JP7083123B2 - A method for manufacturing a transmissive electrochromic element and a method for manufacturing a reflective electrochromic element. - Google Patents

Description

The present disclosure relates to a method for manufacturing a transmissive electrochromic element, a reflective electrochromic element, a transmissive electrochromic element, and a method for manufacturing a reflective electrochromic element.

Electrochemical devices such as electrochromic devices have been actively studied (see Patent Document 1). So far, an acetonitrile solution in which a supporting salt is dissolved has been used as an electrolytic solution for an electrochemical device such as an electrochromic element. Acetonitrile has a stable potential window and is therefore suitable as an electrolytic solution for electrochemical devices.

Japanese Unexamined Patent Publication No. 2004-02928

However, since acetonitrile is volatile, it will volatilize over time when used in the open form. In this case, there is a risk of liquid leakage. Therefore, it is necessary to seal the seal to make it a closed type, which causes a problem that the structure becomes complicated.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a transmissive electrochromic element or a reflective electrochromic element that does not require a seal and is cost-effective. The present invention can be realized as the following forms.

[1]
It is a transmissive electrochromic element.
A display electrode modified with an electrochromic material that electrochemically and reversibly develops color on a transparent conductive film,
A counter electrode that compensates for the electrochemical reaction of the display electrode,
A transparent polymer electrolyte membrane sandwiched between the display electrode and the counter electrode is provided.
The transparent polyelectrolyte film is a gel film containing an ionic liquid and a (meth) acrylic polymer.
A transmissive electrochromic element, wherein at least a part of the transparent polymer electrolyte membrane that does not come into contact with the display electrode and does not come into contact with the counter electrode is in contact with the outside air.

[2]
The transparent polymer electrolyte membrane and the display electrode are in close contact with each other, no air bubbles having a diameter of 1 mm or more are present between the transparent polymer electrolyte membrane and the display electrode, and the transparent polymer electrolyte membrane and the display electrode are described. The transmissive electrochromic element according to [1], wherein the counter electrode is in close contact with the transparent polymer electrolyte membrane, and no air bubbles having a diameter of 1 mm or more are present between the transparent polymer electrolyte membrane and the counter electrode.

[3]
It is a reflective electrochromic element.
A display electrode modified with an electrochromic material that electrochemically and reversibly develops color on a transparent conductive film,
A counter electrode that compensates for the electrochemical reaction of the display electrode,
A white polymer electrolyte membrane sandwiched between the display electrode and the counter electrode is provided.
The white polymer electrolyte membrane is a gel film containing an ionic liquid, a (meth) acrylic polymer, and a white pigment.
A reflective electrochromic element, wherein at least a part of the white polymer electrolyte membrane that does not come into contact with the display electrode and does not come into contact with the counter electrode is in contact with the outside air.

[4]
The white polymer electrolyte membrane and the display electrode are in close contact with each other, no bubbles having a diameter of 1 mm or more are present between the white polymer electrolyte membrane and the display electrode, and the white polymer electrolyte membrane and the display electrode are described. The reflective electrochromic element according to [3], wherein the counter electrode is in close contact with the white polymer electrolyte membrane, and no air bubbles having a diameter of 1 mm or more are present between the white polymer electrolyte membrane and the counter electrode.

[5]
A method for manufacturing a transmissive electrochromic element.
A coating step of applying a transparent ionic liquid gel preparation solution onto either the display electrode or the counter electrode.
A gel film forming step of volatilizing a solvent from the ionic liquid gel preparation solution to form an ionic liquid gel film,
A dissolution step of applying the solvent to one side of the ion liquid gel membrane that is not in contact with the one pole to make only the surface of the one side a low-viscosity liquid.
A method for manufacturing a transmissive electrochromic element, comprising a bonding step of bonding one of the display electrode and the counter electrode to the one side of the ion liquid gel film.

[6]
A method for manufacturing reflective electrochromic elements.
A coating step of applying an ionic liquid gel preparation solution containing a white pigment onto either the display electrode or the counter electrode.
A gel film forming step of volatilizing a solvent from the ionic liquid gel preparation solution to form an ionic liquid gel film,
A dissolution step of applying the solvent to one side of the ion liquid gel membrane that is not in contact with the one pole to make only the surface of the one side a low-viscosity liquid.
A method for manufacturing a reflective electrochromic element, comprising a bonding step of bonding one of the display electrode and the counter electrode to the one side of the ion liquid gel film.

In the transmissive electrochromic element of the present invention, a gel film is used as a transparent polymer electrolyte membrane. Therefore, even if an open type structure in which at least a part of the transparent polymer electrolyte membrane is exposed to the outside air is adopted, the electrolyte does not volatilize and liquid leakage does not occur. As described above, the transmissive electrochromic element of the present invention does not require a seal for sealing, which is advantageous in terms of cost.
When there are no bubbles having a diameter of 1 mm or more between the transparent polymer electrolyte membrane and the display electrode, and there are no bubbles having a diameter of 1 mm or more between the transparent polymer electrolyte membrane and the counter electrode, The uniformity of color change is guaranteed. Further, in this case, since the scattering of light by the bubbles is prevented, the transparency of the transmissive electrochromic element is maintained. Further, in this case, the decrease in the contact area between the transparent polymer electrolyte membrane and the display electrode due to the air bubbles and the decrease in the contact area between the transparent polymer electrolyte membrane and the counter electrode are suppressed. The original function can be fully exhibited.

In the reflective electrochromic element of the present invention, a gel film is used as a white polymer electrolyte membrane. Therefore, even if an open structure in which at least a part of the white polymer electrolyte membrane is exposed to the outside air is adopted, the electrolyte does not volatilize and liquid leakage does not occur. As described above, the reflective electrochromic element of the present invention does not require a seal for sealing, which is advantageous in terms of cost. Further, in this reflective electrochromic element, since the white polymer electrolyte film also functions as a reflective film, it is not necessary to separately provide a reflective film, which is advantageous in terms of cost.
Color when there are no bubbles with a diameter of 1 mm or more between the white polymer electrolyte membrane and the display electrode, and there are no bubbles with a diameter of 1 mm or more between the white polymer electrolyte membrane and the counter electrode. Uniformity of change is guaranteed. Further, in this case, the decrease in the contact area between the white polymer electrolyte membrane and the display electrode due to the air bubbles and the decrease in the contact area between the white polymer electrolyte membrane and the counter electrode are suppressed. The original function can be fully exhibited.

