WO2014119469A1 - 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 - Google Patents

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 Download PDF

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WO2014119469A1
WO2014119469A1 PCT/JP2014/051416 JP2014051416W WO2014119469A1 WO 2014119469 A1 WO2014119469 A1 WO 2014119469A1 JP 2014051416 W JP2014051416 W JP 2014051416W WO 2014119469 A1 WO2014119469 A1 WO 2014119469A1
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thermoelectric conversion
group
conversion element
ring
aromatic hydrocarbon
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PCT/JP2014/051416
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English (en)
French (fr)
Japanese (ja)
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西尾　亮
野村　公篤
丸山　陽一
林　直之
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富士フイルム株式会社
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Priority to CN201480004536.9A priority Critical patent/CN104919609B/zh
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    • H10N10/851—Thermoelectric active materials comprising inorganic compositions
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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.
  • a thermoelectric conversion element (see Patent Document 1) made of a conductive polymer obtained by doping polyphenylene vinylene is representative.
  • a polymer having a fluorene skeleton is known as a binder resin for various molded products (see, for example, Patent Document 2), but is simply a resin for processing a molded product or a binder resin, not a conductive polymer.
  • thermoelectric conversion performance in order to increase the figure of merit ZT from the relational expression of the figure of merit ZT of thermoelectric conversion performance, a material having a low thermal conductivity is required by increasing the Seebeck coefficient and conductivity of the conductive material.
  • a material having a low thermal conductivity is required by increasing the Seebeck coefficient and conductivity of the conductive material.
  • two types of electrically different conductors or semiconductors are used, and practically, the internal resistance as a module through which current flows in actual thermoelectric conversion is lowered.
  • the conductive substance a conjugated bond polymer material and a nano conductive material (a nanometer-sized conductive material) are excellent.
  • thermoelectric conversion layer when producing a thermoelectric conversion layer, if such a nano-conductive material is dispersed as it is in a polymer material such as a thermoelectric conversion layer, it is agglomerated into bundles or particles due to its strong intermolecular force. End up. In order to exhibit high electrical conductivity, it is necessary to eliminate this aggregation and disperse the conductive material in the polymer material at the nano level. In addition, when a dispersing agent is used, the dispersing agent remains in the polymer material, and the voltage generation capability decreases.
  • the present invention provides a thermoelectric conversion material having excellent dispersibility of the nano-conductive material and excellent thermoelectric conversion performance, a thermoelectric conversion element having a thermoelectric conversion layer excellent in thermoelectric conversion performance, and the thermoelectric conversion element. It is an object of the present invention to provide a thermoelectric power generation article and a sensor power source.
  • the present inventors have investigated various conductive polymers as conductive substances that coexist with the nanoconductive material in the thermoelectric conversion layer of the thermoelectric conversion element. As a result, the inventors have developed a specific fluorene structure together with the nanoconductive material. It has been found that a polymer having a repetitive structure can enhance the dispersibility of a nanoconductive material and exhibit excellent thermoelectric conversion performance. 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 includes a nano-conductive material and the following general formula (1A) or ( A thermoelectric conversion element containing a polymer containing at least the fluorene structure represented by 1B) as a repeating structure.
  • R 11 and R 12 each independently represent a substituent.
  • R 13 and R 14 each independently represents an aromatic hydrocarbon ring group, an aromatic heterocyclic group, an alkyl group or an alkoxy group.
  • R 13 and R 14 may be bonded to each other to form a ring.
  • n11 and n12b each independently represents an integer of 0 to 3, and n12 represents an integer of 0 to 2.
  • L a represents a single bond, -N (Ra) - or a divalent aromatic hydrocarbon ring group, a divalent aromatic heterocyclic group, and -N (Ra) - combining a group selected from the group consisting of Represents a linking group.
  • L b represents a single bond, a divalent aromatic hydrocarbon ring group, a divalent aromatic heterocyclic group, —N (Ra) —, or a linking group obtained by combining these groups.
  • Ra represents a substituent.
  • X b represents a trivalent aromatic hydrocarbon ring group, a trivalent aromatic heterocyclic group or> N—. * Represents a bonding position.
  • L a is a linking group represented by the following formula (a) or (b), ⁇ 1> The thermoelectric conversion element according to claim.
  • X a0 represents a single bond, a divalent aromatic hydrocarbon ring group or a divalent aromatic heterocyclic group
  • X a1 and X a2 each independently represent a divalent aromatic hydrocarbon ring group or 2 Represents a valent aromatic heterocyclic group
  • R a0 represents a substituent
  • n a0 represents an integer of 0 to 5.
  • the atom of Xb to which the 2-position of the fluorene ring is bonded is a carbon atom forming an aromatic hydrocarbon ring, a carbon atom forming an aromatic heterocycle or a nitrogen atom, or Xb is> N
  • thermoelectric conversion element according to any one of ⁇ 1> to ⁇ 3>, wherein at least one of R 13 and R 14 is an aromatic hydrocarbon ring group or an aromatic heterocyclic group.
  • the nano conductive material is a nano carbon material or a nano metal material.
  • the nanoconductive material is at least one selected from the group consisting of carbon nanotubes, carbon nanofibers, graphite, graphene, carbon nanoparticles, and metal nanowires
  • Item 1 The thermoelectric conversion element according to Item 1.
  • thermoelectric conversion element according to any one of ⁇ 1> to ⁇ 6>, wherein the nanoconductive material is a carbon nanotube.
  • thermoelectric conversion layer contains a dopant.
  • dopant is at least one selected from an onium salt compound, an oxidizing agent, an acidic compound, and an electron acceptor compound.
  • the thermoelectric conversion element as described in ⁇ 8> or ⁇ 9> which contains a ⁇ 10> dopant in the ratio of more than 0 mass part and 60 mass parts or less with respect to 100 mass parts of said polymers.
