[go: up one dir, main page]

WO2014119468A1 - Matériau de conversion thermoélectrique, élément de conversion thermoélectrique, article de génération d'énergie thermoélectrique utilisant l'élément de conversion thermoélectrique, et alimentation électrique pour des capteurs utilisant l'élément de conversion thermoélectrique - Google Patents

Matériau de conversion thermoélectrique, élément de conversion thermoélectrique, article de génération d'énergie thermoélectrique utilisant l'élément de conversion thermoélectrique, et alimentation électrique pour des capteurs utilisant l'élément de conversion thermoélectrique Download PDF

Info

Publication number
WO2014119468A1
WO2014119468A1 PCT/JP2014/051415 JP2014051415W WO2014119468A1 WO 2014119468 A1 WO2014119468 A1 WO 2014119468A1 JP 2014051415 W JP2014051415 W JP 2014051415W WO 2014119468 A1 WO2014119468 A1 WO 2014119468A1
Authority
WO
WIPO (PCT)
Prior art keywords
thermoelectric conversion
copolymer
group
general formula
conversion element
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2014/051415
Other languages
English (en)
Japanese (ja)
Inventor
亮 浜崎
西尾　亮
丸山　陽一
林　直之
野村　公篤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Corp
Original Assignee
Fujifilm Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Publication of WO2014119468A1 publication Critical patent/WO2014119468A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/026—Wholly aromatic polyamines
    • C08G73/0266—Polyanilines or derivatives thereof
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/01—Manufacture or treatment
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/856—Thermoelectric active materials comprising organic compositions
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3221—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/55—Physical properties thermoelectric
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a thermoelectric conversion material, a thermoelectric conversion element, an article for thermoelectric power generation using the thermoelectric conversion element, and a sensor power source.
  • thermoelectric conversion materials that can mutually convert heat energy and electrical energy are used in thermoelectric conversion elements such as thermoelectric power generation elements and Peltier elements.
  • thermoelectric power generation using thermoelectric conversion materials and thermoelectric conversion elements can directly convert thermal energy into electric power, does not require moving parts, and is used for wristwatches that operate at body temperature, power supplies for remote areas, power supplies for space, etc. ing.
  • thermoelectric conversion performance of the thermoelectric conversion element is a dimensionless figure of merit ZT (hereinafter, simply referred to as a figure of merit ZT).
  • This figure of merit ZT is expressed by the following formula (A).
  • thermoelectromotive force hereinafter sometimes referred to as thermoelectromotive force
  • conductivity ⁇ per absolute temperature 1K Reduction of thermal conductivity ⁇ is important.
  • thermoelectric conversion materials are required to have good thermoelectric conversion performance, so the processing process for thermoelectric conversion elements is complicated, and expensive and may contain harmful substances. Material.
  • organic thermoelectric conversion elements can be manufactured at a relatively low cost, and processing such as film formation is easy. Therefore, research has been actively conducted in recent years, such as thermoelectric conversion materials and thermoelectric conversions using conductive polymers. Devices have been reported.
  • Patent Document 1 describes emeraldine-type conductive polyanilines
  • Patent Document 2 describes an emeraldine-type conductive polyaniline film-like product.
  • thermoelectric conversion materials and thermoelectric conversion elements are known in which polyaniline is used together with carbon nanotubes as one of conductive polymers.
  • Non-Patent Document 1 discloses a nanocomposite of multi-walled carbon nanotubes coated with porous polyaniline (a nanometer-sized composite)
  • Non-Patent Document 2 discloses a carbon nanotube coated with a polyaniline coating layer. Nanocomposites are described.
  • thermoelectric conversion performance can be expected to some extent, but there is room for further improvement.
  • thermoelectric conversion layer of the thermoelectric conversion element is disposed in contact with the electrode surface, the thermoelectric conversion layer is required to be highly adhered to the electrode from the viewpoint of thermoelectric conversion characteristics and quality stability. Has been.
  • the present invention provides a thermoelectric conversion material that is excellent in thermoelectric conversion performance and exhibits high adhesion to the electrode, a thermoelectric conversion layer having excellent adhesion to the electrode (also referred to as electrode adhesion) and thermoelectric conversion performance. It is an object of the present invention to provide a conversion element, a thermoelectric power generation article using the thermoelectric conversion element, and a sensor power source.
  • thermoelectric conversion layer of a thermoelectric conversion element various conductive polymers as conductive polymers that coexist with a nanoconductive material (a nanometer-sized conductive material) in a thermoelectric conversion layer of a thermoelectric conversion element.
  • polyaniline copolymer and polypyrrole copolymer including poly (aniline-pyrrole) copolymer
  • thermoelectric conversion performance and electrode adhesiveness which were excellent in the thermoelectric conversion layer were expressed by improving the dispersibility in presence of a nano electroconductivity material.
  • the present invention has been completed based on these findings.
  • thermoelectric conversion element having a first electrode, a thermoelectric conversion layer, and a second electrode on a substrate, wherein the thermoelectric conversion layer is a nano-conductive material and the following general formula (1)
  • thermoelectric conversion element containing the represented copolymer
  • a and B each independently represent a copolymer unit derived from an aniline derivative or a copolymer unit derived from a pyrrole derivative. However, A and B represent different copolymer units. m and n represent the degree of polymerization.
  • thermoelectric conversion element according to ⁇ 1>, wherein the ratio m / n of the degree of polymerization of the copolymer units A and B is 1/99 to 99/1.
  • Copolymer units A and B are each independently a copolymer unit selected from the group consisting of copolymer units represented by the following general formulas (2) to (5) ⁇ 1> Or the thermoelectric conversion element as described in ⁇ 2>.
  • R 11 to R 14 each independently represents a monovalent substituent.
  • a1 and c1 each independently represents an integer of 0 to 4
  • b1 represents an integer of 0 to 2
  • d1 represents an integer of 0 to 6.
  • X 11 to X 14 each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. * Represents a linking site of copolymer units.
  • Copolymer unit A is a copolymer unit represented by general formula (2) in which a1 is 0, a copolymer unit represented by general formula (3) in which b1 is 0, and c1 is A copolymer unit selected from the group consisting of a copolymer unit represented by general formula (4) being 0 and a copolymer unit represented by general formula (5) wherein d1 is 0,
  • a polymer unit B is a copolymer unit represented by the general formula (2) in which a1 is an integer of 1 to 4, a copolymer unit represented by the general formula (3) in which b1 is 1 or 2, Selected from the group consisting of a copolymer unit represented by general formula (4) wherein c1 is an integer of 1 to 4 and a copolymer unit represented by general formula (5) wherein d1 is an integer of 1 to 6
  • the thermoelectric conversion element according to ⁇ 3> which is a copolymer unit.
  • thermoelectric conversion element according to ⁇ 3> or ⁇ 4>, wherein X 11 to X 14 are hydrogen atoms.
  • ⁇ 6> The thermoelectric conversion element according to any one of ⁇ 3> to ⁇ 5>, wherein the copolymer units A and B are both copolymer units represented by the general formula (2).
  • ⁇ 7> The thermoelectric conversion element according to any one of ⁇ 3> to ⁇ 5>, wherein the copolymer units A and B are both copolymer units represented by the general formula (3).
  • ⁇ 8> The thermoelectric conversion element according to any one of ⁇ 1> to ⁇ 7>, wherein the copolymer unit A has a molecular weight smaller than that of the copolymer unit B.
  • thermoelectric conversion material for forming a thermoelectric conversion layer of a thermoelectric conversion element comprising a nano-conductive material and a copolymer represented by the following general formula (1).
  • a and B each independently represent a copolymer unit derived from an aniline derivative or a copolymer unit derived from a pyrrole derivative. However, A and B represent different copolymer units.
  • thermoelectric conversion material according to ⁇ 11> which contains an organic solvent.
  • thermoelectric conversion material according to ⁇ 12> wherein the organic solvent is at least one selected from halogenated solvents.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the xxx group when the xxx group is referred to as a substituent, the xxx group may have an arbitrary substituent.
  • the xxx group when there are a plurality of groups indicated by the same reference numerals, they may be the same or different.
  • thermoelectric conversion material of the present invention has a high Seebeck coefficient, that is, a figure of merit ZT, is excellent in thermoelectric conversion performance, and exhibits high adhesion to an electrode.
  • thermoelectric conversion material of the present invention has a high Seebeck coefficient, that is, a figure of merit ZT, is excellent in thermoelectric conversion performance, and exhibits high adhesion to an electrode.
  • the heat conversion element of the present invention, the thermoelectric power-generating article of the present invention using the heat conversion element of the present invention, the sensor power supply, and the like exhibit excellent thermoelectric conversion performance and electrode adhesion.
  • thermoelectric conversion element of this invention It is a figure which shows typically an example of the thermoelectric conversion element of this invention.
  • the arrows in FIG. 1 indicate the direction of the temperature difference applied when the element is used.
  • FIG. 2 It is a figure which shows typically another example of the thermoelectric conversion element of this invention.
  • the arrows in FIG. 2 indicate the direction of the temperature difference applied when the element is used.
  • thermoelectric conversion element of the present invention has a first electrode, a thermoelectric conversion layer, and a second electrode on a substrate, and the thermoelectric conversion layer is represented by the nanoconductive material and the general formula (1). Containing a copolymer.
  • This thermoelectric conversion layer is formed on a substrate by the thermoelectric conversion material of the present invention containing a nano-conductive material and the copolymer.
  • thermoelectric conversion performance of the thermoelectric conversion material and the thermoelectric conversion element of the present invention can be measured by a figure of merit ZT represented by the following formula (A).
  • Figure of merit ZT S 2 ⁇ ⁇ ⁇ T / ⁇ (A)
  • thermoelectric conversion material is excellent in thermoelectric conversion material, if the thermoelectric conversion material is difficult to adhere to the electrode, the thermoelectric conversion performance when the thermoelectric conversion layer is formed decreases, and the thermoelectric conversion layer peels off from the electrode. It is easy to use as a thermoelectric conversion material.
  • thermoelectric conversion material of the present invention and the thermoelectric conversion element of the present invention have high electrode adhesion enough to be used as a thermoelectric conversion material and are used as a thermoelectric conversion material as shown in Examples described later.
  • High thermoelectric conversion performance specifically, a thermoelectromotive force S per unit temperature difference and a figure of merit ZT. Since the thermoelectric conversion material of the present invention has high electrode adhesion and is difficult to peel from the electrode, the yield is improved when the thermoelectric conversion element of the present invention is manufactured, and the manufacturing cost is also reduced.
  • thermoelectric conversion element of the present invention functions to transmit a temperature difference in the thickness direction or the surface direction in a state where a temperature difference is generated in the thickness direction or the surface direction of the thermoelectric conversion layer. Therefore, it is necessary to form the thermoelectric conversion layer by forming the thermoelectric conversion material of the present invention into a shape having a certain thickness. For this reason, when the thermoelectric conversion layer is formed by coating, the thermoelectric conversion material is required to have good coatability and film formability.
  • the present invention can also meet such requirements for coating properties and film forming properties.
  • thermoelectric conversion material of the present invention has good dispersibility of the nano-conductive material and the copolymer, is excellent in coating property and film forming property, and is suitable for molding and processing into a thermoelectric conversion layer.
  • a thermoelectric conversion layer with excellent thermoelectric properties and electrode adhesion can be formed without impairing coating properties and film formation even when a halogen-based solvent is used to disperse the copolymer in the presence of a nano-conductive material. it can.
  • thermoelectric conversion material of the present invention and then the thermoelectric conversion element of the present invention will be described.
  • thermoelectric conversion material of the present invention is a thermoelectric conversion composition for forming a thermoelectric conversion layer of a thermoelectric conversion element, and contains a nano-conductive material and a copolymer represented by the above general formula (1). ing.
  • thermoelectric conversion material of the present invention first, each component used for the thermoelectric conversion material of the present invention will be described.
  • the nano-conductive material used in the present invention may be a nanometer-sized and conductive material, and may be a nanometer-sized conductive carbon material (hereinafter referred to as nano-carbon material). And a metal material having a nanometer size (hereinafter sometimes referred to as a nano metal material).
  • the nano conductive material used in the present invention is preferably a carbon nanotube, carbon nanofiber, graphite, graphene and carbon nanoparticle nanocarbon material, and metal nanowire, which will be described later, among nanocarbon materials and nanometal materials. Carbon nanotubes are particularly preferable from the viewpoints of improving conductivity and improving dispersibility in a solvent.
  • the content of the nano conductive material in the thermoelectric conversion material is preferably 2 to 60% by mass in the total solid content of the thermoelectric conversion material, that is, in the thermoelectric conversion layer, and more preferably 5 to 55% by mass.
  • the content is preferably 10 to 50% by mass.
  • a nano electroconductivity material may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types together as a nano electroconductive material, you may use together at least 1 type of nano carbon material and nano metal material, and may use together 2 types of nano carbon materials or nano metal materials, respectively. .
  • Nano-carbon material is a carbon material having a nanometer size and conductivity.
  • a carbon-carbon bond composed of sp 2 hybrid orbitals of carbon atoms. Is a nanometer-sized conductive material formed by chemically bonding carbon atoms together.
  • fullerenes including metal-encapsulated fullerenes and onion-like fullerenes
  • carbon nanotubes including peapods
  • carbon nanohorns with one side closed, carbon nanofibers, carbon nanowalls carbon Examples thereof include nanofilaments, carbon nanocoils, vapor grown carbon (VGCF), graphite, graphene, carbon nanoparticles, and cup-shaped nanocarbon materials having holes at the heads of carbon nanotubes.
  • VGCF vapor grown carbon
  • graphite graphene
  • carbon nanoparticles and cup-shaped nanocarbon materials having holes at the heads of carbon nanotubes.
  • Various carbon blacks having a graphite-type crystal structure and exhibiting conductivity can be used as the nanocarbon material, and examples thereof include