According to the method for manufacturing a transmissive electrochromic element of the present invention, bubbles are suppressed from entering between the ion liquid gel film and the display electrode, and bubbles also enter between the ion liquid gel film and the counter electrode. Is suppressed. Therefore, according to this manufacturing method, a transmissive electrochromic device in which the uniformity of color change is guaranteed is provided. Further, according to this manufacturing method, a transmissive electrochromic element in which transparency is maintained is provided. Further, according to this manufacturing method, the decrease in the contact area between the ion liquid gel film and the display electrode due to air bubbles and the decrease in the contact area between the ion liquid gel film and the counter electrode are suppressed, and the original display electrode and the counter electrode are suppressed. A transmissive electrochromic element capable of fully exerting its function is provided.

According to the method for manufacturing a reflective electrochromic element of the present invention, bubbles are suppressed from entering between the ion liquid gel film and the display electrode, and bubbles also enter between the ion liquid gel film and the counter electrode. Is suppressed. Therefore, according to this manufacturing method, a reflective electrochromic element in which the uniformity of color change is guaranteed is provided. Further, according to this manufacturing method, the decrease in the contact area between the ion liquid gel film and the display electrode due to air bubbles and the decrease in the contact area between the ion liquid gel film and the counter electrode are suppressed, and the original display electrode and the counter electrode are suppressed. A reflective electrochromic element capable of fully exerting its function is provided.

The present invention will be further described in the following detailed description with reference to the plurality of references mentioned, with reference to non-limiting examples of typical embodiments according to the invention.
It is explanatory drawing which shows typically the structure of the transmission type electrochromic element. It is explanatory drawing which shows typically the structure of the reflection type electrochromic element. It is explanatory drawing which shows typically the manufacturing method of the transmission type electrochromic element. It is explanatory drawing which shows typically the manufacturing method of the reflection type electrochromic element.

The matters shown here are for illustrative purposes and embodiments of the present invention, and are the most effective and effortless explanations for understanding the principles and conceptual features of the present invention. It is stated for the purpose of providing what seems to be. In this regard, it is not intended to show structural details of the invention beyond a certain degree necessary for a fundamental understanding of the invention, and some embodiments of the invention are provided by description in conjunction with the drawings. It is intended to clarify to those skilled in the art how it is actually realized.

Hereinafter, the present invention will be described in detail.

1. 1. Transmissive electrochromic element The transmissive electrochromic element 1 of the present invention includes a display electrode 3, a counter electrode 5, and a transparent polymer electrolyte membrane 7 (see FIG. 1).

(1) Display electrode The display electrode is an electrode modified with an electrochromic material that electrochemically and reversibly develops color on a transparent conductive film.
The transparent conductive film is not particularly limited, and a known transparent conductive film can be used. For example, indium tin oxide (ITO), zinc oxide, tin oxide and the like can be preferably used as the transparent conductive film.
The electrochromic material is not particularly limited, and known electrochromic materials can be used. For example, as the electrochromic material, a poly (3,4-ethylenedioxythiophene) (PEDOT) film, a poly (3-hexylthiophene) (P3HT) film, or the like can be preferably used. The PEDOT film can be formed by, for example, an electrolytic polymerization method. The P3HT film can be formed by, for example, a spin coating method.
The side of the display electrode modified with the electrochromic material is in contact with the transparent polymer electrolyte membrane.

(2) Counter electrode The counter electrode is an electrode that compensates for the electrochemical reaction of the display electrode. The counter electrode can be, for example, an electrode modified with a material that compensates for the electrochemical reaction of the display electrode on the transparent conductive film.
The transparent conductive film is not particularly limited, and a known transparent conductive film can be used. For example, indium tin oxide (ITO), zinc oxide, tin oxide and the like can be preferably used as the transparent conductive film.
The material for compensating for the electrochemical reaction is not particularly limited, and known materials can be used. For example, as this material, a poly (3,4-ethylenedioxythiophene) (PEDOT) membrane or the like can be preferably used. The PEDOT film can be formed by, for example, an electrolytic polymerization method.
The side modified with the material compensating for the electrochemical reaction of the counter electrode is in contact with the transparent polymer electrolyte membrane.

(3) Transparent Polymer Electrolyte Membrane The transparent polymer electrolyte membrane is arranged so as to be sandwiched between the display electrode and the counter electrode. At least a part of the transparent polymer electrolyte membrane that does not contact the display electrode and does not contact the counter electrode is exposed to the outside air. That is, the transmissive electrochromic element of the present invention is an open type.
The transparent polyelectrolyte film is a gel film containing an ionic liquid and a (meth) acrylic polymer. The gel film can be formed by volatilizing an organic solvent from a solution containing an organic solvent, an ionic liquid, and a (meth) acrylic polymer. In the present specification, the "gel film" may be referred to as an "ionic liquid gel film", but both are the same.

(3.1) Organic Solvent for Forming Gel Film The organic solvent used for forming the gel film is not particularly limited. Examples of the organic solvent include ether solvents such as tetrahydrofuran (THF), dibutyl ether, dioxane, and anisole, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, nitrile solvents such as acetonitrile, chloroform, dichloromethane, and the like. Examples thereof include halogenated hydrocarbon solvents such as tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene and chlorotoluene, and ester solvents such as ethyl acetate, butyl acetate and amyl acetate. The organic solvent may be used alone or in combination of two or more. Among these, ether-based solvents and ketone-based solvents are more preferable. This is because a transparent gel film is likely to be formed when an ether solvent or a ketone solvent is used. Specifically, tetrahydrofuran (THF) and acetone are particularly preferable. In order to prepare a transparent and uniform gel film, an ether solvent is particularly preferable, and tetrahydrofuran (THF) is most suitable.
When a nitrile solvent, a halogenated hydrocarbon solvent, or an ester solvent is used, a white gel film can be obtained.

(3.2) Ionic liquid The above-mentioned ionic liquid is an ionic substance that is in a molten state at room temperature (25 ° C.) and consists of a cation part and an anion part.
As the cation portion of the ionic liquid, a cation used in a normal ionic liquid can be used. For example, a cation portion selected from the group consisting of an onium cation, a quaternary ammonium cation, and a quaternary phosphonium cation of a 5- to 6-membered ring compound having 1 to 3 nitrogen numbers can be mentioned.

Examples of the onium cation of the 5- to 6-membered ring compound having 1 to 3 nitrogens include onium cations of 5-membered ring compounds such as imidazolium cation and pyrrolidinium cation, and 6 such as pyridinium cation and piperidinium cation. The onium cation of the member ring compound can be mentioned. Among these, the imidazolium cation is preferable because it has a low melting point and tends to become liquid.