  • thermoelectric conversion element according to ⁇ 9> or ⁇ 10>, wherein the onium salt compound is a compound that generates an acid upon application of heat or irradiation with active energy rays.
  • the thermoelectric conversion element according to any one of ⁇ 1> to ⁇ 11>, wherein the thermoelectric conversion layer contains a non-conjugated polymer.
  • the non-conjugated polymer is 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 ⁇ 12>.
  • the thermoelectric conversion element according to 12> is a polyvinyl polymer obtained by polymerizing a vinyl compound, poly (meth) acrylate, polycarbonate, polyester, polyamide, polyimide, and polysiloxane ⁇ 12>.
  • thermoelectric conversion element according to any one of ⁇ 1> to ⁇ 13>, wherein the thermoelectric conversion layer contains a thermal excitation assist agent.
  • thermoelectric conversion element according to any one of ⁇ 1> to ⁇ 14>, wherein the moisture content of the thermoelectric conversion layer is 0.01% by mass or more and 15% by mass or less.
  • the base material has flexibility.
  • thermoelectric conversion for forming a thermoelectric conversion layer of a thermoelectric conversion element, comprising ⁇ 20> a nano conductive material and a polymer containing at least a fluorene structure represented by the following general formula (1A) or (1B) as a repeating structure material.
  • R 11 and R 12 each independently represent a substituent.
  • R 13 and R 14 each independently represents an aromatic hydrocarbon ring group, an aromatic heterocyclic group, an alkyl group or an alkoxy group.
  • R 13 and R 14 may be bonded to each other to form a ring.
  • n11 and n12b each independently represents an integer of 0 to 3, and n12 represents an integer of 0 to 2.
  • L a represents a single bond, -N (Ra) - or a divalent aromatic hydrocarbon ring group, a divalent aromatic heterocyclic group, and -N (Ra) - combining a group selected from the group consisting of Represents a linking group.
  • L b represents a single bond, a divalent aromatic hydrocarbon ring group, a divalent aromatic heterocyclic group, —N (Ra) —, or a linking group obtained by combining these groups.
  • Ra represents a substituent.
  • X b represents a trivalent aromatic hydrocarbon ring group, a trivalent aromatic heterocyclic group or> N—. * Represents a bonding position.
  • thermoelectric conversion material according to ⁇ 20> which contains an organic solvent.
  • thermoelectric conversion material according to ⁇ 21> wherein the nanoconductive material is dispersed in an organic solvent.
  • “(meth) acrylate” represents either or both of acrylate and methacrylate, and includes a mixture thereof.
  • 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 repeating structure represented by each formula includes different repeating structures as long as they are within the range represented by the formula, even if they are not exactly the same repeating structure.
  • the repeating structure represented by each formula may be only a repeating structure having a methyl group, and has another alkyl group such as an ethyl group in addition to the repeating structure having a methyl group. It may contain a repeating structure.
  • thermoelectric conversion material of the present invention has good dispersibility of the nano-conductive material and is excellent in thermoelectric conversion performance.
  • the heat conversion element of the present invention, the thermoelectric power generation 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.
  • 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 includes a nano-conductive material and the following general formula (1A) or (1B And a polymer containing at least a fluorene structure represented by the above formula as a repeating structure.
  • This thermoelectric conversion layer is formed on a base material by the thermoelectric conversion material of the present invention containing a nano conductive material and the polymer.
  • 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 of the present invention and the thermoelectric conversion element of the present invention have high thermoelectric conversion performance in which a nano-conductive material is well dispersed and can be used as a thermoelectric conversion material, specifically, heat generation per unit temperature difference. Electric power S is provided.
  • 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 demands on dispersibility and film formability. That is, the thermoelectric conversion material of the present invention is excellent in dispersibility of the nano-conductive material and excellent in applicability and film formability, and is suitable for molding and processing into a thermoelectric conversion layer.
  • 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 has a nanoconductive material and a fluorene structure represented by the following general formula (1A) or (1B).
  • the polymer contains at least a repeating structure.
  • 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 metal having nm that is a multiple of 3 indicates a metallic property
  • a semiconductor that is not a multiple of 3 indicates a semiconductor.
  • 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 any of the above-mentioned metal-formed, particulate or powdered metal fine particles.
  • the metal fine particles and the metal fine particles may have a surface coated with a protective agent. It 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 polymer used in the present invention is a polymer containing at least a fluorene structure represented by the following general formula (1A) or (1B) as a repeating structure (hereinafter sometimes referred to as a conductive polymer).
  • R 11 and R 12 each independently represent a substituent.
  • R 13 and R 14 each independently represents an aromatic hydrocarbon ring group, an aromatic heterocyclic group, an alkyl group or an alkoxy group.
  • R 13 and R 14 may be bonded to each other to form a ring.
  • n11 and n12b each independently represents an integer of 0 to 3, and n12 represents an integer of 0 to 2.
  • L a represents a single bond, -N (Ra) - or a divalent aromatic hydrocarbon ring group, a divalent aromatic heterocyclic group, and -N (Ra) - combining a group selected from the group consisting of Represents a linking group.
  • L b represents a single bond, a divalent aromatic hydrocarbon ring group, a divalent aromatic heterocyclic group, —N (Ra) —, or a linking group obtained by combining these groups.
  • Ra represents a substituent.
  • X b represents a trivalent aromatic hydrocarbon ring group, a trivalent aromatic heterocyclic group or> N—. * Represents a bonding position.
  • Examples of the substituent in R 11 and R 12 include the following substituent W.
