WO2010147017A1 - 表示素子とそれを用いたカラー電子ペーパー - Google Patents
表示素子とそれを用いたカラー電子ペーパー Download PDFInfo
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- WO2010147017A1 WO2010147017A1 PCT/JP2010/059638 JP2010059638W WO2010147017A1 WO 2010147017 A1 WO2010147017 A1 WO 2010147017A1 JP 2010059638 W JP2010059638 W JP 2010059638W WO 2010147017 A1 WO2010147017 A1 WO 2010147017A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/22—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing two or more pyridine rings directly linked together, e.g. bipyridyl
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1516—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising organic material
- G02F1/15165—Polymers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/153—Constructional details
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F2001/164—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect the electrolyte is made of polymers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2202/00—Materials and properties
- G02F2202/02—Materials and properties organic material
Definitions
- the present invention relates to a display element and color electronic paper using the display element.
- a method using a polarizing plate such as a reflective liquid crystal has a low reflectance of about 40% and is difficult to display white, and many of the production methods used for producing the constituent members are not easy.
- the polymer dispersed liquid crystal requires a high voltage and utilizes the difference in refractive index between organic substances, so that the resulting image has insufficient contrast.
- the polymer network type liquid crystal has problems such as high voltage and the necessity of a complex TFT circuit to improve memory performance.
- a display element based on electrophoresis requires a high voltage of 10 V or more, and there is a concern about durability due to electrophoretic particle aggregation.
- a method for performing color display using these methods a method using a color filter is known. In principle, a bright white display cannot be obtained due to the coloring of the color filter.
- an electrochromic method is known as a method capable of full color display that can be driven at a low voltage.
- the electrochromic method can be driven at a low voltage of 3 V or less, but when displaying full color, it is necessary to stack three layers of different colors, and there is a concern about the high cost due to complicated element configuration,
- a full-color electrochromic element using flat ground mixing (see, for example, Patent Document 1) is known.
- the contrast of color display is not sufficient because of the flat ground mixing, and a method of performing multicolor display in a single layer. Is desired.
- Patent Document 2 discloses that an organic-inorganic hybrid polymer can be formed by complexing a coordination bis (terpyridine) derivative with a metal ion to control color development and decoloration.
- Japanese Patent Laid-Open No. 2003-270670 JP 2007-112957 A International Publication WO2008 / 143324 Pamphlet International Publication WO2008 / 081762 Pamphlet
- Patent Documents 2 to 4 suggest the applicability of organic-inorganic hybrid polymers to display elements, specific configurations as display elements such as color electronic paper have not yet been realized. Is the current situation.
- the present invention has been made in view of the circumstances as described above, and can smoothly switch between display / non-display of a desired symbol, has a memory function, and is driven at a low voltage with a simple member configuration. It is an object of the present invention to provide a display element that can be displayed with high display contrast and can have a large area, and color electronic paper using the display element.
- the present invention is characterized by the following in order to solve the above problems.
- 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 terpyridyl groups
- R 1 to R 4 are each Independently represents a hydrogen atom or a substituent
- n is an integer of 2 or more indicating the degree of polymerization.
- M 1 to M N each independently represents a metal ion
- X 1 to X N (N represents an integer of 2 or more) are each independently represented. represent a counter anion
- R 1 ⁇ R N each independently represent a spacer connecting the spacer or two terpyridyl group directly containing carbon and hydrogen atoms
- R 1 1 to R 1 N , R 2 1 to R 2 N , R 3 N to R 3 N , R 4 1 to R 4 N are each independently a hydrogen atom or a substituent N 1 to n N (N represents an integer of 2 or more), each of which represents an organic-inorganic hybrid polymer represented by the following formula:
- a display element comprising a layer and a polymer gel electrolyte-containing layer.
- the first display element wherein the symbol display layer is formed on a surface of a transparent substrate having a front electrode and / or a substrate having a back electrode.
- the third display element wherein the white particles are titanium dioxide fine particles.
