JPS6070421A - Electrochromic display element - Google Patents

Abstract

PURPOSE:To form a good ion conductor having an excellent characteristic even on an electrochromic material layer which is thermally unstable or is relatively high in vapor deposition pressure by forming the good ion conductor of a thin film contg. at least a high polymer material and deliquescent material. CONSTITUTION:A glass plate 5 on which a thin transparent conductive film consisting of indium oxide, etc. is etched and a transparent electrode 3 for display is provided and thereafter a film 1 is deposited by evaporation by sputtering MoO3 as an electrochromic material. A white paint for forming a good ion conductor is prepd. by dissolving and dispersing PVA and polyethylene glycol as well as pulverous white pigment powder consisting essentially of TiO2 into a solvent mixture composed of pure water and methyl alcohol then dissolving CaCl2 therein. A glass plate provided with the above-described transparent display electrode and electrochromic material layer is dipped therein and is then pulled to form a paint coated film 2 on both surfaces of the glass plate. The unnecessary coated film is wiped away and the substrate is dried. Au is then deposited by vacuum evaporation on the solid good ion conductor layer surface 2 to provide a counter electrode 4. The electrochromic material which is high in vapor pressure or low in thermal decomposition temp. is thus made usable as an electrochromic display element material.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical field to which the invention pertains] The present invention relates to a display system that utilizes an electrochromic phenomenon, and particularly relates to an improvement in a good ionic conductor film constituting an electrochromic display element.

[Prior art and its problems]

Electrochromic phenomena, in which the light absorption spectrum of a substance changes due to an electric field or electric current, or the generation and disappearance of colored species as an electrochemical reversible reaction, are used in liquid crystal display elements, light emitting diodes, electroluminescence sensor display elements, plasma display elements, etc. Conventional displays, such as being able to obtain display elements with a wider variety of colors than display elements, and having display memorability,
Although it has many advantages that A-Riko does not have, and its practical application is desired, various technical problems remain and it has not been put into practical use.

That is, a liquid electrochromic display element in which a liquid containing an electrochromic material and an electrolyte is sealed between a pair of electrodes, and an electrolyte between a pair of electrodes in which a solid electrochromic material layer is fixed on at least one of the electrodes. In a solid-liquid electrochromic display element in which a dissolved liquid is sealed, there is a problem that the sealing material is damaged by the polar solvent used to dissolve the electrolyte, and the liquid tends to leak. In addition, an all-solid-state electrochromic display element using a solid electrochromic material and a solid ionic good conductor, which was devised for the purpose of eliminating the drawbacks common to the liquid-type electrochromic display element and the solid-liquid type electrochromic display element, is, for example, qWf Kaisho 52-73
As disclosed in No. 749 and Japanese Unexamined Patent Publication No. 56-4679, an ion-rich layer is formed on the electrochromic material layer using a method such as vacuum deposition or sputtering. In addition, it is difficult to form 141 protons on the electrochromic material layer with high deposition pressure or low thermal decomposition temperature.

An improved method for forming a solid ion-rich η'1 layer in close contact with an electrochromic material layer is disclosed in JP-A-54-89652 and JP-A-54-115147.
For example, a method of applying a solution of a polystyrene sulfo/acid type polymer or a vinyl monomer P a -containing monomer copolymer to an electrochromic material Xi' layer is disclosed in JP-A-54-151052. For example, on the electrochromic material layer, AA! z
(After coating an alcohol solution of an alkoxide compound such as OC4H9h or S i (OC2H5) 4, drying it forms a thin film of M2O3 or S, which is a solid ion conductor.
A method for forming an i02 thin film has been devised, but in electrochromic display elements in which a polymer electrolyte is used as a proton conductor layer, the response speed of color development and fading is slow, and the alkoxide compound is dried to form a good ionic conductor layer. In the electrochromic display element in which the ion conductor layer is formed, pinholes are likely to occur, making it difficult to manufacture an all-solid-state electrochromic display element that can uniformly develop and fade color.

[Purpose of the invention]

The present invention has been made in view of the above-mentioned points, and is an ionic good conductor that forms an ionic good conductor with excellent characteristics even on an electrochromic material layer that is thermally unstable or has a relatively high deposition pressure. The purpose of the present invention is to provide a coating material for forming a coating material, and to provide an electrochromic display element with uncertain reliability.

