JP6963788B2 - Electrochromic display system - Google Patents

Description

The present invention relates to an electrochromic (EC) display system including an electrochromic pixel unit.

In recent years, electrochromic materials have been attracting attention as display materials. As such electrochromic materials, various organometallic hybrid polymers have been developed, and electrochromic devices using them are known (see, for example, Patent Documents 1 and 2). Patent Documents 1 and 2 disclose an organic / metal hybrid polymer in which an organic ligand is a terpyridine group or a phenanthroline group and a metal ion is coordinated thereto, and an electrochromic device thereof.

Such electrochromic devices are applied to display elements, dimming elements, electronic papers and the like. At this time, the electrochromic device is driven by a static drive method or a matrix drive method, but even if individual pixels or individual segments can be driven individually, they are not physically independent. A new system is expected in which individual pixels constituting an electrochromic device can be displayed even if they are freely arranged without being connected by wiring or the like.

JP-A-2007-112957 Japanese Unexamined Patent Publication No. 2012-188517

An object of the present invention is to provide an electrochromic (EC) display system that does not require wiring.

前記式（Ｉ）において、Ｍは金属イオンを示し、Ｘはカウンターアニオンを示し、Ｒは、炭素原子および水素原子を含むスペーサまたは２つのターピリジン基を直接接続するスペーサを示し、Ｒ^１〜Ｒ^４は、それぞれ独立に水素原子または置換基を示し、ｎは重合度を示す２以上の整数であり、
前記式（ＩＩ）において、Ｍ^１〜Ｍ^Ｎ（Ｎは２以上の整数）は、それぞれ独立に酸化還元電位の異なる金属イオンを示し、Ｘ^１〜Ｘ^ｎ（ｎは２以上の整数）は、それぞれ独立にカウンターアニオンを示し、Ｒ^１〜Ｒ^Ｎ（Ｎは２以上の整数）は、それぞれ独立に炭素原子および水素原子を含むスペーサまたは２つのターピリジン基を直接接続するスペーサを示し、Ｒ^１ _１〜Ｒ^１ _Ｎ、Ｒ^２ _１〜Ｒ^２ _Ｎ、Ｒ^３ _１〜Ｒ^３ _Ｎ、Ｒ^４ _１〜Ｒ^４ _Ｎ（Ｎは２以上の整数）は、それぞれ独立に水素原子または置換基を示し、ｎ_１〜ｎ_Ｎは、それぞれ独立に重合度を示す２以上の整数であり、
前記式（ＩＩＩ）において、Ｍは金属イオンを示し、Ｘはカウンターアニオンを示し、Ａは、炭素原子および水素原子を含むスペーサまたは２つのフェナントロリン基を直接接続するスペーサを示し、Ｒ^１〜Ｒ^４は、それぞれ独立に水素原子または置換基を示し、ｎは重合度を示す２以上の整数である。
前記ＥＣ画素部は、第１の電極と、前記第１の電極上に位置する前記エレクトロクロミック材料からなるエレクトロクロミック層、前記エレクトロクロミック層上に位置する電解質層と、前記電解質層上に位置する第２の電極とを備えてもよい。
前記第１の電極および前記第２の電極の少なくともいずれか一方は、透明導電膜であってもよい。 The electrochromic (EC) display system according to the present invention includes a transmitting unit that emits an electromagnetic wave signal and a plurality of electrochromic (EC) display devices that operate on the electromagnetic wave signal, and each of the plurality of EC display devices includes a plurality of electrochromic (EC) display devices. A plurality of receiving units that receive the electromagnetic wave signal and convert it into an electric signal, and an electrochromic (EC) pixel unit that is electrically connected to the receiving unit and whose color is reversibly changed by the electric signal. Each of the EC display devices of the above is independent of each other, thereby solving the above-mentioned problems.
The EC pixel portion may contain an electrochromic material made of an organic / metal hybrid polymer composed of an organic ligand and a metal ion coordinated to the organic ligand.
The transmitting unit may include an electromagnetic wave source having directivity.
The electromagnetic wave source may be selected from the group consisting of a light emitting diode (LED), a semiconductor laser (LD), a light pen, a flashlight, a radio wave source including an antenna, and a projector.
The transmitting unit includes a manual type that manually operates the transmitting direction of the electromagnetic wave signal, a mechanical drive type that mechanically operates the transmitting direction of the electromagnetic wave signal, and a projector type that projects and transmits the electromagnetic wave signal. May be selected from the group of
The transmitting unit is the machine-driven type or the projector type, stores attribute data indicating the attributes of the receiving unit possessed by each of the plurality of EC display devices, and irradiates the receiving unit based on the attribute data. A central processing unit for creating a pattern to be created may be further provided, and the transmitting unit may transmit the electromagnetic wave signal to the receiving unit based on the pattern from the central processing unit.
The attribute data may include position information of the receiving unit and / or color information of the EC pixel unit connected to the receiving unit.
The receiving unit has an identification mark identified by the imaging device, and the attribute data may be based on the identification mark.
The identification mark may be selected from the group consisting of numbers, letters, barcodes, QR codes (registered trademarks) and color markers.
The pattern may consist of pulses.
The receiver may include at least a solar cell or a photodiode.
The receiving unit includes a first photodiode, a second photodiode, an integrated circuit, and a drive power supply, and the integrated circuit so that the first photodiode and the photodiode have the same polarity. When the electromagnetic signal is received, it is converted into the electric signal and the converted electric signal is transmitted to the integrated circuit, and the integrated circuit is powered by the drive power source. When the integrated circuit receives the electric signal from the first photodiode, a voltage is applied so that the EC pixel portion electrically connected to the receiving portion is colored, and the integrated circuit applies the voltage so as to color the EC pixel portion. When the electric signal from the photodiode of 2 is received, a voltage may be applied by switching the polarity so that the EC pixel unit electrically connected to the receiving unit is discolored.
The receiving unit includes a first solar cell and a second solar cell, and the first solar cell and the second solar cell are connected so that their polarities are opposite to each other. When the solar cell receives the electromagnetic wave signal, the first solar cell converts the electromagnetic wave signal into the electric signal, and the EC pixel part electrically connected to the receiving part is decolorized. When a voltage is applied to the second solar cell and the second solar cell receives the electromagnetic wave signal, the second solar cell converts the electromagnetic wave signal into the electric signal and is electrically connected to the receiving unit. A voltage may be applied so that the EC pixel portion is colored.
The receiver includes a first solar cell, a second solar cell, an integrated circuit, and a drive power source so that the first solar cell and the second solar cell have the same polarity. It is connected to the integrated circuit, and when it receives the electromagnetic signal, it converts it into the electric signal and transmits the converted electric signal to the integrated circuit, and the integrated circuit is powered by the drive power supply. When the integrated circuit receives the electric signal from the first solar cell, the integrated circuit applies a voltage so that the EC pixel portion electrically connected to the receiving portion is colored, and the integrated circuit receives the electric signal. When the electric signal from the second solar cell is received, a voltage may be applied by switching the polarity so that the EC pixel unit electrically connected to the receiving unit is discolored.
The drive power source may be a combination of a third solar cell and a secondary battery or an electric double layer capacitor, or a primary battery.
The organic ligand may be selected from the group consisting of a terpyridine group, a phenanthroline group, a bipyridine group, an imino group and derivatives thereof.
The metal ion may be a metal ion selected from the group consisting of Pt, Cu, Ni, Pd, Ag, Mo, Fe, Co, Ru, Rh, Eu, Zn and Mn.
The organic / metal hybrid polymer may be an organic / metal hybrid polymer represented by a general formula selected from the group consisting of the general formulas (I), (II) and (III).

