storage could not be maintained.
From the above results, by adding a compound of succinimides (a compound represented by the above formula (3) and a compound represented by the above formula (4)), display performance by storage over time It was found that the deterioration of the can be eliminated.

According to the electrochromic display devices 100, 100A, 100B of the present invention described above, the first substrate 10, the first electrodes 20 ..., 20A ..., 20B provided on the upper surface of the first substrate 10, and the first substrate. The second substrate 30 is provided above the substrate 10 so as to be opposed to the first substrate 10 and formed of a transparent material, and is provided on the lower surface of the second substrate 30, and at least a part thereof is formed of a transparent electrode material. 40B, and an electrochromic composition layer 50 provided between the first substrate 10 and the second substrate 30. The electrochromic composition layer 50 includes a leuco dye 52a and a support. An electrochromic composition 52 containing an electrolyte and a polar solvent is provided. The electrochromic composition 52 includes a compound 53 (a compound represented by the above general formula (1) and Or a compound represented by the above general formula (2), a compound represented by the above general formula (3) and / or a compound represented by the above general formula (4), and the above general formula (5) )) Is added.
That is, the electrochromic composition includes a hydroquinone compound such as a compound represented by the above general formula (1) and a compound represented by the above general formula (2), and the above general formula (3). And succinimide compounds such as the compound represented by the above general formula (4), and pyridinium salt compounds such as the compound represented by the above general formula (5) are added.
Therefore, in the electrochromic display devices 100, 100A, 100B using the leuco dye 52a, hydroquinone compounds and succinimides are added, so that display performance deterioration due to repeated display / erasing is eliminated. Since a succinimide compound is added, display performance deterioration due to storage over time can be eliminated. Further, since a pyridinium salt compound is added, a sufficient display density can be obtained even when driven at high speed.

  Moreover, according to the electrochromic display devices 100, 100A, and 100B of the present invention, the polar solvent is at least one organic solvent that exhibits electrical conductivity 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.

  Moreover, according to the electrochromic display devices 100, 100A, and 100B of the present invention, the supporting electrolyte is a compound represented by the general formula (6) and / or a compound represented by the general formula (7). 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 devices 100, 100 </ b> A, and 100 </ b> B of the present invention, the polymer compound 54 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 devices 100 and 100A of the present invention, the first electrodes 20 ..., 20A ... are a plurality of electrodes extending in parallel, and the second electrodes 40 ... are the first electrodes 20, ..., 20A. Is a transparent display electrode composed of a plurality of transparent electrodes extending in parallel to a direction orthogonal to the first electrode 20..., 20 A... And the second electrode 40. The chromic 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 includes predetermined additives (compound 53, polymer compound 54, etc.). The electrochromic composition 52 to which is added) 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 devices 100 and 100A of the present invention, driving for display is performed by passive matrix driving. Therefore, the structure is simple and suitable.

  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 devices 100, 100A, 100B of the present invention, an electro with a predetermined additive added by energizing between the first electrodes 20 ..., 20A ..., 20B and the second electrodes 40 ..., 40B. For example, an electrochromic display device 100C shown in FIG. 9 may include a conductive member 55C that closes the bottom of the pores 51a of the porous body 51, as long as it can energize the chromic composition 52. good.

  Specifically, the electrochromic display device 100C 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> C provided therebetween.

  The electrochromic composition layer 50C includes, for example, a porous body 51 and an electrochromic composition to which predetermined additives (such as the compound 53 and the polymer compound 54) introduced into the pores 51a of the porous body 51 are added. And a conductive member 55 </ b> C that closes the bottom of the pores 51 a of the porous body 51.

  The conductive member 55C is formed in a planar shape, for example, and the porous body 51 is laminated on the upper surface of the conductive member 55C.

  The material of the conductive member 55C is not particularly limited, and for example, a conductive metal or a carbon material can be used. In addition, the conductive member 55C may be constituted by, for example, a single layer made of a single material, or may be constituted by two or more layers made of different materials.

  Of course, the electrochromic display device 100C may be configured by providing the electrochromic display devices 100A and 100B with the conductive member 55C.

(Modification 2)
The electrochromic display device 100 of the present invention only needs to be able to energize the electrochromic composition 52 to which a predetermined additive is added by energizing between the first electrode 20... And the second electrode 40. The first electrodes 20 and the second electrodes 40 may be, for example, the first electrodes 20D and the second electrodes 40D of the electrochromic display device 100D shown in FIG.

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

The first electrodes 20D are formed, for example, in a line shape, and are provided in stripes at equal intervals parallel to each other.
The first electrodes 20D 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 the second electrodes 40D. Yes.
The first electrodes 20D ... are paired with the second electrodes 40D ... and have a function of energizing the electrochromic composition layer 50.
The first electrodes 20D... Intersect with the transparent display electrode portions 41B of the second electrodes 40D..., That is, intersect each other with an interval, and form pixels 60 at the intersections.