〔式（１）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５は、それぞれ独立して、
水素原子、
置換されているかもしくは非置換の炭素数１～２０の飽和もしくは不飽和の直鎖状、分枝状、もしくは環状のアルキル基、
置換されているかもしくは非置換の炭素数６～３０のアリール基、
置換されているかもしくは非置換の炭素数７～３１のアリールアルキル基、又は
炭素数１～２０のアルコキシ基であり、
前記アルキル基、前記アリール基又は前記アリールアルキル基が置換されている場合は、ハロゲン原子、アルキル基、アリール基、アルコキシ基、アリールオキシ基、アルコキシカルボニル基、アシルオキシ基、アシル基、アルキルスルファニル基、アリールスルファニル基、アルキルアミノ基、ジアルキルアミノ基、アリールアミノ基、ヒドロキシ基、カルボキシ基、ホルミル基、メルカプト基、スルホ基、メシル基、ｐ－トルエンスルホニル基、アミノ基、ニトロ基、シアノ基、トリフルオロメチル基、トリクロロメチル基、トリメチルシリル基、ホスフィニコ基、又はホスホノ基で置換されている。〕 The imidazolium cation is not particularly limited. For example, those having the structure of the following general formula (1) can be mentioned.

[In equation (1), R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are independent of each other.
Hydrogen atom,
Substituted or unsaturated linear, branched, or cyclic alkyl groups with 1 to 20 carbon atoms, saturated or unsaturated,
Substituted or unsubstituted aryl groups having 6 to 30 carbon atoms,
A substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms or an alkoxy group having 1 to 20 carbon atoms.
When the alkyl group, the aryl group or the arylalkyl group is substituted, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyloxy group, an acyl group, an alkylsulfanyl group, Arylsulfanyl group, alkylamino group, dialkylamino group, arylamino group, hydroxy group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, tri It is substituted with a fluoromethyl group, a trichloromethyl group, a trimethylsilyl group, a phosphinico group, or a phosphono group. ]

Substituted or unsubstituted linear or unsaturated linear, branched form with 1 to 20 carbon atoms used as R ¹ , R ² , R ³ , R ⁴ , R ⁵ in the chemical formula (1). Or, as an example of the cyclic alkyl group, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and the like. Isoamyl group, tert-pentyl group, neopentyl group, n-hexyl group, 3-methylpentane-2-yl group, 3-methylpentane-3-yl group, 4-methylpentyl group, 4-methylpentane-2- Il group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 3,3-dimethylbutane-2-yl group, n-heptyl group, 1-methylhexyl group, 3-methylhexyl group, 4- Methylhexyl group, 5-methylhexyl group, 1-ethylpentyl group, 1- (n-propyl) butyl group, 1,1-dimethylpentyl group, 1,4-dimethylpentyl group, 1,1-diethylpropyl group, 1,3,3-trimethylbutyl group, 1-ethyl-2,2-dimethylpropyl group, n-octyl group, 2-methylhexane-2-yl group, 2,4-dimethylpentane-3-yl group, 1 , 1-dimethylpentane-1-yl group, 2,2-dimethylhexane-3-yl group, 2,3-dimethylhexane-2-yl group, 2,5-dimethylhexane-2-yl group, 2,5 -Dimethylhexane-3-yl group, 3,4-dimethylhexane-3-yl group, 3,5-dimethylhexane-3-yl group, 1-methylheptyl group, 2-methylheptyl group, 5-methylheptyl group , 2-Methylheptan-2-yl group, 3-methylheptane-3-yl group, 4-methylheptane-3-yl group, 4-methylheptane-4-yl group, 1-ethylhexyl group, 2-ethylhexyl group , 1-propylpentyl group, 2-propylpentyl group, 1,1-dimethylhexyl group, 1,4-dimethylhexyl group, 1,5-dimethylhexyl group, 1-ethyl-1-methylpentyl group, 1-ethyl -4-Methylpentyl group, 1,1,4-trimethylpentyl group, 2,4,4-trimethylpentyl group, 1-isopropyl-1,2-dimethylpropyl group, 1,1,3,3-tetramethylbutyl Group, n-nonyl group, 1-methyloctyl group, 6-methyloctyl group, 1-ethylheptyl group, 1- (n-butyl) pentyl group, 4-methyl-1- (N-propyl) pentyl group, 1,5,5-trimethylhexyl group, 1,1,5-trimethylhexyl group, 2-methyloctane-3-yl group, n-decyl group, 1-methylnonyl group, 1- Ethyloctyl group, 1- (n-butyl) hexyl group, 1,1-dimethyloctyl group, 3,7-dimethyloctyl group, n-undecyl group, 1-methyldecyl group, 1-ethylnonyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, 1-methyltridecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadesyl group, n-eicosyl group, cyclopropyl group. , Cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group and the like. From the viewpoint of availability, substituted or unsubstituted saturated or unsaturated linear or branched alkyl groups having 1 to 8 carbon atoms are preferable, and methyl groups and ethyl groups are particularly preferable.

Examples of substituted or unsubstituted aryl groups having 6 to 30 carbon atoms used as R ¹ , R ² , R ³ , R ⁴ , R ⁵ in the chemical formula (1) include, for example, a phenyl group. Biphenyl group, 1-naphthyl group, 2-naphthyl group, 9-anthrill group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azulenyl group, 9-fluorenyl group, turphenyl Group, quarterphenyl group, mesityl group, pentarenyl group, binaphthalenyl group, turnaphthalenyl group, quarternaphthalenyl group, heptalenyl group, biphenylenyl group, indasenyl group, fluoranthenyl group, acenaphtylenyl group, aceanthrenyl group, phenalenyl group, fluorenyl group. Group, anthryl group, bianthrasenyl group, teranthrasenyl group, quarter anthrasenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthalsenyl group, pleiadenyl group, pisenyl group, perylenel group, pentaphenyl Examples thereof include a group, a pentasenyl group, a tetraphenylenyl group, a hexaphenyl group, a hexasenyl group, a rubisenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptasenyl group, a pyrandrenyl group and an ovalenyl group.

Examples of substituted or unsubstituted arylalkyl groups having 7 to 31 carbon atoms used as R ¹ , R ² , R ³ , R ⁴ , R ⁵ in the chemical formula (1) include, for example, a benzyl group. , Phenylethyl group, 3-phenylpropyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 2- (1-naphthyl) ethyl group, 2- (2-naphthyl) ethyl group, 3- (1-naphthyl) Examples thereof include a propyl group or a 3- (2-naphthyl) propyl group.

Examples of the alkoxy groups having 1 to 20 carbon atoms used as R ¹ , R ² , R ³ , R ⁴ , and R ⁵ in the chemical formula (1) include, for example, a methoxy group, an ethoxy group, and an n-propoxy group. Examples thereof include i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group and the like. Among these, those having 1 to 4 carbon atoms are preferable.

Saturated or unsaturated linear, branched or cyclic alkyl groups with 1 to 20 substituted or unsubstituted carbon atoms as described above, substituted or unsubstituted aryls having 6 to 30 carbon atoms. The hydrogen atom in the group, substituted or unsubstituted arylalkyl group, and alkylene group may be further substituted with another substituent.