  • nanocarbon materials can be manufactured by a conventional manufacturing method. Specifically, catalytic hydrogen reduction of carbon dioxide, arc discharge method, laser evaporation method, CVD method, vapor phase growth method, gas phase flow method, carbon monoxide is reacted with iron catalyst at high temperature and high pressure in the gas phase. Examples include HiPco method for growth.
  • the nanocarbon material produced in this way can be used as it is, or a material purified by washing, centrifugation, filtration, oxidation, chromatography, or the like can be used.
  • the nanocarbon material should be pulverized using a ball-type kneading device such as a ball mill, vibration mill, sand mill, roll mill, etc., or cut short by chemical or physical treatment, etc., as necessary. You can also.
  • a ball-type kneading device such as a ball mill, vibration mill, sand mill, roll mill, etc., or cut short by chemical or physical treatment, etc., as necessary. You can also.
  • the size of the nano conductive material used in the present invention is not particularly limited as long as it is a nanometer size.
  • the nano conductive material is a carbon nanotube, carbon nanohorn, carbon nanofiber, carbon nanofilament, carbon nanocoil, vapor grown carbon (VGCF), cup-shaped nanocarbon substance, etc.
  • the average length is not particularly limited, but the average length is preferably 0.01 ⁇ m or more and 1000 ⁇ m or less, and preferably 0.1 ⁇ m or more and 100 ⁇ m or less, from the viewpoints of manufacturability, film formability, conductivity, and the like. More preferred.
  • the diameter is not particularly limited, but is preferably 0.4 nm or more and 100 nm or less, more preferably 50 nm or less, and still more preferably 15 nm or less from the viewpoint of durability, transparency, film formability, conductivity, and the like. is there.
  • carbon nanotubes are preferable, and carbon nanotubes are particularly preferable.
  • CNT is a single-layer CNT in which a single carbon film (graphene sheet) is wound in a cylindrical shape, a double-layer CNT in which two graphene sheets are wound in a concentric shape, and a plurality of graphene sheets in a concentric shape
  • multi-walled CNTs wound around In the present invention, single-walled CNTs, double-walled CNTs, and multilayered CNTs may be used alone, or two or more kinds may be used in combination.
  • single-walled CNT and double-walled CNT having excellent properties in terms of conductivity and semiconductor properties, and more preferably single-walled CNT.
  • the symmetry of the helical structure based on the hexagonal orientation of graphene on the graphene sheet is called axial chiral
  • the two-dimensional lattice vector from the reference point of a 6-membered ring on graphene is a chiral vector. That's it.
  • the (n, m) obtained by indexing this chiral vector is called a chiral index, and is divided into metallicity and semiconductivity by this chiral index.
  • a material having nm that is a multiple of 3 indicates metallic properties
  • a material that is not a multiple of 3 indicates semiconductor properties.
  • the single-walled CNT that can be used in the present invention may be semiconductive or metallic, and both may be used in combination.
  • a metal or the like may be included in the CNT, and a substance in which a molecule such as fullerene is included (in particular, a substance in which fullerene is included is referred to as a peapod) may be used.
  • CNT can be produced by an arc discharge method, a chemical vapor deposition method (hereinafter referred to as a CVD method), a laser ablation method, or the like.
  • the CNT used in the present invention may be obtained by any method, but is preferably obtained by an arc discharge method and a CVD method.
  • fullerenes, graphite, and amorphous carbon may be produced as by-products at the same time. You may refine
  • the method for purifying CNTs is not particularly limited. In addition to the above-described purification methods, acid treatment with nitric acid, sulfuric acid or the like and ultrasonic treatment are effective for removing impurities. In addition, it is more preferable to perform separation and removal using a filter from the viewpoint of improving purity.
  • CNT After purification, the obtained CNT can be used as it is. Moreover, since CNT is generally produced in a string shape, it may be cut into a desired length depending on the application. CNTs can be cut into short fibers by acid treatment with nitric acid, sulfuric acid or the like, ultrasonic treatment, freeze pulverization method or the like. In addition, it is also preferable to perform separation using a filter from the viewpoint of improving purity. In the present invention, not only cut CNTs but also CNTs produced in the form of short fibers in advance can be used in the same manner.
  • Such short fibrous CNTs are formed by, for example, forming a catalytic metal such as iron or cobalt on a substrate, and thermally decomposing a carbon compound at 700 to 900 ° C. on the surface by CVD to cause vapor growth of the CNTs.
  • a shape oriented in the direction perpendicular to the substrate surface is obtained.
  • the short fiber CNTs thus produced can be taken out by a method such as peeling off from the substrate.
  • the short fibrous CNTs can be obtained by supporting a catalytic metal on a porous support such as porous silicon or an anodic oxide film of alumina and growing the CNTs on the surface by the CVD method.
  • oriented molecules such as iron phthalocyanine containing a catalytic metal in the molecule as a raw material and producing CNTs on a substrate by performing CVD in an argon / hydrogen gas flow, producing oriented short fiber CNTs You can also. Furthermore, it is also possible to obtain short fiber CNTs oriented on the SiC single crystal surface by an epitaxial growth method.
  • Nano metal material is a nanometer-sized fibrous or particulate metal material. Specifically, a fibrous metal material (also referred to as metal fiber), a particulate metal material (metal nanoparticle). Also). The metal nanowire described later is preferable as the nanometal material.
  • the metal fiber preferably has a solid structure or a hollow structure.
  • a metal fiber having a solid structure with an average minor axis length of 1 to 1,000 nm and an average major axis length of 1 to 100 ⁇ m is called a metal nanowire, and an average minor axis length of 1 to 1,000 nm.
  • a metal fiber having an average major axis length of 0.1 to 1,000 ⁇ m and having a hollow structure is called a metal nanotube.
  • the metal fiber material may be any metal having electrical conductivity, and can be appropriately selected according to the purpose.
  • the long period table International Pure and Applied Chemical Association (IUPAC), 1991 revision
  • At least one metal selected from the group consisting of 4 periods, 5th period and 6th period is preferable, at least one metal selected from Group 2 to Group 14 is more preferable, and Group 2 and Group 8 are more preferable.
  • At least one metal selected from Group 9, Group 10, Group 11, Group 12, Group 12, Group 13 and Group 14 is more preferable, and it is particularly preferable that it contains as a main component.
  • metals examples include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantel, titanium, bismuth, antimony, Lead or an alloy thereof can be used.
  • silver and an alloy with silver are preferable in terms of excellent conductivity.
  • the metal used in the alloy with silver include platinum, osmium, palladium, and iridium.
  • a metal may be used individually by 1 type and may use 2 or more types together.
  • the shape of the metal nanowire is not particularly limited as long as the metal nanowire is made of the above-described metal and has a solid structure, and can be appropriately selected according to the purpose.
  • it can take any shape such as a columnar shape, a rectangular parallelepiped shape, a columnar shape with a polygonal cross section, and the corners of the cylindrical shape and the polygonal shape of the cross section are rounded in that the transparency of the thermoelectric conversion layer is increased.
  • a cross-sectional shape is preferred.
  • the cross-sectional shape of the metal nanowire can be examined by observing with a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the average minor axis length of metal nanowires (sometimes referred to as “average minor axis diameter” or “average diameter”) is preferably 50 nm or less, more preferably 1 to 50 nm from the same viewpoint as the above-described nanoconductive material. Preferably, 10 to 40 nm is more preferable, and 15 to 35 nm is particularly preferable.
  • the average short axis length can be calculated as the average value of the short axis lengths of 300 metal nanowires using, for example, a transmission electron microscope (TEM; JEM-2000FX, manufactured by JEOL Ltd.). In addition, the shortest axis length when the short axis of the metal nanowire is not circular is the longest axis.
  • the average major axis length (sometimes referred to as the average length) of the metal nanowire is preferably 1 ⁇ m or more, more preferably 1 to 40 ⁇ m, still more preferably 3 to 35 ⁇ m, and particularly preferably 5 to 30 ⁇ m.
  • the average major axis length can be calculated as an average value of the major axis lengths of 300 metal nanowires using, for example, a transmission electron microscope (TEM; manufactured by JEOL Ltd., JEM-2000FX).
  • TEM transmission electron microscope
  • JEM-2000FX transmission electron microscope
  • the metal nanowire may be manufactured by any manufacturing method, but the metal ions are reduced while heating in a solvent in which a halogen compound and a dispersion additive are dissolved, as described in JP 2012-230881 A.
  • a manufacturing method is preferred. Details of halogen compounds, dispersion additives and solvents, heating conditions, and the like are described in JP 2012-230881 A.
  • a metal nanowire can also be manufactured by the manufacturing method described in each of the above.
  • the shape of the metal nanotube is not particularly limited as long as it is formed of the above-described metal in a hollow structure, and may be a single layer or a multilayer. It is preferable that the metal nanotube is a single wall from the viewpoint of excellent conductivity and heat conductivity.
  • the thickness of the metal nanotube (difference between the outer diameter and the inner diameter) is preferably 3 to 80 nm and more preferably 3 to 30 nm from the viewpoints of durability, transparency, film formability, conductivity, and the like.
  • the average long axis length of the metal nanotubes is preferably 1 to 40 ⁇ m, more preferably 3 to 35 ⁇ m, and even more preferably 5 to 30 ⁇ m, from the same viewpoint as the above-described nanoconductive material.
  • the average minor axis length of the metal nanotube is preferably the same as the average minor axis length of the metal nanowire.
  • the metal nanotube may be manufactured by any manufacturing method, for example, by the manufacturing method described in US Patent Application Publication No. 2005/0056118.
  • the metal nanoparticles may be particulate or powdery metal fine particles formed of the above-described metal, and the surface of the metal fine particles or metal fine particles may be coated with a protective agent, and further the surface coated. May be dispersed in a dispersion medium.
  • Preferred examples of the metal used for the metal nanoparticles include silver, copper, gold, palladium, nickel, rhodium and the like. Also, an alloy composed of at least two of these, an alloy of at least one of these and iron, and the like can be used.
  • Examples of the two alloys include platinum-gold alloy, platinum-palladium alloy, gold-silver alloy, silver-palladium alloy, palladium-gold alloy, platinum-gold alloy, rhodium-palladium alloy, silver-rhodium alloy, Examples thereof include copper-palladium alloy and nickel-palladium alloy.
  • Examples of alloys with iron include iron-platinum alloys, iron-platinum-copper alloys, iron-platinum-tin alloys, iron-platinum-bismuth alloys, and iron-platinum-lead alloys. These metals or alloys can be used alone or in combination of two or more.
  • the average particle diameter (dynamic light scattering method) of the metal nanoparticles is preferably 1 to 150 nm from the viewpoint of excellent conductivity.
  • a protective agent described in JP2012-2222055 is preferably exemplified.
  • the carbon number is 10 to 20
  • the storage stability of the metal nanoparticles is high and the conductivity is excellent.
  • the fatty acids, aliphatic amines, aliphatic thiols and aliphatic alcohols are preferably those described in JP-A-2012-2222055.
  • the metal nanoparticles may be produced by any production method, for example, gas deposition method, sputtering method, metal vapor synthesis method, colloid method, alkoxide method, coprecipitation method, uniform precipitation method, thermal decomposition. Method, chemical reduction method, amine reduction method, solvent evaporation method and the like. Each of these production methods has unique characteristics, but it is preferable to use a chemical reduction method or an amine reduction method particularly for the purpose of mass production. In carrying out these production methods, a known reducing agent or the like can be appropriately used in addition to selecting and using the above-mentioned protective agent as necessary.
  • the copolymer used in the present invention is a copolymer represented by the following general formula (1).
  • a and B each independently represent a copolymer unit derived from an aniline derivative or a copolymer unit derived from a pyrrole derivative. However, A and B represent different copolymer units.
  • the copolymer used in the present invention is a polyaniline copolymer and a polypyrrole copolymer having two different copolymer units A and B. Therefore, the copolymer used for this invention does not contain the homopolymer which consists of a single repeating unit.
  • the copolymer units different from each other refer to copolymer units having different basic skeletons or types, numbers, or substitution positions of substituents, and the bonding mode of the copolymer units (for example, Head to Head, Head to Tail). , Tail to Tail) does not include the difference in copolymer units apparently produced in the copolymer.
  • polyaniline formed by bonding 2-methylaniline units with Head to Tail apparently has two types of copolymer units. However, in the present invention, only one type of 2-methylaniline copolymer unit is present. Suppose you are.
  • Such copolymers having two different copolymer units A and B exhibit excellent dispersibility in the coexistence of the nanoconductive material, and have high thermoelectric conversion performance in the thermoelectric conversion layer. Electrode adhesion can be expressed.
  • the aniline derivative that becomes a copolymer unit of the copolymer is not particularly limited as long as it has an aniline structure, but includes unsubstituted aniline and substituted aniline.
  • the aniline derivative is preferably an aniline derivative that becomes a precursor of a copolymer unit represented by the general formula (2) described later.
  • the pyrrole derivative which becomes a copolymer unit of the copolymer is not particularly limited as long as it has a pyrrole structure, but includes unsubstituted pyrrole, substituted pyrrole and condensed pyrrole.
  • the pyrrole derivative is preferably a pyrrole derivative that becomes a precursor of a copolymer unit represented by the following general formulas (3) to (5), and more preferable in terms of thermoelectric conversion characteristics and electrode adhesion.
  • Examples include pyrrole derivatives that are precursors of copolymer units represented by general formulas (3) and (4) described below, and more preferably precursors of copolymer units represented by general formula (3) described below.
  • the pyrrole derivative which becomes a body is mentioned.
  • copolymer units A and B those different from the above-mentioned copolymer units are selected.
  • copolymer units A and B it is preferable to select two copolymer units having different molecular weights from the above copolymer units in terms of thermoelectric conversion characteristics and electrode adhesion. It is preferable that a copolymer unit having a small molecular weight is selected as the coalescing unit A, and a copolymer unit having a large molecular weight is selected as the copolymer unit B.
  • the molecular weight of the copolymer unit can be adjusted by the difference in the basic skeleton of the copolymer unit, the difference in substituents, the number of substituents, and the like.
  • the difference in molecular weight is preferably due to the difference in substituents and the number of substituents, and more preferably due to differences in substituents.
  • the difference in molecular weight between the copolymer units A and B is not particularly limited, but for example, 1 to 20 carbon atoms constituting the substituent are preferable.
