WO2011055792A1 - Matière électrochromique - Google Patents

Matière électrochromique Download PDF

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WO2011055792A1
WO2011055792A1 PCT/JP2010/069724 JP2010069724W WO2011055792A1 WO 2011055792 A1 WO2011055792 A1 WO 2011055792A1 JP 2010069724 W JP2010069724 W JP 2010069724W WO 2011055792 A1 WO2011055792 A1 WO 2011055792A1
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electrochromic
formula
material according
monomer
carbon atoms
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PCT/JP2010/069724
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English (en)
Japanese (ja)
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章博 田中
操 宮本
利彦 長村
善南 金
秀蘭 金
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国立大学法人九州大学
日産化学工業株式会社
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Priority to JP2011539402A priority Critical patent/JP5689071B2/ja
Publication of WO2011055792A1 publication Critical patent/WO2011055792A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/34—Monomers containing two or more unsaturated aliphatic radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/26—Nitrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • C09K9/02—Organic tenebrescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1408—Carbocyclic compounds
    • C09K2211/1425—Non-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1441—Heterocyclic
    • C09K2211/1466—Heterocyclic containing nitrogen as the only heteroatom

Definitions

  • the present invention relates to an electrochromic material, and more particularly to an electrochromic material comprising a highly branched polymer having a compound that exhibits electrochromic properties as a polymer portion.
  • An electrochromic element applied to a light control element or a display element is an element utilizing a phenomenon called electrochromism that reversibly undergoes a redox reaction when a voltage is applied, and is reversibly colored or colorless.
  • This electrochromic element is generally composed of an element in which, for example, a transparent electrode substrate, an electrochromic layer, and a counter electrode substrate are sequentially provided.
  • Patent Document 1 inorganic compounds such as tungsten oxide have been known as compounds having electrochromic properties (Patent Document 1), and the inorganic oxide is deposited on a transparent electrode by vacuum deposition or sputtering.
  • Patent Document 1 A method for manufacturing an electrochromic device has been proposed.
  • this manufacturing method requires a vacuum technique at the time of film formation, and there is a problem that costs increase.
  • an organic electrochromic compound made of a viologen derivative or the like As an element that can be manufactured by a cheaper and simpler manufacturing process, various electrochromic elements using, for example, an organic electrochromic compound made of a viologen derivative or the like have been proposed.
  • a green electrochromic display viologen compound Patent Document 2
  • an electrochromic mirror using a polymer compound having a viologen structure Patent Document 3
  • An electrochromic element Patent Document 4 provided with an electrolyte layer obtained by polymerization, an electrochromic element using a polymer type electrochromic compound (Patent Document 5), and the like have been proposed.
  • a triazine ring-containing multi-branched polymer that exhibits electrochromic properties by cation doping Patent Document 6
  • Electrochromic device Patent Document 7 having a microsphere (the microsphere is, for example, a dendrimer or a hyperbranched polymer), and a hyperbranched polymer (Patent Document 8) having a compound exhibiting electrochromic properties as a polymer portion
  • the application of hyperbranched polymers to electrochromic devices has also been proposed.
  • JP-A-63-18336 Japanese Patent Laid-Open No. 5-170738 Japanese Patent Laid-Open No. 11-38454 Japanese Patent Laid-Open No. 11-183940 Japanese Patent Laid-Open No. 11-183941 JP 9-302073 A JP 2003-121883 A International Publication No. 2009/136626 Pamphlet
  • the organic electrochromic compounds that have been proposed so far are compared with those of conventional liquid crystal display devices in terms of response speed, coloring efficiency, and repetitive stability, particularly from the viewpoint of application to display devices. Therefore, further improvement in performance was required.
  • the solubility in various organic solvents is low, and usable solvents are limited, and it is difficult to form a thin film at the time of device fabrication. There was a problem.
  • a polymer type electrochromic compound using a copolymer of a monofunctional polymerizable monomer has advantages such as high solubility in various solvents and easy formation of a thin film.
  • the present invention has been made in view of such circumstances, has a high response speed, has high coloring efficiency, is excellent in repeated stability, can be used for a long time, and has excellent solubility in various solvents. Furthermore, it aims at providing the electrochromic material which manufacture is easy.
  • the present inventors have determined that a monomer having an electrochromic property in the same molecule and a monomer having two or more radical polymerizable double bonds to the monomer.
  • the present inventors have found that a hyperbranched polymer obtained by polymerizing in the presence of a polymerization initiator in an amount of 20 to 300 mol% can be a polymer material having excellent electrochromic properties and solubility.
  • the present invention provides a monomer A having a portion exhibiting electrochromic properties and two or more radical polymerizable double bonds in the same molecule in an amount of 20 to 300 mol% relative to the monomer A.
  • the present invention relates to an electrochromic material comprising a hyperbranched polymer obtained by polymerization in the presence of the polymerization initiator B.
  • the monomer A having a moiety that exhibits electrochromic properties in the same molecule and two or more radical polymerizable double bonds is a compound represented by the following formula (1): The electrochromic material described in 1.
  • R 1 and R 2 each independently represent a hydrogen atom or a methyl group, and A 1 and A 2 each independently represent an alkyl group having 1 to 1 carbon atoms which may contain an ether bond or an ester bond. 14 represents a divalent hydrocarbon residue, and E represents a portion that exhibits electrochromic properties.