- the metal ion of the organic-inorganic hybrid polymer is at least one selected from iron ion, cobalt ion, nickel ion, zinc ion, and ruthenium ion, any one of the first to fourth above Display element.
- the counter anion of the organic-inorganic hybrid polymer is at least one selected from acetate ion, chlorine ion, phosphorus hexafluoride ion, boron tetrafluoride ion, and polyoxometalate. Any one of display elements 1 to 5.
- a color electronic paper comprising any one of the first to sixth display elements.
- the seventh color electronic paper as described above which has a display unit having a size of 20 inches or more.
- a symbol display such as a segment display and a digital display by using an electrochromic characteristic of an organic-inorganic hybrid polymer (a characteristic in which a substance color is changed by electrochemical redox), and a simple member configuration. It can be driven at a low voltage. Even if the power is turned off, the display can be continued for a long time (memory action). Further, the display contrast can be increased by adding a white pigment such as titanium dioxide fine particles to the polymer gel electrolyte. Furthermore, a large area display such as a large color electronic paper having a side of 40 cm is also possible.
- Example 4 It is the figure which showed schematically embodiment of the display element of this invention. It is a photograph of the display element obtained in Example 1 (right) and Example 2 (left). 6 is a photograph of a display element obtained in Example 4.
- the organic-inorganic hybrid polymer of formula (I) and formula (II) used in the present invention is composed of a bis (terpyridine) derivative, a metal ion, and a counter anion.
- Organic-inorganic hybrid polymer exhibits color based on charge transfer absorption from a metal to a bis (terpyridine) derivative as a ligand. That is, the color disappears when the organic-inorganic hybrid polymer is electrochemically oxidized. Further, when electrochemically reduced in this decolored state, it returns to the colored state. This phenomenon can occur repeatedly.
- R in the formula (I) and R 1 to R N in the formula (II) are spacers for connecting two terpyridyl groups, and the angle of the pyridyl group of the organic-inorganic hybrid polymer can be arbitrarily set by the spacer. -Material design of inorganic hybrid polymer becomes possible.
- the spacer may be one in which two terpyridyl groups are directly connected, but a divalent organic group containing a carbon atom and a hydrogen atom can be used.
- a divalent organic group include aliphatic groups.
- examples include hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and heterocyclic groups. Of these, arylene groups such as a phenylene group and a biphenylene group are preferable.
- these hydrocarbon groups may have a substituent such as 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, or a halogen atom such as chlorine or bromine.
- a spacer may further contain an oxygen atom or a sulfur atom. Oxygen atoms and sulfur atoms have a modification ability, which is advantageous for material design of organic-inorganic hybrid polymers.
- divalent arylene groups represented by the following formulas (1) to (11) can be exemplified as preferable spacers.
- Examples of the aliphatic hydrocarbon group constituting the spacer include alkyl groups such as C 1 to C 6 , specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, Examples of the divalent organic group constituting the spacer include t-butel group, etc., and 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 may be used.
- Examples of the metal ions of M in the formula (I) and M 1 to MN in the formula (II) include iron ions, cobalt ions, nickel ions, zinc ions, ruthenium ions and the like. These metal ions can not only change the valence by a reduction reaction, but also when the organic-inorganic hybrid polymer represented by the above formula (I) is used, different redox potentials for each metal ion.
- Examples of counter anions of X in formula (I) and X 1 to X N in formula (II) include acetate ion, chlorine ion, phosphorus hexafluoride ion, boron tetrafluoride ion, polyoxometalate and the like. Can be mentioned.
- the counter anion compensates for the metal ion charge and renders the organic-inorganic hybrid polymer electrically neutral.
- R 1 to R 4 in formula (I) and R 1 1 to R 1 N , R 2 1 to R 2 N , R 3 N to R 3 N , and R 4 1 to R 4 N in formula (II) are Independently represents 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 carboxylate group, an amino group, a substituted amino group, an amide group, and a substituted amide. Group, cyano group, nitro group and the like.
- hydrocarbon group examples include 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 can be exemplified, and these hydrocarbon groups as substituents 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, etc. You may use what has a substituent.