  • Copolymer units A and B are preferably selected from aniline derivative-derived copolymer units or pyrrole derivative-derived copolymer units, both in terms of thermoelectric conversion characteristics and electrode adhesion. More preferably, it is selected from copolymer units derived from aniline derivatives.
  • the copolymer unit A is particularly preferably an unsubstituted aniline-derived copolymer unit or a pyrrole derivative-derived copolymer unit.
  • the ratio (m / n) of the degree of polymerization of the copolymer units A and B is preferably 99/1 to 1/99, more preferably 80/20 to 10/90, from the viewpoint of thermoelectric conversion characteristics and electrode adhesion. More preferably, it is 75/25 to 20/80.
  • the copolymer used in the present invention may be any of a random copolymer, an alternating copolymer, a block copolymer, and a graft copolymer of at least two kinds of the above-mentioned copolymer units. Polymers, alternating copolymers and block copolymers are preferred.
  • the copolymer used in the present invention may be doped or undoped, but is preferably doped.
  • the dope means that a part of the main chain of the copolymer, that is, the copolymer units A and B are preferably oxidized with a dopant described later.
  • the proportion of the copolymer units that form the main chain of the copolymer is referred to as the doping ratio, and in the present invention, the doping ratio is the copolymer weight that forms the main chain in that the thermoelectric conversion performance is further improved.
  • the amount is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, based on the total number of moles of the combined units A and B.
  • the copolymer units A and B are preferably independently selected from the group consisting of copolymer units represented by the following general formulas (2) to (5).
  • the copolymer used in the present invention has two kinds of copolymer units represented by these general formulas, nanoconductivity that cannot be realized by conventional polyaniline and polypyrrole, particularly homopolyaniline and homopolypyrrole. Highly dispersible copolymer in the presence of materials.
  • R 11 to R 14 each independently represents a monovalent substituent.
  • a1 and c1 each independently represents an integer of 0 to 4
  • b1 represents an integer of 0 to 2
  • d1 represents an integer of 0 to 6.
  • X 11 to X 14 each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. * Represents a linking site of copolymer units.
  • the substituent R 14 in the general formula (5) may be substituted on any of the two benzene rings.
  • the connecting site is usually the 4-position and nitrogen atom of the benzene ring, but it may be the 2-position and nitrogen atom of the benzene ring.
  • the connecting site is usually at the 2nd and 5th positions of the pyrrole ring, but may be at the 2nd and 3rd positions of the pyrrole ring.
  • the linking site is usually located at the 2nd and 7th positions of the carbazole ring, but may be located at other positions.
  • Monovalent substituents as R 11 to R 14 are halogen atoms such as fluorine and chlorine, alkyl groups, alkoxy groups, aryloxy groups, alkyloxycarbonyl groups, alkylthio groups, arylthio groups, crown ether ring groups, aryl groups , Heteroaryl group, aliphatic heterocycle, dialkylamino group and the like.
  • the monovalent substituent may be further substituted with the same substituent or different substituents, and examples of the monovalent substituent substituted with the substituent include a fluoroalkyl group, a substituted alkyl group, and a substituted alkoxy group. Groups and the like.
  • R 11 to R 14 are preferably a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an aryl group, or a heteroaryl group.
  • a group, an alkoxy group, and an aryl group are more preferable.
  • the alkyl group preferably has 1 to 20 carbon atoms, more preferably 2 to 20 carbon atoms, and still more preferably 4 to 10 carbon atoms.
  • the alkyl group includes a linear, branched or cyclic alkyl group, and a linear or branched alkyl group is preferable.
  • Examples of the linear alkyl group include methyl, ethyl, propyl, butyl, hexyl, heptyl, octyl and dodecyl.
  • Examples of the branched alkyl group include i-propyl, sec-butyl, t-butyl, and 2-ethylhexyl.
  • the cyclic alkyl group preferably has 3 to 14 carbon atoms, and examples thereof include cyclopropy, cyclopentyl, cyclohexyl, bicyclooctyl, norbornyl, and adamantyl.
  • the alkoxy group preferably has 1 to 20 carbon atoms, more preferably 4 to 15 carbon atoms.
  • the alkyl part of the alkoxy group has the same meaning as the above-described alkyl group except that the number of carbon atoms is different.
  • Such an alkoxy group is preferably a linear or branched alkoxy group, and preferred alkoxy groups include methoxy, butoxy, hexyloxy, octyloxy, 2-ethylhexyloxy, and pentadecyloxy.
  • the aryloxy group preferably has 6 to 26 carbon atoms, and examples thereof include phenoxy and 1-naphthyloxy.
  • the alkyloxycarbonyl group is also referred to as an alkoxycarbonyl group, and preferably has 2 to 20 carbon atoms, and examples thereof include methoxycarbonyl, ethoxycarbonyl, 2-ethylhexyloxycarbonyl and the like.
  • the alkylthio group preferably has 1 to 20 carbon atoms, and examples thereof include methylthio, ethylthio, propylthio and the like.
  • the arylthio group preferably has 6 to 20 carbon atoms, and examples thereof include phenylthio and naphthylthio.
  • the crown ether ring group preferably has 8 to 20 carbon atoms, and includes a thia crown ether or an aza crown ether in which at least one oxygen atom is substituted with a sulfur atom or a nitrogen atom.
  • Examples of such a crown ether ring group include 12-crown-4, 15-crown-5, 18-crown-6, dibenzo-18-crown-6, diaza-18-crown-6 and the like.
  • the aryl group may be a single ring or a condensed ring.
  • the aryl group preferably has 4 to 50 carbon atoms, more preferably 6 to 40 carbon atoms, such as a benzene ring.
  • Group, naphthalene ring group, anthracene ring group, phenanthrene ring group, indacene ring group, fluorene ring group, pyrene ring group and the like, and benzene ring group is preferable.
  • the heteroaryl group may be monocyclic or condensed, and the heteroaryl group preferably has 4 to 50 carbon atoms, more preferably 6 to 40 carbon atoms.
  • hetero atom as the atom examples include a 5- or 6-membered heterocyclic group having at least one nitrogen atom, sulfur atom, oxygen atom, silicon atom, phosphorus atom, selenium atom, or tellurium atom.
  • heteroaryl group examples include an aromatic heteroaryl group, an aliphatic heterocyclic group, and a benzo condensed ring and a dibenzodi condensed ring thereof.
  • aromatic heteroaryl group and these benzo or dibenzo condensed rings include a pyrrole ring group, a thiophene ring group, a furan ring group, a selenophene ring group, a tellurophen ring group, an imidazole ring group, a pyrazole ring group, and an oxazole ring group.
  • An aliphatic heterocyclic group is a heterocyclic group that is not aromatic and is a saturated or unsaturated heterocyclic group.
  • Examples of such an aliphatic heterocyclic group and its condensed ring include a pyrrolidine ring group, a piperidine ring group, a piperazine ring group, and a morpholine ring group.
  • the heteroaryl group includes a thiophene ring group, a furan ring group, a pyrrole ring group, an imidazole ring group, an oxazole ring group, a thiazole ring group, a benzothiophene ring group, a pyridine ring group, a dibenzothiophene ring group, and a carbazole ring group.
  • the aryl group and heteroaryl group described above may be in a cationic state such as an onium salt, but are preferably in a neutral state in that they are conjugated with the conjugated structure constituting the main chain of the copolymer. .
  • the dialkylamino group is preferably an amino group having the aforementioned alkyl group, and examples thereof include N, N-dimethylamino, N, N-diethylamino, N, N-dibutylamino, N, N-dihexylamino and the like.
  • Examples of the above-described monovalent substituent substituted with a substituent that can be employed as R 11 to R 14 include a fluoroalkyl group, a substituted alkoxy group, and a substituted alkyl group.
  • the fluoroalkyl group is a group in which at least one hydrogen atom of the above alkyl group is substituted with a fluorine atom, and a perfluoroalkyl group in which all the hydrogen atoms of the alkyl group are substituted with fluorine atoms is preferable.
  • the alkyl group of the fluoroalkyl group has the same meaning as the above-described alkyl group, and preferred ones are also the same. Examples of the fluoroalkyl group include trifluoromethyl, pentafluoroethyl, hexafluoropropyl, and the like.
  • Examples of the substituted alkoxy group include an alkoxyalkyleneoxy group.
  • the number of carbon atoms constituting the alkoxyalkyleneoxy group is preferably 2-20, and more preferably 2-7.
  • Examples of the alkoxyalkyleneoxy group include methoxyethyleneoxy (2-methoxy-1-ethoxy).
  • Examples of the substituted alkyl group include an aryl group, an alkoxycarbonyl group, an alkyl group substituted with an alkylthio group, and an alkoxyalkyleneoxyalkyl group.
  • Examples of the alkyl substituted with an aryl group include benzyl and phenethyl.
  • alkyl group substituted with an alkoxycarbonyl group examples include 2-methoxycarbonylethyl.
  • An example of an alkyl group substituted with an alkylthio group is 2-propylthioethyl.
  • the number of carbon atoms constituting the alkoxyalkyleneoxyalkyl group is preferably 2-20.
  • a1 represents an integer of 0 to 4, and when it is selected as copolymer unit A, it is preferably 0 in view of excellent electrode adhesion, and is selected as copolymer unit B. When it is used, it is preferably an integer of 1 to 4 and more preferably 1 or 2 in terms of excellent thermoelectric conversion characteristics. Regardless of the number of monovalent substituents R 11, substituted position of the substituent R 11 is not particularly limited.
  • b1 represents an integer of 0 to 2, and when selected as the copolymer unit A, it is preferably 0 from the viewpoint of excellent electrode adhesion, and is selected as the copolymer unit B. When it is, it is preferably 1 or 2 in terms of excellent thermoelectric conversion characteristics. Regardless of the number of monovalent substituents R 12, substituted position of the substituent R 12 is not particularly limited.
  • c1 represents an integer of 0 to 4, and when it is selected as the copolymer unit A, it is preferably 0 in terms of excellent electrode adhesion, and is selected as the copolymer unit B. When it is used, it is preferably an integer of 1 to 4 and more preferably 1 or 2 in terms of excellent thermoelectric conversion characteristics. Regardless of the number of monovalent substituents R 13, substituted position of the substituent R 13 is not particularly limited.
  • d1 represents an integer of 0 to 6, and when it is selected as copolymer unit A, it is preferably 0 in view of excellent electrode adhesion, and is selected as copolymer unit B. When it is used, it is preferably an integer of 1 to 6 and more preferably 1 or 2 from the viewpoint of excellent thermoelectric conversion characteristics.
  • the substituent R 14 may be substituted with any of the two benzene rings, and the substitution position of the substituent R 14 in each benzene ring is not particularly limited, For example, the 3rd and 6th positions are preferred.
  • X 11 to X 14 are each independently a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, preferably a hydrogen atom.
  • the alkyl group, aryl group, and heteroaryl group in X 11 to X 14 have the same meanings as the alkyl group, aryl group, and heteroaryl group in the above-described substituents R 11 to R 14 , and preferred ones are also the same.
  • X 11 to X 14 are each independently the same as the substituents R 11 to R 14 described above, and the substituents further included in the substituents R 11 to R 14 such as an alkyl group, aryl group, heteroaryl Group and a hydrophilic group.
  • copolymer units A and B those different from the copolymer units represented by the above general formulas (2) to (5) are selected. At this time, it is preferable to select two copolymer units having different molecular weights in terms of thermoelectric conversion characteristics and electrode adhesion as the copolymer units A and B, and the copolymer unit A has a small molecular weight.
  • a copolymer unit having a large molecular weight is preferably selected as the copolymer unit B.
  • the copolymer unit A in which the copolymer unit A has no monovalent substituents R 11 to R 14 It is preferably a unit, and the copolymer unit B is preferably a copolymer unit having one or more monovalent substituents R 11 to R 14 .
  • the copolymer unit A is a copolymer unit represented by the general formula (2) in which a1 is 0, a copolymer unit represented by the general formula (3) in which b1 is 0, and c1 is 0.
  • thermoelectric power is selected from the group consisting of a copolymer unit represented by the general formula (4) and a copolymer unit represented by the general formula (5) in which d1 is an integer of 1 to 6. This is preferable in that the conversion characteristics and high electrode adhesion are expressed in a balanced manner.
  • X 11 to X 14 are hydrogen atoms.
  • the copolymer units A and B both have the same basic structure in that they are excellent in thermoelectric conversion characteristics and electrode adhesion.
  • the copolymer units A and B are preferably both selected from a copolymer unit derived from an aniline derivative or a copolymer unit derived from a pyrrole derivative.
  • the copolymer units A and B are selected from copolymer units derived from pyrrole derivatives, they are selected from the copolymer units represented by the above general formulas (3) to (5).
  • the copolymer units A and B preferably have the same basic structure but different structures from each other. Specifically, the copolymer units A and B have two different kinds represented by the general formula (2).
  • An aniline copolymer having a copolymer unit, a pyrrole copolymer having two different copolymer units represented by the above general formula (3), and each other represented by the above general formula (4) A benzopyrrole copolymer having two different types of copolymer units and a carbazole copolymer having two different types of copolymer units represented by the general formula (5) are preferable, and an aniline copolymer is preferable. More preferred are polymers and pyrrole copolymers.
  • the copolymer used in the present invention may contain other copolymer units as the third copolymer unit that forms the main chain of the copolymer, in addition to the copolymer units described above.
  • the other copolymer unit preferably has a conjugated structure.
  • the third copolymer unit include copolymer units represented by the above general formulas (2) to (5).
  • the compound containing a copolymer unit having a conjugated structure include, for example, thiophene compounds, pyrrole compounds, aniline compounds, acetylene compounds, p-fluorenylene compounds, polyacenes.
  • the copolymer used in the present invention preferably contains 30 mol% or less of the above-mentioned other structure with respect to a total of 100 mol of the copolymerized units represented by the above formulas.
  • the terminal of the copolymer used in the present invention is not particularly limited, and examples thereof include a hydrogen atom and a substituent such as the above-described monovalent substituent, such as a hydrogen atom, an unsubstituted aniline or aniline derivative, Substituted pyrrole or pyrrole derivative, amino group NHX 11 , halogen atom (chlorine atom, bromine atom and iodine atom), known boric acid derivative, hydrophilic group (carboxylic acid group, sulfonic acid group, hydroxyl group, phosphoric acid group, etc.) You may have.
  • a substituent such as the above-described monovalent substituent, such as a hydrogen atom, an unsubstituted aniline or aniline derivative, Substituted pyrrole or pyrrole derivative, amino group NHX 11 , halogen atom (chlorine atom, bromine atom and iodine atom), known boric acid derivative,
  • examples of the aniline derivative include those that become a copolymer unit represented by the above general formula (2), and those that become a copolymer unit represented by the above-described general formulas (3) to (5) of the pyrrole derivative. .
  • X 11 amino groups NHX 11 has the same meaning as X 11 described above.
  • the molecular weight of the copolymer used in the present invention is not particularly limited, and may be a high molecular weight oligomer or an oligomer having a lower molecular weight (for example, a weight average molecular weight of about 1,000 to 10,000).
  • the molecular weight is preferably 5,000 to 100,000, more preferably 8,000 to 50,000 in terms of weight average molecular weight. More preferably, it is from 20,000 to 20,000.
  • the weight average molecular weight can be obtained by converting a value measured by gel permeation chromatography (GPC) into standard polystyrene.