  • the present invention relates to the electrochromic material according to the second aspect, wherein A 1 and A 2 in the formula (1) are structures represented by any of the following formulas (2) to (5).
  • p, q, r and s are repeating numbers, each independently represents an integer of 1 to 6, and * is a side linked to E which is a portion that develops electrochromic properties.
  • the present invention relates to the electrochromic material according to the second aspect, in which the monomer A represented by the formula (1) is a compound represented by the following formula (6).
  • the monomer A represented by the formula (1) is a compound represented by the following formula (6).
  • E represents the same meaning as said Formula (1).
  • the part E expressing the electrochromic property in the formula (6) is a quaternary bipyridinium salt structure part, a 1,4-diacetylbenzene structure part, a terephthalic acid diester structure part, or biphenyl-4. , 4′-dicarboxylic acid diester structure-related electrochromic material according to the fourth aspect.
  • the present invention relates to the electrochromic material according to the fifth aspect, wherein the portion E that exhibits the electrochromic characteristics in the formula (6) has a structure represented by the following formula (7).
  • R 3 to R 10 each independently represents a hydrogen atom, or a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may contain an ether bond or an ester bond.
  • X ⁇ and Y ⁇ are each independently Cl ⁇ , Br ⁇ , I ⁇ , ClO 4 ⁇ , BF 4 ⁇ , PF 6 ⁇ , CH 3 COO ⁇ , PhSO 3 ⁇ , p-TolSO 3 ⁇ or R 27 represents SO 4 — (wherein Ph represents a phenyl group, p-Tol represents a para-tolyl group, and R 27 represents a linear, branched or cyclic alkyl having 1 to 30 carbon atoms) Represents a group).
  • the present invention relates to the electrochromic material according to the fifth aspect, in which the part E expressing the electrochromic property in the formula (6) is represented by the following formula (8).
  • R 11 to R 14 each independently represents a hydrogen atom, or a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may contain an ether bond or an ester bond.
  • the present invention relates to the electrochromic material according to the fifth aspect, in which the portion E expressing the electrochromic property in the formula (6) is represented by the following formula (9).
  • R 15 to R 18 each independently represents a hydrogen atom, or a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may contain an ether bond or an ester bond.
  • the present invention relates to the electrochromic material according to the fifth aspect, in which the portion E expressing the electrochromic property in the formula (6) is represented by the following formula (10).
  • R 19 to R 26 each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may contain an ether bond or an ester bond.
  • the present invention relates to the electrochromic material according to any one of the first aspect to the ninth aspect, in which the polymerization initiator B is an azo polymerization initiator.
  • the eleventh aspect relates to the electrochromic material according to the tenth aspect, in which the polymerization initiator B is dimethyl 2,2′-azobisisobutyrate.
  • the weight average molecular weight (Mw) measured by gel permeation chromatography of the hyperbranched polymer is 1,000 to 2,000,000 in terms of polyethylene glycol, or 1,000 to 200,000 in terms of polystyrene.
  • the electrochromic material according to any one of the first to eleventh aspects which is 000.
  • the monomer A represented by the following formula (6) having a portion that exhibits electrochromic properties is polymerized in the presence of a polymerization initiator B in an amount of 20 to 300 mol% with respect to the monomer A. It is related with the hyperbranched polymer obtained by making it.
  • E represents the part which expresses an electrochromic characteristic.
  • the present invention relates to the hyperbranched polymer according to the thirteenth aspect, in which the part E expressing the electrochromic property in the formula (6) is a structure represented by the following formula (7).
  • R 3 to R 10 each independently represents a hydrogen atom, or a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may contain an ether bond or an ester bond.
  • X ⁇ and Y ⁇ are each independently Cl ⁇ , Br ⁇ , I ⁇ , ClO 4 ⁇ , BF 4 ⁇ , PF 6 ⁇ , CH 3 COO ⁇ , PhSO 3 ⁇ , p-TolSO 3 ⁇ or R 27 represents SO 4 — (wherein Ph represents a phenyl group, p-Tol represents a para-tolyl group, and R 27 represents a linear, branched or cyclic alkyl having 1 to 30 carbon atoms) Represents a group).
  • the present invention relates to the hyperbranched polymer according to the thirteenth aspect, in which the part E expressing the electrochromic property in the formula (6) is a structure represented by the following formula (8).
  • R 11 to R 14 each independently represents a hydrogen atom, or a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may contain an ether bond or an ester bond.
  • the present invention relates to the hyperbranched polymer according to the thirteenth aspect, in which the part E expressing the electrochromic property in the formula (6) is a structure represented by the following formula (9).
  • R 15 to R 18 each independently represents a hydrogen atom, or a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may contain an ether bond or an ester bond.
  • the present invention relates to the hyperbranched polymer according to the thirteenth aspect, in which the part E expressing the electrochromic property in the formula (6) is a structure represented by the following formula (10).
  • R 19 to R 26 each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may contain an ether bond or an ester bond.
  • the present invention relates to a varnish characterized in that the electrochromic material according to any one of the first aspect to the twelfth aspect is dissolved or dispersed in at least one solvent.
  • the present invention relates to a thin film structure containing the electrochromic material according to any one of the first to twelfth aspects.
  • the present invention relates to a chromic element.
  • the electrochromic material of the present invention has a fast response speed, high coloring efficiency, excellent repetitive stability, and electrochromic characteristics that can be used for a long time.