- n is an integer of 2 or more indicating the degree of polymerization, for example, 2 to 5000, preferably 10 to 1000.
- n 1 to n N are each independently an integer of 2 or more indicating the degree of polymerization, and the total n 1 + n 2 +... + N N is, for example, 2 to 5000, preferably 10 to 1000.
- the organic-inorganic hybrid polymers of the formulas (I) and (II) can be produced, for example, by the methods described in Patent Documents 2 to 4 and the like.
- the organic-inorganic hybrid polymer of formula (I) when produced, it can be produced by refluxing a bisterpyridine derivative and a metal salt at 150 ° C. for about 24 hours in acetic acid or methanol.
- the reflux conditions vary depending on the selected spacer and metal salt, but those skilled in the art can easily select optimum conditions.
- the mixture obtained by refluxing may be heated to evaporate the solvent and form a powder.
- the powder has, for example, a color such as purple and is in a reduced state. Since such powder is easily dissolved in methanol, it is easy to handle.
- the organic-inorganic hybrid polymer of the formula (II) includes, for example, each of the bisterpyridine derivatives corresponding to the first to Nth of the formula (II) and each of the metal salts corresponding to the first to Nth. , And refluxing each in acetic acid and methanol, and a step of mixing the first to N-th (N is an integer of 2 or more) reactants obtained in this step.
- the polymer gel electrolyte used in the present invention is a gel electrolyte using an organic solvent and a polymer.
- the electrolyte used for the polymer gel electrolyte is preferably a compound such as a lithium salt, a sodium salt, a potassium salt, or an ammonium salt that is soluble in an organic solvent and has a sufficient electric conductivity (0.2 S / m or more).
- ammonium hexafluorophosphate such as tetrabutylammonium hexafluorophosphate, tetraethylammonium hexafluorophosphate, and tetrapropylammonium hexafluorophosphate.
- an organic solvent having a boiling point in the range of 120 to 300 ° C. that can remain in the electrolyte without causing volatilization after the electrolyte is formed can be used.
- examples of such an organic solvent include propylene carbonate, ethylene carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate, butylene carbonate, ⁇ -butyl lactone, tetramethyl urea, sulfolane, dimethyl sulfoxide, 1,3-dimethyl-2- Imidazolidinone, 2- (N-methyl) -2-pyrrolidinone, hexamethylphosphortriamide, N-methylpropionamide, N, N-dimethylacetamide N-methylacetamide, N, N dimethylformamide, N-methylformamide, Butyronitrile, propionitrile, acetonitrile, acetylacetone, 4-methyl-2-pentanone, 2-butanol, 1-butan
- cyclic carboxylic acid ester compounds such as propylene carbonate, ethylene carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate, butylene carbonate, and ⁇ -butyl lactone are preferably used.
- the polymer for dispersing the electrolyte is preferably a highly transparent polymer that dissolves or swells (gelates) when the above organic solvent is added.
- a highly transparent polymer that dissolves or swells (gelates) when the above organic solvent is added.
- the blend of the electrolyte and the polymer in the polymer gel electrolyte is preferably about 1: 1 by mass ratio.
- white particles are contained in the polymer gel electrolyte from the viewpoint of further improving display contrast and improving visibility.
- white particles applicable in the present invention include titanium dioxide (anatase type or rutile type), barium sulfate, calcium carbonate, aluminum oxide, zinc oxide, magnesium oxide, zinc hydroxide, magnesium hydroxide, magnesium phosphate, Examples include magnesium hydrogen phosphate, alkaline earth metal salts, talc, kaolin, zeolite, and acid clay.
- titanium dioxide zinc oxide, and zinc hydroxide are preferably used.
- titanium dioxide surface-treated with inorganic oxides Al 2 O 3 , AlO (OH), SiO 2, etc.
- inorganic oxides such as trimethylolethane, triethanolamine acetate, trimethylcyclosilane, etc.
- titanium dioxide subjected to organic treatment can be used.
- titanium oxide or zinc oxide from the viewpoint of coloring prevention at high temperature and the reflectance of the element due to the refractive index.