  • the reason why the above-mentioned copolymer is excellent in thermoelectric conversion performance and can exhibit high adhesion with the electrode in the thermoelectric conversion layer is considered as follows. That is, since the copolymer has two different copolymer units, preferably two different copolymer units selected as described above, the copolymer is highly dispersed even in the presence of the nanoconductive material. Thus, it is difficult to form aggregates, and it is considered that high thermoelectric conversion performance and electrode adhesion are exhibited.
  • the copolymer having copolymer units A and B described above is prepared by subjecting an aniline derivative or pyrrole derivative having a copolymer unit represented by the general formulas (2) to (5) to an ordinary oxidative polymerization method or a cup. It can be produced by polymerization by a ring polymerization method.
  • the content of the copolymer in the thermoelectric conversion material of the present invention is preferably 3 to 80% by mass, more preferably 5 to 60% by mass, based on the total solid content of the thermoelectric conversion material. It is especially preferable that it is 50 mass%.
  • the content of the copolymer in the thermoelectric conversion material is preferably 3 to 70% by mass in the total solid content of the material. The amount is more preferably 60% by mass, and particularly preferably 10 to 50% by mass.
  • the thermoelectric conversion material contains a conductive polymer other than the copolymer represented by the above general formula (1), the copolymer represented by the above general formula (1) in the thermoelectric conversion material.
  • the content of the copolymer having a combined unit as a repeating unit is preferably 0 to 70% by mass, more preferably 3 to 50% by mass, and more preferably 5 to 20% by mass in the total solid content of the material. It is particularly preferred that
  • examples of the other conductive polymer include a polymer having at least one other copolymer unit as a repeating unit.
  • the thermoelectric conversion material of the present invention preferably contains a non-conjugated polymer in that the thermoelectric conversion characteristics are further improved.
  • a non-conjugated polymer is a polymer compound having no conjugated molecular structure, that is, a polymer whose main chain is not conjugated with ⁇ electrons or lone electron pairs.
  • the type of the non-conjugated polymer is not particularly limited, and a conventionally known non-conjugated polymer can be used.
  • a polymer selected from the group consisting of a polyvinyl polymer obtained by polymerizing a vinyl compound, poly (meth) acrylate, polycarbonate, polyester, polyamide, polyimide, and polysiloxane is used.
  • (meth) acrylate represents either or both of acrylate and methacrylate, and includes a mixture thereof.
  • vinyl compounds that form polyvinyl polymers include styrene, vinyl pyrrolidone, vinyl carbazole, vinyl pyridine, vinyl naphthalene, vinyl phenol, vinyl acetate, styrene sulfonic acid, and vinyl arylamines such as vinyl triphenylamine. And vinyltrialkylamines such as vinyltributylamine.
  • (meth) acrylate compounds that form poly (meth) acrylates include hydrophobic alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate, 2-hydroxyethyl acrylate, and 1-hydroxy Hydroxyalkyl acrylates such as ethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 1-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, 2-hydroxybutyl acrylate, 1-hydroxybutyl acrylate
  • Examples include acrylate monomers such as esters, and methacrylate monomers obtained by replacing the acryloyl group of these monomers with methacryloyl groups.
  • polycarbonate examples include general-purpose polycarbonate composed of bisphenol A and phosgene, Iupizeta (trade name, manufactured by Mitsubishi Gas Chemical Co., Ltd.), Panlite (trade name, manufactured by Teijin Chemicals Ltd.), and the like.
  • the compound forming the polyester examples include polyalcohols, polycarboxylic acids, and hydroxy acids such as lactic acid.
  • Specific examples of polyester include Byron (trade name, manufactured by Toyobo Co., Ltd.) and the like.
  • polyamide examples include PA-100 (trade name, manufactured by T & K TOKA Corporation).
  • polyimide examples include Solpy 6,6-PI (trade name, manufactured by Solpy Kogyo Co., Ltd.).
  • the non-conjugated polymer may be a homopolymer or a copolymer with each of the above-described compounds. In the present invention, it is more preferable to use a polyvinyl polymer obtained by polymerizing a vinyl compound as the non-conjugated polymer.
  • the non-conjugated polymer is preferably hydrophobic and more preferably has no hydrophilic group such as sulfonic acid or hydroxyl group in the molecule. Further, a non-conjugated polymer having a solubility parameter (SP value) of 11 or less is preferable.
  • the solubility parameter indicates the Hildebrand SP value, and a value based on the Fedors estimation method is adopted.
  • thermoelectric conversion performance of the thermoelectric conversion material can be improved by including a non-conjugated polymer together with the copolymer represented by the general formula (1) in the thermoelectric conversion material.
  • the mechanism is not yet clear, (1) since the non-conjugated polymer has a wide gap (band gap) between the HOMO level and the LUMO level, the carrier concentration in the above-mentioned copolymer is appropriately set. In view of the fact that it can be kept low, the Seebeck coefficient can be maintained at a higher level than a system that does not contain a non-conjugated polymer. This is considered to be because the high conductivity can be maintained.
  • thermoelectric conversion performance (ZT) Value) is greatly improved.
  • the content of the non-conjugated polymer in the thermoelectric conversion material is preferably 10 to 1500 parts by mass, and 30 to 1200 parts by mass with respect to 100 parts by mass of the copolymer represented by the general formula (1). More preferably, it is more preferably 80 to 1000 parts by mass.
  • ZT value Seebeck coefficient and thermoelectric conversion performance
  • nano conductive material due to mixing of non-conjugated polymers. This is preferable because there is no deterioration in dispersibility and deterioration in conductivity and thermoelectric conversion performance.
  • the thermoelectric conversion material of the present invention preferably contains a solvent.
  • the thermoelectric conversion material of the present invention is more preferably a nanoconductive material dispersion in which a nanoconductive material is dispersed in a solvent.
  • the solvent should just be able to disperse
  • an organic solvent an alcohol, dichloromethane, chloroform, carbon tetrachloride, ethane dichloride, aliphatic halogen solvents such as trichloroethylene, trichloroethane, tetrachloroethylene, aprotic polar solvents such as DMF, NMP, DMSO, chlorobenzene, Aromatic halogen solvents such as dichlorobenzene, aromatic solvents such as benzene, toluene, xylene, mesitylene, tetralin, tetramethylbenzene and pyridine, ketone solvents such as cyclohexanone, acetone and methylethylkenton, diethyl ether, tetrahydrofuran ( THF), t-butyl methyl ether, dimethoxyethane, diglyme, and other ether solvents are preferred.
  • aliphatic halogen solvents such as trichloroethylene
  • Aliphatic halogen solvents, aromatic halogen solvents, aprotic polar solvents, aromatic solvents Medium, ether solvents are more preferred, even more preferably aliphatic halogenated solvents and aromatic halogenated solvent.
  • the halogen-based solvent is one in which at least one hydrogen atom of a compound serving as a solvent is substituted with a halogen atom.
  • the halogen-based solvent is classified into an aliphatic halogen-based solvent and an aromatic halogen-based solvent. Therefore, in the present invention, the aliphatic halogen solvent and the aromatic halogen solvent may be collectively referred to as a halogen solvent.
  • the solvent is preferably degassed in advance.
  • the dissolved oxygen concentration in the solvent is preferably 10 ppm or less.
  • Examples of the degassing method include a method of irradiating ultrasonic waves under reduced pressure, a method of bubbling an inert gas such as argon, and the like.
  • the solvent is preferably dehydrated in advance.
  • the amount of water in the solvent is preferably 1000 ppm or less, and more preferably 100 ppm or less.
  • the water content in the solvent is set in the above range in advance, the water content of the thermoelectric conversion material and the thermoelectric conversion layer can be adjusted to 0.01 to 15% by mass.
  • a method for dehydrating the solvent a known method such as a method using molecular sieve or distillation can be used.
  • the amount of solvent in the thermoelectric conversion material is preferably 25 to 99.99% by mass, more preferably 30 to 99.95% by mass, and more preferably 30 to 99.9% with respect to the total amount of the thermoelectric conversion material. More preferably, it is mass%.
  • the thermally conductive material of the present invention comprising a nanoconductive material and a solvent, particularly an organic solvent, together with the above-mentioned copolymer exhibits good nanoconductive material dispersibility, and the organic solvent is a halogen-based solvent.
  • the copolymer of the present invention exhibits remarkable dispersibility in the presence of a nanoconductive material.
  • the above-mentioned copolymer, nanoconductive material and solvent preferably an organic solvent, particularly preferably a halogen-based solvent
  • the nano electroconductive material dispersion dispersed in a solvent, an organic solvent or a halogen-based solvent is included.
  • the nano-conductive material can exhibit high original conductivity, and can be suitably used for various conductive materials including a thermoelectric conversion material.
  • the copolymer used in the present invention appropriately selects a solvent suitable for the production equipment, application, production environment, etc. from the halogen-based solvent without significantly impairing the coating property and film forming property of the thermoelectric conversion material. Can be used.
  • the thermoelectric conversion material of the present invention may contain a dopant as appropriate in order to further improve conductivity by increasing the carrier concentration in the thermoelectric conversion material of the present invention.
  • the dopant is a compound doped in the copolymer represented by the above general formula (1), and the copolymer is obtained by protonating the copolymer or removing electrons from the ⁇ -conjugated system of the copolymer. Any material that can dope the coalescence with positive charge (p-type doping) may be used. Specifically, the following onium salt compounds, oxidizing agents, acidic compounds, electron acceptor compounds and the like can be used.
  • Onium salt compound used as a dopant is preferably a compound (acid generator, acid precursor) that generates an acid upon application of energy such as irradiation of active energy rays (radiation, electromagnetic waves, etc.) or application of heat.
  • onium salt compounds include sulfonium salts, iodonium salts, ammonium salts, carbonium salts, phosphonium salts, and the like.
  • sulfonium salts, iodonium salts, ammonium salts and carbonium salts are preferable, sulfonium salts, iodonium salts and carbonium salts are more preferable, and sulfonium salts and iodonium salts are particularly preferable.
  • anion moiety constituting the salt include a strong acid counter anion.
  • the compound represented by the following general formula (I) or (II) is used as the sulfonium salt
  • the compound represented by the following general formula (III) is used as the iodonium salt
  • the following general formula is used as the ammonium salt.
  • the compound represented by (IV) and the carbonium salt include compounds represented by the following general formula (V), which are preferably used in the present invention.
  • R 21 to R 23 , R 25 to R 26 and R 31 to R 33 each independently represents an alkyl group, an aralkyl group, an aryl group, or an aromatic heterocyclic group.
  • R 27 to R 30 each independently represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an aromatic heterocyclic group, an alkoxy group, or an aryloxy group.
  • R 24 represents an alkylene group or an arylene group.
  • the substituents of R 21 to R 33 may be further substituted with a substituent.
  • X ⁇ represents an anion of a strong acid.
  • Any two groups of R 21 ⁇ R 23 in the general formula (I) is, R 21 and R 23 in the general formula (II) is, the R 25 and R 26 in formula (III), general formula (IV)
  • Any two groups of R 27 to R 30 are bonded to any two groups of R 31 to R 33 in the general formula (V) to form an aliphatic ring, an aromatic ring, or a heterocyclic ring, respectively. May be.
  • the alkyl group includes a linear, branched or cyclic alkyl group, and the linear or branched alkyl group is preferably an alkyl group having 1 to 20 carbon atoms. Specific examples include methyl, ethyl, propyl, n-butyl, sec-butyl, t-butyl, hexyl, octyl, dodecyl and the like.
  • cyclic alkyl group an alkyl group having 3 to 20 carbon atoms is preferable, and specific examples include cyclopropyl, cyclopentyl, cyclohexyl, bicyclooctyl, norbornyl, adamantyl and the like.
  • the aralkyl group is preferably an aralkyl group having 7 to 15 carbon atoms, and specific examples include benzyl and phenethyl.
  • the aryl group is preferably an aryl group having 6 to 20 carbon atoms, and specific examples include phenyl, naphthyl, anthranyl, phenanthyl, pyrenyl and the like.
  • aromatic heterocyclic group pyridine ring group, pyrazole ring group, imidazole ring group, benzimidazole ring group, indole ring group, quinoline ring group, isoquinoline ring group, purine ring group, pyrimidine ring group, oxazole ring group, Examples include a thiazole ring group and a thiazine ring group.
  • the alkoxy group is preferably a linear or branched alkoxy group having 1 to 20 carbon atoms, and specific examples include methoxy, ethoxy, iso-propoxy, butoxy, hexyloxy and the like.
  • the aryloxy group is preferably an aryloxy group having 6 to 20 carbon atoms, and specific examples include phenoxy and naphthyloxy.
  • the alkylene group includes a linear, branched, or cyclic alkylene group, and an alkylene group having 2 to 20 carbon atoms is preferable. Specific examples include ethylene, propylene, butylene, hexylene and the like.
  • the cyclic alkylene group a cyclic alkylene group having 3 to 20 carbon atoms is preferable, and specific examples include cyclopentylene, cyclohexylene, bicyclooctylene, norbornylene, adamantylene and the like.
  • the arylene group an arylene group having 6 to 20 carbon atoms is preferable, and specific examples include phenylene, naphthylene, anthranylene, and the like.
  • the substituent of R 21 to R 33 is preferably an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom (a fluorine atom, a chlorine atom, iodine) Atom), aryl group having 6 to 10 carbon atoms, aryloxy group having 6 to 10 carbon atoms, alkenyl group having 2 to 6 carbon atoms, cyano group, hydroxy group, carboxy group, acyl group, alkoxycarbonyl group, alkylcarbonylalkyl Group, arylcarbonyl group, arylcarbonylalkyl group, nitro group, alkylsulfonyl group, trifluoromethyl group, —S—R 41 and the like.
  • the substituents of R 41 has the same meaning as above R 21.
  • X ⁇ is preferably an arylsulfonic acid anion, a perfluoroalkylsulfonic acid anion, a perhalogenated Lewis acid anion, a perfluoroalkylsulfonimide anion, a perhalogenate anion, or an alkyl or arylborate anion. These may further have a substituent, and examples of the substituent include a fluoro group.
  • anions of aryl sulfonic acid include p-CH 3 C 6 H 4 SO 3 ⁇ , C 6 H 5 SO 3 ⁇ , an anion of naphthalene sulfonic acid, an anion of naphthoquinone sulfonic acid, an anion of naphthalenedisulfonic acid, anthraquinone Examples include sulfonic acid anions.
  • Specific examples of the anion of perfluoroalkylsulfonic acid include CF 3 SO 3 ⁇ , C 4 F 9 SO 3 ⁇ , and C 8 F 17 SO 3 — .
  • the anion of the perhalogenated Lewis acid include PF 6 ⁇ , SbF 6 ⁇ , BF 4 ⁇ , AsF 6 ⁇ and FeCl 4 ⁇ .
  • Specific examples of the anion of perfluoroalkylsulfonimide include CF 3 SO 2 —N —— SO 2 CF 3 and C 4 F 9 SO 2 —N —— SO 2 C 4 F 9 .
  • Specific examples of the perhalogenate anion include ClO 4 ⁇ , BrO 4 ⁇ and IO 4 ⁇ .
  • alkyl or aryl borate anion examples include (C 6 H 5 ) 4 B ⁇ , (C 6 F 5 ) 4 B ⁇ , (p-CH 3 C 6 H 4 ) 4 B ⁇ , (C 6 H 4 F) 4 B -, and the like.
  • onium salts are shown below, but the present invention is not limited thereto.
  • X ⁇ represents PF 6 ⁇ , SbF 6 ⁇ , CF 3 SO 3 ⁇ , p—CH 3 C 6 H 4 SO 3 ⁇ , BF 4 ⁇ , (C 6 H 5 ) 4 B ⁇ . , RfSO 3 ⁇ , (C 6 F 5 ) 4 B ⁇ , or an anion represented by the following formula, and Rf represents a perfluoroalkyl group.