  • the electrochromic material of the present invention can increase coloring efficiency by incorporating an electrochromic site into a highly branched polymer, and can provide high contrast even when the film thickness is reduced. Response speed can be improved by thinning.
  • the electrochromic material of the present invention is easy to manufacture because it can be synthesized in one step from a monomer having an electrochromic moiety introduced. Also, by taking advantage of the characteristics of a polymer compound, it can be made into a thin film by a simple coating / drying operation. It is possible to form the structure. Moreover, the electrochromic material of the present invention is soluble not only in N, N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) but also in alcohol, water, etc. Thus, a thin film structure can be formed. Furthermore, the electrochromic material of the present invention can form a thin film-like structure not only on a normal flat plate-like substrate but also on a flexible film-like substrate. It is also possible to produce a chromic element.
  • DMF N-dimethylformamide
  • DMSO dimethyl sulfoxide
  • FIG. 1 is a cross-sectional view showing an example of the configuration of an electrochromic element manufactured using the electrochromic material of the present invention.
  • FIG. 2 is a cross-sectional view showing another configuration example of an electrochromic element manufactured using the electrochromic material of the present invention.
  • FIG. 3 is a diagram showing a TEM image of the hyperbranched polymer synthesized in Example 1.
  • FIG. 4 shows the time change of absorbance at a wavelength of 530 nm when a positive voltage or a negative voltage is applied to an electrochromic cell (EC color-developing layer film thickness: about 200 nm) using the hyperbranched polymer 1 prepared in Example 6. It is a figure shown (refer Example 7).
  • FIG. 4 shows the time change of absorbance at a wavelength of 530 nm when a positive voltage or a negative voltage is applied to an electrochromic cell (EC color-developing layer film thickness: about 200 nm) using the hyperbranched polymer 1 prepared in Example 6. It is a figure shown (re
  • FIG. 5 is a view showing the flexibility of the flexible electrochromic device using the hyperbranched polymer 1 produced in Example 8.
  • FIG. 6 is a diagram showing the EC layer thickness dependence of the current-voltage characteristics of EC cells A and C produced in Example 9 (see Example 10).
  • FIG. 7 is a diagram showing the EC layer thickness dependence of the transmittance of EC cells A and C created in Example 9 (see Example 11).
  • FIG. 8 is a graph showing the applied voltage dependence of the absorbance of EC cell B prepared in Example 9 (see Example 12).
  • FIG. 9 is a graph showing the applied voltage dependence of the color development response speed of the EC cell C created in Example 9 (see Example 13).
  • FIG. 10 is a diagram showing the time change of absorbance at a wavelength of 550 nm when a positive voltage or a negative voltage is applied to the EC cell C created in Example 9 (see Example 14).
  • a monomer A having a portion exhibiting electrochromic properties and two or more radical polymerizable double bonds in the same molecule is polymerized in an amount of 20 to 300 mol% with respect to the monomer A. It is a highly branched polymer obtained by polymerizing in the presence of initiator B.
  • the hyperbranched polymer of the present invention is a so-called initiator fragment-incorporating hyperbranched polymer, and has a fragment of the polymerization initiator B used for polymerization at the terminal.
  • the monomer A has a portion that expresses electrochromic properties in the same molecule, and two or more vinyl groups or (meth) acryl groups, or a combination of both. It is preferable that it is a compound, More preferably, it is a compound represented by the said Formula (1).
  • R 1 and R 2 each independently represent a hydrogen atom or a methyl group
  • a 1 and A 2 each independently represent a carbon atom that may contain an ether bond or an ester bond. It represents a divalent hydrocarbon residue of formulas 1 to 14, and E represents a moiety that exhibits electrochromic properties.
  • the A 1 and A 2 preferably represent structures represented by the formulas (2) to (5), and in the formulas (2) to (5), p, q, r, and s are repeating numbers. Each independently represents an integer of 1 to 6, and * is the side linked to E, which is a part that develops electrochromic properties.
  • the compound represented by the said Formula (6) is preferable (In Formula (6), E represents the part which expresses an electrochromic characteristic).
  • the portion E that exhibits electrochromic properties is a quaternary bipyridinium salt structure portion, a 1,4-diacetylbenzene structure portion, a terephthalic acid diester structure portion, or a biphenyl-4,4′-dicarboxylic acid diester.
  • examples of the structure include structures represented by the formulas (7) to (10).
  • R 3 to R 10 are each independently a hydrogen atom, a linear, branched or cyclic group having 1 to 30 carbon atoms which may contain an ether bond or an ester bond.
  • X ⁇ and Y ⁇ are each independently Cl ⁇ , Br ⁇ , I ⁇ , ClO 4 ⁇ , BF 4 ⁇ , PF 6 ⁇ , CH 3 COO ⁇ , PhSO 3 ⁇ , p-TolSO 3. - or R 27 SO 4 - represents a.
  • Ph represents a phenyl group
  • p-Tol represents a para-tolyl group
  • R 27 represents a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms.
  • R 11 to R 14 in the formula (8), R 15 to R 18 in the formula (9), and R 19 to R 26 in the formula (10) are each independently a hydrogen atom. Or a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may contain an ether bond or an ester bond.
  • Specific examples of the linear alkyl group for R 19 to R 26 include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-hexyl group.
  • Specific examples of the branched alkyl group include isopropyl group, isobutyl group, 2-methylpropyl group and the like.
