CN104937734A - Thermoelectric conversion material, thermoelectric conversion element, and thermoelectric power generation article and sensor power source using thermoelectric conversion element - Google Patents

Thermoelectric conversion material, thermoelectric conversion element, and thermoelectric power generation article and sensor power source using thermoelectric conversion element Download PDF

Info

Publication number
CN104937734A
CN104937734A CN201480005086.5A CN201480005086A CN104937734A CN 104937734 A CN104937734 A CN 104937734A CN 201480005086 A CN201480005086 A CN 201480005086A CN 104937734 A CN104937734 A CN 104937734A
Authority
CN
China
Prior art keywords
thermoelectric conversion
compound
ring
group
conversion element
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201480005086.5A
Other languages
Chinese (zh)
Inventor
西尾亮
野村公笃
丸山阳一
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Corp
Original Assignee
Fujifilm Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Publication of CN104937734A publication Critical patent/CN104937734A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/851—Thermoelectric active materials comprising inorganic compositions
    • H10N10/854—Thermoelectric active materials comprising inorganic compositions comprising only metals
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/856—Thermoelectric active materials comprising organic compositions
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N15/00—Thermoelectric devices without a junction of dissimilar materials; Thermomagnetic devices, e.g. using the Nernst-Ettingshausen effect
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/12—Copolymers
    • C08G2261/124—Copolymers alternating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/142—Side-chains containing oxygen
    • C08G2261/1424—Side-chains containing oxygen containing ether groups, including alkoxy
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
    • C08G2261/3142—Condensed aromatic systems, e.g. perylene, anthracene or pyrene fluorene-based, e.g. fluorene, indenofluorene, or spirobifluorene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3246—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing nitrogen and sulfur as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
    • C08G2261/344—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/55—Physical properties thermoelectric
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/70—Post-treatment
    • C08G2261/79—Post-treatment doping
    • C08G2261/794—Post-treatment doping with polymeric dopants
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Provided is a thermoelectric conversion element having a first electrode, a thermoelectric conversion layer, and a second electrode on a substrate. The thermoelectric conversion layer contains a nano-conductive material, and a low-molecular conjugated compound having a fused polycyclic structure obtained by fusing at least three rings selected from a group comprising aromatic hydrocarbon rings and aromatic heterocyclic rings. Further provided are a thermoelectric power generation article and a sensor power source in which the thermoelectric element is used, and a thermoelectric conversion material containing the nano-conductive material and the low-molecular conjugated compound.