  • an onium salt compound represented by the following general formula (VI) or (VII) is particularly preferable.
  • Y represents a carbon atom or a sulfur atom
  • Ar 1 represents an aryl group
  • Ar 2 to Ar 4 each independently represents an aryl group or an aromatic heterocyclic group.
  • Ar 1 to Ar 4 may be further substituted with a substituent.
  • Ar 1 is preferably a fluoro-substituted aryl group or an aryl group substituted with at least one perfluoroalkyl group, more preferably a pentafluorophenyl group or a phenyl group substituted with at least one perfluoroalkyl group And particularly preferably a pentafluorophenyl group.
  • the aryl group and aromatic heterocyclic group of Ar 2 to Ar 4 have the same meanings as the aryl group and aromatic heterocyclic group of R 21 to R 23 and R 25 to R 33 described above, and preferably an aryl group Yes, more preferably a phenyl group. These groups may be further substituted with a substituent, and examples of the substituent include the above-described substituents R 21 to R 33 .
  • Ar 1 represents an aryl group
  • Ar 5 and Ar 6 each independently represent an aryl group or an aromatic heterocyclic group.
  • Ar 1 , Ar 5 and Ar 6 may be further substituted with a substituent.
  • Ar 1 has the same meaning as Ar 1 in the general formula (VI), and the preferred range is also the same.
  • Ar 5 and Ar 6 have the same meanings as Ar 2 to Ar 4 in the general formula (VI), and preferred ranges thereof are also the same.
  • the said onium salt compound can be manufactured by normal chemical synthesis. Moreover, a commercially available reagent etc. can also be used. As an embodiment of the method for synthesizing the onium salt compound, a method for synthesizing triphenylsulfonium tetrakis (pentafluorophenyl) borate is shown below, but the present invention is not limited to this. Other onium salts can be synthesized by the same method.
  • the acidic compound examples include polyphosphoric acid, hydroxy compound, carboxy compound, or sulfonic acid compound, protonic acid (HF, HCl, HNO 3 , H 2 SO 4 , HClO 4 , FSO 3 H, CISO 3 H, CF 3) SO 3 H, various organic acids, amino acids, etc.).
  • electron acceptor compounds examples include TCNQ (tetracyanoquinodimethane), tetrafluorotetracyanoquinodimethane, halogenated tetracyanoquinodimethane, 1,1-dicyanovinylene, 1,1,2-tricyanovinylene, benzoquinone.
  • Polyphosphoric acid- Polyphosphoric acid includes diphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, metaphosphoric acid and polyphosphoric acid, and salts thereof. A mixture thereof may be used.
  • the polyphosphoric acid is preferably diphosphoric acid, pyrophosphoric acid, triphosphoric acid, or polyphosphoric acid, and more preferably polyphosphoric acid.
  • Polyphosphoric acid can be synthesized by heating H 3 PO 4 with sufficient P 4 O 10 (anhydrous phosphoric acid) or by heating H 3 PO 4 to remove water.
  • the hydroxy compound may be a compound having at least one hydroxyl group, and preferably has a phenolic hydroxyl group.
  • a compound represented by the following general formula (VIII) is preferable.
  • R represents a sulfo group, a halogen atom, an alkyl group, an aryl group, a carboxy group, or an alkoxycarbonyl group
  • n represents 1 to 6
  • m represents 0 to 5.
  • R is preferably a sulfo group, an alkyl group, an aryl group, a carboxy group, or an alkoxycarbonyl group, and more preferably a sulfo group.
  • n is preferably 1 to 5, more preferably 1 to 4, and still more preferably 1 to 3.
  • m is 0 to 5, preferably 0 to 4, and more preferably 0 to 3.
  • the carboxy compound may be a compound having at least one carboxy group, and a compound represented by the following general formula (IX) or (X) is preferable.
  • A represents a divalent linking group.
  • the divalent linking group is preferably a combination of an alkylene group, an arylene group or an alkenylene group and an oxygen atom, a sulfur atom or a nitrogen atom, and more preferably a combination of an alkylene group or an arylene group and an oxygen atom or a sulfur atom. preferable.
  • the divalent linking group is a combination of an alkylene group and a sulfur atom
  • the compound also corresponds to a thioether compound.
  • the use of such a thioether compound is also suitable.
  • the divalent linking group represented by A includes an alkylene group, the alkylene group may have a substituent. As the substituent, an alkyl group is preferable, and a carboxy group is more preferable as a substituent.
  • R represents a sulfo group, a halogen atom, an alkyl group, an aryl group, a hydroxy group, or an alkoxycarbonyl group
  • n represents 1 to 6
  • m represents 0 to 5.
  • R is preferably a sulfo group, an alkyl group, an aryl group, a hydroxy group or an alkoxycarbonyl group, more preferably a sulfo group or an alkoxycarbonyl group.
  • n is preferably 1 to 5, more preferably 1 to 4, and still more preferably 1 to 3.
  • m is 0 to 5, preferably 0 to 4, and more preferably 0 to 3.
  • the sulfonic acid compound is a compound having at least one sulfo group, and a compound having two or more sulfo groups is preferable.
  • the sulfonic acid compound is preferably one substituted with an aryl group or an alkyl group, and more preferably one substituted with an aryl group.
  • the compound which has a sulfo group as a substituent is classified into a hydroxy compound and a carboxy compound as mentioned above. Therefore, the sulfonic acid compound does not include a hydroxy compound having a sulfo group and a carboxy compound.
  • dopants it is not essential to use these dopants.
  • the use of dopants is preferable because further improvement in thermoelectric conversion characteristics can be expected due to improvement in conductivity.
  • a dopant it can be used individually by 1 type or in combination of 2 or more types.
  • the dopant is used in an amount of more than 0 parts by mass and 60 parts by mass or less with respect to 100 parts by mass of the copolymer represented by the general formula (1) from the viewpoint of controlling the optimum carrier concentration. It is preferably 2 to 50 parts by mass, more preferably 5 to 40 parts by mass.
  • an onium salt compound from the viewpoint of improving the dispersibility of the thermoelectric conversion material and improving the film formability.
  • the onium salt compound is neutral in a state before acid release, and decomposes upon application of energy such as light and heat to generate an acid, and this acid exhibits a doping effect. Therefore, after the thermoelectric conversion material is formed and processed into a desired shape, doping can be performed by light irradiation or the like to develop a doping effect. Furthermore, since it is neutral before acid release, each component such as the copolymer and nano-conductive material is uniformly dissolved or dispersed in the thermoelectric conversion material without agglomerating and precipitating the above-mentioned copolymer. To do. Due to the uniform solubility or dispersibility of this thermoelectric conversion material, it is possible to exhibit excellent conductivity after doping, and furthermore, good applicability and film formability can be obtained. Excellent.
  • thermoelectric conversion material of the present invention preferably contains a thermal excitation assisting agent in terms of further improving thermoelectric conversion characteristics.
  • the thermal excitation assist agent is a substance having a molecular orbital having a specific energy level difference with respect to the energy level of the molecular orbital of the copolymer represented by the general formula (1).
  • the thermal excitation assisting agent used in the present invention is a compound having a LUMO having a lower energy level than the LUMO (Lowest Unoccupied Molecular Orbital) of the above-mentioned copolymer, Refers to a compound that does not form
  • the aforementioned dopant is a compound that forms a dope level in the copolymer, and forms a dope level regardless of the presence or absence of a thermal excitation assisting agent. Whether or not a doped level is formed in the copolymer can be evaluated by measuring an absorption spectrum.
  • the compound that forms the doped level and the compound that does not form the doped level are evaluated by the following method. Say something.
  • the LUMO of the thermal excitation assisting agent has a lower energy level than the LUMO of the above-mentioned copolymer, and the acceptor level of thermally excited electrons generated from the HOMO (Highest Occupied Molecular Orbital) of the copolymer. Function as. Furthermore, when the absolute value of the HOMO energy level of the copolymer and the absolute value of the LUMO energy level of the thermal excitation assist agent satisfy the following formula (I), the thermoelectric conversion material has excellent heat Equipped with an electromotive force.
  • the above formula (I) represents the energy difference between the LUMO of the thermal excitation assist agent and the HOMO of the copolymer, and when this is smaller than 0.1 eV (the LUMO energy level of the thermal excitation assist agent is that of the copolymer). Since the activation energy of electron transfer between the HOMO (donor) of the copolymer and the LUMO (acceptor) of the thermal excitation assisting agent is very small, Aggregation may occur due to an oxidation-reduction reaction between the coalescence and the thermal excitation assist agent. As a result, the film formability of the material is deteriorated and the conductivity is deteriorated.
  • the energy difference between both orbits is larger than 1.9 eV, the energy difference becomes much larger than the thermal excitation energy, so that almost no thermally excited carriers are generated, that is, the addition of the thermal excitation assisting agent. The effect may be almost lost.
  • the energy difference between both orbits is within the range of the above formula (I).
  • the HOMO and LUMO energy levels of the copolymer and the thermal excitation assist agent regarding the HOMO energy level, a single coating film (glass substrate) of each component was prepared, and the HOMO level was determined by photoelectron spectroscopy. Can be measured.
  • the LUMO energy can be calculated by measuring the band gap using an ultraviolet-visible spectrophotometer and then adding it to the HOMO energy measured above.
  • the values measured and calculated by the method are used for the energy levels of HOMO and LUMO of the copolymer and the thermal excitation assist agent.
  • thermoelectric conversion material When the thermal excitation assist agent is used, the thermal excitation efficiency is improved and the number of thermally excited carriers is increased, so that the thermoelectromotive force of the thermoelectric conversion material is improved.
  • Such an effect of improving the thermoelectromotive force by the thermal excitation assisting agent is different from the method of improving the thermoelectric conversion performance by the doping effect of the copolymer.
  • the absolute value of the Seebeck coefficient S and the conductivity ⁇ of the thermoelectric conversion material are increased, and the thermal conductivity ⁇ is decreased.
  • the Seebeck coefficient is a thermoelectromotive force per 1 K absolute temperature.
  • the thermal excitation assist agent improves the thermoelectric conversion performance by increasing the Seebeck coefficient.
  • a thermal excitation assist agent When a thermal excitation assist agent is used, electrons generated by thermal excitation exist in the LUMO of the thermal excitation assist agent, which is the acceptor level, so that the holes on the copolymer and the electrons on the thermal excitation assist agent Exists physically apart. Therefore, the doped level of the copolymer is less likely to be saturated by electrons generated by thermal excitation, and the Seebeck coefficient can be increased.
  • Compounds, fullerene compounds, phthalocyanine compounds, perylene dicarboxyimide compounds, or tetracyanoquinodimethane compounds are preferred, and are from benzothiadiazole skeleton, benzothiazole skeleton, dithienosilole skeleton, cyclopentadithiophene skeleton, and thienothiophene skeleton.
  • n represents an integer (preferably an integer of 10 or more), and Me represents a methyl group.
  • the thermal excitation assisting agent can be used alone or in combination of two or more.
  • the content of the thermal excitation assisting agent in the thermoelectric conversion material is preferably 0 to 35% by mass, more preferably 3 to 25% by mass, and more preferably 5 to 20% by mass in the total solid content. Is particularly preferred.
  • the thermal excitation assisting agent is preferably used in an amount of 0 to 100 parts by weight, more preferably 5 to 70 parts by weight, and more preferably 10 to 50 parts by weight with respect to 100 parts by weight of the copolymer. Is more preferable.
  • the thermoelectric conversion material of the present invention preferably contains a metal element as a simple substance, ions, or the like from the viewpoint of improving thermoelectric conversion characteristics.
  • a metal element is added, the transport of electrons is promoted by the metal element in the formed thermoelectric conversion layer, so that it is considered that the thermoelectric conversion characteristics are improved.
  • the metal element is not particularly limited, but is preferably a metal element having an atomic weight of 45 to 200 in terms of thermoelectric conversion characteristics, more preferably a transition metal element, and zinc, iron, palladium, nickel, cobalt, molybdenum, platinum, and tin. It is particularly preferred.
  • the concentration of the metal element in the solid content of the thermoelectric conversion material of the present invention is preferably 50 to 30000 ppm, more preferably 100 to 10000 ppm, and 200 to 5000 ppm. Is particularly preferred.
  • thermoelectric conversion material of the present invention for example, an ICP mass spectrometer (for example, “ICPM-8500” (trade name) manufactured by Shimadzu Corporation), energy dispersive X-ray fluorescence analysis It can be quantified by a known analysis method such as an apparatus (for example, “EDX-720” (trade name) manufactured by Shimadzu Corporation).
  • ICP mass spectrometer for example, “ICPM-8500” (trade name) manufactured by Shimadzu Corporation
  • EDX-720 trade name
  • the thermoelectric conversion material of the present invention may appropriately contain an antioxidant, a light stabilizer, a heat stabilizer, a plasticizer and the like in addition to the above components.
  • the content of these components is preferably 5% by mass or less, more preferably 0 to 2% by mass, based on the total solid content of the material.
  • antioxidants Irganox 1010 (manufactured by Cigabi Nippon, Inc.), Sumilizer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer GS (manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer GM (Sumitomo Chemical Industries, Ltd.) Manufactured) and the like.
  • Examples of the light-resistant stabilizer include TINUVIN 234 (manufactured by BASF), CHIMASSORB 81 (manufactured by BASF), and Siasorb UV-3853 (manufactured by Sun Chemical).
  • IRGANOX 1726 (made by BASF) is mentioned as a heat-resistant stabilizer.
  • Examples of the plasticizer include Adeka Sizer RS (manufactured by Adeka).
  • thermoelectric conversion material of the present invention can be prepared by mixing the above components.
  • the nanoconductive material and the copolymer represented by the above general formula (1) are added to a solvent and mixed, and each component is dissolved or dispersed.
  • each component in the thermoelectric conversion material is preferably in a dispersed state of the nano-conductive material, and other components such as the copolymer are dispersed or dissolved, and the components other than the nano-conductive material are dissolved. It is more preferable that It is preferable that components other than the nano-conductive material are in a dissolved state because an effect of suppressing the decrease in conductivity due to the grain boundary can be obtained.
  • the dispersed state is an aggregate state of molecules having a particle size that does not settle in a solvent even when stored for a long time (generally 1 month or longer), and a dissolved state is in a solvent.
  • each component may be prepared by stirring, shaking, kneading, dissolving or dispersing in a solvent. Sonication may be performed to promote dissolution and dispersion.
  • the dispersibility of the nano-conductive material is increased by heating the solvent to a temperature not lower than the room temperature and not higher than the boiling point, extending the dispersion time, or increasing the applied strength of stirring, soaking, kneading, ultrasonic waves, etc. Can be increased.
  • thermoelectric conversion material of the present invention thus prepared preferably has a moisture content of 0.01% by mass or more and 15% by mass or less.