  • a halogen atom an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, an arylboron group, a hydroboron group, a heterocyclic group (including a heteroaryl group, and a ring constituent atom)
  • a halogen atom an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, an arylboron group, a hydroboron group, a heterocyclic group (including a heteroaryl group, and a ring constituent atom)
  • an alkoxy group an aryloxy group, an alkylthio group, an arylthio group, an alkyl or aryl sulfonyl group, an alkyl or aryl sulfinyl group
  • an aromatic hydrocarbon ring group, an aromatic heterocyclic group, an alkyl group, an alkoxy group, an alkylthio group, an amino group, and a hydroxyl group are preferable, an aromatic hydrocarbon ring group, an aromatic heterocyclic group, an alkyl group, An alkoxy group and a hydroxyl group are more preferable, an aromatic hydrocarbon ring group, an aromatic heterocyclic group, an alkyl group, and an alkoxy group are more preferable, and an alkyl group is particularly preferable.
  • R 11 and R 12 are alkthio groups
  • the number of carbon atoms is preferably 1 to 24, more preferably 1 to 20, and even more preferably 6 to 16.
  • the alkylthio group may have a substituent, and examples of the substituent include the substituent W.
  • examples of the alkylthio group include methylthio, ethylthio, isopropylthio, t-butylthio, n-hexylthio, n-octylothio, 2-ethylhexylthio, and n-octadecylthio.
  • R 11 and R 12 are an amino group
  • the amino group includes an amino group, an alkylamino group, and an arylamino group, and the number of carbon atoms is preferably 0 to 24, more preferably 1 to 20, and further preferably 1 to 16.
  • the alkyl, aryl, or heterocyclic amino group may have a substituent, and examples of the substituent include the above substituent W.
  • Examples of the amino group include amino, methylamino, N, N-diethylamino, phenylamino, and N-methyl-N-phenylamino, with alkylamino and arylamino groups being preferred.
  • R 11 and R 12 are an aromatic hydrocarbon ring group, an aromatic heterocyclic group, an alkyl group, and an alkoxy group, an aromatic hydrocarbon ring group, an aromatic heterocyclic group, and an alkyl group in R 13 and R 14 described later And an alkoxy group.
  • the preferred carbon number of the alkyl group or alkoxy group is 1-18, more preferably 1-12, and still more preferably 1-8.
  • the preferred ranges of the aromatic hydrocarbon ring group and the aromatic heterocyclic group are the same as those for R 13 and R 14 .
  • N11, n12, and n12b are preferably 0 or 1.
  • the aromatic hydrocarbon ring of the aromatic hydrocarbon ring group for R 13 and R 14 preferably has 6 to 24 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 18 carbon atoms.
  • the aromatic hydrocarbon ring include a benzene ring and a naphthalene ring, and the ring may be condensed with a ring such as an aromatic hydrocarbon ring, an aliphatic hydrocarbon ring, or a hetero ring.
  • the aromatic hydrocarbon ring group may have a substituent, and examples of the substituent include the substituent W.
  • an alkyl group, an alkoxy group, an alkylthio group, an amino group, and a hydroxyl group are preferable, an alkyl group, an alkoxy group, and a hydroxyl group are more preferable, and an alkyl group and an alkoxy group are further preferable.
  • the aromatic heterocyclic ring of the aromatic heterocyclic group for R 13 and R 14 preferably has 2 to 24 carbon atoms, more preferably 3 to 20 carbon atoms, and still more preferably 3 to 18 carbon atoms.
  • the ring-constituting hetero atom is preferably a nitrogen atom, an oxygen atom or a sulfur atom, and preferably a 5- or 6-membered ring.
  • the ring may be condensed with a ring such as an aromatic hydrocarbon ring, an aliphatic hydrocarbon ring or a hetero ring.
  • the aromatic hydrocarbon ring group may have a substituent, and examples of the substituent include the substituent W.
  • Aromatic heterocycles include pyrrole ring, thiophene ring, imidazole ring, pyrazole ring, thiazole ring, isothiazole ring, pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, triazine ring, indole ring, isoindole ring, quinoline ring , Isoquinoline ring, quinazoline ring, phthalazine ring, pteridine ring, coumarin ring, chromone ring, 1,4-zenzodiazepine ring, benzimidazole ring, benzofuran ring, purine ring, acridine ring, phenox
  • the alkyl group for R 13 and R 14 preferably has 1 to 24 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 6 to 16 carbon atoms.
  • the alkyl group may be linear, branched or cyclic, and may further have a substituent. Examples of the substituent include the substituent W described above. Examples of the alkyl group include methyl, ethyl, isopropyl, t-butyl, n-hexyl, n-octyl, 2-ethylhexyl, and n-octadecyl.
  • the alkoxy group for R 13 and R 14 preferably has 1 to 24 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 6 to 16 carbon atoms.
  • the alkoxy group may have a substituent, and examples of the substituent include the substituent W.
  • Examples of the alkoxy group include methoxy, ethoxy, isopropoxy, t-butoxy, n-hexyloxy, n-octyloxy, 2-ethylhexyloxy and n-octadecyloxy.
  • At least one of R 13 and R 14 is preferably an aromatic hydrocarbon ring group or an aromatic heterocyclic group.
  • R 13 and R 14 may combine with each other to form a ring, and the ring is preferably a 3- to 7-membered ring, which is a saturated hydrocarbon ring, an unsaturated hydrocarbon ring, an aromatic hydrocarbon ring, a hetero ring Even if it is a ring (including an aromatic heterocycle), the formed ring may be a single ring, or it may be condensed and polycyclic. Further, the formed ring may have a substituent, and examples of the substituent include the substituent W. In the present invention, these formed rings are preferably fluorene rings, and preferably have a spiro structure at the 9-position, that is, the following structure.
  • R 11, R 12, n11 and n12 are the same meaning as R 11, R 12, n11 and n12 in the general formula (1A) or (1B), and the preferred range is also the same.