  • examples of the cyclic alkyl group include alicyclic aliphatic groups having a monocyclic, polycyclic or bridged cyclic structure having 3 to 30 carbon atoms. Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo, pentacyclo structure or the like having 3 or more carbon atoms.
  • an azo polymerization initiator is preferably used as the polymerization initiator B in the present invention.
  • the azo polymerization initiator include compounds shown in the following (1) to (5).
  • Azonitrile compound 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 1,1′-azobis ( 1-cyclohexanecarbonitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2- (carbamoylazo) isobutyronitrile and the like;
  • Azoamide compound 2,2′-azobis ⁇ 2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide ⁇ , 2,2′-azobis ⁇ 2-methyl-N- [2- ( 1-hydroxybutyl)] propionamide ⁇ , 2,2′-azobis [2-methyl-methyl-azobis [2-methyl-methyl-
  • the resulting hyperbranched polymer has a fragment of the polymerization initiator used for the polymerization at its terminal. Therefore, dimethyl 2,2′-azobisisobutyrate is preferable from the viewpoint that the solubility of the polymer can be controlled by chemical conversion of the ester group incorporated at the polymer terminal.
  • the polymerization initiator B is used in an amount of 20 to 300 mol%, preferably 50 to 300 mol%, more preferably 50 to 200 mol% with respect to the monomer A.
  • the electrochromic material (hyperbranched polymer) of the present invention is obtained by polymerizing the above-mentioned monomer in the presence of a predetermined amount of polymerization initiator B.
  • polymerization method known methods such as solution polymerization and dispersion are used. Polymerization, precipitation polymerization, bulk polymerization and the like can be mentioned, among which solution polymerization or precipitation polymerization is preferable. In particular, it is preferable to carry out the reaction by solution polymerization in an organic solvent from the viewpoint of molecular weight control.
  • organic solvent used here examples include aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and tetralin; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirit, and cyclohexane Solvent: Halogen solvents such as methyl chloride, methyl bromide, methyl iodide, methylene dichloride, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, orthodichlorobenzene; ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate , Ethyl cellosolve acetate, propylene glycol monomethyl ether acetate and other ester-based or ester ether-based solvents; diethyl ether, tetrahydrofuran, 1,4-d
  • aromatic hydrocarbon solvents preferred are aromatic hydrocarbon solvents, halogen solvents, ester solvents, ether solvents, ketone solvents, alcohol solvents, amide solvents, sulfoxide solvents, etc., and particularly preferred are toluene.
  • aromatic hydrocarbon solvents halogen solvents, ester solvents, ether solvents, ketone solvents, alcohol solvents, amide solvents, sulfoxide solvents, etc.
  • toluene preferred are toluene.
  • the content of the organic solvent in the entire polymerization reaction product is preferably 1 to 100 parts by weight, more preferably 5 to 50 parts by weight with respect to 1 part by weight of the monomer A. is there.
  • the polymerization reaction is carried out under normal pressure, under pressure and under pressure, or under reduced pressure, and is preferably carried out under normal pressure in view of simplicity of the apparatus and operation. Further, preferably carried out in an atmosphere of inert gas such as N 2.
  • the temperature of the polymerization reaction is preferably 50 to 200 ° C., more preferably 70 to 150 ° C., and the polymerization time is preferably 1 to 24 hours, more preferably 3 to 10 hours.
  • the obtained hyperbranched polymer (electrochromic material) is collected by an arbitrary method, and post-treatment such as washing is performed as necessary.
  • Examples of a method for recovering the hyperbranched polymer from the reaction solution include a method such as reprecipitation.
  • the weight average molecular weight (hereinafter abbreviated as Mw) of the obtained hyperbranched polymer (electrochromic material) is 1,000 to 2,000,000, preferably 10,000 in terms of polyethylene glycol by gel permeation chromatography (GPC). To 1,000,000, or 1,000 to 200,000 in terms of polystyrene, preferably 5,000 to 100,000.
  • the polymer thus obtained is also an object of the present invention. That is, in the present invention, the monomer A represented by the formula (6) having a portion exhibiting electrochromic properties is polymerized in the presence of 20 to 300 mol% of the polymerization initiator B with respect to the monomer A.
  • the present invention also relates to a hyperbranched polymer obtained by the treatment.
  • the hyperbranched polymer of the present invention is a so-called initiator fragment-incorporating hyperbranched polymer, and has a fragment of the polymerization initiator B used for polymerization at the terminal. For this reason, it is possible to easily adjust the physical properties (solvent solubility, etc.) of the obtained hyperbranched polymer.
  • the part E that exhibits electrochromic properties in the formula (6) is preferably a hyperbranched polymer having a structure represented by the formula (7), formula (8), formula (9), or formula (10). .
  • the electrochromic material of the present invention can be used as a material for an electrochromic device.
  • the electrochromic element includes at least one transparent conductive substrate, an ion conductive material layer interposed between the substrates, and the ion conductive material layer and any one of the conductive substrates. It is composed of an electrochromic coloring layer inserted in The electrochromic coloring layer contains the electrochromic material of the present invention. A typical configuration example of such an electrochromic element is shown in FIG.
  • the electrochromic element has an electrochromic (EC) layer 3 formed on the surface of a transparent conductive substrate having a transparent electrode layer 2 formed on one surface of the transparent substrate 1.