  • thermoelectric conversion material containing the above-described copolymer and nanoconductive material as essential components when the moisture content is in the above range, high thermoelectric conversion performance can be obtained while maintaining excellent coatability and film formability. Can do. Further, even when the thermoelectric conversion material is used under high temperature conditions, corrosion of the electrode and decomposition of the material itself can be suppressed. Since thermoelectric conversion materials are used in a high temperature state for a long time, there is a problem that electrode corrosion or decomposition reaction of the material itself is likely to occur due to the influence of moisture in the thermoelectric conversion material. By doing so, various problems caused by moisture in the thermoelectric conversion material can be improved.
  • the moisture content of the thermoelectric conversion material is more preferably 0.01% by mass or more and 10% by mass or less, and further preferably 0.1% by mass or more and 5% by mass or less.
  • the moisture content of the thermoelectric conversion material can be evaluated by measuring the equilibrium moisture content at a constant temperature and humidity. The equilibrium moisture content was allowed to stand for 6 hours at 25 ° C. and 60% RH, and then reached equilibrium, and then Karl Fischer was used with a moisture meter and a sample dryer (CA-03, VA-05, both Mitsubishi Chemical Corporation). The water content (g) can be calculated by dividing the moisture content (g) by the sample weight (g).
  • the moisture content of the thermoelectric conversion material is determined by leaving the thermoelectric conversion material in a constant temperature and humidity chamber (temperature 25 ° C., humidity 85% RH) (in the case of improving the moisture content) or in a vacuum dryer (temperature 25 ° C.). It can control by making it dry (when water content is reduced). Further, when preparing the thermoelectric conversion material, a necessary amount of water is added to the solvent (in order to improve the water content), or a dehydrating solvent (for example, various dehydrating solvents manufactured by Wako Pure Chemical Industries, Ltd.) can be mentioned. The water content can also be controlled by mixing each component (when reducing the water content) in a glove box under a nitrogen atmosphere using.
  • thermoelectric conversion element has a first electrode, a thermoelectric conversion layer, and a second electrode on a substrate, and the thermoelectric conversion layer is represented by the nano-conductive material and the general formula (1) described above. Containing a copolymer.
  • thermoelectric conversion element of this invention should just have a 1st electrode, a thermoelectric conversion layer, and a 2nd electrode on a base material, The position of a 1st electrode, a 2nd electrode, and a thermoelectric conversion layer There are no particular limitations on other configurations such as relationships.
  • the thermoelectric conversion layer may be disposed on at least one surface thereof so as to be in contact with the first electrode and the second electrode.
  • the thermoelectric conversion layer is sandwiched between the first electrode and the second electrode, that is, the thermoelectric conversion element of the present invention has the first electrode, the thermoelectric conversion layer, and the second electrode in this order on the base material. It may be an embodiment.
  • thermoelectric conversion layer is disposed on one surface thereof so as to be in contact with the first electrode and the second electrode, that is, the thermoelectric conversion element of the present invention is formed on the substrate so as to be separated from each other.
  • stacked on the 1st electrode and the 2nd electrode may be sufficient.
  • the structure of the thermoelectric conversion element of the present invention the structure of the element shown in FIGS. 1 and 2, the arrows indicate the direction of temperature difference when the thermoelectric conversion element is used.
  • the thermoelectric conversion element 1 shown in FIG. 1 includes a pair of electrodes including a first electrode 13 and a second electrode 15 on a first base 12, and the thermoelectric conversion material of the present invention between the electrodes 13 and 15.
  • thermoelectric conversion layer 14 formed by is provided.
  • a second base material 16 is disposed on the other surface of the second electrode 15, and the metal plates 11 and 17 face each other outside the first base material 12 and the second base material 16. Is arranged.
  • the thermoelectric conversion element of the present invention it is preferable to provide a thermoelectric conversion layer in the form of a film (film) with the thermoelectric conversion material of the present invention on the base material via an electrode, and this base material functions as the first base material. . That is, the thermoelectric conversion element 1 is provided with the first electrode 13 or the second electrode 15 on the surface of the two base materials 12 and 16 (formation surface of the thermoelectric conversion layer 14), and between these electrodes 13 and 15. It is preferable that the structure has a thermoelectric conversion layer 14 formed of the thermoelectric conversion material of the present invention.
  • thermoelectric conversion element 2 shown in FIG. 2 is provided with a first electrode 23 and a second electrode 25 on a first base material 22, and a thermoelectric conversion formed on the thermoelectric conversion material of the present invention on the first electrode 23 and the second electrode 25.
  • a layer 24 is provided.
  • thermoelectric conversion layer 14 of the thermoelectric conversion element 1 is covered with the first base material 12 via the first electrode 13.
  • the second base material 16 is preferably pressure-bonded to the other surface.
  • the second electrode 15 is preferably interposed between the thermoelectric conversion layer 14 and the base material 16.
  • One surface of the thermoelectric conversion layer 24 of the thermoelectric conversion element 2 is covered with the first electrode 23, the second electrode 25, and the first base material 22.
  • the second base material 26 is pressure-bonded also to the other surface. That is, it is preferable that the second electrode 15 is formed in advance on the surface of the second base material 16 used for the thermoelectric conversion element 1 (the pressure contact surface of the thermoelectric conversion layer 14).
  • the pressure bonding between the electrode and the thermoelectric conversion layer is preferably performed by heating to about 100 ° C. to 200 ° C. from the viewpoint of improving adhesion.
  • the base material of the thermoelectric conversion element of the present invention, and the first base material 12 and the second base material 16 in the thermoelectric conversion element 1 may be a base material such as glass, transparent ceramics, metal, or plastic film.
  • the base material has flexibility. Specifically, the flexibility in which the number of bending resistances MIT according to the measurement method specified in ASTM D2176 is 10,000 cycles or more. It is preferable to have.
  • the substrate having such flexibility is preferably a plastic film.
  • polyethylene terephthalate polyethylene isophthalate, polyethylene naphthalate, polybutylene terephthalate, poly (1,4-cyclohexylenedimethylene terephthalate), Polyethylene film such as polyethylene-2,6-phthalenedicarboxylate, polyester film of bisphenol A, iso and terephthalic acid, ZEONOR film (trade name, manufactured by ZEON Corporation), ARTON film (trade name, manufactured by JSR Corporation), Sumilite Polycycloolefin films such as FS1700 (trade name, manufactured by Sumitomo Bakelite), Kapton (trade name, manufactured by Toray DuPont), Apical (trade name, manufactured by Kaneka), Upilex (trade name, Ube Ko) Polyimide films such as Pomilan (trade name, manufactured by Arakawa Chemical Co., Ltd.), polycarbonate films such as Pure Ace (trade name, manufactured by Teijin Kasei Co., Ltd.), Elmec (trade name, manufactured by Kaneka Corporation), Sumilite
  • polyethylene terephthalate polyethylene naphthalate
  • various polyimides polycarbonate films, and the like are preferable from the viewpoints of availability, preferably heat resistance of 100 ° C. or higher, economy, and effects.
  • a base material in which an electrode is provided on the pressure contact surface with the thermoelectric conversion layer.
  • electrode materials for forming the first electrode and the second electrode provided on the base material transparent electrodes such as ITO and ZnO, metal electrodes such as silver, copper, gold and aluminum, and carbon materials such as CNT and graphene
  • An organic material such as PEDOT / PSS, a conductive paste in which conductive fine particles such as silver and carbon are dispersed, and a conductive paste containing metal nanowires such as silver, copper, and aluminum can be used.
  • aluminum, gold, silver or copper is preferable.
  • thermoelectric conversion element 1 is configured in the order of the base material 11, the first electrode 13, the thermoelectric conversion layer 14, and the second electrode 15, and the second base material is disposed outside the second electrode 15. Even if 16 adjoins, the 2nd electrode 15 may be exposed to air as the outermost surface, without providing the 2nd substrate 16.
  • the thermoelectric conversion element 2 includes a base material 22, a first electrode 23, a second electrode 25, and a thermoelectric conversion layer 24 in this order.
  • a second base material 26 is disposed outside the thermoelectric conversion layer 24. Even if it adjoins, the thermoelectric conversion layer 24 may be exposed to air as the outermost surface, without providing the 2nd base material 26.
  • the thickness of the substrate is preferably from 30 to 3000 ⁇ m, more preferably from 50 to 1000 ⁇ m, still more preferably from 100 to 1000 ⁇ m, particularly preferably from 200 to 800 ⁇ m from the viewpoints of handleability and durability. If the substrate is too thick, the thermal conductivity may decrease, and if it is too thin, the film may be easily damaged by external impact.
  • thermoelectric conversion layer of the thermoelectric conversion element of the present invention is preferably formed of the thermoelectric conversion material of the present invention, and in addition to these, preferably contains at least one of the non-conjugated polymer and the thermal excitation assist agent described above, A dopant or a decomposition product thereof, a metal element, and other components may be contained. These components and contents in the thermoelectric conversion layer are as described above.
  • the layer thickness of the thermoelectric conversion layer is preferably 0.1 to 1000 ⁇ m, more preferably 1 to 100 ⁇ m. If the layer thickness is thin, it is not preferable because it is difficult to provide a temperature difference and the resistance in the layer increases.
  • a thermoelectric conversion element can be easily produced as compared with a photoelectric conversion element such as an organic thin film solar cell element.
  • the thermoelectric conversion material of the present invention when used, it is not necessary to consider the light absorption efficiency as compared with the element for an organic thin film solar cell, so that the film thickness can be increased by about 100 to 1000 times. Chemical stability against moisture is improved.
  • the thermoelectric conversion layer preferably has a moisture content of 0.01% by mass to 15% by mass.
  • the moisture content of the thermoelectric conversion layer is more preferably 0.01% by mass or more and 10% by mass or less, and further preferably 0.1% by mass or more and 5% by mass or less.
  • the moisture content of the thermoelectric conversion layer can be evaluated by measuring the equilibrium moisture content at a constant temperature and humidity. The equilibrium moisture content was allowed to stand for 6 hours at 25 ° C.
  • thermoelectric conversion layer is not particularly limited.
  • spin coating, extrusion die coating, blade coating, bar coating, screen printing, stencil printing, roll coating, curtain coating, spray coating, dip coating, and the like are known.
  • a coating method can be used.
  • screen printing is particularly preferable from the viewpoint of excellent adhesion of the thermoelectric conversion layer to the electrode.
  • a drying process is performed as necessary.
  • the solvent can be volatilized and dried by spraying with heat and hot air.
  • the moisture content control process is preferably performed after the thermoelectric conversion material is formed into a film and before or after doping by applying energy, which will be described later, and more preferably before doping.
  • energy which will be described later
  • each component of the nano-conductive material and copolymer is mixed and dispersed in a solvent, and the mixture is molded, formed into a film, etc., and then subjected to a moisture content control treatment to obtain a moisture content within the above range.
  • the moisture content control process can employ the above-mentioned method as appropriate.
  • the moisture content control process is a method for controlling the moisture content of the thermoelectric conversion material of the present invention.
  • the applied thermoelectric conversion material of the present invention is dried in a vacuum dryer (temperature 25 ° C.) (when the moisture content is reduced). The method of making it preferable is.
  • thermoelectric conversion material contains the above-described onium salt compound as a dopant
  • the film is irradiated or heated to perform doping treatment to improve conductivity. It is preferable to make it.
  • an acid is generated from the onium salt compound, and this acid protonates the above-described copolymer, thereby doping the copolymer with a positive charge (p-type doping).
  • Active energy rays include radiation and electromagnetic waves, and radiation includes particle beams (high-speed particle beams) and electromagnetic radiation.
  • Particle rays include alpha rays ( ⁇ rays), beta rays ( ⁇ rays), proton rays, electron rays (which accelerates electrons with an accelerator regardless of nuclear decay), charged particle rays such as deuteron rays,
  • Examples of the electromagnetic radiation include gamma rays ( ⁇ rays) and X-rays (X rays, soft X rays).
  • Examples of the electromagnetic wave include radio waves, infrared rays, visible rays, ultraviolet rays (near ultraviolet rays, far ultraviolet rays, extreme ultraviolet rays), X-rays, gamma rays, and the like.
  • the line type used in the present invention is not particularly limited.
  • an electromagnetic wave having a wavelength near the maximum absorption wavelength of the onium salt compound (acid generator) to be used may be appropriately selected.
  • active energy rays ultraviolet rays, visible rays, and infrared rays are preferable from the viewpoint of doping effect and safety, and specifically, the maximum is 240 to 1100 nm, preferably 240 to 850 nm, more preferably 240 to 670 nm. It is a light beam having an emission wavelength.
  • Radiation or an electromagnetic wave irradiation device is used for irradiation with active energy rays.
  • the wavelength of the radiation or electromagnetic wave to be irradiated is not particularly limited, and a radiation or electromagnetic wave in a wavelength region corresponding to the sensitive wavelength of the onium salt compound to be used may be selected.
  • Equipment that can irradiate radiation or electromagnetic waves includes LED lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, deep UV lamps, low-pressure UV lamps and other mercury lamps, halide lamps, xenon flash lamps, metal halide lamps, ArF excimer lamps, and KrF excimer lamps.
  • UV irradiation can be performed using a normal ultraviolet irradiation apparatus, for example, a commercially available ultraviolet irradiation apparatus for curing / adhesion / exposure (USHIO INC. SP9-250UB, etc.).
  • the exposure time and the amount of light may be appropriately selected in consideration of the type of onium salt compound to be used and the doping effect.
  • the light intensity is 10 mJ / cm 2 to 10 J / cm 2 , preferably 50 mJ / cm 2 to 5 J / cm 2 .
  • the formed film When doping is performed by heating, the formed film may be heated above the temperature at which the onium salt compound generates an acid.
  • the heating temperature is preferably 50 to 200 ° C, more preferably 70 to 150 ° C.
  • the heating time is preferably 1 to 60 minutes, more preferably 3 to 30 minutes.
  • timing of the doping treatment is not particularly limited, it is preferably performed after the thermoelectric conversion material of the present invention is processed, such as film formation.
  • thermoelectric conversion layer also referred to as thermoelectric conversion film