[Overview of the invention]

Unexploded Yuan 1 uses an electrochromic material that is capable of electrochemical redox reactions and has different light absorption spectra in the oxidized and reduced states between at least a pair of electrodes, and a thin film that is a good ionic conductor and magnetic insulator. In the electrochromic compound, the good ionic conductor is at least a polymer! It is characterized by being a thin film containing PiJ quality and deliquescent curve.

The paint for forming an ion-rich body used in the practice of the present invention is prepared by first dissolving a polymer in a commonly used organic solvent, and then dispersing or dissolving a deliquescent substance, such as CaCl2+MgCl2, in the polymer solution. can get.

The image quality 2 that was removed in the process described in fifJ. Segment 43 for displaying the paint for caries formation! By applying and drying the electrochromic material layer formed on the surface of the electrochromic material layer using a tracing method, Imenryo2! By forming a solid ion body and further providing a counter electrode on the formed solid ion body by a conventional method,
An improved electrochromic display element is disclosed.

In order to produce the paint for forming a Groton resin, which is necessary for carrying out the present invention, polyvinyl chloride resin, vinylidene chloride, vinyl chloride copolymer resin, polyvinyl alcohol resin, polyvinyl O acecool resin, polyethylene, polypropylene are used. , polystyrene-based at fat, styrene, acrylonitrile-based resin, acrylic resin, cellulose derivative,
Various alkyd paulownia resins, polycarbonate resins, polyacetal resins, chlorinated polyether resins, fluorine resins, various silicone resins, and various phenolic resins.

All kinds of 41゛d resins such as various urea resins, melamine resins, unsaturated polyester resins, various epoxy resins, and diallyl phthalate resins can be used, but especially water-soluble polymers such as polyvinyl alcohol and polyvinyl Preferred are pyrrolidone, methyl vinyl ether and maleic anhydride copolymer, polyethylene glycol, cellulose derivatives, egg albumin, casein, glue, gelatin, gum arabic, and the like.

In addition, many compounds can be mentioned as deliquescent substances used in the production of the ionic good conductor-forming paint necessary for the present invention, but white or colorless glue 1-7'4=body;' :, Objective f is ZllCll 21 ANC1
3r S bCll 3 TYC13, InCl3. G
dCl3. GaClz, GaCl3. CrC1z, Cr
Cl3゜5rC12, CsC6, CeC113, ThC
14, BiCl3, BeCA'2, LaCl,
BeF2.

1'eF3, 5nF4, KF + uF6. Sb
F3, N) 14F +NI (411IF 2, Z
nBr 2 , YBr 31Cdr3. CdBr2. G
aBr3. CaBr2. SnBr4. CeBr3. Be
Br2゜MgBr2, C1Br, AlI3, Ca
I2, SrI2, NaI, MgI2, LiI
, KI31PSC13, etc., IQ'JO2, NaN
O2, Al(NO3)a, Yb(NO3) 31Y(
NO3)3, Y(NO3)3, In(NOa
) 3 +Ga(NOa) 3. Ca(NO3) 2
+LiNO3, Mg (NO3) 2 , (NH3
0H) NO3, La (NO3) 3, Zr (NO
3) 4 +Hg(NO3) 2 +5e(NO3)2
, Ce(NO3) 3. 'L'1 (NO3) 3, T
h(NO3) 4 IZn(ClO3) 2 , LiC
lO3, Ca (C103) 2 , In (C13)
4, Pb(ClO:()zAgclo4, NaCl
4, Mg(ClO4) 2 , Ca(Clo) 2 ,
2S eo 3 to HzSe03+, NH45O3NH
2, H2PH03, K2PH03, (N)I4)PH
03.

NaHPHOa, NazPHO3, 2021P204
．． P2O51As205. Na2O.

P203, Ni2S, Na2se, Cs2
S, Na2S, Rb2S, ILPI (202
, NaPH20z.

NH4CN, KCN, Au(CN)3, Cs
CN, NaCN, KOI-1, Sr (OH) 21C
sOH, NaOH, RbOH, Cs2CO3, Na
2C03, Li 2CO3, Zn (SCN) 21
NH4SCN, KSCN, Ca'(5CN) 2
, Na5CN, Ba(5CN)2, KS
eCN.

(NH4) 2Zn(SO4) 2.5b2C8O4)
3. Yb 2 (SO4) 3 , Gaz (SO4) 3
゜HgSO4,KH8O,s, Na1(SO4,5n
(SOa) 2113i 2 (SO4) 31(N
2H6) 2SO4, (PH4) 2SO4, H3PO
4, KzHPo 4 , Na 2klPo 4 .