  • the transparent electrode layers 5 of the laminated body are opposed to each other at an appropriate interval so as to face each other, and a charge transport (CT) layer 4 having an ion conductive material is sandwiched therebetween.
  • CT charge transport
  • the element can cause an electrochromic phenomenon by applying a voltage between the electrodes, and can cause color development and decoloration.
  • a well-known thing can be utilized as a voltage application means.
  • a method for forming each film and layer constituting the electrochromic element is not particularly limited, and it can be produced by a conventional method for forming a film and a layer.
  • a glass substrate with ITO is adopted as a transparent conductive substrate having a transparent electrode layer 2 formed on one surface of a transparent substrate 1, and an electrochromic material is formed on the substrate by a method exemplified below.
  • EC electrochromic
  • layer 3 containing is formed, and a first laminate (laminate A) is produced.
  • this glass substrate with ITO is also said 2nd laminated body (laminate board B).
  • a transparent resin or the like can be used in addition to a glass substrate, and it may be a hard plate or a flexible film.
  • the resin used as the transparent substrate include transparent resins such as polyethylene terephthalate, polyester, polyethylene, polypropylene, nylon, polyvinyl chloride, polycarbonate, polyvinyl alcohol, polymethyl methacrylate, fluororesin, ethylene, and vinyl alcohol.
  • the transparent electrode layer provided on the transparent substrate in addition to the above-mentioned ITO (tin-added indium oxide), ATO (antimony-added tin oxide), FTO (fluorine-added tin oxide), AZO (aluminum-added zinc oxide), GZO ( Gallium-doped zinc oxide), noble metal thin films such as Au, Ag, and Pt can be used.
  • ITO indium oxide
  • ATO antimony-added tin oxide
  • FTO fluorine-added tin oxide
  • AZO aluminum-added zinc oxide
  • GZO Gallium-doped zinc oxide
  • noble metal thin films such as Au, Ag, and Pt can be used.
  • an electrochromic material is dissolved or dispersed in a solvent to form a varnish (film forming material), and the varnish is cast on a substrate, a spin coating method, Apply by blade coating method, dip coating method, roll coating method, bar coating method, die coating method, ink jet method, printing method (letter plate, intaglio plate, planographic plate, screen printing, etc.), then dry in a hot plate or oven, etc.
  • the spin coating method is preferable. In the case of using the spin coating method, since it can be applied in a single time, even a highly volatile solution can be used, and there is an advantage that highly uniform application can be performed.
  • the solvent used in the form of the varnish examples include N, N′-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), methanol, ethanol, propanol, water, tetrahydrofuran (THF), and trichloromethane. These solvents may be used alone, or two or more kinds of solvents may be mixed.
  • the concentration in which the solvent is dissolved or dispersed is arbitrary, but the concentration of the electrochromic material is 0.001 to 90% by mass with respect to the total mass (total mass) of the electrochromic material and the solvent, preferably 0. 0.002 to 80% by mass, more preferably 0.005 to 70% by mass.
  • the thickness of the formed EC layer is usually 0.01 ⁇ m to 50 ⁇ m, preferably 0.1 ⁇ m to 20 ⁇ m. Further, if necessary, in addition to the electrochromic material of the present invention, a film or a layer may be formed using a compound further promoting color development.
  • the electrochromic layer 3 of the laminated plate A and the transparent electrode layer 5 of the laminated plate B are opposed to each other at an interval of about 1 to 1,000 ⁇ m, and the periphery excluding the injection port is sealed with a sealing material 7.
  • An empty cell with a mark is produced.
  • a liquid ion conductive material is injected from the injection port, and the injection port is appropriately sealed, thereby forming a CT (charge transport) layer 4 to complete the electrochromic device.
  • a liquid ion conductive material is dropped on the EC layer 3 of the laminate A (or the electrode layer 5 of the laminate B), and the electrode layer 5 (or laminate) of the laminate B is added to the dropped ion conductive material.
  • the laminated plate B (or laminated plate A) is overlapped so that the EC layer 3) of A is in contact, and the periphery is sealed to complete the electrochromic device.
  • the ion conductive substance used for the CT layer 4 of the electrochromic element is preferably a substance that usually exhibits an ion conductivity of 1 ⁇ 10 ⁇ 7 S / cm or more at room temperature.
  • the ion conductive material is not particularly limited, and examples thereof include a liquid ion conductive material, a gel ion conductive material, and a solid ion conductive material. Among these, for example, as a liquid material, a solution in which a supporting electrolyte such as a salt, an acid, or an alkali is dissolved in a solvent can be used.
  • the solvent is not particularly limited as long as it can dissolve the supporting electrolyte, but a solvent having polarity is particularly preferable.
  • organic polar solvents such as propiononitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, N, N-dimethylacetamide, methylpyrrolidinone, dioxolane, trimethylphosphate, and polyethylene glycol. These can be used alone or as a mixture in use.
  • the salt as the supporting electrolyte is not particularly limited, and examples thereof include inorganic ion salts such as various alkali metal salts and alkaline earth metal salts, quaternary ammonium salts, cyclic quaternary ammonium salts, and the like.
  • a spacer can be used to ensure a constant distance between the laminate A and the laminate B.
  • seat comprised with glass, a polymer, etc. can be used.
  • the spacer can be inserted by a gap between the conductive substrates facing each other, or can be provided by a method of forming a projecting object made of an insulating material such as resin on the electrode of the conductive substrate.