  The material of the first electrodes 20D 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 40D are formed in a line shape with the transparent display electrode portions 41D provided in positions corresponding to the pixels 60, for example, and are formed in a line shape provided in stripes at equal intervals parallel to each other. The electrode portions 42D, etc. are provided. The transparent display electrode portions 41D are connected to the line electrode portion 42D.
The second electrodes 40D 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 opposite the first electrodes 20D. Yes.
The second electrodes 40D ... are paired with the first electrodes 20D ... and have a function of energizing the electrochromic composition layer 50.
The transparent display electrodes 41D of the second electrodes 40D ... intersect with the first electrodes 20D ... with a three-dimensional intersection, that is, with an interval, and form a pixel 60 in the region of the intersection.

The material of the transparent display electrode portions 41D is not particularly limited as long as it is a material that can constitute the 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 41D can function even if the material is gold or platinum as long as it is a thin film.

  The material of the line-shaped electrode portions 42D 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 40D 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 40D ... 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 41D and the line-shaped electrode portion 42D are formed by a single deposition method, plating method, sputtering, and 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 100D of Modification 2, the first electrodes 20D are a plurality of line-shaped electrodes extending in parallel, and the second electrodes 40D are transparent display electrode portions 41D and transparent display electrodes. It is comprised by the line-shaped electrode part 42D ... connected to the part 41D .... Therefore, since the second electrodes 40D (transparent display electrode portions 41D) 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 42D of the first electrode 20D... And the second electrode 40D. The potential difference between the two becomes small, and power can be saved.

  In the second modification, the first electrode 20D 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 20D... And the transparent display electrode portion 41D of the second electrode 40D.

  In the above-described embodiment 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.

  The electrochromic display device 100B according to the above-described embodiment may include the porous body 51 instead of the holding body 51B.

It is a figure which shows typically the electrochromic display device (1st example) of this invention. It is a figure which shows typically the electrochromic display device (2nd example) of this invention. It is a figure which shows typically the electrochromic display device (3rd example) of this invention. 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. It is a figure which shows the evaluation result of the high-speed display of the electrochromic display device (display device [A-1]) of this invention, and the electrochromic display device for comparison (display device [B]). It is a figure which shows the evaluation result of temporal stability of the electrochromic display device (display device [A-2], [A-2-10]) of this invention. It is a figure which shows the evaluation result of temporal stability of the electrochromic display device (display device [E], [E-10]) for a comparison. 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

10 1st board | substrate 20,20A, 20B, 20D 1st electrode 30 2nd board | substrate 40,40B, 40D 2nd electrode 50,50B, 50C Electrochromic composition layer 51 Porous body 51a Pore 52 Electrochromic composition 52a Leuco Dye (dye)
53 Compound (compound represented by general formula (1) and / or compound represented by general formula (2), compound represented by general formula (3) and / or compound represented by general formula (4) And a compound represented by the general formula (5))
54 Polymer Compound 60 Pixel 100, 100A, 100B, 100C, 100D Electrochromic Display Device

Claims (6)

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; In an electrochromic display device comprising:
The electrochromic composition layer comprises an electrochromic composition comprising a leuco dye, a supporting electrolyte, and a polar solvent,
The electrochromic composition includes a compound represented by the following general formula (1) and / or a compound represented by the following general formula (2), a compound represented by the following general formula (3) and / or Or the compound represented by the following general formula (4) and the compound represented by the following general formula (5) are added, The electrochromic display device characterized by the above-mentioned.

(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 R11, R9 and R12, R10 and R11 or R10 and R12 in the formula are bonded to each other. Represents a double bond.)

(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 formula, R13 represents a linear or branched alkyl group having 1 to 16 carbon atoms and a halogen atom. In the formula, R14, R15 and R16 represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkylcarbonyl group, Represents an alkoxy group, a carbonylalkoxy group or a dialkylamino group, wherein X represents a halogen atom, a BF ₄ group, a PF ₆ group, a CH ₃ SO ₃ group, a CF ₃ SO ₃ group or a p-toluenesulfonic acid group; However, in the formula, R13 and X are not simultaneously halogen atoms.) The electrochromic display device according to claim 1.
The electrochromic display device, wherein the polar solvent is at least one organic solvent that exhibits electrical conductivity using the supporting electrolyte. The electrochromic display device according to claim 1 or 2,
The electrochromic display device, wherein the supporting electrolyte is a compound represented by the following general formula (6) and / or a compound represented by the following general formula (7).

(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, R 17 represents an alkyl group or an aryl group. In the formula, R 18 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 3,
An 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 4,
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 5,
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.

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