  • R 11 ′, R 12 ′ and n12 ′ have the same meanings as R 11 , R 12 and n12, and preferred ranges are also the same.
  • n11 ′ represents an integer of 0 to 4.
  • Rx represents a bond in the case of the general formula (1A) (that is, in the case where it is incorporated into the polymer main chain by two benzene rings of the fluorene ring), and in the case of the general formula (1B) (that is, one (When the benzene ring is bonded to the polymer main chain) represents a hydrogen atom or a substituent.
  • substituent in Rx include the above-described substituent W.
  • Rx ′ represents a hydrogen atom or a substituent.
  • substituent W an aromatic hydrocarbon ring group, an aromatic heterocyclic group, an alkyl group, an alkoxy group, an alkylthio group, an amino group, and a hydroxyl group are preferable.
  • An alkoxy group and a hydroxyl group are more preferable, and an alkoxy group is more preferable.
  • the aromatic hydrocarbon ring of the divalent aromatic hydrocarbon ring group in L a and L b preferably has 6 to 24 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 18 carbon atoms.
  • the aromatic hydrocarbon ring include a benzene ring and a naphthalene ring, and the ring may be condensed with a ring such as an aromatic hydrocarbon ring, an aliphatic hydrocarbon ring, or a hetero ring.
  • the aromatic hydrocarbon ring group may have a substituent, and examples of the substituent include the substituent W.
  • an alkyl group, an alkoxy group, an alkylthio group, an amino group, and a hydroxyl group are preferable, an alkyl group, an alkoxy group, and a hydroxyl group are more preferable, and an alkyl group and an alkoxy group are further preferable.
  • the aromatic hydrocarbon ring is preferably a benzene ring, a naphthalene ring, or a fluorene ring.
  • the aromatic heterocyclic ring of the divalent aromatic heterocyclic group in L a and L b has preferably 2 to 24 carbon atoms, more preferably 3 to 20 carbon atoms, and further preferably 3 to 18 carbon atoms.
  • the ring-constituting hetero atom is preferably a nitrogen atom, an oxygen atom or a sulfur atom, and preferably a 5- or 6-membered ring.
  • the ring may be condensed with a ring such as an aromatic hydrocarbon ring, an aliphatic hydrocarbon ring or a hetero ring.
  • the aromatic hydrocarbon ring group may have a substituent, and examples of the substituent include the substituent W.
  • an alkyl group, an alkoxy group, and an alkylthio group are preferable, an alkyl group and an alkoxy group are more preferable, and an alkyl group is further preferable.
  • the aromatic heterocycle is, for example, thiazole ring, pyrrole ring, furan ring, pyrazole ring, imidazole ring, imidazole ring, triazole ring, thiadiazole ring, oxadiazole ring, pyridine ring, pyrimidine ring, pyrimidine ring, pyridazine ring, Triazine ring, benzothiazole ring, indole ring, benzothiadiazole ring, quinoxaline ring, phenoxazine ring, dibenzofuran ring, dibenzothiazole ring, dibenzosilanocyclopentadiene ring, carbazole ring, phenothiazine ring, thiophene ring, isothiazole ring, indole ring, Isoindole ring, quinoline ring, isoquinoline ring, quinazoline ring, phthal
  • Ra of —N (Ra) — in L a and L b represents a substituent, and examples of the substituent include the substituent W described above.
  • Ra is preferably an alkyl group, an aryl group, or a heterocyclic group, and each of these groups may further have a substituent. Examples of the substituent that may be substituted on the group include the above-described substituent W.
  • the alkyl group in Ra preferably has 1 to 18 carbon atoms.
  • the aryl group in Ra preferably has 6 to 24 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 12 carbon atoms.
  • the heterocyclic group for Ra is preferably an aromatic heterocyclic group, and is preferably an aromatic heterocyclic group for R 13 or R 14 .
  • a divalent aromatic hydrocarbon ring group, a divalent aromatic heterocyclic group or a linking group that combines —N (Ra) — is a group that combines two or more of these.
  • Any combination may be used.
  • a bivalent aromatic hydrocarbon ring group, a bivalent aromatic hydrocarbon ring group, a bivalent aromatic heterocyclic group, a bivalent aromatic heterocyclic group, and a bivalent aromatic group is a group that combines two or more of these.
  • L a is a divalent aromatic hydrocarbon ring group, a divalent aromatic heterocyclic group, and said -N (Ra) - linking group is a group selected from the group consisting of combined two or more are preferred .
  • L b is preferably a divalent aromatic hydrocarbon ring group, a divalent aromatic heterocyclic group, —N (Ra) — or a linking group obtained by combining these groups.
  • L a is a linking group preferably represented by the following formula (a) or (b).
  • X a0 represents a single bond, a divalent aromatic hydrocarbon ring group or a divalent aromatic heterocyclic group
  • X a1 and X a2 each independently represent a divalent aromatic hydrocarbon ring group or Represents a divalent aromatic heterocyclic group
  • R a0 represents a substituent
  • n a0 represents an integer of 0 to 5.
  • R a0 The above includes the substituent W, preferably an alkyl group, an alkoxy group, an alkylthio group, an acyl group, an alkoxycarbonyl group, and a halogen atom, and an alkoxycarbonyl group is particularly preferable.
  • n a0 is preferably 0 or 1.
  • Examples of the aromatic hydrocarbon ring in the trivalent aromatic hydrocarbon ring group for X b include the aromatic hydrocarbon rings for L a and L b , and the preferred ranges are also the same. Among these, a benzene ring is preferable, and a fluorene ring having a benzene ring bonded to the 5-position of the phenylene group constituting the polymer main chain with a 1,3-phenylene group is preferable.