  • the electrochromic element is not limited to the above-described configuration and manufacturing method, and may further include other structures or elements.
  • Other structures or elements include, for example, UV-cutting layers such as UV-reflecting layers and UV-absorbing layers, and in the case of applications for electrochromic mirrors, the entire mirror layer or an overcoat layer for the purpose of protecting the surface of each film layer Etc.
  • the main reagents used in the synthesis examples and examples are as follows. Chloromethylstyrene: AGC Seimi Chemical Co., Ltd. CMS-14 4,4′-bipyridine: manufactured by Tokyo Chemical Industry Co., Ltd. Special grade terephthalic acid: produced by Tokyo Chemical Industry Co., Ltd. Special grade 4,4′-biphenylcarboxylic acid: produced by Aldrich Co., Ltd. 1,4-diacetylbenzene: Tokyo Chemical Industry Co., Ltd. First grade 4-vinyl benzoic acid: Wako Pure Chemical Industries, Ltd. 2,6-lutidine: Tokyo Chemical Industry Co., Ltd. First grade 6-bromohexanoyl chloride: Tokyo Chemical Industry Co., Ltd.
  • Example 1 Synthesis of Hyperbranched Polymer 1 1.15 g (2.5 mmol) of monomer 1 obtained in Synthesis Example 1 and 1.15 g (5 mmol) of dimethyl 2,2′-azobisisobutyrate in a reactor under a nitrogen atmosphere. And 44 g of ethylene glycol was added and stirred at 100 ° C. for 6 hours. After completion of the reaction, the reaction mixture was concentrated. The residue was dissolved in 5 mL of methanol, and 400 mL of ethyl acetate was added for reprecipitation. The precipitated solid was filtered and dried to obtain 1.5 g of hyperbranched polymer 1 as a light pink solid (yield: 65%). The obtained hyperbranched polymer 1 had a weight average molecular weight (Mw) in terms of polyethylene glycol of 1,300,000.
  • Example 1 TEM (Transmission Electron Microscope) Observation of Hyperbranched Polymer 1
  • a 0.01% by mass methanol solution of hyperbranched polymer 1 obtained in Example 1 was dropped on a carbon mesh grid, dried, and TEM.
  • An observation sample was prepared. When this sample was observed by TEM, spherical particles having a particle size of about 10 nm were observed. The observed TEM image is shown in FIG.
  • a linear polymer cannot be observed as a TEM image even if a sample is prepared under the same conditions and observed by TEM, and only a highly branched polymer can be observed by TEM. It was suggested that it was highly branched.
  • Example 2 Synthesis of Hyperbranched Polymer 2
  • 0.40 g (1 mmol) of monomer 2 obtained in Synthesis Example 2 in a reactor 0.46 g (2 mmol) of dimethyl 2,2′-azobisisobutyrate and toluene 16g was added and it stirred at 100 degreeC for 5 hours. After completion of the reaction, the reaction mixture was concentrated. The residue was dissolved in a small amount of chloroform and re-precipitated by adding diisopropyl ether. After the precipitated solid was filtered, a reprecipitation operation was performed again in the same manner. The precipitated solid was filtered and dried to obtain 0.30 g of hyperbranched polymer 2 as a white solid (yield 35%).
  • the resulting hyperbranched polymer 2 had a weight average molecular weight (Mw) in terms of polystyrene of 8,800.
  • Example 3 Synthesis of Hyperbranched Polymer 3
  • 0.48 g (1 mmol) of monomer 3 obtained in Synthesis Example 3 in a reactor 0.46 mg (2 mmol) of dimethyl 2,2′-azobisisobutyrate and toluene 20g was added and it stirred at 100 degreeC for 5 hours. After completion of the reaction, the reaction mixture was concentrated. The residue was dissolved in a small amount of chloroform and re-precipitated by adding diisopropyl ether. After the precipitated solid was filtered, a reprecipitation operation was performed again in the same manner. The precipitated solid was filtered and dried to obtain 0.28 g of hyperbranched polymer 3 as a white solid (yield 30%).
  • the resulting hyperbranched polymer 3 had a weight average molecular weight (Mw) in terms of polystyrene of 8,100.
  • the obtained wet product was dried to obtain 5.5 g of white solid 1,4-bis (2-bromoacetyl) benzene (yield 86%). Under a nitrogen atmosphere, 4.2 g (13 mmol) of 1,4-bis (2-bromoacetyl) benzene obtained, 3.9 g (26 mmol) of 4-vinylbenzoic acid, and 70 mL of tetrahydrofuran (hereinafter abbreviated as THF) were added. To the reactor, 5 mL (36 mmol) of triethylamine was added dropwise and stirred at room temperature for 16 hours. After completion of the reaction, the reaction mixture was filtered, and the filtrate was washed with water and ethyl acetate. The obtained wet product was dried to obtain 4.8 g of monomer 4 as a white solid (yield 81%).
  • Example 4 Synthesis of Hyperbranched Polymer 4
  • 0.45 g (1 mmol) of monomer 4 obtained in Synthesis Example 4 in a reactor 0.46 g (2 mmol) of dimethyl 2,2′-azobisisobutyrate and 17 g of DMF And stirred at 100 ° C. for 5 hours. After completion of the reaction, the reaction mixture was concentrated. The residue was dissolved in a small amount of THF and re-precipitated by adding diisopropyl ether. After the precipitated solid was filtered, a reprecipitation operation was performed again in the same manner. The precipitated solid was filtered and dried to obtain 0.53 g of a hyperbranched polymer 4 as a white solid (yield 60%).