Examples of such a substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkyl group such as a methyl group, an ethyl group, a tert-butyl group and a dodecyl group, a phenyl group and a p-tolyl. Aryl group such as group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, alkoxy group such as methoxy group, ethoxy group, tert-butoxy group, aryloxy group such as phenoxy group and p-tolyloxy group, methoxy Alkoxycarbonyl groups such as carbonyl group, butoxycarbonyl group, phenoxycarbonyl, etc., acyloxy groups such as acetoxy group, propionyloxy group, benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, metoxalyl group and the like. Alkyl sulfanyl group such as acyl group, methyl sulfanyl group, tert-butyl sulfanyl group, aryl sulfanyl group such as phenyl sulfanyl group and p-tolyl sulfanyl group, alkyl amino group such as methyl amino group and cyclohexyl amino group, dimethyl amino group, In addition to dialkylamino groups such as diethylamino group, morpholino group and piperidino group, arylamino group such as phenylamino group and p-tolylamino group, hydroxy group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group and p. -Examples include a toluenesulfonyl group, an amino group, a nitro group, a cyano group, a trifluoromethyl group, a trichloromethyl group, a trimethylsilyl group, a phosphinico group, a phosphono group and the like.

As the imidazolium cation represented by the above formula (1), 1,3-disubstituted imidazolium cations and 1,2,3-trisubstituted imidazolium cations are preferably used from the viewpoint of ease of synthesis, and in particular, 1,3-Disubstituted imidazolium cations are preferably used.
Specifically, the imidazolium cations include 1-ethyl-3-methylimidazolium cation, 1,3-dimethylimidazolium cation, 1-methyl-3-propylimidazolium cation, and 1-butyl-3-methylimidazolium cation. , 1-Methyl-3-pentylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-heptyl-3-methylimidazolium cation, 1-methyl-3-octylimidazolium cation, 1-decyl-3 -Dialkylimidazolium cations such as methylimidazolium cation, 1-dodecyl-3-methylimidazolium cation, 1-ethyl-3-propylimidazolium cation, 1-butyl-3-ethylimidazolium cation; 3-ethyl-1 , 2-Dimethyl-imidazolium cation, 1,2-dimethyl-3-propylimidazolium cation, 1-butyl-2,3-dimethylimidazolium cation, 1,2-dimethyl-3-hexylimidazolium cation, 1, Examples thereof include trialkylimidazolium cations such as 2-dimethyl-3-octylimidazolium cation, 1-ethyl-3,4-dimethylimidazolium cation, and 1-isopropyl-2,3-dimethylimidazolium cation.

Examples of the pyrrolidinium cation include N, N-dimethylpyrrolidinium cation, N-ethyl-N-methylpyrrolidinium cation, N-methyl-N-propylpyrrolidinium cation, and N-butyl-N-methyl. Pyrrolidinium cation, N-methyl-N-pentylpyrrolidinium cation, N-hexyl-N-methylpyrrolidinium cation, N-methyl-N-octylpyrrolidinium cation, N-decyl-N-methylpyrrolizi Nium cation, N-dodecyl-N-methylpyrrolidinium cation, N- (2-methoxyethyl) -N-methylpyrrolidinium cation, N- (2-ethoxyethyl) -N-methylpyrrolidinium cation, N -(2-Propoxyethyl) -N-methylpyrrolidinium cation, N- (2-isopropoxyethyl) -N-methylpyrrolidinium cation and the like can be mentioned.

Examples of the pyridinium cation include a pyridinium cation substituted with an alkyl group having 1 to 16 carbon atoms such as N-methylpyridinium cation, N-ethylpyridinium cation, N-butylpyridinium cation, and N-propylpyridinium cation. Can be done.

Examples of the piperidinium cation include N, N-dimethylpiperidinium cation, N-ethyl-N-methylpiperidinium cation, N-methyl-N-propylpiperidinium cation, and N-butyl-N-methyl. Piperidinium cation, N-methyl-N-pentylpiperidinium cation, N-hexyl-N-methylpiperidinium cation, N-methyl-N-octylpiperidinium cation, N-decyl-N-methylpiperidinium Nium cation, N-dodecyl-N-methylpiperidinium cation, N- (2-methoxyethyl) -N-methylpiperidinium cation, N- (2-methoxyethyl) -N-ethylpiperidinium cation, N -(2-ethoxyethyl) -N-methylpiperidinium cation, N-methyl-N- (2-methoxyphenyl) piperidinium cation, N-methyl-N- (4-methoxyphenyl) piperidinium cation, Examples thereof include N-ethyl-N- (2-methoxyphenyl) piperidinium cation, N-ethyl-N- (4-methoxyphenyl) piperidinium cation and the like.

The anion portion of the ionic liquid (1) is not particularly limited, and an anion used in a general ionic liquid can be used. For example, as the anion part, ^Cl- , Br- ^, AlCl _4- ^, Al ₂ Cl _7- ^, BF _4- ^, PF _6- ^, ClO _4- ^, NO _3- ^, CH ₃ COO- ^, CF ₃ COO- ^, CH ₃ SO _3- ^, CF ₃ SO _3- ^, (CF ₃ SO ₂ ) ₂ N- ^, (CF ₃ SO ₂ ) ₃ C- ^, AsF _6- ^, SbF _6- ^, NbF _6- ^, TaF _6- ^, F (HF) n- ^, (CN) ₂ N- ^, SCN- ^, C ₄ F ₉ SO _3- ^, (C ₂ F ₅ SO ₂ ) ₂ N- ^, C ₃ F ₇ COO- ^, (CF ₃ SO ₂ ) (CF ₃ CO) ) It is possible ^to use anions used in common ionic liquids such as N-.
Among these, an anion having a halogen atom is preferable, a fluorine atom-containing anion is particularly preferable, and a fluorine-containing imide anion represented by the following general formula (2) is more preferable.

(Cn F _{2n + 1} SO ₂ ) ₂ N -... ⁽ 2)
(In the formula, n is an integer from 0 to 15)

As the fluorine-containing imide anion represented by the general formula (2), specifically, a bis (trifluoromethanesulfonyl) imide anion and a bis (fluorosulfonyl) imide anion are preferably used. The n is usually 0 to 15, preferably 0 to 8, and particularly preferably 0 to 4.

The method for producing the ionic liquid is not particularly limited. For example, as a production method, a known method such as an anion exchange method or an acid ester method can be applied. More specifically, for example, it can be obtained by an anion exchange reaction using a halogenated salt of the organic cation to be used and an alkali metal salt of the perfluoroalkyl sulfonate anion. Examples of the halogen of the halogenated salt include chlorine and bromine. Examples of the alkali metal of the alkali metal salt include sodium and potassium.