In the formula (I), M represents a metal ion, X represents a counter anion, R represents a spacer containing a carbon atom and a hydrogen atom, or a spacer directly connecting two terpyridine groups, and R ^{1 to} R ⁴ Independently indicate a hydrogen atom or a substituent, and n is an integer of 2 or more indicating the degree of polymerization.
In the above formula (II), M ^{1 to MN} (N is an integer of 2 or more) independently represent metal ions having different oxidation-reduction potentials, and X ^{1 to} X ⁿ (n is an integer of 2 or more) are. each independently represents a counter anion, ^R 1 ~R ^N (N is an integer of 2 or more) each independently represent a spacer connecting the spacer or two terpyridine groups directly containing carbon and hydrogen atoms, R ¹ ₁ ~ R ¹ _N , R ² ₁ ~ R ² _N , R ³ ₁ ~ R ³ _N , R ⁴ ₁ ~ R ⁴ _N (N is an integer of 2 or more) independently indicate a hydrogen atom or a substituent, and n _{1 to} n _N are integers of 2 or more that independently indicate the degree of polymerization.
In the above formula (III), M represents a metal ion, X represents a counter anion, A represents a spacer containing a carbon atom and a hydrogen atom, or a spacer directly connecting two phenanthroline groups, R ^{1 to} R ⁴ Independently indicate a hydrogen atom or a substituent, and n is an integer of 2 or more indicating the degree of polymerization.
The EC pixel portion is located on the first electrode, an electrochromic layer made of the electrochromic material located on the first electrode, an electrolyte layer located on the electrochromic layer, and the electrolyte layer. A second electrode may be provided.
At least one of the first electrode and the second electrode may be a transparent conductive film.

The electrochromic (EC) display system of the present invention includes a transmitting unit that emits an electromagnetic wave signal and a plurality of electrochromic (EC) display devices that operate by the electromagnetic wave signal, and each of the plurality of EC display devices emits an electromagnetic wave signal. It includes a receiving unit that receives and converts it into an electric signal, and an electrochromic (EC) pixel unit that is electrically connected to the receiving unit and whose color is reversibly changed by the electric signal. Further, each of the plurality of EC display devices is physically independent of each other. Even if each of the receiving unit and the EC display device including the EC pixel unit is not physically wired, the EC pixel unit is driven by the receiving unit receiving an electromagnetic wave signal and reversibly changes its color. As a result, in the EC display system of the present invention, the user can freely arrange a plurality of EC display devices in any number, so that the degree of freedom in design is further increased.

In particular, if an organic / metal hybrid polymer is used as the electrochromic material for the EC pixel portion, the power consumption is extremely small, so that the EC display device is easily driven by the electromagnetic wave signal.

The figure which shows typically the electrochromic (EC) display system (A) and the electrochromic (EC) display device (B) of this invention. The figure which shows typically another EC display system of this invention. Schematic diagram showing the EC pixel portion The figure which shows typically the EC display device of this invention. The figure which shows typically another EC display device of this invention. The figure which shows still another EC display device of this invention schematically. The figure which shows typically the EC pixel 1 in Reference Example 1. The figure which shows the time change (A) of the current density at the time of erasing and the time change (B) of the current density at the time of coloring of EC pixel 1 in Reference Example 1. The figure which shows typically the EC pixel 2 in Reference Example 2. The figure which shows the time change (A) of the current density at the time of erasing and the time change (B) of the current density at the time of coloring of EC pixel 2 in Reference Example 2.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. The same elements are given the same numbers, and the description thereof will be omitted.

The configuration and operation of the electrochromic (EC) display system 100 of the present invention will be described.
FIG. 1 is a diagram schematically showing an electrochromic (EC) display system (A) and an electrochromic (EC) display device (B) of the present invention.

As shown in FIG. 1A, the EC display system 100 of the present invention includes a transmitting unit 120 that emits an electromagnetic wave signal 110, and a plurality of EC display devices 130 that are operated by the electromagnetic wave signal 110. Here, each of the plurality of EC display devices 130 is not connected by wiring or the like and is independent of each other. In the specification of the present application, the electromagnetic wave signal is intended to be light such as infrared rays, visible light and ultraviolet rays, and radio waves such as microwaves and ultra-short waves having a frequency lower than that of light.

As shown in FIG. 1 (B), each of the plurality of EC display devices 130 is electrically connected to a receiving unit 140 that receives an electromagnetic wave signal 110 and converts it into an electric signal, and an electric signal. It is provided with an electrochromic (EC) pixel unit 150 whose color is reversibly changed by. Further, the receiving unit 140 includes at least a solar cell or a photodiode. These solar cells and photodiodes can receive the electromagnetic signal 110 and convert it into an electrical signal. As will be described later, when light is selected as the electromagnetic wave signal 110, a light source such as a laser or LED is used for the transmitting unit 120. When a radio wave having a frequency lower than that of light is selected as the electromagnetic wave signal 110, the transmitting unit 120 includes an oscillation circuit having a corresponding frequency and an antenna for transmitting the radio wave with directivity. Further, the receiving unit 140 includes an antenna for receiving radio waves and a circuit for converting the antenna into an electric signal.

According to the present invention, the color is reversibly changed by the electric signal obtained from the receiving unit 120 from the electromagnetic wave signal 110 using light or radio waves, and the changed colored / decolorized state can be maintained without power consumption. Since the EC pixel unit 150 using the chromic material is adopted, the plurality of EC display devices 130 as described above enable the EC display system 100 which is independent of each other. Therefore, the user can add or reduce an arbitrary number of EC display devices 130 and can arrange them freely. Therefore, if the EC display system 100 of the present invention is used, the degree of freedom in design is increased to each stage. be able to.

The EC pixel portion 150 uses an electrochromic material as described above, but preferably an electrochromic material made of an organic / metal hybrid polymer composed of an organic ligand and a metal ion coordinated to the organic ligand. Contains. Since such an organic / metal hybrid polymer has low power consumption, it is easily colored and decolorized by an electric signal converted from an electromagnetic wave signal.

Here, the organometallic hybrid polymer will be described in detail. The organic ligand is not particularly limited as long as it is an organic compound capable of coordinating metal ions and polymerizable by polymerization, but is preferably a terpyridine group, a phenanthroline group, a bipyridine group, an imino group and these. Selected from the group consisting of derivatives of. By coordinating these organic ligands with metal ions and forming a complex, the organic ligands and the metal ions are alternately linked to form an organic / metal hybrid polymer.

The terpyridine group is typically 2,2': 6', 2 "-terpyridine, but may be a derivative having various substituents. An exemplary substituent is a halogen. Examples of the hydrocarbon group include an atom, a hydrocarbon group, a hydroxyl group, an alkoxy group, a carbonyl group, a carboxylic acid ester group, an amino group, a substituted amino group, an amide group, a substituted amide group, a cyano group and a nitro group. For example, _{linear or branched alkyl groups such as C 1 to} C ₁₀ , specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group and the like are exemplified. As a substituent, these hydrocarbon groups are alkyl groups such as methyl group, ethyl group and hexyl group, alkoxy groups such as methoxy group and butoxy group, and substituents such as halogen atoms such as chlorine and bromine. Not limited to this.