- FIG. 1 is a diagram conceptually illustrating a display element of the present invention, where (a) is a cross-sectional view, (b) is a top view in an undisplayed state, and (c) is a top view in a display state.
- the display element of the present invention is an organic compound represented by the following formula (I) or formula (II) between a transparent substrate 1 having a front electrode and a substrate 4 having a back electrode. It has a pattern display layer 2 containing an inorganic hybrid polymer and a polymer gel electrolyte-containing layer 3. The front electrode and the back electrode constitute a counter electrode.
- a transparent substrate having a surface electrode has a transparent surface electrode such as an ITO electrode.
- a transparent conductive film ITO, SnO 2 , In 2 O 3
- a transparent substrate having a surface resistance value of 3 to 600 ⁇ coated with a film such as
- the light transmittance of the transparent substrate can be measured in accordance with the method for measuring the total light transmittance according to JIS K7105.
- a transparent substrate glass, a polymer film, etc. can be used, for example.
- Glass means a substrate transparent to visible light, etc.
- glass mainly composed of silicon dioxide, glass of inorganic materials of various compositions, organic materials such as transparent acrylic resin, polycarbonate resin, etc.
- the used resin glass can also be used.
- polymer film examples include polyester films such as polyethylene terephthalate, polyolefin films such as polypropylene, polyvinyl chloride, acrylic resin films, polyether sulfone films, polyarylate films, polycarbonate films, and the like.
- polyester films such as polyethylene terephthalate, polyolefin films such as polypropylene, polyvinyl chloride, acrylic resin films, polyether sulfone films, polyarylate films, polycarbonate films, and the like.
- a polyethylene terephthalate film is preferable because it is excellent in transparency and excellent in moldability, adhesiveness, workability, and the like.
- the thickness of the surface electrode of the transparent substrate is preferably 10 to 5000 nm, and the thickness of the transparent substrate is not particularly limited.
- the thickness of the transparent substrate is not particularly limited.
- 1 to 15 mm is preferable, and in the case of a polymer film, 10 to 200 ⁇ m is preferable.
- the substrate having the back electrode may be a transparent substrate as described above or an opaque substrate.
- a stainless steel plate can be used as a counter electrode, and electronic paper that is not easily damaged can be manufactured.
- a conductive metal thin film such as aluminum, gold, or silver may be used.
- the display element of the present invention can be manufactured as follows.
- an organic-inorganic hybrid polymer coating solution is prepared, applied to a transparent substrate having a surface electrode, and dried.
- the organic-inorganic hybrid polymer coating solution can be prepared by dissolving the organic-inorganic hybrid polymer in a volatile solvent such as methanol that dissolves the organic-inorganic hybrid polymer.
- a desired pattern pattern is formed.
- a pattern can be easily formed by the following methods (i) to (iii).
- (I) Method of wiping unnecessary parts with methanol after spin-coating a polymer dissolved in methanol As an example, an organic / inorganic hybrid polymer such as Fe-MEPE is dissolved in methanol and 20 mg / mL (2.8 mM) Prepare a solution of concentration (concentration is arbitrary, eg dissolves in the range of 1 mg / mL to 100 mg / mL). An organic / inorganic hybrid polymer dissolved in methanol is spin-coated (for example, 300 rpm, 200 sec) on an electrode substrate such as ITO.
- the spin coating rotation speed and spin coating time are arbitrary, and a film having a desired thickness (color density) can be obtained by adjusting the rotation speed and rotation time.
- a desired pattern can be produced by wiping off a polymer film at an unnecessary portion with a cloth or a rolling pin soaked with methanol.
- an organic / inorganic hybrid polymer such as Fe-MEPE is dissolved in methanol to prepare a solution having a concentration of 20 mg / mL (2.8 mM) (the concentration is arbitrary) For example, it dissolves in the range of 1 mg / mL to 100 mg / mL).
- An electrode substrate such as ITO is preheated with a hot plate (between 30 ° C. and 80 ° C.), and a polymer dissolved in methanol is drawn on the electrode substrate such as ITO using a paintbrush or brush. Since the solvent methanol begins to evaporate simultaneously with the plotting, any plotting is possible.