  • thermoelectric conversion material of the present invention has a high thermoelectric conversion performance index ZT, excellent initial thermoelectric conversion performance, and high temperature and high temperature. Even in a severe environment such as humidity, the thermoelectric conversion performance is stable over time and high initial thermoelectric conversion performance can be maintained over a long period of time. Therefore, the thermoelectric conversion element of the present invention can be suitably used as a power generation element of an article for thermoelectric power generation.
  • power generation elements include power generators such as hot spring thermal generators, solar thermal generators, waste heat generators, wristwatch power supplies, semiconductor drive power supplies, (small) sensor power supplies, and the like.
  • thermoelectric conversion material of the present invention and the thermoelectric conversion layer formed of the thermoelectric conversion material of the present invention are suitably used as the thermoelectric conversion element, thermoelectric power generation element material, thermoelectric power generation film, or various conductive films of the present invention. Specifically, it is suitably used as the above-described thermoelectric conversion material for a power generation element or a film for thermoelectric power generation.
  • Copolymers 1 to 7 and homopolymers 1 to 4 were synthesized as follows using the following monomers as aniline derivatives or pyrrole derivatives.
  • Synthesis Example 1 (Synthesis of Copolymer 1) The monomer 1 (1 mmol) and the monomer 2 (99 mmol) were dissolved in 100 mL of a toluene / butyl acetate mixed solvent (volume ratio 80/20) to prepare an aniline derivative solution 1.
  • a toluene / butyl acetate mixed solvent volume ratio 80/20
  • FeCl 3 300 mmol was dissolved in 250 mL of a toluene / butyl acetate mixed solvent (volume ratio 80/20) and filtered through a reactor equipped with a thermometer, a stirrer, and an air introduction tube to remove insoluble matters. Prepared.
  • the aniline derivative solution 1 was dropped from the dropping funnel and reacted at a reaction temperature of 25 ⁇ 5 ° C. for 5 hours. After the reaction, methanol was added to stop the reaction. The following copolymer 1 was obtained by filtering, washing and neutralizing the reaction slurry. The weight average molecular weight of this copolymer 1 was 25,000. This molecular weight was determined by GPC measurement using a mixed solution of dimethylformamide and tetrahydrofuran as a solvent and polystyrene as a standard sample. The following molecular weights were determined in the same manner.
  • Synthesis Example 2 (Synthesis of Copolymer 2) Instead of the aniline derivative solution 1, the aniline derivative solution 2 prepared by dissolving the monomer 1 (99 mmol) and the monomer 2 (1 mmol) in 100 mL of a toluene / butyl acetate mixed solvent (volume ratio 80/20) was used. The following copolymer 2 was obtained in the same manner as in Synthesis Example 1. The weight average molecular weight of this copolymer 2 was 35,000.
  • Synthesis Example 3 (Synthesis of Copolymer 3) Instead of the aniline derivative solution 1, the aniline derivative solution 3 prepared by dissolving the monomer 3 (50 mmol) and the monomer 4 (50 mmol) in 100 mL of a toluene / butyl acetate mixed solvent (volume ratio 80/20) was used. Produced the following copolymer 3 in the same manner as in Synthesis Example 1. The weight average molecular weight of this copolymer 3 was 27,000.
  • Synthesis Example 4 (Synthesis of Copolymer 4) Instead of aniline derivative solution 1, pyrrole derivative solution 1 prepared by dissolving monomer 5 (75 mmol) and monomer 6 (25 mmol) in 100 mL of a toluene / butyl acetate mixed solvent (volume ratio 80/20) was used. The following copolymer 4 was obtained in the same manner as in Synthesis Example 1. The weight average molecular weight of this copolymer 4 was 38,000.
  • Synthesis Example 5 (Synthesis of Copolymer 5) Instead of aniline derivative solution 1, pyrrole derivative solution 2 prepared by dissolving monomer 5 (25 mmol) and monomer 7 (75 mmol) in 100 mL of a toluene / butyl acetate mixed solvent (volume ratio 80/20) was used. The following copolymer 5 was obtained in the same manner as in Synthesis Example 1. The weight average molecular weight of this copolymer 5 was 33,000.
  • Synthesis Example 6 (Synthesis of copolymer 6) Instead of the aniline derivative solution 1, the pyrrole derivative solution 3 prepared by dissolving the monomer 8 (75 mmol) and the monomer 9 (25 mmol) in 100 mL of a toluene / butyl acetate mixed solvent (volume ratio 80/20) was used. Produced the following copolymer 6 in the same manner as in Synthesis Example 1. The weight average molecular weight of this copolymer 6 was 31,000.
  • Synthesis Example 7 (Synthesis of Copolymer 7) Under a nitrogen atmosphere, the monomer 10 (50 mmol) and the monomer 11 (50 mmol) were mixed with Pd 2 dba 3 (1 mmol), tris (o-tolyl) phosphine (4 mmol), 20% by mass tetraethylammonium hydroxide (0.5 mL). In addition, the mixture was heated to reflux in toluene for 5 hours. After the reaction, 300 mL of methanol was added to stop the reaction. By filtering, washing, neutralizing, and deprotecting the reaction slurry, the following copolymer 7 was obtained. The weight average molecular weight of this copolymer 7 was 12,000.
  • Example 1 [Tape peeling test] 4 mg of copolymer 1, 3 mg of single-walled CNT (ASP-100F, manufactured by Hanwha Nanotech, dispersion (CNT concentration 60% by mass), CNT average length 10 ⁇ m, diameter 1.1 nm) and 2 mg of dopant shown below, It was added to 4.0 mL of orthodichlorobenzene and dispersed in an ultrasonic water bath for 70 minutes. This dispersion was applied as a bar to the electrode surface of a polyethylene terephthalate film (thickness: 125 ⁇ m) having gold (thickness 20 nm, length 1 cm, width: 1 cm) as an electrode on one side surface, and heated to 80 ° C.
  • ASP-100F single-walled CNT
  • ASP-100F single-walled CNT
  • dopant shown below
  • thermoelectric conversion layer 101 as the thermoelectric conversion layer 14 was formed into a film by making it dry under vacuum of 80 degreeC for 8 hours.
  • the polyethylene terephthalate film used in Example 1 had the flexibility that the number of bending resistances MIT by the measurement method specified in the above-mentioned ASTM D2176 was 50,000 cycles or more.
  • thermoelectric conversion layers 102 to 111 and the comparative thermoelectric conversion layers c101 to c104 are the same as the thermoelectric conversion layer 101 except that the type of copolymer, the presence or absence of dopant, and / or the type of solvent are changed as shown in Table 1. Was deposited.
  • thermoelectric conversion layers 101 to 111 (excluding 108) and c101 to c104 produced as described above were dried, and then irradiated with ultraviolet rays using an ultraviolet irradiation machine (ECS-401GX, manufactured by Eye Graphics Co., Ltd.). (Light amount: 1.06 J / cm 2 ) was doped. Then, apply a scotch tape (trade name, manufactured by Sumitomo 3M Co., Ltd.) to the surface of the thermoelectric conversion layer so that bubbles do not enter the surface of the thermoelectric conversion layer, peel off the scotch tape vigorously, and perform a peel test. It was. The peel test was evaluated in five stages according to the peel area of the thermoelectric conversion layer.
  • ECS-401GX ultraviolet irradiation machine
  • thermoelectric conversion layer when the thermoelectric conversion layer was not peeled at all, B when the area was peeled off more than 0% and 25% or less, and C and 75% when the area was peeled more than 25% and 75% or less.
  • D the case where it exceeded and less than 100% peeled
  • E the case where it peeled the whole surface
  • thermoelectric of the present invention comprising a polyaniline copolymer having two types of copolymer units derived from aniline or pyrrole, copolymers 1 to 7 containing a polypyrrole copolymer, and CNTs. All the thermoelectric conversion layers 101 to 111 formed of the conversion material had high adhesion to the first electrode 12. This is highly dispersed even in the presence of carbon nanotubes, which are suitable nano-conductive materials for polyaniline copolymers and polypyrrole copolymers having two types of copolymer units derived from aniline or pyrrole.
  • thermoelectric conversion layer containing these polyaniline copolymer and polypyrrole copolymer and carbon nanotubes exhibited high electrode adhesion.
  • thermoelectric conversion layers 101 and 108 to 110 formed of the thermoelectric conversion material of the present invention using the copolymer 1 and a halogen-based solvent have an evaluation result of the tape peeling test of A, and the copolymer 1 and tetrahydrofuran are used. It was superior to the evaluation result B of the thermoelectric conversion layer 111 formed of the thermoelectric conversion material of the present invention, and had high adhesion.
  • Example 2 [Measurement of Thermoelectric Characteristics (Thermoelectric Power S)] 4 mg of the copolymer 1, 3 mg of single-walled CNT (ASP-100F, manufactured by Hanwha Nanotech) and 2 mg of the above-mentioned dopant were added to 4.0 mL of orthodichlorobenzene and dispersed in an ultrasonic water bath for 70 minutes. This dispersion was used as a first electrode 12 (thickness 20 nm, length 1 cm, width: 1 cm) on a surface of the electrode 12 of a base material 11 made of a polyethylene terephthalate film (thickness: 125 ⁇ m) having gold on one surface. After removing the solvent by heating at 80 ° C.
  • thermoelectric conversion layer 14 was formed by making it dry under a 80 degreeC vacuum for 8 hours. After drying, the thermoelectric conversion layer 14 was doped by irradiating with ultraviolet rays (light quantity: 1.06 J / cm 2 ) with an ultraviolet irradiator (ECS-401GX, manufactured by Eye Graphics Co., Ltd.). Thereafter, a base material 16 made of a polyethylene terephthalate film (thickness: 125 ⁇ m) on which gold is vapor-deposited as a second electrode 15 (thickness 20 nm, length 1 cm, width: 1 cm) is formed on the thermoelectric conversion layer 14.
  • the thermoelectric conversion element 201 of the present invention which is the thermoelectric conversion element 1 shown in FIG.
  • Example 1 was manufactured by bonding at 80 ° C. so that the electrode 15 was opposed to the thermoelectric conversion layer 14.
  • the polyethylene terephthalate film used in Example 2 had the flexibility that the number of bending resistances MIT according to the measurement method specified in ASTM D2176 was 50,000 cycles or more.
  • thermoelectric conversion elements 202 to 211 of the present invention and the comparative thermoelectrics were compared in the same manner as the thermoelectric conversion element 201 except that the type or presence of the copolymer, the presence or absence of the dopant, and / or the type of solvent were changed as shown in Table 2. Conversion elements c201 to c205 were produced. In addition, when the dopant is not used, the doping process by the above-mentioned ultraviolet irradiation is not implemented.
  • thermoelectromotive force also referred to as thermoelectric characteristics
  • thermoelectric characteristics also referred to as thermoelectric characteristics
  • the first electrode 13 of the thermoelectric conversion element was placed on a hot plate maintained at a constant temperature, and a temperature control Peltier element was placed on the second electrode 15. While maintaining the temperature of the hot plate constant (100 ° C.), the temperature of the Peltier element was lowered to give a temperature difference (over 0K to 10K or less) between both electrodes.
  • thermoelectromotive force S ( ⁇ V / K) per unit temperature difference is obtained by dividing the thermoelectromotive force ( ⁇ V) generated between both electrodes by the specific temperature difference (K) generated between both electrodes. This value was calculated as the thermoelectric characteristic value of the thermoelectric conversion element.
  • the calculated thermoelectric characteristic values are shown in Table 2 as relative values to the calculated values of the comparative thermoelectric conversion element c205 (the calculated value of the thermoelectric conversion element c205 is set to “50”).
  • thermoelectric of the present invention comprising a polyaniline copolymer having two types of copolymer units derived from aniline or pyrrole, copolymers 1 to 7 containing a polypyrrole copolymer, and CNTs.
  • Each of the conversion elements 201 to 211 exhibited high thermoelectric conversion performance. The reason is considered to be that the copolymers 1 to 7 are highly dispersed even in the presence of suitable carbon nanotubes as described in Example 1.
  • thermoelectric conversion elements 201 and 208 to 210 of the present invention using the copolymer 1 and the halogen-based solvent have higher thermoelectric conversion performance than the thermoelectric conversion elements 211 of the present invention using the copolymer 1 and tetrahydrofuran.
  • thermoelectric conversion elements c201, c203, and c204 were inferior in thermoelectric characteristics.
  • the homopolymer 2 was dissolved in orthodichlorobenzene, the influence of the hydrophobic substituent was great, and the thermoelectric conversion element c202 was inferior in thermoelectric characteristics.
  • Example 3 [Addition of metal element] Copolymer 1 4 mg, single-walled CNT (ASP-100F, manufactured by Hanwha Nanotech) 3 mg, and palladium chloride at an addition amount shown in Table 3 were added to 4.0 mL of orthodichlorobenzene, and the mixture was added 70 in an ultrasonic water bath. Dispersed for minutes. This dispersion was used as a first electrode 12 (thickness 20 nm, length 1 cm, width: 1 cm) on the surface of the electrode 12 of a base material 11 made of a polyethylene terephthalate film (thickness: 125 ⁇ m) having gold on one surface. After removing the solvent by heating at 80 ° C. for 80 minutes.
  • thermoelectric conversion layer 14 was formed by making it dry under a 80 degreeC vacuum for 8 hours. Thereafter, a base material 16 made of a polyethylene terephthalate film (thickness: 125 ⁇ m) on which gold was vapor-deposited as a second electrode 15 (thickness 20 nm, length 1 cm, width: 1 cm) was formed on the thermoelectric conversion layer 14.
  • the thermoelectric conversion element 301 of the present invention which is the thermoelectric conversion element 1 shown in FIG. 1, was produced by bonding at 80 ° C. so that the electrode 15 faces the thermoelectric conversion layer 14.
  • the polyethylene terephthalate film used in Example 3 had the flexibility that the number of bending resistances MIT by the measurement method specified in the above-mentioned ASTM D2176 was 50,000 cycles or more.
  • thermoelectric conversion elements 302 to 304 of the present invention were produced in the same manner as the thermoelectric conversion element 301 except that the type or addition amount of the metal salt was changed as shown in Table 3.
  • thermoelectric conversion elements 301 to 304 manufactured as described above were measured in the same manner as in Example 2, and the calculated thermoelectric characteristic value was used as a relative value to the calculated value of the comparative thermoelectric conversion element c205. The results are shown in Table 3.
  • thermoelectric conversion elements 301 to 304 of the present invention containing a metal element in addition to the polyaniline copolymer and polypyrrole copolymer having two types of copolymer units derived from aniline or pyrrole, and CNT.
  • the thermoelectric characteristic value was improved with respect to the relative value of the comparative thermoelectric conversion element c205.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne un élément de conversion thermoélectrique comprenant, sur une base, une première électrode, une couche de conversion thermoélectrique et une seconde électrode, et contenant, dans la couche de conversion thermoélectrique, un matériau conducteur à l'échelle nanométrique et un copolymère qui est représenté par la formule générale (1) ; un article destiné à la génération d'énergie thermoélectrique et une alimentation électrique destinée à des capteurs, chacun desquels utilise ledit élément de conversion thermoélectrique ; et un matériau de conversion thermoélectrique qui contient le copolymère susmentionné et un matériau conducteur à l'échelle nanométrique. Dans la formule générale (1), A et B représentent chacun indépendamment un motif copolymère dérivé d'un dérivé d'aniline ou un motif copolymère dérivé d'un dérivé de pyrrole. À cet égard, A et B représentent des motifs copolymères différents l'un de l'autre. FIG. 1: AA%%%Formule générale (1)
PCT/JP2014/051415 2013-01-29 2014-01-23 Matériau de conversion thermoélectrique, élément de conversion thermoélectrique, article de génération d'énergie thermoélectrique utilisant l'élément de conversion thermoélectrique, et alimentation électrique pour des capteurs utilisant l'élément de conversion thermoélectrique Ceased WO2014119468A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013-014114 2013-01-29
JP2013014114A JP2014146681A (ja) 2013-01-29 2013-01-29 熱電変換材料、熱電変換素子並びにこれを用いた熱電発電用物品及びセンサー用電源