The bipyridine groups are 2,2'-bipyridine, 3,3'-bipyridine, 4,4'-bipyridine, 2,3'-bipyridine, 2,4'-bipyridine, and 3,4'-bipyridine. It may be a derivative having various substituents. Here again, exemplary substituents are as described above.

The imino group can be a derivative having C = N and various substituents on the imino group. Exemplary derivatives are as described above.

The phenanthroline group is obtained by substituting any two carbon atoms of phenanthrene with a nitrogen atom, and may be a derivative having various substituents. Exemplary substituents include, but are not limited to, a methyl group, a t-butyl group, a phenyl group, a thienyl group, a bitienyl group, a turtieryl group, a phenylacetyl group and the like.

The metal ion can be any metal ion whose valence is changed by a redox reaction, but preferably Pt, Cu, Ni, Pd, Ag, Mo, Fe, Co, Ru, Rh, Eu, Zn and Mn. It is a metal ion selected from the group consisting of. These metal ions coordinate with the organic ligands described above. More preferably, when the organic ligand is a terpyridine group or a derivative thereof, a 6-coordinated metal ion is selected and the organic ligand is a phenanthroline group, a bipyridine group, an imino group or a derivative thereof. In the case, a 4-coordinated metal ion is selected.

The organometallic hybrid polymer is preferably represented by a general formula selected from the group consisting of the general formulas (I), (II) and (III).

Both the organic / metal hybrid polymers represented by the formulas (I) and (II) consist of a terpyridine group or a derivative thereof as an organic ligand and a metal ion coordinated thereto. The organic / metal hybrid polymer represented by the formula (III) consists of a phenanthroline group or a derivative thereof as an organic ligand and a metal ion coordinated thereto.

In formula (I), M represents a metal ion, X represents a counter anion, R represents a spacer containing a carbon atom and a hydrogen atom, or a spacer directly connecting two terpyridine groups, and R ^{1 to} R ⁴ are. , Each independently represents a hydrogen atom or a substituent, and n is an integer of 2 or more indicating the degree of polymerization.

In formula (II), M ^{1 to MN} (N is an integer of 2 or more) independently represent metal ions having different oxidation-reduction potentials, and X ^{1 to} X ⁿ (n is an integer of 2 or more) are respectively. independently represents a counter anion, ^R 1 ~R ^N (N is an integer of 2 or more) each independently represent a spacer connecting the spacer or two terpyridine groups directly containing carbon and hydrogen atoms, R ¹ ₁ ~ R ¹ _N , R ² _{1 to} R ² _N , R ³ _{1 to} R ³ _N , R ⁴ _{1 to} R ⁴ _N (N is an integer of 2 or more) independently indicate a hydrogen atom or a substituent, and n ₁ ~ _{N N} are integers of 2 or more that independently indicate the degree of polymerization.

Here, the metal ion in the formula (I) and the formula (II) can be preferably a metal ion selected from the group consisting of Fe, Co, Ni, Zn and Rh. Since these metal ions are 6-coordinated, they allow complex formation with organic ligands.

The counter anion in formulas (I) and (II) can be selected from the group consisting of acetate ion, phosphate ion, chlorine ion, phosphorus hexafluoride ion, boron tetrafluoride ion, and polyoxometallate. These counter anions make the organometallic hybrid polymer electrically neutral and stable.

When the spacers in formulas (I) and (II) are spacers containing carbon and hydrogen atoms, such spacers can be divalent organic groups containing carbon and hydrogen atoms. Examples thereof include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group and the like. Of these, an arylene group such as a phenylene group or a biphenylene group is preferable. Further, these hydrocarbon groups may have an alkyl group such as a methyl group, an ethyl group or a hexyl group, an alkoxy group such as a methoxy group or a butoxy group, and a substituent such as a halogen atom such as chlorine or bromine. Further, such a spacer may further contain an oxygen atom or a sulfur atom. Oxygen atoms and sulfur atoms have a modifying ability, which is advantageous for material design of organic / metal hybrid polymers.

Among the divalent arylene groups, the arylene groups shown below are preferable. These stabilize the organometallic hybrid polymer.

Examples of the aliphatic hydrocarbon group constituting the spacer, for example, alkyl groups such as C ₁ -C _6, specifically, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, Examples thereof include t-butyl groups, and as divalent organic groups constituting the spacer, these groups include alkyl groups such as methyl group, ethyl group and hexyl group, alkoxy groups such as methoxy group and butoxy group, chlorine and bromine. Those having a substituent such as a halogen atom such as, etc. may be used.

^{R 1 to} R ⁴ of the formula (I) ^{and R 1} _{1 to} R ¹ _{N of the} formula (II), R ² _{1 to} R ² _N , R ³ _{N to} R ³ _N , and R ⁴ _{1 to} R ⁴ _N , respectively. It independently indicates a hydrogen atom or a substituent, and examples of the substituent include a halogen atom, a hydrocarbon group, a hydroxyl group, an alkoxy group, a carbonyl group, a carboxylic acid ester group, an amino group, a substituted amino group, an amide group, and a substituted amide. Examples include groups, cyano groups, nitro groups and the like. Examples of the hydrocarbon group include _{a linear or branched alkyl group such as C 1 to} C ₁₀ , specifically, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, t. -Butyl groups and the like can be exemplified, and as substituents, these hydrocarbon groups include alkyl groups such as methyl group, ethyl group and hexyl group, alkoxy groups such as methoxy group and butoxy group, halogen atoms such as chlorine and bromine. Those having a substituent may be used.

In the formula (I), n is an integer of 2 or more indicating the degree of polymerization, for example, 2 to 5000, preferably 10 to 1000. In the formula (II), n _{1 to} n _N are integers of 2 or more independently indicating the degree of polymerization, and the total n ₁ + n ₂ ... + n _N is, for example, 2 to 5000, preferably 10 to 1000. Is.

In formula (III), M represents a metal ion, X represents a counter anion, A represents a spacer containing a carbon atom and a hydrogen atom, or a spacer directly connecting two phenanthroline groups, and R ^{1 to} R ⁴ are. , Each independently represents a hydrogen atom or a substituent, and n is an integer of 2 or more indicating the degree of polymerization.

Here, the metal ion in the formula (III) can be a metal ion selected from the group consisting of Pt, Cu, Ni, Ag and Pd. Since these metal ions are tetra-coordinated, they allow complex formation with organic ligands. The counter anion in formula (III) can be selected from the group consisting of perchlorate ion, triflate ion, boron tetrafluoride ion, chloride ion and phosphate hexafluoride ion. These counter anions make the organometallic hybrid polymer electrically neutral and stable.

When the spacer in the formula (III) is a spacer containing a carbon atom and a hydrogen atom, the spacer is typically represented by a phenyl group, a biphenyl group, a terphenyl group, a thienyl group, a bitienyl group, or a terthienyl group, as shown below. Can be mentioned. It is also desirable to use a spacer modified with an alkyl group (1 to 16 carbon atoms) or an alkoxy group (1 to 16 carbon atoms) in order to increase the solubility of the bis (phenanthroline) derivative. Further, a spacer in which phenyl groups are linked by a dioxoalkyl group (2 to 16 carbon atoms) can also be used.

^{Examples of R 1} and R ² in the formula (III) include hydrogen, methyl group, t-butyl group, phenyl group, thienyl group, bitienyl group and turtieryl group, as shown below. ^{Examples of R 3} and R ⁴ in the formula (III) include hydrogen, a phenyl group, and a phenyl acetyl group.

In formula (III), n is an integer of 2 or more indicating the degree of polymerization, for example, 2 to 5000, preferably 10 to 1000.