  • the resulting hyperbranched polymer 4 had a weight average molecular weight (Mw) in terms of polystyrene of 20,000.
  • Example 5 Synthesis of hyperbranched polymer 5 0.39 g (0.5 mmol) of monomer 5 obtained in Synthesis Example 5 and 0.23 g (1 mmol) of dimethyl 2,2'-azobisisobutyrate in a reactor in a nitrogen atmosphere And 12 g of ethylene glycol was added and stirred at 100 ° C. for 6 hours. After completion of the reaction, the reaction mixture was concentrated. The residue was dissolved in a small amount of methanol, and a THF-hexane mixed solution (volume ratio 1: 1) was added to cause reprecipitation. After the precipitated solid was filtered, a reprecipitation operation was performed again in the same manner.
  • the precipitated solid was filtered and dried to obtain 0.24 g of a hyperbranched polymer 5 as a yellow solid (yield 38%). Since the obtained hyperbranched polymer 5 was hardly soluble in both THF and 20 mM sodium nitrate, the weight average molecular weight could not be measured by GPC.
  • Example 6 Electrochromic evaluation (color development with voltage application) Using the hyperbranched polymers 1 to 5 obtained in Examples 1 to 5, an electrochromic cell according to the configuration shown in FIG. 1 was prepared and evaluated by the following method. ⁇ Cleaning of ITO glass substrate> The dust on the surface of the ITO glass substrate (26 mm ⁇ 22 mm) was blown off with an air duster, and the ITO glass substrate was washed with boiling ethanol. ⁇ Preparation of electrochromic (EC) layer> Hyperbranched polymers 1 to 5 were dissolved in the solvents shown in Table 1 to prepare 5 mass% solutions.
  • EC electrochromic
  • the mixture was stirred for 24 hours while heating at 110 ° C. to prepare a lithium electrolyte solution.
  • the obtained lithium electrolyte solution was uniformly cast on an ITO glass substrate and dried on a hot plate at 40 ° C. for 1 hour.
  • ⁇ Production of EC cell> The above-mentioned lithium electrolyte solution was dropped on the EC layer produced on the ITO glass substrate, and an ITO glass substrate on which a CT layer was arranged so that the glass substrate side was on the outer side was placed thereon. As a result, the lithium electrolyte solution spread across the entire surface between the two glass substrates, and a uniform film was formed. This was dried on a hot plate at 40 ° C. for 1 day to produce an EC cell.
  • Example 7 Electrochromic evaluation (discoloration with positive / negative voltage application) A change in absorbance at a wavelength of 530 nm when a positive / negative voltage of 2 V was alternately applied to the EC cell using the highly branched polymer 1 produced in Example 6 was measured. A xenon lamp was used as the light source, and the light passing through the heat cut filter and the UV cut filter was measured with a detector. It was confirmed that the EC cell that developed a color of magenta at ⁇ 2V disappeared when a reverse voltage of + 2V was applied, and reversibly disappeared. Further, it was confirmed that when the applied voltage was raised to -2.5 V, the contrast was increased and the color was erased more clearly. The results are shown in FIG.
  • Example 8 Production of flexible electrochromic device ⁇ Production of patterned ITO substrate> A positive resist (Tokyo Ohka Kogyo Co., Ltd., TMSR-8900) is applied to the ITO electrode surface of a polycarbonate ITO substrate (Teijin Ltd., 76 mm ⁇ 70 mm) by spin coating (300 rpm ⁇ 3 seconds, then 4, 000 rpm ⁇ 30 seconds) and dried by heating on a 40 ° C. hot plate for 5 minutes. The obtained resist film was exposed to a mask and then developed with a developer (Tokyo Ohka Kogyo Co., Ltd., NMD-3).
  • a developer Tokyo Ohka Kogyo Co., Ltd., NMD-3
  • CT charge transport
  • Example 9 Production of electrochromic devices (EC cells) A, B and C ⁇ Cleaning of ITO glass substrate> The dust on the surface of the ITO glass substrate (10 mm ⁇ 20 mm) was blown off with an air duster, and the ITO glass substrate was washed with boiling ethanol. ⁇ Preparation of electrochromic (EC) layer> Hyperbranched polymer 1 was dissolved in methanol to prepare methanol solutions having the concentrations shown in Table 2, respectively. Each of the obtained solutions was applied to the ITO surface of the ITO glass substrate by the spin coating method under the conditions shown in Table 2, and then dried on a 40 ° C. hot plate for 1 day to form a film.
  • EC electrochromic
  • a part of the obtained film was scratched with a razor and observed with a laser microscope, and the film thickness was determined from the difference in focal length between the scratched part and the film part.
  • the results are shown in Table 2.
  • ⁇ Preparation of charge transport (CT) layer> Lithium perchlorate (2.0 g) was dissolved in propylene carbonate (40 mL), and polymethyl methacrylate (10 g) and acetonitrile (80 mL) were added to the mixture. The mixture was stirred for 6 hours while heating at 90 ° C. to prepare a lithium electrolyte solution. The obtained lithium electrolyte solution was cast uniformly on an ITO glass substrate.