  • Examples of the aromatic heterocyclic ring in the trivalent aromatic heterocyclic group for X b include the aromatic heterocyclic ring for L a and L b , and the preferred ranges are also the same. Of these, those in which the benzene ring of the fluorene ring is bonded to the 10th position of the phenoxazine ring, the 10th position of the phenothiazine ring, the 9th position of the carbazole ring, and the 1st position of the pyrrole are preferable.
  • X b is atom
  • X b are preferably has either a carbon atom or nitrogen atom forming a carbon atom or an aromatic heterocyclic ring to form an aromatic hydrocarbon ring, or X b is> N-, > N- is particularly preferred.
  • the weight average molecular weight (polystyrene equivalent GPC measurement value) of the conductive polymer containing at least the fluorene structure represented by the general formula (1A) or (1B) as a repeating structure is not particularly limited, but is 4000 to 100,000. Is preferable, 6000 to 80000 is more preferable, and 8000 to 50000 is particularly preferable.
  • the terminal group of the conductive polymer containing at least the fluorene structure represented by the general formula (1A) or (1B) as a repeating structure is, for example, a parenthesis of the repeating unit represented by the general formula (1A) or (1B).
  • the substituent is located outside and bonded to the repeating unit.
  • the substituent used as the terminal group varies depending on the synthesis method of the polymer, but as a side reaction of a halogen atom (for example, fluorine, chlorine, bromine, iodine) derived from a synthesis raw material, hydrogen, a boron-containing substituent, or a polymerization reaction.
  • It can be a hydrogen atom to be substituted or a phosphorus-containing substituent derived from a catalyst ligand. After the polymerization, it is also preferable to convert the terminal group to a hydrogen atom or an aryl group by a reduction reaction or a substitution reaction.
  • the conductive polymer containing at least the fluorene structure represented by the general formula (1A) or (1B) as a repeating structure is a known method described in, for example, Chem. Rev. Journal, 2011, 111, pp. 1417 Thus, it can be produced by polymerization by a usual coupling polymerization method.
  • the content of the conductive polymer 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. A content of ⁇ 50% by weight is particularly preferred. Further, when the thermoelectric conversion material contains a non-conjugated polymer described later, the content of the conductive polymer in the thermoelectric conversion material is preferably 3 to 70% by mass in the total solid content of the material. More preferably, it is ⁇ 60% by mass, and particularly preferably 10 ⁇ 50% by mass.
  • thermoelectric conversion material contains another conductive polymer other than the conductive polymer having the fluorene structure represented by the above general formula (1A) or (1B) as a repeating structure
  • the content of the conductive polymer having a fluorene structure represented by the above general formula (1A) or (1B) as a repeating structure is preferably 3 to 60% by mass in the total solid content of the material, It is more preferably 5 to 50% by mass, and particularly preferably 10 to 40% by mass.
  • the polymer containing at least the fluorene structure represented by the general formula (1A) or (1B) as a repeating structure improves the dispersibility of the nanoconductive material is that the fluorene ring structure is electronically coupled with the surface of the nanoconductive material. This is considered to be because these conductive polymers function as a dispersant for the nanoconductive material because they easily interact with each other (for example, ⁇ - ⁇ interaction).
  • the thermoelectric conversion material of the present invention preferably contains a non-conjugated polymer in that the thermoelectric conversion characteristics are further improved.
  • the non-conjugated polymer is a polymer compound having no conjugated molecular structure, that is, a compound in which the main chain is not conjugated with a lone pair of ⁇ electrons or lone electrons.
  • 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.
  • 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 material by including non-conjugated polymer together with conductive polymer containing at least the fluorene structure represented by the above general formula (1A) or (1B) as a repeating structure in the thermoelectric conversion material
  • conductive polymer containing at least the fluorene structure represented by the above general formula (1A) or (1B) as a repeating structure in the thermoelectric conversion material The performance can be improved.
  • 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 conductive polymer is moderate.
  • the coexistence of the above-mentioned conductive polymer and nano-conductive material allows the carrier transport route to be maintained at a low level. This is presumed to be due to the formation of a high conductivity.
  • thermoelectric conversion performance ZT value
  • the content of the nonconjugated polymer in the thermoelectric conversion material is 10 to 10 parts by mass with respect to 100 parts by mass of the conductive polymer containing at least the fluorene structure represented by the general formula (1A) or (1B) as a repeating structure.
  • the amount is preferably 1500 parts by mass, more preferably 30 to 1200 parts by mass, and particularly preferably 80 to 1000 parts by mass.
  • ZT value Seebeck coefficient 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
  • organic solvents aliphatic halogen solvents such as alcohol and chloroform, aprotic polar solvents such as DMF, NMP and DMSO, chlorobenzene, dichlorobenzene, benzene, toluene, xylene, mesitylene, tetralin and tetramethylbenzene.
  • An aromatic solvent such as pyridine, a ketone solvent such as cyclohexanone, acetone, and methylethylkenton, and an ether solvent such as diethyl ether, THF, t-butylmethyl ether, dimethoxyethane, and diglyme are preferable, and halogen such as chloroform More preferred are system solvents, aprotic polar solvents such as DMF and NMP, aromatic solvents such as dichlorobenzene, xylene, tetralin and tetramethylbenzene, and ether solvents such as THF.
  • aprotic polar solvents such as DMF and NMP
  • aromatic solvents such as dichlorobenzene, xylene, tetralin and tetramethylbenzene
  • ether solvents such as THF.
  • 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, a solvent, particularly an organic solvent, together with a conductive polymer containing at least the fluorene structure represented by the general formula (1A) or (1B) as a repeating structure. Shows good dispersibility of the nanoconductive material.