Publications (1)

Publication Number Publication Date
WO2014119468A1 true WO2014119468A1 (fr) 2014-08-07

Family

ID=51262182

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/051415 Ceased WO2014119468A1 (fr) 2013-01-29 2014-01-23 Matériau de conversion thermoélectrique, élément de conversion thermoélectrique, article de génération d'énergie thermoélectrique utilisant l'élément de conversion thermoélectrique, et alimentation électrique pour des capteurs utilisant l'élément de conversion thermoélectrique

Country Status (2)

Country Link
JP (1) JP2014146681A (fr)
WO (1) WO2014119468A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020009184A1 (fr) * 2018-07-05 2020-01-09 日産化学株式会社 Composition permettant de former un film mince de transport de charge
CN112920758A (zh) * 2021-01-20 2021-06-08 华南理工大学 一种通过苯胺基交联的双组分半导体型胶粘剂及其制备方法与应用
CN113140666A (zh) * 2021-03-30 2021-07-20 武汉工程大学 一种复合热电材料及其制备方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6220984B2 (ja) * 2014-09-08 2017-10-25 富士フイルム株式会社 熱電変換素子、熱電変換層、熱電変換層形成用組成物
JP6980284B2 (ja) * 2016-03-09 2021-12-15 ウェイク フォレスト ユニバーシティ 熱電圧電発電機
JPWO2020255898A1 (fr) * 2019-06-20 2020-12-24

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010095688A (ja) * 2008-10-20 2010-04-30 Three M Innovative Properties Co 導電性高分子複合体及び導電性高分子材料を用いた熱電素子
JP2012009462A (ja) * 2009-09-14 2012-01-12 Tokyo Univ Of Science 有機−無機ハイブリッド熱電材料、当該熱電材料を用いた熱電変換素子及び有機−無機ハイブリッド熱電材料の製造方法
WO2012054504A2 (fr) * 2010-10-18 2012-04-26 Wake Forest University Appareil thermoélectrique et ses applications
JP2012251132A (ja) * 2011-03-28 2012-12-20 Fujifilm Corp 導電性組成物、当該組成物を用いた導電性膜及びその製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010095688A (ja) * 2008-10-20 2010-04-30 Three M Innovative Properties Co 導電性高分子複合体及び導電性高分子材料を用いた熱電素子
JP2012009462A (ja) * 2009-09-14 2012-01-12 Tokyo Univ Of Science 有機−無機ハイブリッド熱電材料、当該熱電材料を用いた熱電変換素子及び有機−無機ハイブリッド熱電材料の製造方法
WO2012054504A2 (fr) * 2010-10-18 2012-04-26 Wake Forest University Appareil thermoélectrique et ses applications
JP2012251132A (ja) * 2011-03-28 2012-12-20 Fujifilm Corp 導電性組成物、当該組成物を用いた導電性膜及びその製造方法

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020009184A1 (fr) * 2018-07-05 2020-01-09 日産化学株式会社 Composition permettant de former un film mince de transport de charge
CN112920758A (zh) * 2021-01-20 2021-06-08 华南理工大学 一种通过苯胺基交联的双组分半导体型胶粘剂及其制备方法与应用
CN112920758B (zh) * 2021-01-20 2022-06-14 华南理工大学 一种通过苯胺基交联的双组分半导体型胶粘剂及其制备方法与应用
CN113140666A (zh) * 2021-03-30 2021-07-20 武汉工程大学 一种复合热电材料及其制备方法
CN113140666B (zh) * 2021-03-30 2023-09-26 武汉工程大学 一种复合热电材料及其制备方法

Also Published As

Publication number Publication date
JP2014146681A (ja) 2014-08-14

Similar Documents

Publication Publication Date Title
TWI619275B (zh) 熱電轉換元件的製造方法及熱電轉換層用分散物的製造方法
JP5951539B2 (ja) 熱電変換材料、熱電変換素子ならびにこれを用いた熱電発電用物品およびセンサー用電源
JP5789580B2 (ja) 熱電変換材料及び熱電変換素子
JP5976604B2 (ja) 熱電変換材料、熱電変換素子、熱電発電用物品及びセンサー用電源
JP5848284B2 (ja) 熱電変換素子及びこれを用いた熱電変換材料
JP6047468B2 (ja) 熱電変換材料、熱電変換素子、熱電発電用物品およびセンサー用電源
JP6110818B2 (ja) 熱電変換材料、熱電変換素子ならびにこれを用いた熱電発電用物品およびセンサー用電源
WO2013047730A1 (fr) Matériau de conversion thermoélectrique et élément de conversion thermoélectrique
JP2013098299A (ja) 熱電変換材料及び熱電変換素子
WO2014119468A1 (fr) Matériau de conversion thermoélectrique, élément de conversion thermoélectrique, article de génération d'énergie thermoélectrique utilisant l'élément de conversion thermoélectrique, et alimentation électrique pour des capteurs utilisant l'élément de conversion thermoélectrique
JP5931764B2 (ja) 熱電変換材料、熱電変換素子並びにこれを用いた熱電発電用物品及びセンサー用電源
JP6698565B2 (ja) 熱電変換層、熱電変換素子、熱電変換モジュール
JP5931763B2 (ja) 熱電変換材料、熱電変換素子並びにこれを用いた熱電発電用物品及びセンサー用電源
JP5931762B2 (ja) 熱電変換材料、熱電変換素子並びにこれを用いた熱電発電用物品及びセンサー用電源
WO2014178284A1 (fr) Matériau de conversion thermoélectrique, élément de conversion thermoélectrique, article pour la génération de puissance thermoélectrique, et alimentation électrique pour capteurs
WO2015050114A1 (fr) Matériau de conversion thermoélectrique, élément de conversion thermoélectrique et procédé de fabrication d'un élément de conversion thermoélectrique

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14746803

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14746803

Country of ref document: EP

Kind code of ref document: A1