Organic / metal hybrid polymers exhibit coloration based on charge transfer absorption from metal ions to organic ligands. When it is electrochemically oxidized, it becomes a decolorized state in which the color is lost, and when it is electrochemically reduced, it becomes a colored state. This phenomenon can occur repeatedly. Therefore, it functions as a low power consumption electrochromic material. The above-mentioned organometallic hybrid polymer can be produced by referring to, for example, Patent Document 1 and Patent Document 2.

In addition, the organometallic hybrid polymer may further contain an ionic liquid. Here, the ionic liquid can form an ionic bond with the above-mentioned organic / metal hybrid polymer to form a complex. By forming the complex, the counter anions from the adjacent electrolyte layers 230 can be retained in the complex, so that quick response characteristics can be achieved.

As such an ionic liquid, any ionic liquid in which an organic / metal hybrid polymer forms an ionic bond is adopted, and specifically, tetrafluoroborate, hexafluorophosphate, bis (trifluoromethanesulfonyl) imide, etc. And a combination of an anion selected from the group consisting of bis (pentafluoroethylsulfonyl) imide and a cation selected from the group consisting of imidazolium, pyrrolidinium, and tetraalkylammonium.

More preferably, the ionic liquid has a melting point below room temperature. This promotes the gelation of macromolecules in the manufacture of electrochromic devices. More preferably, the ionic liquid has a melting point of 0 ° C. or lower. This ensures that the ionic liquid becomes a liquid at room temperature, which is advantageous in the manufacture of electrochromic devices. In the present specification, the room temperature is intended to be in a temperature range higher than 0 ° C. and 50 ° C. or lower.

More preferably, the ionic liquid has a potential window in the range of at least -1 V vs Ag / Ag ⁺ or less negative potential to + 2 V vs Ag / Ag ^{+ or more positive potential.} More preferably, the ionic liquid has a potential window in the range from a negative potential of -3V or less to a positive potential of + 3V or more. As a result, the electrochemical stability of the ionic liquid is further enhanced, so that the durability of the electrochromic device can be further improved.

See FIG. 1 again. The transmitting unit 120 includes an electromagnetic wave source having directivity. By using an electromagnetic wave source having directivity, the desired receiving unit 140 is irradiated with the electromagnetic wave signal 110, and the desired EC pixel unit 150 can be reliably colored and decolorized.

The electromagnetic wave source is preferably selected from the group consisting of light emitting diodes (LEDs), semiconductor lasers (LDs), light pens, flashlights, radio sources with antennas, and projectors. Since these have directivity and versatility, it is easy to construct the EC display system of the present invention. For the sake of clarity, the LED, LD, light pen, and flashlight that emit light may be referred to as a light source.

The transmitting unit 120 may be a manual type in which the transmitting direction of the electromagnetic wave signal 110 is manually operated, a mechanical drive type in which the transmitting direction of the electromagnetic wave signal 110 is mechanically operated, or an electromagnetic wave signal. It may be a projector type that projects and transmits 110.

When the transmitting unit 120 is a manual type, it is convenient because the user can operate the transmitting unit 120, which is a light source typified by a light pen or a flashlight, by hand. When the transmitter 120 is a mechanical drive type, for example, a light source such as a light emitting diode (LED), a semiconductor laser (LD), a light pen and a flashlight, or an electromagnetic wave source typified by a radio wave source provided with an antenna is used. It can be mechanically driven by connecting to an actuator or the like. In particular, if an instruction is given to the actuator from a central processing unit such as a PC (for example, 210 in FIG. 2), machine control by programming becomes possible. When the transmitting unit 120 is a projector type, it is possible to irradiate a plurality of receiving units 140 with an electromagnetic wave signal 110 at a time so as to display a desired pattern or pattern.

FIG. 2 is a diagram schematically showing another EC display system of the present invention.

As shown in FIG. 2, in another EC display system 200 of the present invention, in the EC display system 100 of the present invention of FIG. 1, the transmitter 120 is a machine-driven type or a projector type, and is connected to the transmitter 120. The difference is that the central processing device 210 is provided. The description of the same elements as in FIG. 1 will be omitted.

As described above, the central processing unit 210 may have information for controlling the operation of the transmission unit 120. Specifically, the central processing unit 210 stores attribute data indicating the attributes of the receiving unit 140 possessed by each of the plurality of EC display devices 130. Here, the attribute of the receiving unit 140 preferably has the position information of each receiving unit 140 and / or the color information of the EC pixel unit 150 connected to the receiving unit 140, but may include other information. good. The central processing unit 210 can create a pattern to irradiate the receiving unit 140 based on the above-mentioned attribute data, and the transmitting unit 120 transmits the electromagnetic wave signal 110 to the desired receiving unit 140 based on the created pattern. do.

Further, the receiving unit 140 may have an identification mark identified by an imaging device such as a digital camera. The identification mark is exemplifiedly selected from the group consisting of numbers, letters, barcodes, QR codes (registered trademarks) and color marks and processed in the central processing unit 210. Image recognition software or the like may be used for the processing. If such an identification mark is attached to each of the receiving units 140, position information and / or color information can be easily obtained, and the above-mentioned attribute data is formed based on such an identification mark. ..

The pattern created by the central processing unit 210 includes image and character information to be drawn. For example, when the transmitting unit 120 is a machine-driven type, it is possible to irradiate a predetermined receiving unit among a plurality of receiving units 140 in a predetermined order based on the pattern. For example, when the transmitting unit 120 is a projector type, it is possible to irradiate a predetermined receiving unit among a plurality of receiving units 140 at a time based on a pattern and display an image or a character to be drawn at a time.

The pattern may be a pulse including the above-mentioned image or character information to be drawn. For example, when each of the EC pixel units 150 has three colors of R (red), G (green), and B (blue), the pulse pattern can be obtained by modulating the pulse width, pulse period, pulse intensity, and the like. R, G and B can be associated with each other. It is also possible to read the pulse pattern by an electronic circuit installed in the receiving unit 140 and display only a predetermined color of the EC pixel unit 150. Here, an example of three colors of RGB is shown, but the present invention is not limited to this. Since the EC pixel unit 150 uses an electrochromic material, various colors can be developed.

FIG. 3 is a schematic view showing an EC pixel portion.

The EC pixel portion 150 includes a first electrode 310, an electrochromic layer 320 made of an electrochromic material located on the first electrode 310, an electrolyte layer 330 located on the electrochromic layer 320, and an electrolyte layer 330. It is provided with a second electrode 340 located at.

At least one of the first electrode 310 and the second electrode 340 is a transparent electrode, which enables the color development of the electrochromic layer 320. As the electrode material, a SnO ₂ film, an In ₂ O ₃ film, or an ITO film which is a mixture of _{In 2} O ₃ and SnO _{2 is preferable.} Further, in the first electrode 210 and the second electrode 340, the above-mentioned transparent electrode material is made transparent of a resin substrate such as plastic, a glass substrate or the like by an arbitrary physical vapor deposition method or chemical vapor deposition method. Obtained by forming on a substrate.

The electrochromic layer 320 is not particularly limited as long as it is an electrochromic material having low power consumption, but is preferably an electrochromic material made of the above-mentioned organic / metal hybrid polymer.

The electrolyte layer 330 has a function of compensating for the charge of the change in valence associated with the redox reaction of the metal ion in the electrochromic layer 320. Such an electrolyte layer 330 contains at least a polymer and a supporting salt. The above charge compensation function is achieved by the polymer and the supporting salt.