KE(2PO4, Ca (H2PO4) 2 , (N
)I4) 2s 2031 to 2s 203, KzT
3As04 to eO4+, KAsO'2, 2S 1
o3r↑'JH4BO2, I (BO2, ni2'MOO4
.

(NH4)ZnCA! 4, (Nf(4)MgC1
3, N0BF 4 , NaNf(, z , N11zOI
(.

Na 28207, Ni4P 207, KaH, Na
5H, 3As S 4. Nz)16C12(I(PO
3) It is possible to use a colorless or white deliquescent compound such as Among the deliquescent compounds, compounds with i'&(high or low reducing ability) are preferred, and among the -LD compounds, experiments using CaC1z, MgCl2, LiCl, etc. have shown that the best electrochromic display elements are obtained. A good ion conductor was obtained.

Furthermore, when it is necessary to make the background color of the electrochromic display element greenish-blue-yellow or red, the above-mentioned deliquescent compound and pigment or dye may be dispersed or dissolved in a polymer solution. YbCl
3. uC14+uc15. SmCl3゜FeCl3,
CuCA2 (NH4)NiCd3. VC62, VOC
62, Ni ((jlo4) 2 .

KNH2, MoOCl4. uOzBr 2 , Ni (
NO3) 2 , Fe I 21F'i 2 (804
)3 *Mnz(SO4)3 and the like may be appropriately selected and used. ErCl3 is a deliquescent compound that exhibits a red color.
, AuC13uc13. PbCl2. MnCl2. R
hCl3. CoBr2. FeBr2. FeBr3゜Mn
Br 2 , MnI 2 +Ge I 4 , NH4C
oCl3, NaIvln04, Mn03, CrO
3+Rb5s, Co (NO3)2, Fe(SCN
)3, 2C83, ZnCr No.o7. Na2Cr2
0yNa3(Fe(CN)6), uOI+Iz, Au2
(SO+)3. It is possible to use Pd5O4"?, and as a deliquescent compound that exhibits blue color, 0sC12,I
rBr4, Cu(NO3)z, TiCl3. F”e(NO3)3. Deliquescent compounds that exhibit yellow color include InC6, NbCl5,
N1Cdz, IC73,5eC14rAd]3r 3
1 InBr 3 , SmBr3+ Sm13r3 ,
TlBr: (, TiBr4.NiBr 21B iB
r 3 , l-12Ptc16. ) LAuC14, Kz
)ig I 4 , AgF , InI 3 , uo
zG03)z(NH4)2ce(NO3)6, Pb
(NO3) 2 , Be (NO3) 2 , CsC・
z, Li2S.

Na2C83,](2(Pt(CN)4), Fe2(
804)3 and the like are known, and may be appropriately selected from the above compounds for use.

A coating film obtained by coating an electrochromic material with a polymer solution containing the above-mentioned deliquescent compound has a large amount of ions generated in the coating film as the deliquescent compound deliquesces, and a pair of 1B poles are formed. Ions move due to the electric field between the two. That is, it exhibits ionic conductivity. For this reason, while dissolving the above deliquescent compound in a polymer solution,
Furthermore, other types of strong electrolytes such as I(F, KCl, KBr,
KI, HP, NaC/I! , NaBr.

If NaI or LiCIO4 is added, a paint for forming a good proton conductor with improved ionic conductivity can be obtained, but a coating film with excellent ionic conductivity cannot be obtained from a polymer solution in which only a strong electrolyte is dissolved without containing deliquescent compounds. cannot be obtained.

The polarizing material provided on the formed ionic good conductor material is not particularly limited as long as it is a conductive material that is not corroded by the deliquescent compound or strong electrolyte used, and may be made of metals such as Au and Cr and corrosion-resistant metal powders thereof. You may also use a paste consisting of:

〔Effect of the invention〕

According to the present invention, a solid proton good conductor layer can be formed without using complicated means such as vacuum evaporation or sputtering, and an electrochromic display element can be provided at low cost.

In addition, if the paint film is thin, most of the solvent contained in the paint for forming a good ionic conductor may be dispersed at room temperature, or if the paint film is thick,
Even if the used solvent has a high Foss point, it can be sufficiently removed by drying under reduced pressure, etc. Therefore, the electrochromic material can be heated gently as in the conventional method. /-
Furthermore, electrochromic materials with low vapor pressures and low thermal decomposition temperatures can also be used as electrochromic display mustard materials.

[Embodiments of the invention]

The first aspect of the present invention will be explained in detail based on embodiments without reference to the drawings.