(3.3) (Meta) Acrylic Polymer In the present specification, the (meth) acrylic polymer is used in the sense of including both an acrylic resin and a methacrylic resin. As used herein, "(meth) acrylic" means "acrylic" and / or "methacrylic" (one or both of "acrylic" and "methacrylic").
The (meth) acrylic polymer is not particularly limited. The (meth) acrylic polymer may be, for example, a polymer containing 50% by mass or more of a (meth) acrylic acid alkyl ester having a linear or branched alkyl group having 1 to 20 carbon atoms as a monomer unit. preferable. For example, polymethyl methacrylate (hereinafter, also referred to as “PMMA”) is preferably used.
The weight average molecular weight of the (meth) acrylic polymer is not particularly limited. The weight average molecular weight is, for example, 1 × 10 ⁴ to 1 × 10 ⁶ , preferably 5 × 10 ⁴ to 2 × 10 ⁵ .

(3.4) Method for producing a gel film The method for producing a gel film is not particularly limited, but is organic from a transparent ionic liquid gel preparation solution containing an organic solvent, an ionic liquid, and a (meth) acrylic polymer. A method of volatilizing a solvent to form a gel film can be preferably adopted.
Here, with respect to the "organic solvent", the "ionic liquid", and the "(meth) acrylic polymer", the above-mentioned description can be applied as it is.
This production method is characterized in that a (meth) acrylic polymer is dissolved in a transparent ionic liquid gel preparation solution.

The mixing ratio of the organic solvent, the ionic liquid, and the (meth) acrylic polymer is not particularly limited. For example, the ionic liquid and the (meth) acrylic polymer can be dissolved in the organic solvent at the following ratios. That is, the ionic liquid to be dissolved in 1 mL of the organic solvent is preferably 1 to 100 mg, more preferably 5 to 50 mg, and further preferably 10 to 20 mg. The amount of the (meth) acrylic polymer to be dissolved in 1 mL of the organic solvent is preferably 1 to 100 mg, more preferably 5 to 50 mg, still more preferably 10 to 20 mg. Within these ranges, dissolving an ionic liquid and a (meth) acrylic polymer in an organic solvent tends to give a good gel film.

The temperature at which the organic solvent is volatilized depends on the boiling point of the organic solvent used, but is usually 0 to 180 ° C, preferably 0 to 120 ° C, and more preferably 15 to 60 ° C.
Further, the volatilization of the organic solvent may be carried out under normal pressure, under reduced pressure, or under pressure.

(4) Preferred Embodiment of Transmissive Electrochromic Device The transmissive electrochromic device preferably has the following characteristics.
The transparent polyelectrolyte membrane and the display electrode are in close contact with each other, there are no bubbles having a diameter of 1 mm or more between the transparent polyelectrolyte membrane and the display electrode, and the transparent polyelectrolyte membrane and the counter electrode are in close contact with each other. Therefore, it is preferable that there are no bubbles having a diameter of 1 mm or more between the transparent polyelectrolyte membrane and the counter electrode.
In this configuration, the uniformity of color change in the transmissive electrochromic element is ensured. Further, since the scattering of light by bubbles is prevented, the transparency of the transmissive electrochromic element is maintained. In addition, the decrease in the contact area between the transparent polyelectrolyte film and the display electrode due to air bubbles and the decrease in the contact area between the transparent polyelectrolyte film and the counter electrode are suppressed, so that the original functions of the display electrode and the counter electrode are sufficient. Can be demonstrated.

(5) Method for manufacturing a transmissive electrochromic element Although the method for manufacturing a transmissive electrochromic element is not particularly limited, the following manufacturing method can be preferably exemplified.
That is, [1] a coating step of applying an ionic liquid gel preparation solution onto either the display electrode or the counter electrode, and [2] volatilizing a solvent from the ionic liquid gel preparation solution to form an ionic liquid gel film. [3] A solvent is applied to one side of the ion liquid gel film (the side that is not in contact with one pole) to make only one side of the gel film a low-viscosity liquid. 4] A manufacturing method comprising a bonding step of bonding one of the display pole and the counter electrode to one side of the ion liquid gel film can be suitably adopted.
FIG. 3 shows a schematic diagram of this manufacturing method. In FIG. 3, reference numeral 31 indicates one pole, reference numeral 33 indicates an ionic liquid gel preparation solution, reference numeral 35 indicates an ionic liquid gel film, reference numeral 37 indicates a low-viscosity liquid, and reference numeral 39 indicates the other pole. .. Further, FIGS. 3A and 3B show the coating process of [1]. FIG. 3C shows the gel film forming step of [2]. FIG. 3D shows the dissolution step of [3]. FIG. 3 (E) shows the bonding step of [4]. By drying after the bonding step of [4], the transmissive electrochromic element shown in FIG. 3 (F) is completed.

Here, the above-mentioned description can be applied as it is to the "display electrode", the "opposite electrode", and the "ionic liquid gel film (same as the above-mentioned" gel film ")".
The "ionic liquid gel preparation solution" is a solution containing an organic solvent, an ionic liquid, and a (meth) acrylic polymer. As for the "organic solvent", "ionic liquid", and "(meth) acrylic polymer", the above-mentioned explanations can be applied as they are. The mixing ratio of the organic solvent, the ionic liquid, and the (meth) acrylic polymer in the ionic liquid gel preparation solution is not particularly limited. For example, the ionic liquid and the (meth) acrylic polymer can be dissolved in the organic solvent at the following ratios. That is, the ionic liquid to be dissolved in 1 mL of the organic solvent is preferably 1 to 100 mg, more preferably 5 to 50 mg, and further preferably 10 to 20 mg. The amount of the (meth) acrylic polymer to be dissolved in 1 mL of the organic solvent is preferably 1 to 100 mg, more preferably 5 to 50 mg, still more preferably 10 to 20 mg. Within these ranges, dissolving an ionic liquid and a (meth) acrylic polymer in an organic solvent tends to give a good gel film.

The temperature at which the organic solvent is volatilized depends on the boiling point of the organic solvent used, but is usually 0 to 180 ° C, preferably 0 to 120 ° C, and more preferably 15 to 60 ° C.
Further, the volatilization of the organic solvent may be carried out under normal pressure, under reduced pressure, or under pressure.

In the above-mentioned production method, in the gel film forming step of [2], the solvent is volatilized from the ionic liquid gel preparation solution to form an ionic liquid gel film, and then in the dissolution step of [3], one side of the ionic liquid gel film is formed. , A solvent is applied to make only the surface of one side a low-viscosity liquid, and the other poles are bonded in the bonding step of [4]. The reason for forming the sandwich structure by liquefying only the surface layer of the ion liquid gel film again after forming the ion liquid gel film in this way is as follows. Since the ionic liquid gel preparation solution is a highly viscous substance, if the ionic liquid gel preparation solution is applied on one pole and the other pole is attached without drying, the wettability to the other pole will be poor and bubbles will occur. Will be mixed. Further, if there are upper and lower electrodes when the solvent volatilizes, it can volatilize only from the open side surface, and bubbles are generated at the time of volume shrinkage. On the other hand, as in the above-mentioned manufacturing method, once dried in an open system, no bubbles are generated in the ionic liquid gel film. After that, when the surface layer is liquefied with a solvent, it becomes a low-viscosity liquid, and when the other poles are overlapped, wetting is improved and air bubbles can be prevented from being mixed.