  • the conductive polymer, the nanoconductive material and the solvent described above are contained, particularly the organic solvent, and the nanoconductive material is contained in the solvent, particularly the organic solvent. It includes a nano-conductive material dispersion formed by dispersion. Since the dispersion has good dispersibility of the nano-conductive material, the nano-conductive material can exhibit high original conductivity, and can be suitably used for various conductive materials including a thermoelectric conversion material.
  • 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 that is doped into a conductive polymer containing at least the fluorene structure represented by the above general formula (1A) or (1B) as a repeating structure.
  • the dopant is protonated or highly aromatic. Any material that can dope the conductive polymer with positive charges (p-type doping) by removing electrons from the ⁇ -conjugated system of the molecule 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 amount of the dopant used is 0 with respect to 100 parts by mass of the conductive polymer containing at least the fluorene structure represented by the general formula (1A) or (1B) as a repeating structure from the viewpoint of controlling the optimum carrier concentration. It is preferably used in a proportion of more than 60 parts by weight and less than 60 parts by weight, more preferably 2-50 parts by weight, and even more preferably 5-40 parts by weight.
  • an 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 conductive polymer and nano-conductive material is uniformly dissolved in the thermoelectric conversion material without agglomerating and precipitating the above-mentioned conductive polymer. Or disperse. 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.
  • the 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 has a specific energy level difference with respect to the energy level of the molecular orbital of the conductive polymer containing at least the fluorene structure represented by the general formula (1A) or (1B) as a repeating structure. It is a substance having molecular orbitals, and by using it together with the conductive polymer, the thermal excitation efficiency can be increased and the thermoelectromotive force of the thermoelectric conversion material can be improved.
  • the thermal excitation assisting agent used in the present invention is a compound having a LUMO having a lower energy level than the above-mentioned conductive polymer LUMO (Lowest Unoccupied Molecular Orbital), and is doped into the conductive polymer.
  • the aforementioned dopant is a compound that forms a doped level in a conductive polymer, and forms a doped level regardless of the presence or absence of a thermal excitation assisting agent. Whether or not a doped level is formed in a conductive polymer can be evaluated by measuring an absorption spectrum.
  • a compound that forms a doped level and a compound that does not form a doped level are evaluated by the following method. It means what was done.
  • component B is defined as a dopant.
  • component B is defined as an excitation assist agent.
  • the LUMO of the thermal excitation assist agent has a lower energy level than the LUMO of the above-described conductive polymer, and accepts thermally excited electrons generated from the HOMO (High Occupied Molecular Orbital) of the conductive polymer. It functions as a level. Furthermore, when the absolute value of the HOMO energy level of the conductive polymer and the absolute value of the LUMO energy level of the thermal excitation assisting agent satisfy the following formula (I), the thermoelectric conversion material is excellent. A thermoelectromotive force is provided.
  • the above formula (I) represents the energy difference between the LUMO of the thermal excitation assist agent and the HOMO of the conductive polymer, and when this is smaller than 0.1 eV (the LUMO energy level of the thermal excitation assist agent has a high conductivity level).
  • the activation energy of electron transfer between the HOMO (donor) of the conductive polymer and the LUMO (acceptor) of the thermal excitation assist agent is very small.
  • an oxidation-reduction reaction occurs between the conductive polymer and the thermal excitation assist agent, thereby causing aggregation.
  • 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 conductive polymer and the thermal excitation assist agent are as follows. Regarding the HOMO energy level, a single coating film (glass substrate) of each component is prepared, and the HOMO level is determined by photoelectron spectroscopy. The position 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 energy level of HOMO and LUMO of the conductive polymer and the thermal excitation assist agent uses values measured and calculated by the method.
  • 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.
  • the effect of improving the thermoelectromotive force by such a thermal excitation assist agent is different from the method of improving the thermoelectric conversion performance by the doping effect of the conductive polymer.
  • 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 are present in the LUMO of the thermal excitation assist agent, which is the acceptor level. Therefore, holes on the conductive polymer and electrons on the thermal excitation assist agent are present. And exist physically apart. Therefore, the doped level of the conductive polymer 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 assist 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 conductive polymer. More preferably.
  • 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.
  • a nano-conductive material and a conductive polymer containing at least the fluorene structure represented by the above general formula (1A) or (1B) as a repeating structure are added and mixed in a solvent, and each component is dissolved or dispersed.
  • each component in the thermoelectric conversion material is in a dispersed state of the nano-conductive material, and other components such as the conductive polymer are in a dispersed or dissolved state, and the components other than the nano-conductive material are dissolved. More preferably, it is in a state.
  • 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 conductive polymer and nanoconductive material as essential components when the moisture content is in the above range, high thermoelectric conversion performance is obtained while maintaining excellent coating properties and film formability. be able to. 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 composed of a nano-conductive material and the general formula (1A) or ( It contains a conductive polymer containing at least the fluorene structure represented by 1B) as a repeating structure.
  • 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.
  • each component of the nano conductive material and the conductive polymer is mixed and dispersed in a solvent, and after the mixture is formed and formed into a film, the moisture content is controlled to obtain the moisture content within the above range. It is preferable.
  • 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 conductive polymer, thereby doping the conductive polymer 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 element of the present invention have good dispersibility of the nanoconductive material and excellent thermoelectric conversion performance. 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.
  • the structures of the polymer and dopant used are as follows. In the following repeating structure of the conductive polymer, * represents a connecting part of the repeating structure.
  • the conductive polymer 3 was synthesized as follows, and the conductive polymers 1, 2, 4 to 8 were synthesized in the same manner as the conductive polymer 3.