The macromolecules are preferably polymethylmethacrylate (PMMA), polyethylene oxide (PEO), poly (vinylidene fluoride-co-hexafluoroisopropyl) (PVdF-co-PHFP), polypropylene carbonate (PPC), polycarbonate, and Selected from the group consisting of polyacrylonitrile. These polymers are advantageous in the composition of the gel electrolyte layer.

The supporting salts are preferably LiClO ₄ , LiBF ₄ , LiAsF ₆ , LiPF ₆ , LiCF ₃ SO ₃ , LiCF ₃ COO, lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), LiCH ₃ COO, tetrabutylammonium perchlorate. , Tetraethylammonium perchlorate, KCl, NaClO ₃ , NaCl, NaBF ₄ , NaSCN, KBF ₄ , Mg (ClO ₄ ) ₂ and Mg (BF ₄ ) ₂ . These supporting salts effectively function as counter anions for organometallic hybrid polymers.

Preferably, the electrolyte layer 330 contains a plasticizer selected from the group consisting of propylene carbonate (PC), ethylene carbonate, dimethyl carbonate, diethylene carbonate, γ-butyrolactone, succinonitrile, and ionic liquids. As the ionic liquid as the plasticizer, the same ionic liquid as the above-mentioned ionic liquid can be adopted, and thus the description thereof will be omitted. For example, if the above-mentioned polymer and supporting salt are dissolved in a dehydrating solvent (described later), cast, and then the solvent is removed, the polymer, the plasticizer, and the supporting salt are uniformly dispersed in the gel electrolyte. Since layers can be formed, it leads to improvement and stabilization of electrochromic device characteristics.

The electrolyte layer 330 may further contain an ion storage material selected from the group consisting of viologens, N, N, N', N'-tetramethyl-p-phenylenediamine and organometallic complexes. As a result, it is possible to suppress the accumulation of electric charges between the first electrode 310 and the electrochromic layer 320, so that physical damage to the first electrode 310 caused by the accumulation of electric charges can be suppressed. Exemplary organometallic complexes are ferrocene, Prussian blue, porphyrins and the like. The organic / metal hybrid polymer contained in the electrochromic layer 320 can also suppress the accumulation of electric charges, but if the above-mentioned ion accumulating material is further contained, the first electrode 310 and the substrate provided with the first electrode 310 are further damaged. It can be effectively prevented.

The EC pixel unit 150 is typically manufactured as follows.

A material containing the above-mentioned organometallic hybrid polymer is applied onto the first electrode 310 (FIG. 3) to form the electrochromic layer 320 (FIG. 3). The application may be applied by any means as long as the electrochromic layer 320 is formed on the first electrode 310, but when the material is liquid, it is applied, immersed, sprayed or the like. The above-mentioned organometallic hybrid polymer may be dissolved in a solvent such as methanol, ethanol, or 2-propanol.

Next, an electrolyte substance is applied onto the electrochromic layer 320 to form the electrolyte layer 330 (FIG. 3). The electrolyte layer 330 may be formed by applying the electrolyte substance (arbitrarily containing a polymer, a supporting salt, an ionic liquid, etc.) constituting the electrolyte layer 330 on the electrochromic layer 320, but the application may be applied. , Immersion, spraying, electrolytic polymerization and the like can be used.

The electrolyte material preferably contains a dehydrating solvent. This not only facilitates the application of the electrolyte substance, but also suppresses the crystallization of the above-mentioned polymer (polymer matrix) constituting the electrolyte layer 330, and can prevent a decrease in the response speed. The dehydrating solvent is preferably a solvent selected from the group consisting of acetonitrile, acetone, and tetrahydrofuran, and more preferably dehydrated.

The electrolyte layer 330 and the second electrode 340 (FIG. 3) are combined to form a structure including the first electrode 310, the electrochromic layer 320, the electrolyte layer 330, and the second electrode 340. All you have to do is bring them into contact and press them together.

The structure is then heat treated to remove unwanted solvents (eg, acetonitrile used in the examples) in the structure. As a result, the response speed, contrast, and repeat drive stability (durability) can be improved.

Next, the EC display device 130 will be described more specifically.
FIG. 4 is a diagram schematically showing the EC display device of the present invention.

FIG. 4 shows an EC display device 400 using a solar cell for the receiving unit 140. The receiving unit 140 includes a first solar cell 410 and a second solar cell 420 connected to the first solar cell 410 so that the polarities are opposite to each other. The receiving unit 140 further includes a switch 430 so that either solar cell and the EC pixel unit 150 are connected to each other.

The operation of such an EC display device 400 will be described.
When the switch 430 is connected to the first solar cell 410 and the first solar cell 410 receives the electromagnetic wave signal 110, the electromagnetic wave signal 110 is converted into an electric signal, and the first solar cell 410 is electrically connected to the receiving unit 140. A voltage (here, a positive Va voltage) is applied to the EC pixel unit 150 that is specifically connected. As a result, the electrochromic layer of the EC pixel portion 150 is decolorized by the oxidation reaction.

When the switch 430 is connected to the second solar cell 420 and the second solar cell 420 receives the electromagnetic wave signal 110, the electromagnetic wave signal 110 is converted into an electric signal, and the second solar cell 420 has the receiving unit 140 and electricity. A reverse voltage (here, a negative Va voltage) is applied to the EC pixel unit 150 connected to the object. As a result, the electrochromic layer of the EC pixel portion 150 is colored by the reduction reaction.

In the EC display device 400, the switch 430 can be switched by, for example, a manual changeover switch, but the electromagnetic wave signal 110 is transmitted to only one of the first solar cell 410 and the second solar cell 420. When not irradiated, the switch 430 can be omitted, and the first solar cell 410 and the second solar cell 420 connected in parallel in opposite directions can be directly connected to the EC pixel unit 150. At this time, the electromagnetic wave signal 110 has a sufficiently high directivity such as a semiconductor laser (LD) at the transmitting unit 120, and the irradiation spot does not straddle both the first solar cell 410 and the second solar cell 420. Is preferably used.

FIG. 5 is a diagram schematically showing another EC display device of the present invention.

FIG. 5 shows another EC display device 500 using a solar cell for the receiving unit 140. The receiving unit 140 includes a first solar cell 410, a second solar cell 420, an integrated circuit 510, and a drive power supply 520.

The first solar cell 410 and the second solar cell 420 are connected to the integrated circuit 510 so as to have the same polarity, and when they receive the electromagnetic wave signal 110, they convert it into an electric signal and convert it into an integrated circuit. Send to 510. In FIG. 5, the first solar cell 410 and the second solar cell 420 are connected to the input IN1 and the input IN2 of the integrated circuit 510, respectively. The integrated circuit 510 switches the output according to the received electric signal, and applies a voltage to the EC pixel unit 150 via the outputs OUT1 and OUT2. The drive power supply 520 supplies power to the integrated circuit 510. Here, the drive power supply 520 supplies Vcc power to the integrated circuit 510.

The drive power source 520 is not particularly limited as long as it can supply electric power, but exemplifiedly, it includes a third solar cell 530 and an electric double layer capacitor or a secondary battery 540. As a result, the third solar cell 530 that has received natural light or artificial light can continuously generate electric power and store the electric power in the electric double layer capacitor or the secondary battery 540. The electric double layer capacitor or the secondary battery 540 supplies power only when the EC pixel portion 150 is decolorized or colored. The drive power supply 520 may include a primary battery instead of the combination of the third solar cell 530 and the electric double layer capacitor or the secondary battery 540.