2. 2. Reflective electrochromic element Next, the reflective electrochromic element will be described.
The reflective electrochromic element 11 of the present invention includes a display electrode 13, a counter electrode 15, and a white polymer electrolyte membrane 17 (see FIG. 2).

(1) Display pole As for the "display pole", the description of "1 (1) display pole" in the above-mentioned transmissive electrochromic element can be applied as it is.
The side of the display electrode modified with the electrochromic material is in contact with the white polymer electrolyte membrane.

(2) Counter electrode As for the “opposite electrode”, the description of “1 (2) counter electrode” in the above-mentioned transmissive electrochromic element can be applied as it is.
The side modified with the material compensating for the electrochemical reaction of the counter electrode is in contact with the white polymer electrolyte membrane.

(3) White Polymer Electrolyte Membrane The white polymer electrolyte membrane is arranged so as to be sandwiched between the display electrode and the counter electrode. At least a part of the white polymer electrolyte membrane that does not contact the display electrode and does not contact the counter electrode is exposed to the outside air. That is, the reflective electrochromic element of the present invention is an open type.
The white polymer electrolyte membrane is a gel film containing an ionic liquid, a (meth) acrylic polymer, and a white pigment. The gel film can be formed by volatilizing an organic solvent from a solution containing an organic solvent, an ionic liquid, a (meth) acrylic polymer, and a white pigment. In the present specification, the "gel film" may be referred to as an "ionic liquid gel film", but both are the same.

(3.1) Organic solvent used for forming a gel film Regarding "organic solvent used for forming a gel film", refer to "(3.1) Organic solvent used for forming a gel film" in the above-mentioned transmissive electrochromic device. The description can be applied as is.

(3.2) Ionic liquid As for the "ionic liquid", the description of "(3.2) ionic liquid" in the above-mentioned transmissive electrochromic element can be applied as it is.

(3.3) (Meta) Acrylic Polymer As for the "(meth) acrylic polymer", the description of "(3.3) (meth) acrylic polymer" in the above-mentioned transmissive electrochromic device can be applied as it is.

(3.4) White Pigment The white pigment is not particularly limited, and a known white pigment can be used. As the white pigment, titanium oxide (titanium dioxide) can be preferably used. The crystal type of titanium oxide may be anatase type, rutile type or brookite type. Further, it may contain two or more kinds of crystal types among anatase type, rutile type and brookite type.

(3.5) Method for producing a gel film The method for producing a gel film is not particularly limited, but is from an ionic liquid gel preparation solution containing an organic solvent, an ionic liquid, a (meth) acrylic polymer, and a white pigment. , A method of volatilizing an organic solvent to form a gel film can be preferably adopted.
Here, the above-mentioned description can be applied as it is to the "organic solvent", "ionic liquid", "(meth) acrylic polymer", and "white pigment".
This production method is characterized in that a (meth) acrylic polymer is dissolved in an ionic liquid gel preparation solution.

The ionic liquid gel preparation solution is a transparent ionic liquid gel preparation solution in which a white pigment is dispersed as described in "(3.4) Method for producing a gel film" in the above-mentioned transmissive electrochromic device.
The mixing ratio of the organic solvent, the ionic liquid, the (meth) acrylic polymer, and the white pigment is not particularly limited. For example, the ratio can be as follows. That is, the ionic liquid to be dissolved in 1 mL of the organic solvent is preferably 1 to 100 mg, more preferably 5 to 50 mg, and further preferably 10 to 20 mg. The amount of the (meth) acrylic polymer to be dissolved in 1 mL of the organic solvent is preferably 1 to 100 mg, more preferably 5 to 50 mg, still more preferably 10 to 20 mg.
The amount of the white pigment is preferably 1 to 100 mg, more preferably 5 to 50 mg, and further preferably 1 to 100 mg with respect to 1 g of the transparent ionic liquid gel preparation solution (solution containing an organic solvent, an ionic liquid, and a (meth) acrylic polymer). It is preferably mixed in a proportion of 10 to 20 mg.
When the mixing ratio is within these ranges, a good gel film tends to be obtained.

(4) Preferred Embodiment of Reflective Electrochromic Device The reflective electrochromic device preferably has the following features.
The white polymer electrolyte membrane and the display electrode are in close contact with each other, there are no bubbles having a diameter of 1 mm or more between the white polymer electrolyte membrane and the display electrode, and the white polymer electrolyte membrane and the counter electrode are in close contact with each other. Therefore, it is preferable that there are no bubbles having a diameter of 1 mm or more between the white polymer electrolyte membrane and the counter electrode.
In this configuration, the uniformity of color change in the reflective electrochromic element is ensured. In addition, the decrease in the contact area between the white polymer electrolyte membrane and the display electrode due to bubbles and the decrease in the contact area between the white polymer electrolyte film and the counter electrode are suppressed, so that the original functions of the display electrode and the counter electrode are sufficient. Can be demonstrated.

(5) Method for manufacturing a reflective electrochromic element The method for manufacturing a reflective electrochromic element is not particularly limited, but the following manufacturing method can be preferably exemplified.
That is, [1] a coating step of applying a white pigment-containing ionic liquid gel preparation solution onto either the display electrode or the counter electrode, and [2] volatilizing the solvent from the ionic liquid gel preparation solution. A gel film forming step of forming an ionic liquid gel film, and [3] dissolving a solvent on one side of the ionic liquid gel film (a surface not in contact with one pole) to make only one surface a low-viscosity liquid. A manufacturing method including a step and a bonding step of bonding one of the display poles and the counter electrode to one side of the ion liquid gel film can be suitably adopted.
FIG. 4 shows a schematic diagram of this manufacturing method. In FIG. 4, reference numeral 31 indicates one pole, reference numeral 33 indicates an ionic liquid gel preparation solution, reference numeral 35 indicates an ionic liquid gel film, reference numeral 37 indicates a low-viscosity liquid, and reference numeral 39 indicates the other pole. .. Further, FIGS. 4A and 4B show the coating process of [1]. FIG. 4C shows the gel film forming step of [2]. FIG. 4D shows the dissolution step of [3]. FIG. 4E shows the bonding step of [4]. The reflective electrochromic element shown in FIG. 4 (F) is completed by drying after the bonding step of [4].