  • Example 1 Conductive polymer 1 6 mg, single layer CNT (ASP-100F, manufactured by Hanwha Nanotech, dispersion (CNT concentration 60 mass%), average length of CNT: about 5 to 20 ⁇ m, average diameter: about 1.0 to 1 .2 nm) 2 mg was added to 4.0 ml of orthodichlorobenzene and dispersed in an ultrasonic water bath for 70 minutes. This dispersion was applied to the surface of the electrode 12 of the glass substrate 11 (thickness: 0.8 mm) having gold (thickness 20 nm, width: 5 mm) on one side surface as the first electrode 13 by a screen printing method. For 30 minutes to remove the solvent.
  • thermoelectric conversion layer 14 with a film thickness of 2.8 ⁇ m and a size of 8 mm ⁇ 8 mm was formed by drying at room temperature under vacuum for 10 hours. Thereafter, a glass substrate 16 in which gold is deposited as the second electrode 15 on the thermoelectric conversion layer 14 (the thickness of the electrode 15: 20 nm, the width of the electrode 15: 5 mm, the thickness of the glass substrate 16: 0.8 mm). Were bonded together at 80 ° C. so that the second electrode 15 was opposed to the thermoelectric conversion layer 14, thereby producing the thermoelectric conversion element 101 of the present invention which is the thermoelectric conversion element 1 shown in FIG. 1.
  • thermoelectric conversion elements 102 to 108 of the present invention and the comparative thermoelectric conversion elements c01 to c04 are the same as the thermoelectric conversion element 101 except that the type of polymer, the presence or absence of CNT, and the electrode material are changed as shown in Table 1 below. Was made.
  • thermoelectric conversion element was evaluated for thermoelectromotive force (also referred to as thermoelectric characteristics) and CNT dispersibility by the following method. The results are shown in Table 1.
  • thermoelectric characteristic value thermoelectric conversion element
  • the first electrode 13 of each 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 keeping 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 4K or less) between both electrodes.
  • the 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 1 as relative values with respect to the calculated values of the comparative thermoelectric conversion element c01.
  • CNT dispersibility evaluation The CNT dispersibility in the dispersion liquid after ultrasonic dispersion obtained above was evaluated as follows. Using a Microtrac MT3300 laser diffraction / scattering particle size distribution measuring device manufactured by Nikkiso Co., Ltd., a range of 0.1 to 2000 ⁇ m was measured, and a volume average particle size (D50) at 50% cumulative frequency was calculated. . From the value of the volume average particle diameter, the CNT dispersibility was classified into the following ranks A to E as follows. Practically, it is preferable to satisfy the criteria of A to C.
  • volume average particle diameter is less than 150 nm
  • B Volume average particle diameter is 150 nm or more and less than 300 nm
  • C Volume average particle diameter is 300 nm or more and less than 600 nm
  • D Volume average particle diameter is 600 nm or more, but precipitates and aggregates are visually observed I can't.
  • E Precipitates and aggregates are visually observed.
  • thermoelectric conversion elements 101 to 108 containing CNT and a conductive polymer having a fluorene structure represented by the general formula (1A) or (1B) as a repeating structure are dispersed in CNTs.
  • the thermoelectric characteristics were more than twice that of the standard thermoelectric conversion element, which was excellent.
  • the comparative thermoelectric conversion elements c01 to c03 using the conventional conductive polymer or the non-conductive polymer were all poor in CNT dispersibility and low in thermoelectric characteristics.
  • the initial thermoelectromotive force S was below the detection limit, and the thermoelectric performance was very low.
  • Example 2 3 mg of conductive polymer 1, 2 mg of CNT (ASP-100F, manufactured by Hanwha Nanotech), 2 mg of dopant 1, and 5 mg of polystyrene (430102 manufactured by Aldrich) as a non-conjugated polymer were added to 5 ml of orthodichlorobenzene. It was dispersed in a sonic water bath for 70 minutes. Using this dispersion, a thermoelectric conversion layer was formed in the same manner as in Example 1, and then irradiated with ultraviolet rays using an ultraviolet irradiator (ECS-401GX, manufactured by Eye Graphics Co., Ltd.) (light quantity: 1.06 J / cm 2 ). , Doped. Then, the 2nd electrode was bonded together like Example 1, and the thermoelectric conversion element 201 of this invention was produced.
  • ECS-401GX ultraviolet irradiator
  • thermoelectric conversion elements 202 to 211 of the present invention comparative thermoelectric conversion, except that the types of polymers, dopants, and non-conjugated polymers and the presence or absence of addition were changed as shown in Table 2 below. Elements c11 and c12 were produced. Note that the thermoelectric conversion elements 207 to 210 were not subjected to doping treatment by ultraviolet irradiation.
  • the imide compound shown in Table 2 as a non-conjugated polymer is Solpy 6,6-PI (trade name, manufactured by Solpy Industrial Co., Ltd.), and the carbonate compound is Iupizeta PCZ-300 (trade name, manufactured by Mitsubishi Gas Chemical Co., Ltd.).
  • Polyvinyl acetate is manufactured by Wako Pure Chemical Industries, Ltd.
  • Polylactic acid is PLA-0015 (trade name, Wako Pure Chemical Industries, Ltd.)
  • Polymethyl methacrylate is manufactured by Wako Pure Chemical Industries, Ltd.
  • Polyvinylpyrrolidone is manufactured by Wako Pure Chemical Industries, Ltd. Those manufactured by Yakuhin Kogyo Co., Ltd. were used.
  • thermoelectric characteristic value thermoelectromotive force S
  • CNT dispersibility were evaluated in the same manner as in Example 1. The results are shown in Table 2.
  • the thermoelectric characteristic values shown in Table 2 are relative values with respect to the calculated values of the comparative thermoelectric conversion element c01 produced in Example 1.
  • thermoelectric conversion elements 201 to 211 of the invention exhibited further excellent CNT dispersibility and thermoelectric characteristic values.