- an organic / inorganic hybrid polymer such as Fe-MEPE is dissolved in methanol to prepare a solution having a concentration of 20 mg / mL (2.8 mM). For example, it dissolves in the range of 1 mg / mL to 100 mg / mL).
- an electrode substrate such as ITO is immersed, and after a few minutes, the electrode is pulled up from the solution to form a film (dip coating).
- a film having a desired thickness (color density) is obtained by adjusting the solution concentration of the polymer.
- a desired pattern can be created by wiping off the unnecessary polymer film with a cloth or rolling pin soaked with methanol.
- the symbol display layer can be formed on the surface of the transparent substrate having the surface electrode, the surface of the substrate having the back electrode, or both of these surfaces.
- a polymer gel electrolyte coating solution is prepared and applied to the transparent substrate having the surface electrode of the organic-inorganic hybrid polymer and / or the substrate having the back electrode so as to cover the pattern display layer.
- the polymer gel electrolyte coating solution is a bar coater method, applicator method, doctor blade method, roll coater method, die coater method, comma coater method, gravure coating method, roll brush method, spray coating method, air knife coating method, The impregnation method and the curtain coating method are applied alone or in combination.
- a coating film may be formed in only one side among the transparent substrate which has a surface electrode, and the board
- Any solvent may be used as long as it dissolves the electrolyte material and can be removed by drying or the like after each coating.
- Methyl ethyl ketone, acetone, tetrahydrofuran, toluene, heptane, cyclohexane, ether acetate, ethanol, methanol, 2-propanol, isoamyl acetate, Hexyl acetate, N, N-dimethylformamide, N-methyl-2-pyrrolidone, water and the like can be used.
- the front surface electrode of the transparent substrate and the back surface electrode of the substrate are connected to a power source, respectively, a pattern display layer containing an organic-inorganic hybrid polymer represented by the formula (I) or the formula (II), and a polymer gel electrolyte A predetermined voltage is applied to the containing layer. Thereby, the oxidation-reduction of the symbol display layer can be controlled.
- the symbol display layer is made of a single organic-inorganic hybrid polymer represented by the formula (I)
- color development and decoloration may be controlled by oxidation-reduction of metal ions in the symbol display layer.
- the pattern display layer is composed of an organic-inorganic hybrid polymer represented by the formula (II)
- color development and decoloring can be controlled by adjusting the potential to oxidize and reduce multiple types of metal ions. can do.
- the color development of the organic-inorganic hybrid polymer is based on charge transfer absorption from a metal in the polymer to an organic site (bis (terpyridine) derivative). Specifically, when the organic-inorganic hybrid polymer is electrochemically oxidized, the color disappears, and when it is electrochemically reduced in this decolored state, it returns to the colored state.
- the organic-inorganic hybrid polymer causes electron transfer between a bis (terpyridine) derivative as a ligand and a metal ion.
- metal ions By selecting metal ions as appropriate, colors such as blue and red are produced.
- the rate of charge transfer differs depending on the combination of the bis (terpyridine) derivative as the ligand and the metal ion, so the desired color can be obtained by appropriately combining the bis (terpyridine) derivative as the ligand and the metal ion. It is done.
- the rate of this charge transfer can also be controlled by changing the counter anion.
- the organic-inorganic hybrid polymer repeats coloring and decoloring by adjusting the potential. These phenomena are reversible by adjusting the potential.
- the metal ions M 1 to MN have different charge transfer rates between the metal ions and the ligand bis (terpyridine) derivative. Can be different.
- the organic-inorganic hybrid polymer can have a plurality of colors by appropriately combining metal ions having different colors.
- organic-inorganic hybrid polymer of the formula (II) has different redox potentials for each of the metal ions M 1 to MN , only the color based on the specific metal ion can be developed by controlling the potential. Can do.