The operation of such an EC display device 500 will be described.
When the first solar cell 410 receives the electromagnetic wave signal 110, the electromagnetic wave signal 110 is converted into an electric signal, and the input IN1 of the integrated circuit 510 is set to voltage High by supplying power from the drive power source 520. As a result, a voltage (here, the voltage of the output OUT1 of the integrated circuit 510 is High) is applied to the EC pixel unit 150 electrically connected to the receiving unit 140. As a result, the electrochromic layer of the EC pixel portion 150 is colored by the reduction reaction.

When the second solar cell 420 receives the electromagnetic wave signal 110, the electromagnetic wave signal 110 is converted into an electric signal, and the input IN2 of the integrated circuit 510 is set to voltage High by supplying power from the drive power source 520. As a result, the opposite voltage (here, the voltage of the output OUT2 of the integrated circuit 510 is High) is applied to the EC pixel unit 150 electrically connected to the receiving unit 140. As a result, the electrochromic layer of the EC pixel portion 150 is decolorized by the oxidation reaction.

FIG. 6 is a diagram schematically showing still another EC display device of the present invention.

FIG. 6 shows another EC display device 600 using a photodiode in the receiving unit 140. The receiving unit 140 includes a first photodiode 610, a second photodiode 620, an integrated circuit 510, and a drive power supply 520. The EC display device 600 is an EC display device except that the first photodiode 610 and the second photodiode 620 are used in place of the first solar cell 410 and the second solar cell 420 in the EC display device 500. It is the same as 500. In FIG. 6, the first photodiode 610 and the second photodiode 620 each show a parallel array in which the photodiodes are connected in parallel, but may be a series array in which the photodiodes are connected in series.

The operation of the EC display device 600 is the same as that of the EC display device 500 of FIG. 5, and is therefore omitted.

Although the specific EC display device of the present invention is shown in FIGS. 4 to 6, the EC display device is electrically connected to a receiving unit that receives an electromagnetic signal and converts it into an electric signal, and is electrically connected to the receiving unit. The EC display system of the present invention can be realized without any limitation as long as it is provided with an EC pixel portion whose color is reversibly changed by an electric signal.

Next, the present invention will be described in detail with reference to specific examples, but it should be noted that the present invention is not limited to these examples.

[material]
The materials used in the following reference examples and examples will be described. All materials were special grade reagents and were used without purification. A glass substrate coated with poly (methyl methacrylate) (PMMA, weight average molecular weight = 350 kg / mol) and indium tin oxide (ITO) (ITO thickness was 0.1 μm. Therefore, it is referred to as an ITO substrate. Resistance = 8 to 12 Ω / cm ² ) is used in Sigma-Aldrich Co., Ltd. LLC. I bought from.

Methanol (MeOH), acetonitrile (ACN), 1-butyl-1-methylpyrrolidinium bis (trifluoromethylsphonyl) imide (hereinafter referred to as BMP-TFSI for simplicity), Wako Pure Chemical Industries, Ltd. I bought it from the company.

Lithium perchlorate (LiClO ₄ ) was purchased from Kanto Chemical Co., Inc.

A polymer material represented by the formula (A) was used as the organic / metal hybrid polymer. The polymer material is described in Patent Document 1 or F.I. S. Han et al. J. Am. Chem. Soc. , 2008, 130 (6), pp2073-2081 and manufactured by Nard Laboratory Co., Ltd. Hereinafter, for the sake of simplicity, the organometallic hybrid polymer will be referred to as polyFe.

[Reference example 1]
FIG. 7 is a diagram schematically showing the EC pixel 1 in Reference Example 1.

Reference Example 1 is an EC pixel portion 150, an ITO substrate as a first electrode 310, polyFe as an electrochromic layer 320, _{an electrolyte substance containing BMP-TFSI, LiClO 4} and PMMA as an electrolyte layer 330, and a second electrode. EC pixel 1 (3 mm × 3 mm) using an ITO substrate as 340 was manufactured.

The EC pixel 1 was manufactured as follows. PolyFe was applied onto an ITO substrate (a glass substrate having a thickness of 1 to 3 mm having an ITO film having a thickness of 0.1 μm) to form an electrochromic layer 320. The solution containing polyFe was prepared by dissolving polyFe (4 mg) in MeOH (1 mL) and filtering with a syringe filter (polyvinylidene fluoride (PVDF), 0.45 μm) to remove insoluble residues. The obtained solution containing polyFe (4 mL) was applied onto an ITO substrate (3 × 3 cm) by a spray coating method. The thickness of the electrochromic layer 320 was 0.2 to 0.3 μm.

An electrolyte substance was applied onto the electrochromic layer 320 to form an electrolyte layer 330. BMP-TFSI as an ionic liquid _{and LiClO 4} as a supporting salt were dissolved in ACN as a dehydrating solvent, PMMA was added as a polymer, and the mixture was vigorously stirred until PMMA was completely dissolved to obtain an electrolyte substance. The electrolyte substance thus obtained was a colorless, transparent, semi-gel-like viscous liquid. The weight ratio of PMMA, LiClO ₄ , BMP-TFSI, and ACN was 7: 3: 20: 70. The obtained electrolyte substance was dropped onto the electrochromic layer 320 by the drop casting method to form the electrolyte layer 330. The thickness of the electrolyte layer 330 was in the range of 0.1 to 1.0 mm.

The second electrode 340 was aligned with the electrolyte layer 330 to obtain a structure composed of an ITO substrate, a polyFe membrane, an electrolyte layer, and an ITO substrate. The structure was left at room temperature for 24 hours to remove the insoluble solvent. Next, the structure was heat-treated at 100 ° C. for 3 hours at a relative humidity of 40% to remove unnecessary solvents. The heat treatment was performed using a vacuum oven (EYELA, VOS-201SD). In this way, the EC pixel 1 was manufactured as the EC pixel unit 150.

The time change of the current density at the time of coloring and bleaching of the obtained EC pixel 1 was measured by an electrochemical analyzer (BAS Inc., ALS / CH Instruments Electrochemical Analyzer model 612B). The results are shown in FIG.

FIG. 8 is a diagram showing a time change (A) of the current density when the EC pixel 1 is decolorized and a time change (B) of the current density when the EC pixel 1 is colored in Reference Example 1.

According to FIG. 8A, the EC pixel 1 was decolorized at an applied voltage of Va = 3V with an electric energy of 0.0573 mC (electrical energy per unit area: 0.637 mC / cm ² ). According to FIG. 8B, the EC pixel 1 was colored with an electric energy of 0.109 mC (electric energy per unit area: 1.21 mC / cm ^{2) at an applied voltage Va = -3V.}

[Reference example 2]
FIG. 9 is a diagram schematically showing the EC pixel 2 in Reference Example 2.

Reference Example 2 is an EC pixel portion 150, an ITO substrate as a first electrode 310, polyFe as an electrochromic layer 320, _{an electrolyte substance containing BMP-TFSI, LiClO 4} and PMMA as an electrolyte layer 330, and a second electrode. EC pixel 2 (100 mm × 100 mm) using an ITO substrate as 340 was manufactured. Since it is the same as Reference Example 1 except that the size of the electrochromic layer is changed, the description thereof will be omitted. Similar to Reference Example 1, the time change of the current density at the time of coloring and bleaching of the EC pixel 2 was measured. The results are shown in FIG.

FIG. 10 is a diagram showing a time change (A) of the current density when the EC pixel 2 is decolorized and a time change (B) of the current density when the EC pixel 2 is colored in Reference Example 2.