  • thermoelectric conversion element c11 containing no conductive polymer and the comparative thermoelectric conversion element c12 using the conventional conductive polymer have low thermoelectric characteristics and CNT dispersibility compared to the thermoelectric conversion element of the present invention. inferior.
  • Example 3 The conductive polymer 1 is changed to the conductive polymer 2, and the solvent is changed to a mixed solvent of 5 vol% tetrahydrofuran + 95 vol% chloroform instead of orthodichlorobenzene alone, and further, for 5 hours under vacuum at room temperature after coating.
  • the thermoelectric conversion layer 14 subjected to doping treatment was formed in the same manner as the thermoelectric conversion element 201 after removing the solvent, and the thermoelectric conversion element 301 of the present invention was manufactured.
  • tetrahydrofuran and chloroform used dehydrated tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) and dehydrated chloroform (manufactured by Wako Pure Chemical Industries, Ltd.).
  • the moisture content (equilibrium moisture content) of the thermoelectric conversion layer 14 subjected to the doping treatment was calculated by dividing the moisture content (g) by the sample mass (g) by the Karl Fischer method. Specifically, the thermoelectric conversion layer 14 formed on the first substrate 12 is cut into a size of 5 cm ⁇ 5 cm, and this is subjected to Karl Fischer reagent after the water content has reached equilibrium in the above environment. Then, the water content was measured using a moisture measuring device (manufactured by DIA INSTRUMENTS CO., LTD.) By the Karl Fischer method.
  • thermoelectric conversion elements 302 to 305 of the present invention were produced in the same manner as the thermoelectric conversion element 301 except that the thermoelectric conversion element 301, whether or not the solvent was dehydrated, and the solvent removal time were changed as shown in Table 3 below.
  • thermoelectric characteristic value thermoelectromotive force S
  • CNT dispersibility were evaluated in the same manner as in Example 1. The results are shown in Table 3.
  • the thermoelectric characteristic values shown in Table 3 are relative values with respect to the calculated values of the comparative thermoelectric conversion element c01 produced in Example 1.
  • thermoelectric conversion elements 301 to 303 in which the moisture content of the thermoelectric conversion layer 14 is in the range of 0.01 to 15.0% by mass are more than the thermoelectric conversion elements 304 and 305 that are out of this range. Excellent thermoelectric property value was shown.
  • Example 4 The type and presence / absence of the conductive polymer, CNT, dopant, and non-conjugated polymer were changed as shown in Table 4, and the same as the thermoelectric conversion element 201 except that the thermal excitation assisting agent shown below was added in the solvent.
  • the thermoelectric conversion elements 401 to 406 of the present invention were produced.
  • the addition amount of the dopant and the thermal excitation assist agent was 1 mg each.
  • thermoelectric characteristic value thermoelectromotive force S
  • CNT dispersibility were evaluated in the same manner as in Example 1. The results are shown in Table 4.
  • the thermoelectric characteristic values shown in Table 4 are relative values with respect to the calculated values of the comparative thermoelectric conversion element c01 produced in Example 1.
  • thermoelectric conversion elements 401 to 406 containing the thermal excitation assisting agent all have improved thermoelectric characteristic values. Furthermore, thermoelectric conversion elements 401 and 402 containing an onium salt compound (dopant 1 or 4) as a dopant were superior in CNT dispersibility compared to thermoelectric conversion elements 403 and 405 using hydrochloric acid or FeCl 3 as a dopant.
  • Example 5 As the first substrate 12 having the first electrode 13, a polyethylene terephthalate film having flexibility (flexion resistance MIT according to the measurement method prescribed in the above-mentioned ASTM D2176 is 50,000 cycles or more) instead of glass ( The thickness was 125 ⁇ m), except that the second base material (made of glass) 16 having the second electrode 15 formed of copper paste (trade name: ACP-080, made by Asahi Chemical Research Co., Ltd.) was used.
  • the thermoelectric conversion element 501 of the present invention which is the thermoelectric conversion element 1 was produced in the same manner as the thermoelectric conversion element 101 of Example 1. When a temperature difference of 3 ° C. was applied between the first base material (polyethylene terephthalate film) 12 having the first electrode 13 and the second electrode 15 through the second base material 16, both electrodes A voltmeter confirmed that a thermoelectromotive force of 218 ⁇ V was generated.
  • thermoelectric conversion element c51 was produced in the same manner as the thermoelectric conversion element 501 except that the thermoelectric conversion material produced in the thermoelectric conversion element c01 of Example 1 was used as the thermoelectric conversion material.
  • a temperature difference of 3 ° C. is applied between the first substrate having the first electrode and the second electrode via the second substrate, a thermoelectromotive force of 93 ⁇ V is generated between both electrodes. This was confirmed with a voltmeter.
  • thermoelectric conversion element 501 containing the conductive polymer 1 having the fluorene skeleton of the present invention and CNT does not contain the conductive polymer having the fluorene skeleton of the present invention, Compared with the comparative thermoelectric conversion element c51 containing polystyrene and CNT which are conductive polymers, the generated thermoelectromotive force was large.
  • thermoelectric conversion elements 601 to 604 of the present invention were prepared in the same manner as the thermoelectric conversion element 101 except that the metal salt shown in Table 5 was added to the conductive polymer 1 and the single-walled CNT in the addition amount shown in Table 5. It produced and it carried out similarly to Example 1, and evaluated CNT dispersibility and a thermoelectric characteristic value (relative value with respect to the calculated value of the thermoelectric conversion element c101). The results are shown in Table 5.
  • thermoelectric conversion element 601 of the present invention containing a metal element in addition to the conductive polymer and CNT having a fluorene structure represented by the general formula (1A) or (1B) as a repeating structure.
  • ⁇ 604 showed good CNT dispersibility and thermoelectric conversion characteristics.

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