Here, the above-mentioned description can be applied as it is to the "display electrode", the "opposite electrode", and the "ionic liquid gel film (same as the above-mentioned" gel film ")".
The "ionic liquid gel preparation solution" is a solution containing an organic solvent, an ionic liquid, a (meth) acrylic polymer, and a white pigment. As for the "organic solvent", "ionic liquid", "(meth) acrylic polymer", and "white pigment", the above-mentioned explanations can be applied as they are. The mixing ratio of the organic solvent, the ionic liquid, the (meth) acrylic polymer, and the white pigment in the ionic liquid gel preparation solution is not particularly limited. For example, the ratio can be as follows. That is, the ionic liquid to be dissolved in 1 mL of the organic solvent is preferably 1 to 100 mg, more preferably 5 to 50 mg, and further preferably 10 to 20 mg. The amount of the (meth) acrylic polymer to be dissolved in 1 mL of the organic solvent is preferably 1 to 100 mg, more preferably 5 to 50 mg, still more preferably 10 to 20 mg.
The amount of the white pigment is preferably 1 to 100 mg, more preferably 5 to 50 mg, and further preferably 1 to 100 mg with respect to 1 g of the transparent ionic liquid gel preparation solution (solution containing an organic solvent, an ionic liquid, and a (meth) acrylic polymer). It is preferably mixed in a proportion of 10 to 20 mg.
When the mixing ratio is within these ranges, a good gel film tends to be obtained.

The temperature at which the organic solvent is volatilized depends on the boiling point of the organic solvent used, but is usually 0 to 180 ° C, preferably 0 to 120 ° C, and more preferably 15 to 60 ° C.
Further, the volatilization of the organic solvent may be carried out under normal pressure, under reduced pressure, or under pressure.

In the above-mentioned production method, in the gel film forming step of [2], the solvent is volatilized from the ionic liquid gel preparation solution to form an ionic liquid gel film, and then in the dissolution step of [3], one side of the ionic liquid gel film is formed. , A solvent is applied to make only the surface of one side a low-viscosity liquid, and the other poles are bonded in the bonding step of [4]. The reason for forming the sandwich structure by liquefying only the surface layer of the ion liquid gel film again after forming the ion liquid gel film in this way is as follows. Since the ionic liquid gel preparation solution is a highly viscous substance, if the ionic liquid gel preparation solution is applied on one pole and the other pole is attached without drying, the wettability to the other pole will be poor and bubbles will occur. Will be mixed. Further, if there are upper and lower electrodes when the solvent volatilizes, it can volatilize only from the open side surface, and bubbles are generated at the time of volume shrinkage. On the other hand, as in the above-mentioned manufacturing method, once dried in an open system, no bubbles are generated in the ionic liquid gel film. After that, when the surface layer is liquefied with a solvent, it becomes a low-viscosity liquid, and when the other poles are overlapped, wetting is improved and air bubbles can be prevented from being mixed.

Hereinafter, a more specific description will be given with reference to Examples.

1. 1. Transmission type electrochromic element (Example 1)
(1) Manufacture of display electrode or counter electrode using PEDOT film A PEDOT film was formed on an ITO electrode (indium tin oxide electrode). Specifically, it was as follows. The PEDOT film is a triode system using an ITO electrode as an working electrode, an Ag / Ag ⁺ electrode as a reference electrode, and a platinum coil wire as a counter electrode, and the current is controlled by a potentiostat, and 0 mM ethylenedioxythiophene (EDOT) monomer is contained. A film was formed by constant current electrolysis at 1 mA for 60 seconds on an ITO electrode with an acetonitrile solution using 1M tetrabutylammonium hexafluorophosphate (TBA ⁺ PF _6- ⁾ as a supporting electrolyte.

(2) Manufacture of display electrode using P3HT film A P3HT film was formed on the ITO electrode.
The P3HT film was formed by dropping a P3HT solution dissolved in a chloroform solvent onto an ITO electrode, rotating it with a spin coater at a rotation speed of 1000 rpm for 60 seconds, and drying it. The film thickness was controlled by adjusting the P3HT concentration and the rotation speed.

(3) Production of transparent ionic liquid gel preparation solution As a transparent ionic liquid gel preparation solution, 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide (EMIm ^{+ TFSI-} ) was added to a THF solvent (1 mL). A viscous solution in which 380 mg and 127 mg of polymethyl methacrylate (PMMA) were dissolved was used.

(4) Manufacture of transmissive electrochromic element A transparent ionic liquid gel preparation solution is applied on a facing electrode (ITO electrode modified with a PEDOT film), and a volatile THF solvent is volatilized at room temperature to make a transparent ionic liquid. A gel film was prepared. After that, the THF solvent was applied again on the transparent ionic liquid gel film to make only the surface of the ionic liquid gel film a low-viscosity liquid, and the display electrode (ITO electrode modified with the PEDOT film or the P3HT film) was modified on the display electrode (ITO electrode modified with the PEDOT film). (ITO electrode) was laminated to form a sandwich structure. When THF was allowed to stand overnight and volatilized, the viscous liquid gelled into a solid film, eliminating the need for sealing.

(5) Actions and effects of the transmissive electrochromic element In the transmissive electrochromic element of this embodiment, a transparent ion liquid gel film is used as the electrolyte, so that the solvent does not volatilize or ignite. Moreover, since the electrolyte is gelled, there is no risk of liquid leakage, and the element process can be simplified and seal-free can be realized.
In a transmissive electrochromic element using an ITO electrode modified with a PEDOT film as a display electrode, a phenomenon in which the color changes due to electricity, that is, a phenomenon in which the color changes between dark blue and light blue was observed. Therefore, it was confirmed that this transmissive electrochromic element has basic performance as an element.
In a transmissive electrochromic element using an ITO electrode modified with a P3HT film as a display electrode, a phenomenon in which the color changes due to electricity, that is, a phenomenon in which the color changes between magenta and light blue was observed. Therefore, it was confirmed that this transmissive electrochromic element has basic performance as an element.

Further, as the display electrode, the transparent polymer electrolyte membrane and the display electrode are used in both the transmissive electrochromic element using the ITO electrode modified with the PEDOT film and the transmissive electrochromic element using the ITO electrode modified with the P3HT film. There were no bubbles having a diameter of 1 mm or more between them, and no bubbles having a diameter of 1 mm or more were present between the transparent polymer electrolyte membrane and the counter electrode. The uniformity of color change was ensured in any of the transmissive electrochromic elements. Further, since the scattering of light by bubbles is prevented, the transparency of the transmissive electrochromic element is maintained. In addition, the decrease in the contact area between the transparent polymer electrolyte membrane and the display electrode due to air bubbles and the decrease in the contact area between the transparent polymer electrolyte membrane and the counter electrode are suppressed, and the original functions of the display electrode and the counter electrode are sufficiently sufficient. It was demonstrated and the color change was also practical.