According to FIG. 10A, the EC pixel 2 was decolorized at an applied voltage of Va = 3V with an electric energy of 221.8 mC (electrical energy per unit area: 2.22 mC / cm ² ). According to FIG. 10B, the EC pixel 2 was colored with an electric energy of 181.9 mC (electrical energy per unit area: 1.82 mC / cm ^{2) at an applied voltage Va = -3V.}

[Reference example 3]
Reference Example 3 is an EC pixel portion 150, an ITO substrate as a first electrode 310, polyFe as an electrochromic layer 320, _{an electrolyte substance containing BMP-TFSI, LiClO 4} and PMMA as an electrolyte layer 330, and a second electrode. EC pixel 3 (20 mm × 60 mm) using an ITO substrate as 340 was manufactured. Since it is the same as Reference Example 1 except that the size of the electrochromic layer is changed, the description thereof will be omitted. Similar to Reference Example 1, the time change of the current density at the time of coloring and bleaching of the EC pixel 3 was measured. When the applied voltage Va = 3V, the color is decolorized at 16.8 mC (electricity per unit area: 1.4 mC / cm ² ), and when the applied voltage Va = -3V, the electricity amount is 20.4 mC (per unit area). The amount of electricity: 1.7 mC / cm ² ) was used for coloring.

[Example 1]
In the first embodiment, the EC display system of the present invention including the EC display device and the transmitter shown in FIG. 4 was constructed.

A manually operated white LED flashlight was used as the transmitter 120. The white LED flashlight had a power density of 19 mW / cm ² @ wavelength of 550 nm and an illuminance of 49 klx.

The EC pixel 1 of Reference Example 1 was used as the EC pixel portion 150 (FIG. 4) of the EC display device 400 (FIG. 4). As the receiving unit 140 (FIG. 4), Panasonic solar cell model number AM5815 was used as the first solar cell 410 (FIG. 4) and the second solar cell 420 (FIG. 4). AM5815 had an optimum operating voltage Vope = 4.5V and an optimum operating current Iope = 2.5mA at a power density of 100 mW / cm ^{2 AM-1.5 (25 ° C.).}

Hold the white LED flashlight in your hand, keep the distance from the receiver 140 at 30 cm, connect the first solar cell 410 and the switch 430 (FIG. 4), irradiate the first solar cell 410, and turn it off. I checked the color time. Next, the second solar cell 420 and the switch 430 were connected, the second solar cell 420 was irradiated, and the coloring time was examined. The results are shown in Table 2.

[Example 2]
In the second embodiment, the EC display system of the present invention including the EC display device and the transmitter shown in FIG. 4 was constructed. In Example 2, it was the same as in Example 1 except that an ultra-small white LED light was used as the transmitting unit 120 instead of the white LED flashlight of Example 1. The ultra-small white LED light had a power density of 1.6 mW / cm ² @ wavelength of 550 nm and an illuminance of 0.1 klx.

Hold the ultra-small white LED light in your hand, keep the distance from the receiver 140 at 10 cm, connect the first solar cell 410 and the switch 430, irradiate the first solar cell 410, and set the decoloring time. Examined. Next, the second solar cell 420 and the switch 430 were connected, the second solar cell 420 was irradiated, and the coloring time was examined. The results are shown in Table 2.

[Example 3]
In Example 3, the EC display system of the present invention including the EC display device and the transmitter shown in FIG. 4 was constructed. Example 3 was the same as that of Example 2 except that the EC pixel 2 of Reference Example 2 was used instead of the EC pixel 1 of Example 2 as the EC pixel unit 150. The decoloring time and the coloring time were examined in the same manner as in Example 2. The results are shown in Table 2.

[Example 4]
In Example 4, the EC display system of the present invention including the EC display device and the transmitter shown in FIG. 5 was constructed.

As the transmitter 120, an ultra-small white LED light operated manually was used. The EC pixel 1 of Reference Example 1 was used as the EC pixel portion 150 (FIG. 5) of the EC display device 500 (FIG. 5). The receiving unit 140 (FIG. 5) uses the Panasonic solar cell model number AM5815 as the first solar cell 410 (FIG. 5) and the second solar cell 420 (FIG. 5), and uses the TI model number DRV8832 as the integrated circuit 510. , Panasonic solar cell model number AM5613 is used as the third solar cell 530, and the electric double layer capacitor (SII model number CPZ10080C104F, 3.3V) and the lithium polymer secondary battery (Shenzhen) are used as the electric double layer capacitor or the secondary battery 540. Leftong Electronics Co., Ltd. Model No. 501417, 3.7 V, 70 mAh) were used, respectively. AM5613 had an optimum operating voltage Vope = 3.3V and an optimum operating current Iope = 31.6mA at a power density of 100 mW / cm ^{2 AM-1.5 (25 ° C.).} The DRV8832 is equipped with an H-bridge driver that switches the polarity, and is driven in the range of Vcc = 2.75V to 6V. When the decolorization and coloring were examined in the same manner as in Example 2, it was confirmed that the color was erased and colored by irradiation with the LED light.

[Example 5]
In Example 5, the EC display system of the present invention including the EC display device and the transmitter shown in FIG. 4 was constructed. In Example 5, the same as in Example 1 except that a projector (Epson model number EB-2265U) was used as the transmitting unit 120 instead of the white LED flashlight of Example 1. The projector had a brightness of 5,500 lm and a resolution of WUXGA (1920 x 1200).

A projector was installed, the distance from the receiving unit 140 was maintained at 1.8 m, the first solar cell 410 and the switch 430 were connected, the first solar cell 410 was irradiated, and the decolorization time was examined. Next, the second solar cell 420 and the switch 430 were connected, the second solar cell 420 was irradiated, and the coloring time was examined. The results are shown in Table 2.

[Example 6]
In Example 6, the EC display system of the present invention including the EC display device and the transmitter shown in FIG. 4 was constructed. In Example 6, the EC pixel portion 150 was the same as in Example 5 except that the EC pixel 3 of Reference Example 3 was used instead of the EC pixel 1 of Example 5. The decoloring time and the coloring time were examined in the same manner as in Example 5. The results are shown in Table 2.

For simplicity, the details of the EC display system of Examples 1 to 6 and the decoloring time and the coloring time are shown in Tables 1 and 2, respectively.

As shown in Table 2, in any of the embodiments, the EC display system including the transmitting unit and the EC display device simply irradiates the electromagnetic wave signal from the transmitting unit, and the EC pixels included in the EC display device. It was shown that the coloring and decolorization of the part can be controlled. In the embodiment, only the EC display system having a single EC display device was carried out, but even if this is extended to a plurality of EC display devices, it is carried out by the same principle, and wiring is not required between each EC display device. It is easy for those skilled in the art to understand that.

The EC display system of the present invention can be applied to digital signage, indoor / outdoor display devices, and projection mapping.