Example-1 The first example is a schematic process diagram for explaining an example of the present invention.

As shown schematically in cross section in Fig. 1(a), a glass plate on which a transparent four-electroconductive thin film of indium oxide or the like is laminated is etched to form a transparent display magnetic pole. After that, MoO3 was deposited as an electrochromic material using a sputtering device to a thickness of 100X.

On the other hand, polyvinyl alcohol (polymerization degree 2400 butylation degree 9
0 gr solid powder) 10 gr and polyethylene glycol (degree of polymerization 400, liquid) 10 gr, white pigment fine powder mainly composed of TiO2 30 gr, agate in a mixed solvent of 90 gr pure water and 30 gr methyl alcohol. After melting and dispersing using a mortar, 23 gr of CaC,h was dissolved to prepare a white paint for forming a good ionic conductor.

After immersing a glass plate with 11 layers of transparent display electrodes and an electrochromic layer as shown in Figure 8i41(a) into the obtained white paint, the glass plate was coated with the paint at a constant rate of 10α for 4D. It was pulled up from inside and a paint film was formed on both sides of the glass plate. After that, wipe off the paint film adhering to the glass surface on which the electrochromic material is not applied and dry it in a dryer at 70°C for 1 hour to remove the electrochromic material layer. A good ion conductor layer was formed on the same material. The cross-sectional shape of sample 1 obtained through the steps up to this point is t+'', as shown in 11y8I(b).

Next, a thin layer of Au was applied to the surface of the formed solid ion conductor layer using a vacuum evaporation device as a counter electrode of a transparent display electrode, and an electrochromic display assembly having a single crest shape as shown in FIG. 1(c) was formed. I got it.

After exposing the obtained electrochromic material 7J<element to an atmosphere with a relative humidity of 80% for 1σ for 30 minutes, a voltage of 107 volts was applied between the transparent display electrode and the pair of electrodes. When the electrochromic phenomenon was observed, 1. When the white electrode was an anode, 1.5Vodt was applied, and within 1 second, the same body as the i-pole shape or 8 colors VC97,
Set the display magnetic pole to 1 town and display Ili, wander around and see the evening
When fJ, 7Vo7t is applied between adults, 73 within 1 second
The color scale lost its f' angle, and the display surface ``1'' became uniformly white.

1, with the display 'ljL'j' as the anode'1 (apply pressure, display polarization and contact IQj: change the electrochromic old to blue, and then change the drowsiness circuit to 1) cI ↓ (In an experiment where I left it for a while, I noted that the blue statue lasted for more than a month, so it should be kept for a long time.)

In addition, instead of CaCl2, which is a strong compound,
Tunjing.

Using KCIJ, which is a
As a result of conducting experiments, it was found that the width and pressure required to produce a blue image were 10 volts or more, and that the entire display was uniform.
It took more than 1 minute to turn blue, and CaC4
It was confirmed that the electrochromic display element of this example using No. 2 was superior.

Example-2 Polyvinyl alcohol (degree of polymerization 2400. degree of polymerization 90)
% solid powder) 5gr, polyethylene glycol (N 400%) 3gr, TiO2 fine powder, 3gr pure water and 20gr methyl alcohol were dissolved in a mixed medium using an agate mortar and then deliquescent. 7.8gr of CaCl2 as a compound, KC as a supporting flux γη,
Dissolve 5.2 gr of #L ion white base material for forming a good conductor.
I would like to ask you to adjust this.

An electrochromic display element was prepared in the same manner as in Example 1 except that the white a material for forming an ion-favorable body was used.

The operating characteristics V of this electrochromic display element are 1. O Vo
It was found that the time required for erasing the color was less than 0.5 seconds, which was further improved than in Example-1.

Example-3 Co-existence of methyl vinyl ether and hydrothermal maleic acid j. ■ Combined GANTRH; ZoAN-1 6 9 (Gen
e rrJ An 1line & Fi1m Corpo
ration company's four product names, molecular formula: Coal (degree of polymerization 400
) 3gr, TiO2 fine powder: 30gr.

Pure water 90g, Methylalcohol: I-/l/20g
r, CaCl2 7.8gr, KCl5.2
Using gr, Example-1, Example-2 and Dowa: ion conscience body no 1', Iru, use! An electrochromic transducer was obtained in the same manner as in Example 1 and Example 2 except that this paint was used.