- a segment display or other arbitrarily shaped symbol display layer is formed of an organic / inorganic hybrid polymer, so that display / non-display of the symbol display layer can be switched by electric potential driving, and further, the type of coloring can be changed. Switching is possible, and even if the power is turned off, the display can be continued for a long time (for example, 30 minutes or more) (memory action).
- the display element of the present invention is suitable for color electronic paper, color electronic posters, color electronic signs, and the like.
- the display element of the present invention can be used directly, but depending on the application, for example, the display element of the present invention can be used by holding it on two substrates, or can be attached to one side of the substrate. Or may be used.
- a base material glass, a polymer film, or the like used as the transparent substrate can be used.
- LiClO 4 was dissolved in acetonitrile (0.9 g / 6 mL), and 6 mL of propylene carbonate was further added to prepare Solution B.
- Solution A and solution B were mixed to obtain a gel electrolyte.
- a glass solution of 20 mg / mL (2.8 mM) of an organic-inorganic hybrid polymer in methanol was spin-coated (300 rpm, 200 sec) on ITO glass (manufactured by Geomat Co., Ltd., 10 ⁇ / cm) and allowed to air dry overnight.
- a gel electrolyte was applied on the entire surface of the formed Fe-MEPE and allowed to air dry overnight. Similarly, gel electrolyte was applied to the ITO glass of the counter electrode. These two sheets were bonded together, and the protruding gel electrolyte was removed. As a result, a color electronic paper having a pattern display layer of Fe-MEPE digital display (7 segments) was produced.
- the drive system was a battery powered device (maximum 6V) (approximately 1.5V per segment).
- LiClO 4 was dissolved in acetonitrile (0.9 g / 6 mL), and 6 mL of propylene carbonate was further added to prepare Solution B.
- the gel electrolyte was applied to the entire surface of the film-formed Fe-MEPE and allowed to air dry overnight. Similarly, gel electrolyte was applied to the ITO glass of the counter electrode. These two sheets were bonded together, and the protruding gel electrolyte was removed. As a result, a color electronic paper having a pattern display layer of Fe-MEPE digital display (7 segments) was produced.
- the drive system used the apparatus (maximum 3V) which uses a dry cell as a power supply.
- This color electronic paper realized a smooth display from 0 to 9, and achieved segment display within 1 second as driving characteristics (left side of Fig. 2).
- the device showed excellent electrochromic behavior even in the presence of titanium dioxide and succeeded in producing a device with good visibility.
- Example 3 [Synthesis of organic-inorganic hybrid polymer] Fe-MEPE was synthesized in the same manner as in Example 1. [Preparation of gel electrolyte] A gel electrolyte was prepared in the same manner as in Example 2. [Production of display element] ITO glass (10 ⁇ / cm) and a stainless steel plate were used as substrates.
- the organic-inorganic hybrid polymer methanol solution 20 mg / mL (2.8 mM) was spin coated (300 rpm, 200 sec) on segment-deposited ITO glass (manufactured by Geomat Co., Ltd., 10 ⁇ / cm) and allowed to air dry overnight.
- the gel electrolyte was applied to the entire surface of the film-formed Fe-MEPE and allowed to air dry overnight. Similarly, a gel electrolyte was applied to the counter electrode stainless steel plate. These two sheets were bonded together, and the protruding gel electrolyte was removed. As a result, a color electronic paper having a pattern display layer of Fe-MEPE digital display (7 segments) was produced.
- the drive system used the apparatus (maximum 3V) which uses a dry cell as a power supply.
- the color at each voltage differs.
- the same multi-color change was confirmed when Co-MEPE cobalt, Ni-MEPE, or the like was used as the combination of polymers to be mixed.
- the color display paper was formed not only on the surface of the transparent substrate having the front electrode but also on the surface of the substrate having the back electrode to produce color electronic paper.
- the same driving characteristics and display characteristics as described above were obtained. As a result, multi-color display in a large area was achieved (FIG. 3).
- Example 5 [Synthesis of organic-inorganic hybrid polymer]
- the same 1,4-bis (terpyridyl) benzene and nickel (II) acetate tetrahydrate as in Example 1 were mixed in ethanol at a molar ratio of 1: 1, and the mixture was heated and stirred at 80 ° C. for 18 hours in a solvent. The resulting yellow solution was transferred to a petri dish and the solvent was distilled off to quantitatively obtain the desired product.