  • Example 10 Dependence of Current-Voltage Characteristics on EC Layer Thickness
  • positive voltage application means that the electrode on the EC layer side is the positive electrode
  • negative voltage application means that the electrode on the CT layer side is the positive electrode.
  • a current started to flow from around ⁇ 2 V, and a magenta color was developed. It was also confirmed that the thicker the EC layer, the greater the current value and the greater the contrast. The results are shown in FIG.
  • Example 11 Dependence of transmittance on EC layer film thickness A voltage of -2.8 V was applied to EC cell A (EC layer thickness 150 nm) and EC cell C (EC layer thickness 300 nm) fabricated in Example 9, The transmittance of each EC cell that developed a magenta color was measured. In addition, the transmittance
  • Example 12 Dependence of absorbance on applied voltage
  • the absorbance of the EC cell was measured when voltages of -2.5 V, -2.0 V, and 0 V were applied to the EC cell B prepared in Example 9, respectively.
  • the absorbance was measured in the same manner as in Example 7.
  • the absorbance of the EC cell was dependent on the applied voltage, and it was confirmed that coloring with a higher color by applying a higher negative voltage.
  • the obtained spectrum is shown in FIG.
  • Example 13 Dependence of color development response speed on applied voltage
  • EC cells C produced in Example 9 were applied with voltages of -2.8 V, -2.4 V, and -2.0 V, respectively.
  • the time change of absorbance at a wavelength of 550 nm was measured.
  • the absorbance was measured in the same manner as in Example 7.
  • the change in absorbance of the EC cell was dependent on the applied voltage, and it was confirmed that color development was faster, that is, the color development response speed was faster by applying a higher negative voltage.
  • the obtained spectrum is shown in FIG.
  • Example 14 Color fading accompanying application of positive and negative voltages
  • the EC cell C produced in Example 9 was measured for changes in absorbance at a wavelength of 550 nm when a positive and negative voltage of 2.5 V was applied.
  • the absorbance was measured in the same manner as in Example 7. It was confirmed that EC cells that developed a magenta color at ⁇ 2.5 V were colored as they were even when the voltage application was stopped, and exhibited a memory property. In addition, it was confirmed that the color disappears when the voltage of +2.5 V is applied, and the color disappears reversibly.

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Abstract

L'invention porte sur un polymère hautement ramifié obtenu par polymérisation d'un monomère (A) en présence de 20 à 300 % en moles (par rapport au monomère (A)) d'un amorceur de polymérisation (B), ledit monomère (A) ayant, dans une molécule, à la fois un segment présentant des caractéristiques électrochromiques et au moins deux doubles liaisons polymérisables par voie radicalaire ; et une matière électrochromique qui consiste en le polymère hautement ramifié. Le polymère hautement ramifié présente une vitesse élevée de réponse et une efficacité élevée de développement de la couleur, et peut être utilisé sur une longue période de temps en vertu d'une excellence stabilité en termes de cycles de développement de couleur/décoloration. De plus, le polymère hautement ramifié manifeste présente une excellente solubilité dans divers solvants de telle sorte que la formation d'un film mince du polymère hautement ramifié, qui est nécessaire pour la production d'un élément électrochromique, peut être facilement conduite par la préparation d'un vernis de polymère hautement ramifié.
PCT/JP2010/069724 2009-11-06 2010-11-05 Matière électrochromique WO2011055792A1 (fr)

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JP2013043841A (ja) * 2011-08-22 2013-03-04 Fuji Xerox Co Ltd 新規な反応性化合物、電荷輸送性膜及び光電変換装置
JP2015101691A (ja) * 2013-11-27 2015-06-04 株式会社リコー エレクトロクロミック化合物及び表示素子
US9188885B2 (en) 2011-08-22 2015-11-17 Fuji Xerox Co., Ltd. Reactive compound, charge transporting film, photoelectric conversion device, electrophotographic photoreceptor and method of producing the same, process cartridge, and image forming apparatus
JP2017019747A (ja) * 2015-07-10 2017-01-26 株式会社リコー エレクトロクロミック化合物、エレクトロクロミック組成物及びエレクトロクロミック表示素子
JP2017039710A (ja) * 2015-08-20 2017-02-23 Jnc株式会社 両端にアルケニルを有する化合物、液晶組成物および液晶表示素子
WO2023074408A1 (fr) 2021-10-28 2023-05-04 四国化成工業株式会社 Composé thiophène, son procédé de synthèse et composition contenant ledit composé thiophène

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KR102038495B1 (ko) * 2017-02-27 2019-10-30 서울시립대학교 산학협력단 전기 변색 화합물, 전기 변색 소자, 및 이의 구동 방법
US20240272506A1 (en) * 2021-10-14 2024-08-15 Korea University Of Technology And Education Industry-University Cooperation Foundation Composition for electrochromic device having optical transmission, high flexibility, and high moisture resistance, and manufacturing method of electrochromic member

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JP2017019747A (ja) * 2015-07-10 2017-01-26 株式会社リコー エレクトロクロミック化合物、エレクトロクロミック組成物及びエレクトロクロミック表示素子
JP2017039710A (ja) * 2015-08-20 2017-02-23 Jnc株式会社 両端にアルケニルを有する化合物、液晶組成物および液晶表示素子
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WO2023074408A1 (fr) 2021-10-28 2023-05-04 四国化成工業株式会社 Composé thiophène, son procédé de synthèse et composition contenant ledit composé thiophène

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