1! The element is J! electrochromic material. il
Custom made by Nosaku (lJ2, the voltage required to change the color of MOO3 from white to blue using the display electrode as the anode is 0.9V.
olt, 10 minutes to change color is within 05 seconds t),
Ichikawa and Menma changed the display electrode from red to green within 0.5 seconds at 0.8Vo7t.

Example-4 Polyvinylhyloridone powder P'VP K-90 was used instead of the copolymer of methyl vinyl ether and maleic anhydride.
(GeneralAniline & Film C
An electrochromic display element was obtained in the same manner as in Example 3, except that the product name (trade name, molecular formula: % formula %) manufactured by Corporation was used.

The properties of the printed electrochromic display element were similar to those of Example-3 and lI'JI.

Example 5 As shown in Fig. 1(a), a glass plate on which a transparent conductive thin film made of indium oxide was previously formed was etched to provide electrodes for transparent display C, and then an electrochromic The material used was W)3, which was formed into a thin layer with a thickness of 3000× using a lath batter device.

On the other hand, 5 gr of polymethyl methacrylate and 3 gr of polyethylene glycol were dissolved in 100 gr of methyl isobutyl ketone, and 20 g of a white fine powder pigment containing TiO2 as a main component was dispersed in this solution. Then add 10gr of CaCl2 to this solution as a deliquescent compound.

LiC as a supporting solution. A white paint for forming an ionic conductor was obtained by adding 3gri¥rM of d04.

A: Coat the previously prepared paint on the VVo 3 directions j and q in the same manner as in Example 1 and dry it. A bright display ``1.'' An electrochromic display element was constructed by providing a pair of recording electrodes 1'lt/lO!41.).

? 6 la: h fc electrochromic table 71, element (dlNVC) 3 used for electrochromic removal,
L lCeO4 such as glubylene carbonate (・;
1) Solid i% type electrochromic display element of Takahata, which was dissolved in a strong solvent and made into a good ionic conductor layer, and Domura's display tooth.
1.5 Voet between the polar total cathode and a pair of display electrodes at 17
When Ichikawa applies the same amount of energy, a blue image appears on the white display surface by 0.3
It was confirmed that the blue image appeared within seconds, and when the reverse market was applied, the blue image disappeared within 3 seconds and 1υ.

As shown in one example, this compound is a deliquescent compound due to the composition of the white paint for forming ion-like paint 14. An electrochromic display element obtained using a similar process required a voltage of 1.7 Volt or more for color development/decolorization, and a time required for color development/decolorization of 0.5 seconds or more.

In addition, as a deliquescent compound, IsiIg (-121b 1'
-131L t An electrochromic display element made using Cl+NaC704, AuC73, etc. is K
The results showed that the Vc adsorption pressure for developing and decoloring was lower and the rate of coloring and decoloring was faster than that of an electrochromic display element using only Cl or NaCl as a supporting substance.

[Brief explanation of drawings]

FIG. 1 is a cross-sectional view showing the manufacturing process of an electrothalomic display element according to the present invention. Electrode, 4... Counter electrode,
5...Glass substrate. Agent: Patent attorney Noriyuki Chika (and 1 other person) Figure 1, -?

Claims (5)

[Claims] (1) An electrochromic material that allows an electrochemical redox reaction between at least one pair of electrodes and has a different light absorption spectrum depending on the oxidized state and the reduced state, and an electrochromic material that has an electronically insulating thin film that is a good ionic conductor. An electrochromic display device, characterized in that the ionic good conductor thin film contains at least a polymeric substance and a deliquescent substance. Sky (2) The electrochromic display element according to claim 1, wherein the ionic good conductor thin film forming material is comprised of a water-soluble polymeric substance and a deliquescent electrolyte. (3) The electrochromic device according to claim 1, wherein the ion conductive layer is formed using a solution for forming an ion conductor consisting of a resin, a resin solvent, a deliquescent compound, and a supporting electrolyte. Chromic display element. (4) In the electrochromic device according to claim 1, one layer of ion filtering is formed using a paint for forming a good ion conductor consisting of a resin, a resin solvent, a deliquescent compound, a supporting electrolyte, and a pigment. An electrochromic display system featuring (5) In the electrochromic display unit 9 according to any one of items 1 to 5, polyvinyl alcohol, polyethylene glycol. Polyhinylpyrrolidone, menarvinyl ether and maleic anhydride co-coated with 1 heather, casein, and segitin. At least 1 stoma selected from glue, ovalbumin, gum arabic, and cellulose derivatives・1IIt
Electrochromic drinking water 51, which is characterized by using i as a material for forming a good ionic conductor layer.