# US 9,753,347 B2 · Electrochromic gel, method for producing the gel, method for controlling electronic printing and erasing on electrochromic gel, and stretchable display

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- Number: US 9,753,347 B2
- Document ID: US9753347B2
- Status: Granted
- Kind: B2
- Application number: 14/364,126
- Filed: 2013-01-30
- Published: 2014-11-13
- Granted: 2017-09-05
- Earliest claimed: 2012-01-30
- Assignees: National Institute for Materials Science
- Applicants: National Institute for Materials Science
- Inventors: Masayoshi Higuchi; Jian Zhang
- Web page: https://patentgrep.com/patent/US9753347B2

## CPC

- G02F 1/133305: {Flexible substrates, e.g. plastics, organic film}
- B41J 2/385: characterised by selective supply of electric current or selective application of magnetism to a printing or impression-transfer material (B41J2/005 takes precedence)
- G02F 1/15165: {Polymers}
- G02F 1/153: Constructional details
- G02F 2001/164: {the electrolyte is made of polymers}
- Y10T 428/31507: Of polycarbonate
- Y10T 428/31935: Ester, halide or nitrile of addition polymer
- Y10T 428/31938: Polymer of monoethylenically unsaturated hydrocarbon
- G02F: OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- B41J: TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

The problem to be solved by the present invention is to provide an electrochromic gel which is excellent in flexibility and which is stretchable, a method for producing the gel, a method for controlling electronic printing and erasing, and a stretchable display. The problem is solved by using an electrochromic gel obtained by laminating an electrolyte-containing gel layer consisting only of an electrolyte-containing gel and an organic-metallic hybrid polymer-containing layer obtained by containing an organic-metallic hybrid polymer in the electrolyte-containing gel.

## Claims

### Claim 1

An electrochromic gel comprising:
an electrolyte-containing gel layer consisting only of the electrolyte-containing gel, wherein the electrolyte-containing gel comprises a polymer gel containing an organic solvent and an inorganic electrolyte dispersed into said polymer gel; and
an organic-metallic hybrid polymer-containing layer which comprises an organic-metallic hybrid polymer contained in the electrolyte-containing gel,
wherein the electrolyte-containing gel layer and the organic-metallic hybrid polymer-containing layer are laminated onto each other with the electrolyte-containing gel being shared by the electrolyte-containing gel layer and the organic-metallic hybrid polymer-containing layer, and
wherein the electrochromic gel itself is stretchable,
wherein the organic-metallic hybrid polymer is represented by the following formula (I):
wherein M1 to MN denote a plurality of types of metal ions having different oxidation-reduction potential from each other, and N denotes an integer of 2 or more,
wherein X1 to Xn denote, independently for each occurrence, a counter anion, and n denotes an integer of 2 or more,
wherein R1 to RN denote, independently for each occurrence, a spacer including a carbon atom and a hydrogen atom or a spacer directly connecting two terpyridyl groups to each other, and N denotes an integer of 2 or more,
wherein R11 to R1N, R21 to R2N, R31 to R3N, and R41 to R4N denote, independently for each occurrence, a hydrogen atom or a substituent group, and N denotes an integer of 2 or more, and
wherein n1 to nN denote an integer of 2 or more showing independently a polymerization degree,
wherein the organic-metallic hybrid polymer-containing layer has a thickness of less than 1 μm, and
wherein the electrolyte-containing gel layer and the organic-metallic hybrid polymer-containing layer have a total thickness of not less than 10 μm and not more than 1 cm.

### Claim 2 (depends on 1)

The electrochromic gel of claim 1 , wherein the organic-metallic hybrid polymer is a Fe-MEPE polymer.

### Claim 3 (depends on 1)

The electrochromic gel of claim 1, wherein the inorganic electrolyte has electrolytic conductivity of 0.2 S/m or more.

### Claim 4 (depends on 3)

The electrochromic gel of claim 3, wherein the inorganic electrolyte is any one of lithium salt, sodium salt, potassium salt, ammonium salt or compounds thereof.

### Claim 5 (depends on 1)

The electrochromic gel of claim 1, wherein a polymer constituting the polymer gel is any one of poly(methacrylic acid ester)s and polycarbonates.

### Claim 6 (depends on 1)

The electrochromic gel of claim 1, wherein the organic solvent is any one of propylene carbonate, ethylene carbonate, and diethyl carbonate.

### Claim 7 (depends on 1)

A method for producing an electrochromic gel according to claim 1, which comprises:
Step S1 of forming a polymer film consisting of an organic-metallic hybrid polymer to a thickness of less than 1 μm, in which an organic-metallic hybrid polymer solution is prepared, the organic-metallic hybrid polymer solution is coated onto a flat surface, and the solution is dried,
Step S2 of coating an electrolyte-containing gel comprising a polymer gel containing an organic solvent and an inorganic electrolyte dispersed into said polymer gel onto one surface of the polymer film to a thickness of not less than 10 μm and not more than 1 cm, in which an electrolyte-containing coating gel comprising the polymer gel containing the organic solvent and the inorganic electrolyte dispersed into said polymer gel including an organic solvent is prepared and is coated onto the polymer film, and
Step S3 of forming an organic-metallic hybrid polymer-containing layer comprising the electrolyte-containing gel and the organic-metallic hybrid polymer contained in said gel, in which a laminated body of the polymer film and the electrolyte-containing gel is maintained at room temperature in the air so as to volatilize a predetermined amount of the organic solvent in the electrolyte-containing coating gel, and the polymer film is inmmersed into the other surface side of the electrolyte-containing coating gel.

### Claim 8 (depends on 7)

The method for producing an electrochromic gel according to claim 7, wherein the electrolyte-containing coating gel including the organic solvent in Step S2 is prepared by dispersing a polymer which is any one of poly(methacrylic acid ester)s and polycarbonates, and an inorganic electrolyte which is any one of lithium salt, sodium salt, potassium salt, ammonium salt or compounds thereof, into an organic solvent which is any one of propylene carbonate, ethylene carbonate, and diethyl carbonate.

### Claim 9 (depends on 7)

The method for producing an electrochromic gel according to claim 7, wherein the electrolyte-containing coating gel including the organic solvent in Step S2 is prepared such that an amount of the organic solvent in the electrolyte-containing coating gel is 65 weight % or less.

### Claim 10 (depends on 1)

A method for controlling electronic printing and erasing on the electrochromic gel, said electrochromic gel being the electrochromic gel according to claim 1, the method comprising connecting a first electrode to the organic-metallic hybrid polymer-containing layer and connecting a second electrode to the electrolyte-containing gel layer, then applying an electric field between the two electrodes so as to oxidize and reduce the organic-metallic hybrid polymer in a region of the electrolyte-containing gel layer to which the first electrode is connected, so that oxidization de-colors the region and reduction colors the region, thereby carrying out the electronic printing and erasing.

### Claim 11 (depends on 1)

A stretchable display comprising:
an electrochromic gel of claim 1;
a bendable frame holding the electrochromic gel, and
a band attached to the frame.

### Claim 12 (depends on 5)

The electrochromic gel of claim 5, wherein the poly(methacrylic acid ester) is any one of poly(methyl methacrylate), poly(ethyl methacrylate), poly(butyl methacrylate), poly(cyclohexyl methacrylate), and poly(phenyl methacrylate).

### Claim 13 (depends on 8)

The method for producing an electrochromic gel according to claim 8, wherein the poly(methacrylic acid ester) is any one of poly(methyl methacrylate), poly(ethyl methacrylate), poly(butyl methacrylate), poly(cyclohexyl methacrylate), and poly(phenyl methacrylate).