2. 2. Reflective electrochromic element (Example 2)
(1) Manufacture of Display Pole or Opposite Electrode Using PEDOT Membrane The display electrode or counter electrode using the PEDOT film was manufactured in the same manner as in the case of the transmissive electrochromic element (Example 1).

(2) Manufacture of Display Pole Using P3HT Film The display pole using the P3HT film was manufactured in the same manner as in the case of the transmissive electrochromic element (Example 1).

(3) Production of Ion Liquid Gel Preparation Solution Containing White Pigment Highly dispersed white pigment ion liquid in which titanium oxide fine particles, which are white pigments, are dispersed in a transparent ion liquid gel preparation solution in a transmissive electrochromic device (Example 1). A gel preparation solution (an ionic liquid gel preparation solution containing a white pigment) was prepared. This makes it possible to omit the separator that serves as a diffuse reflection film. In order to make the titanium oxide fine particles highly dispersed, even if an attempt is made to disperse the titanium oxide fine particles after preparing a transparent ionic liquid gel preparation solution, uniform dispersion cannot be performed because of the highly viscous liquid. Therefore, after the titanium oxide fine particle powder was highly dispersed in a THF solvent which is a low viscosity solvent by ultrasonic vibration, an ionic liquid and methyl polymethacrylate were added to prepare a highly dispersed white pigment ionic liquid preparation solution. The composition of each component is as follows.
THF solvent: 2 mL
Titanium oxide fine particles: 30 mg
EMIm ⁺ TFSI- ^: 760mg
Polymethyl methacrylate (PMMA): 253 mg

(4) Manufacture of reflective electrochromic element A highly dispersed white pigment ion liquid gel preparation solution is applied on a facing electrode (ITO electrode modified with a PEDOT film), and the volatile THF solvent is volatilized at room temperature to achieve high dispersion. A white pigment ion liquid gel film (ion liquid gel film) was prepared. After that, the THF solvent is applied again on the ion liquid gel film to make only the surface of the ion liquid gel film a low-viscosity liquid, and the display electrode (ITO electrode modified with PEDOT film or ITO electrode modified with P3HT film) is placed on the display electrode (ITO electrode modified with PEDOT film or ITO electrode modified with P3HT film). ) Was pasted together to form a sandwich structure. When THF was allowed to stand overnight and volatilized, the viscous liquid gelled into a solid film, eliminating the need for sealing.

(5) Action and effect of the reflective electrochromic element In the reflective electrochromic element of this embodiment, since an ionic liquid gel film is used as the electrolyte, the solvent does not volatilize or ignite. Moreover, since the electrolyte is gelled, there is no risk of liquid leakage, and the element process can be simplified and seal-free can be realized.
In a reflective electrochromic element using an ITO electrode modified with a PEDOT film as a display electrode, a phenomenon in which the color changes due to electricity, that is, a phenomenon in which the color changes between dark blue and light blue was observed. Therefore, it was confirmed that this reflective electrochromic element has basic performance as an element.
In a reflective electrochromic element using an ITO electrode modified with a P3HT film as a display electrode, a phenomenon in which the color changes due to electricity, that is, a phenomenon in which the color changes between magenta and light blue was observed. Therefore, it was confirmed that this reflective electrochromic element has basic performance as an element.

Further, as the display electrode, the white polymer electrolyte membrane and the display electrode are used in both the reflective electrochromic element using the ITO electrode modified with the PEDOT film and the reflective electrochromic element using the ITO electrode modified with the P3HT film. There were no bubbles having a diameter of 1 mm or more between them, and no bubbles having a diameter of 1 mm or more were present between the white polymer electrolyte membrane and the counter electrode. And, in any of the reflective electrochromic elements, the uniformity of the color change was guaranteed. In addition, the decrease in the contact area between the white polymer electrolyte membrane and the display electrode due to air bubbles and the decrease in the contact area between the white polymer electrolyte membrane and the counter electrode are suppressed, and the original functions of the display electrode and the counter electrode are sufficiently sufficient. It was demonstrated and the color change was also practical.

The above examples are for illustration purposes only and are not to be construed as limiting the invention. Although the present invention has been described with reference to examples of typical embodiments, the wording used in the description and illustration of the invention is understood to be descriptive and exemplary rather than limited wording. As detailed here, modifications may be made within the scope of the appended claims without departing from the scope or nature of the invention in its form. Although specific structures, materials and examples have been referred to herein in detail of the invention, it is not intended to limit the invention to the disclosures herein, but rather the invention is claimed in the accompanying claims. It shall cover all functionally equivalent structures, methods and uses within the scope.

The present invention is not limited to the embodiments detailed above, and various modifications or modifications can be made within the scope of the claims of the present invention.

The transmissive electrochromic element and the reflective electrochromic element of the present invention are highly practical and very useful because they do not require a seal and are cost-effective.

1 ... Transmission type electrochromic element 3 ... Display electrode 5 ... Opposite electrode 7 ... Transparent polyelectrolyte film 11 ... Reflective electrochromic element 13 ... Display electrode 15 ... Opposite electrode 17 ... White polymer electrolyte film 31 ... One pole 33 ... Ion liquid gel preparation solution 35 ... Ion liquid gel film 37 ... Low viscosity liquid 39 ... The other electrode

Claims (2)

A method for manufacturing a transmissive electrochromic element.
An ionic liquid gel preparation solution containing THF, an ionic liquid, and a (meth) acrylic polymer was prepared.
A coating step of applying the transparent ionic liquid gel preparation solution onto either the display electrode or the counter electrode.
A gel film forming step of volatilizing the THF from the ionic liquid gel preparation solution at 15 to 60 ° C. to form an ionic liquid gel film.
A dissolution step of applying the THF to one side of the ion liquid gel membrane that is not in contact with the one pole to make only the surface of the one side a low-viscosity liquid.
A method for manufacturing a transmissive electrochromic element, comprising a bonding step of bonding one of the display electrode and the counter electrode to the one side of the ion liquid gel film. A method for manufacturing reflective electrochromic elements.
An ionic liquid gel preparation solution containing THF, an ionic liquid, a (meth) acrylic polymer, and a white pigment was prepared.
A coating step of applying the ionic liquid gel preparation solution containing a white pigment onto either the display electrode or the counter electrode.
A gel film forming step of volatilizing the THF from the ionic liquid gel preparation solution at 15 to 60 ° C. to form an ionic liquid gel film.
A dissolution step of applying the THF to one side of the ion liquid gel membrane that is not in contact with the one pole to make only the surface of the one side a low-viscosity liquid.
A method for manufacturing a reflective electrochromic element, comprising a bonding step of bonding one of the display electrode and the counter electrode to the one side of the ion liquid gel film.

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