- This organic-inorganic hybrid polymer Ni-MEPE had an absorption at 483 nm according to the ultraviolet-visible absorption spectrum, and the oxidation-reduction potential measured by pulse voltammetry (DPV) was 1.69 V.
- DPV pulse voltammetry
- This color electronic paper realized a smooth display from 0 to 9, and achieved segment display within 1 second as driving characteristics. It was also confirmed that the display continued for more than 30 minutes even after the power was turned off (memory effect).
Abstract
Description
2 図柄表示層
3 高分子ゲル電解質
4 基板
(i)メタノールに溶解させたポリマーをスピンコート後、不要な部分をメタノールにより拭き取る方法
一例としては、Fe-MEPE等の有機/無機ハイブリッドポリマーをメタノールに溶解させ、20mg/mL (2.8mM)の濃度の溶液を調製する(濃度は任意であり、例えば1mg/mLから100mg/mLの範囲では溶解する)。メタノールに溶解させた有機/無機ハイブリッドポリマーをITO等の電極基板上にスピンコート(例えば300rpm, 200sec)する。なお、スピンコートの回転数とスピンコート時間は任意であり、回転数と回転時間を調節することで所望の厚さ(色の濃さ)の膜が得られる。
(ii)ホットプレートを用いて温めながら塗る方法
一例としては、Fe-MEPE等の有機/無機ハイブリッドポリマーをメタノールに溶解させ、20mg/mL (2.8 mM)の濃度の溶液を調製する(濃度は任意であり、例えば1mg/mLから100mg/mLの範囲では溶解する)。
(iii)ディップコートを用いて作図する方法
一例としては、Fe-MEPE等の有機/無機ハイブリッドポリマーをメタノールに溶解させ、20mg/mL (2.8 mM)の濃度の溶液を調製する(濃度は任意であり、例えば1mg/mLから100mg/mLの範囲では溶解する)。
<実施例1>
[有機-無機ハイブリッドポリマーの合成]
100mlの二口フラスコに、1,4-ビス(ターピリジル)ベンゼン30mg(0.0054mol)を2.5mlの酢酸に加熱しながら溶解させた。次いで酢酸鉄(II)9.39mg(0.0054mo1)を含むメタノール溶液5mlを二口フラスコに加えた。混合物を窒素雰囲気中150℃、24時間加熱還流した。
[ゲル電解質の調製]
PMMA(ポリメタクリル酸メチル)2.1gをアセトニトリルに溶解させ、一晩攪拌し溶液Aを調製した。
[表示素子の作製]
有機-無機ハイブリッドポリマーのメタノール溶液20mg/mL(2.8mM)をセグメント蒸着したITOガラス(ジオマテック社製、10Ω/cm)にスピンコート(300rpm、200sec)し、一晩自然乾燥させた。
<実施例2>
[有機-無機ハイブリッドポリマーの合成]
実施例1と同様にしてFe-MEPEを合成した。
[ゲル電解質の調製]
PMMA(ポリメタクリル酸メチル)2.1gをアセトニトリル21mLに溶解させ、一晩攪拌し溶液Aを調製した。
[表示素子の作製]
有機-無機ハイブリッドポリマーのメタノール溶液20mg/mL(2.8mM)をセグメント蒸着したITOガラス(ジオマテック社製、10Ω/cm)にスピンコート(300rpm、200sec)し、一晩自然乾燥させた。
<実施例3>
[有機-無機ハイブリッドポリマーの合成]
実施例1と同様にしてFe-MEPEを合成した。
[ゲル電解質の調製]
実施例2と同様にしてゲル電解質を調製した。
[表示素子の作製]
ITOガラス(10Ω/cm)およびステンレス板を基板として用いた。有機-無機ハイブリッドポリマーのメタノール溶液20mg/mL(2.8mM)をセグメント蒸着したITOガラス(ジオマテック社製、10Ω/cm)にスピンコート(300rpm、200sec)し、一晩自然乾燥させた。
<実施例4>
[有機-無機ハイブリッドポリマーの合成]