100, 200 Electrochromic (EC) display system 110 Electromagnetic signal 120 Transmitter 130, 400, 500, 600 Electrochromic (EC) display device 140 Receiver 150 Electrochromic (EC) pixel 210 Central processing device 310 First electrode 320 Electrochromic layer 330 Electrolyte layer 340 Second electrode 410 First solar cell 420 Second solar cell 430 Switch 510 Integrated circuit 520 Drive power supply 530 Third solar cell 540 Electric duplex capacitor or secondary battery 610 First Photodiode 620 Second photodiode

Claims (18)

A transmitter that emits electromagnetic signals and
It is equipped with a plurality of electrochromic (EC) display devices operated by the electromagnetic wave signal.
Each of the plurality of EC display devices
A receiver that receives the electromagnetic signal and converts it into an electrical signal,
It is provided with an electrochromic (EC) pixel unit that is electrically connected to the receiving unit and whose color is reversibly changed by the electric signal.
Each of the plurality of EC display devices is independent of each other and is independent of each other .
The receiver includes a first photodiode, a second photodiode, an integrated circuit, and a drive power supply.
The first photodiode and the photodiode are connected to the integrated circuit so that the polarities are in the same direction. When the electromagnetic signal is received, the first photodiode and the photodiode are converted into the electric signal, and the converted electric signal is converted into the electric signal. Send to the integrated circuit
The integrated circuit is supplied with power by the drive power source.
When the integrated circuit receives the electric signal from the first photodiode, the integrated circuit applies a voltage so that the EC pixel portion electrically connected to the receiving portion is colored.
When the integrated circuit receives the electric signal from the second photodiode, the integrated circuit switches the polarity and applies a voltage so that the EC pixel portion electrically connected to the receiving portion is discolored. Electrochromic (EC) display system. A transmitter that emits electromagnetic signals and
With a plurality of electrochromic (EC) display devices operated by the electromagnetic wave signal
With
Each of the plurality of EC display devices
A receiver that receives the electromagnetic signal and converts it into an electrical signal,
With an electrochromic (EC) pixel unit that is electrically connected to the receiving unit and whose color is reversibly changed by the electrical signal.
With
Each of the plurality of EC display devices is independent of each other and is independent of each other.
The receiver includes a first solar cell and a second solar cell.
The first solar cell and the second solar cell are connected so that their polarities are opposite to each other.
When the first solar cell receives the electromagnetic wave signal, the first solar cell converts the electromagnetic wave signal into the electric signal, and the EC pixel unit electrically connected to the receiving unit is erased. Apply voltage to color and
When the second solar cell receives the electromagnetic wave signal, the second solar cell converts the electromagnetic wave signal into the electric signal, and the EC pixel part electrically connected to the receiving part is colored. An electrochromic (EC) display system that applies a voltage so that it does. A transmitter that emits electromagnetic signals and
With a plurality of electrochromic (EC) display devices operated by the electromagnetic wave signal
With
Each of the plurality of EC display devices
A receiver that receives the electromagnetic signal and converts it into an electrical signal,
With an electrochromic (EC) pixel unit that is electrically connected to the receiving unit and whose color is reversibly changed by the electrical signal.
With
Each of the plurality of EC display devices is independent of each other and is independent of each other.
The receiver includes a first solar cell, a second solar cell, an integrated circuit, and a drive power source.
The first solar cell and the second solar cell are connected to the integrated circuit so that the polarities are in the same direction, and when the electromagnetic wave signal is received, it is converted into the electric signal and the converted electricity. The signal is transmitted to the integrated circuit and
The integrated circuit is supplied with power by the drive power source.
When the integrated circuit receives the electric signal from the first solar cell, the integrated circuit applies a voltage so that the EC pixel portion electrically connected to the receiving portion is colored.
When the integrated circuit receives the electric signal from the second solar cell, the integrated circuit switches the polarity and applies a voltage so that the EC pixel unit electrically connected to the receiving unit is discolored. Electrochromic (EC) display system. The EC pixel portion according to any one of claims 1 to 3, which contains an electrochromic material made of an organic / metal hybrid polymer composed of an organic ligand and a metal ion coordinated to the organic ligand. The described EC display system. The EC display system according to any one of claims 1 to 3, wherein the transmitting unit includes an electromagnetic wave source having directivity. The EC display system according to claim 5, wherein the electromagnetic wave source is selected from a group consisting of a light emitting diode (LED), a semiconductor laser (LD), a light pen, a flashlight, a radio wave source including an antenna, and a projector. .. The transmitting unit includes a manual type that manually operates the transmitting direction of the electromagnetic wave signal, a mechanical drive type that mechanically operates the transmitting direction of the electromagnetic wave signal, and a projector type that projects and transmits the electromagnetic wave signal. The EC display system according to any one of claims 1 to 3, which is selected from the group. The transmitter is a machine-driven type or a projector type.
A central processing unit that stores attribute data indicating the attributes of the receiving unit of each of the plurality of EC display devices and creates a pattern for irradiating the receiving unit based on the attribute data is further provided.
The EC display system according to claim 7, wherein the transmitting unit transmits the electromagnetic wave signal to the receiving unit based on the pattern from the central processing unit. The EC display system according to claim 8, wherein the attribute data has position information of the receiving unit and / or color information of the EC pixel unit connected to the receiving unit. The receiving unit has an identification mark identified by the imaging device and has an identification mark.
The EC display system according to claim 8, wherein the attribute data is based on the identification mark. The EC display system according to claim 10, wherein the identification mark is selected from a group consisting of numbers, letters, barcodes, QR codes (registered trademarks) and color markers. The EC display system according to claim 8, wherein the pattern comprises pulses. The EC display system according to claim 3, wherein the drive power source is a combination of a third solar cell and a secondary battery or an electric double layer capacitor, or a primary battery. The EC labeling system according to claim 4, wherein the organic ligand is selected from the group consisting of a terpyridine group, a phenanthroline group, a bipyridine group, an imino group and derivatives thereof. The EC display according to claim 4, wherein the metal ion is a metal ion selected from the group consisting of Pt, Cu, Ni, Pd, Ag, Mo, Fe, Co, Ru, Rh, Eu, Zn and Mn. system. The EC display according to claim 4, wherein the organometallic hybrid polymer is an organometallic hybrid polymer represented by a general formula selected from the group consisting of the general formulas (I), (II) and (III). system.

In the formula (I), M represents a metal ion, X represents a counter anion, R represents a spacer containing a carbon atom and a hydrogen atom, or a spacer directly connecting two terpyridine groups, and R ^{1 to} R ⁴ Independently indicate a hydrogen atom or a substituent, and n is an integer of 2 or more indicating the degree of polymerization.
In the above formula (II), M ^{1 to MN} (N is an integer of 2 or more) independently represent metal ions having different oxidation-reduction potentials, and X ^{1 to} X ⁿ (n is an integer of 2 or more) are. each independently represents a counter anion, ^R 1 ~R ^N (N is an integer of 2 or more) each independently represent a spacer connecting the spacer or two terpyridine groups directly containing carbon and hydrogen atoms, R ¹ ₁ ~ R ¹ _N , R ² ₁ ~ R ² _N , R ³ ₁ ~ R ³ _N , R ⁴ ₁ ~ R ⁴ _N (N is an integer of 2 or more) independently indicate a hydrogen atom or a substituent, and n _{1 to} n _N are integers of 2 or more that independently indicate the degree of polymerization.
In the above formula (III), M represents a metal ion, X represents a counter anion, A represents a spacer containing a carbon atom and a hydrogen atom, or a spacer directly connecting two phenanthroline groups, R ^{1 to} R ⁴ Independently indicate a hydrogen atom or a substituent, and n is an integer of 2 or more indicating the degree of polymerization. The EC pixel portion is located on the first electrode, an electrochromic layer made of the electrochromic material located on the first electrode, an electrolyte layer located on the electrochromic layer, and the electrolyte layer. The EC display system according to claim 4, further comprising a second electrode. The EC display system according to claim 17, wherein at least one of the first electrode and the second electrode is a transparent conductive film.

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