酢酸鉄の代わりに塩化ルテニウム・4ジメチルスルホキシド(Ru(DMSO)4Cl2)を用い、溶媒としてエチレングリコールを用い、それ以外の条件は実施例1と同様にして有機-無機ハイブリッドポリマー(Ru-MEPE)を収率95%で合成した。
[ゲル電解質の調製]
実施例1と同様にしてゲル電解質を調製した。
[表示素子の作製]
Ru-MEPEと実施例1のFe-MEPEを3:1で混合したものをメタノールに溶解させ、前述した(i)~(iii)の各種の方法で、ITOガラス(10インチサイズ)×8枚(デバイス躯体:ポリカーボネート製)に図柄を形成した。それ以外は実施例1と同様にして、大面積のカラー電子ペーパーを作製した。
<実施例5>
[有機-無機ハイブリッドポリマーの合成]
実施例1と同様の1,4-ビス(ターピリジル)ベンゼンと酢酸ニッケル(II)4水和物をエタノール中で1:1のモル比で混合し、溶媒中80℃で18時間加熱攪拌した。得られた黄色溶液をシャーレに移し、溶媒を留去して目的物を定量的に得た。
[ゲル電解質の調製]
実施例1と同様にしてゲル電解質を調製した。
[表示素子の作製]
実施例1と同様にしてカラー電子ペーパーを作製した。
Claims (8)
- 表面電極を有する透明基板と、表面電極に対向する裏面電極を有する基板との間に、下記式(I)または式(II)
- 図柄表示層は、表面電極を有する透明基板および/または裏面電極を有する基板の面に形成されていることを特徴とする請求項1に記載の表示素子。
- 高分子ゲル電解質は、白色粒子を含有することを特徴とする請求項1または2に記載の表示素子。
- 白色粒子は、二酸化チタン微粒子であることを特徴とする請求項3に記載の表示素子。
- 有機-無機ハイブリッドポリマーの金属イオンは、鉄イオン、コバルトイオン、ニッケルイオン、亜鉛イオン、およびルテニウムイオンから選ばれる少なくとも1種であることを特徴とする請求項1~4のいずれかに記載の表示素子。
- 有機-無機ハイブリッドポリマーのカウンターアニオンは、酢酸イオン、塩素イオン、六フッ化リンイオン、四フッ化ホウ素イオン、およびポリオキソメタレートから選ばれる少なくとも1種であることを特徴とする請求項1~5のいずれかに記載の表示素子。
- 請求項1~6のいずれかに記載の表示素子からなることを特徴とするカラー電子ペーパー。
- サイズが20インチ以上の表示部を有することを特徴とする請求項7に記載のカラー電子ペーパー。
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US13/378,772 US20120127554A1 (en) | 2009-06-18 | 2010-06-07 | Display device and color electronic paper using the same |
JP2011519733A JPWO2010147017A1 (ja) | 2009-06-18 | 2010-06-07 | 表示素子とそれを用いたカラー電子ペーパー |
EP10789392A EP2444839A4 (en) | 2009-06-18 | 2010-06-07 | DISPLAY ELEMENT AND COLORED ELECTRONIC PAPER USING THE SAME |
US13/967,417 US20140009812A1 (en) | 2009-06-18 | 2013-08-15 | Display device and color electronic paper using the same |
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JP6183763B2 (ja) | 2014-05-02 | 2017-08-23 | 国立研究開発法人物質・材料研究機構 | 有機/ヘテロ金属ハイブリットポリマー、その合成方法、有機/ヘテロ金属ハイブリットポリマーの膜、有機/マルチ金属ハイブリットポリマー、その合成方法、及び有機/マルチ金属ハイブリットポリマーの膜 |
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US20120127554A1 (en) | 2012-05-24 |
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JPWO2010147017A1 (ja) | 2012-12-06 |
US20140009812A1 (en) | 2014-01-09 |
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