Description

Thermo-electric converting material, thermoelectric conversion element and employ thermoelectric power generation article and the sensor-use source of this thermoelectric conversion element
Technical field
The present invention relates to thermo-electric converting material, thermoelectric conversion element and employ thermoelectric power generation article and the sensor-use source of this thermoelectric conversion element.
Background technology
The thermo-electric converting material that heat energy and electric energy are changed mutually can be used in the such thermoelectric conversion element of such as thermoelectric generation elements, Peltier element.Apply thermo-electric converting material, thermal power transfer directly can become electric power by the thermoelectric power generation of thermoelectric conversion element, do not need movable part, be used in the wrist-watch that works under body temperature or isolated area's power supply, space power supply etc.
As one of the index of thermoelectricity conversion performance evaluating thermoelectric conversion element, there is dimensionless performance index ZT (hereinafter sometimes referred to as performance index ZT).This performance index ZT following formula (A) represents, for the raising of thermoelectricity conversion performance, the reduction of thermo-electromotive force (being hereinafter the sometimes referred to as thermo-electromotive force) S of every 1K absolute temperature and the raising of conductivityσ, conductive coefficient κ is very important.
Performance index ZT=S 2σ T/ κ (A)
In formula (A), S (V/K): the thermo-electromotive force (Seebeck coefficient) of every 1K absolute temperature
σ (S/m): conductivity
κ (W/mK): conductive coefficient
T (K): absolute temperature
Thermo-electric converting material being required to have good thermoelectricity conversion performance, from the relational expression of above-mentioned performance index ZT, in order to improve performance index ZT, requiring the Seebeck coefficient S and the conductivityσ that improve conductive material.
From this respect, as the conductive material for thermo-electric converting material, electroconductive polymer, carbon nano-tube etc. receive publicity.Such as, report by polyvinyl acetate, multilayer carbon nanotube and through porphines stabilisation multilayer carbon nanotube prepared by VA compound (non-patent literature 1); And comprise the dispersion (patent documentation 1) etc. of carbon nano-tube, poly-(3-hexyl thiophene) and dimethyl silicone polymer.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2012-102209 publication
Non-patent literature
Non-patent literature 1:Carbon, 50 (2012), 885-895
Summary of the invention
The problem that invention will solve
When especially utilizing the dispersion liquid of carbon nano-tube to make the thermoelectric conversion layer of thermoelectric conversion element, easily because of strong molecular separating force, aggegation is pencil or granular to carbon nano-tube, is difficult to be scattered in decentralized medium.In the VA compound recorded in the dispersion that this phenomenon is recorded in patent documentation 1 and non-patent literature 1 too, in these materials, the dispersiveness of carbon nano-tube is also not enough.But, in order to improve the performance index ZT of thermoelectric conversion element, eliminating the aggegation of carbon nano-tube, that carbon nano-tube is highly dispersed in decentralized medium be very important.
On the other hand, if for improve carbon nano-tube dispersiveness object and use dispersant in a large number, then because the dispersant remained in thermoelectric conversion layer can cause the thermoelectricity conversion performance of thermoelectric conversion element to reduce.
Therefore, dispersiveness and the thermoelectricity conversion performance of taking into account carbon nano-tube is required.
Therefore, problem of the present invention is to provide a kind of excellent dispersion of conductive nano material and the also excellent thermo-electric converting material of thermoelectricity conversion performance; There is the thermoelectric conversion element of the thermoelectric conversion layer of thermoelectricity conversion performance excellence; And employ thermoelectric power generation article and the sensor-use source of thermoelectric conversion element.
For solving the scheme of problem
In view of above-mentioned problem, as the material coexisted with conductive nano materials (at least the length on diameter or 1 limit is the conductive material of nano-scale) such as carbon nano-tube in the thermoelectric conversion layer of thermoelectric conversion element, the present inventor is studied various compound, found that, the low molecular compound of the thick multiring structure that the aromatic rings with more than 3 rings condenses can improve the dispersiveness of conductive nano material.And find, contrary with prediction, this low molecular compound can build and at the intermolecular charge carrier path carrying out electronics movement of conductive nano material, also can be able to contribute to the raising of the performance index ZT of thermoelectric conversion element, i.e. thermoelectricity conversion performance.The present invention completes based on these technological thoughts.
That is, above-mentioned problem realizes by following scheme.
<1> thermoelectric conversion element, it for having the thermoelectric conversion element of the 1st electrode, thermoelectric conversion layer and the 2nd electrode on base material, thermoelectric conversion layer contains conductive nano material and has the low molecule conjugated compound of thick multiring structure, and this thick multiring structure is that at least 3 rings be selected from the group that is made up of aromatic hydrocarbon ring and heteroaromatic condense.
The thermoelectric conversion element of <2> as described in <1>, wherein, low molecule conjugated compound has the thick multiring structure that 3 ~ 6 rings in the group being selected from and being made up of aromatic hydrocarbon ring and heteroaromatic condense.
The thermoelectric conversion element of <3> as described in <1> or <2>, wherein, the Ppolynuclear aromatic hydrocarbon compound that at least 3 rings that low molecule conjugated compound is the Ppolynuclear aromatic heterocyclic compound that condenses according at least 3 rings selected by the mode comprising at least 1 heteroaromatic from the group be made up of aromatic hydrocarbon ring and heteroaromatic or aromatic hydrocarbon ring condense.
The thermoelectric conversion element of <4> according to any one of <1> ~ <3>, wherein, Ppolynuclear aromatic hydrocarbon compound is the Ppolynuclear aromatic hydrocarbon compound except the Ppolynuclear aromatic hydrocarbon compound with perylene structure.
The thermoelectric conversion element of <5> according to any one of <1> ~ <4>, wherein, Ppolynuclear aromatic hydrocarbon compound is except having the Ppolynuclear aromatic hydrocarbon compound condensed on 1 ring except the Ppolynuclear aromatic hydrocarbon compound of the structure of the ring of more than 4.
The thermoelectric conversion element of <6> according to any one of <1> ~ <5>, wherein, Ppolynuclear aromatic hydrocarbon compound has that condense with 1 ring, 2 rings or 3 rings, that at least 3 aromatic hydrocarbon rings condense thick multiring structure.
The thermoelectric conversion element of <7> according to any one of <1> ~ <6>, wherein, heteroaromatic is 5 rings or 6 rings.
The thermoelectric conversion element of <8> as described in <7>, wherein, heteroaromatic is thiphene ring, furan nucleus or pyrrole ring.
The thermoelectric conversion element of <9> according to any one of <1> ~ <8>, wherein, low molecule conjugated compound has the thick multiring structure in following formula (1A) ~ (1D) represented by any one formula.
The thermoelectric conversion element of <10> as described in <9>, wherein, at least 1 person in the C ring ~ F ring of formula (1A) ~ (1D) is represented by following formula (1-1) or (1-2).
In formula (1-1) or (1-2), X represents carbon atom or hetero-atom, and * 1 to represent respectively with * 2 and ring carbons that identical ring condenses.
The thermoelectric conversion element of <11> according to any one of <1> ~ <10>, wherein, thick multiring structure has at least 1 substituting group.
The thermoelectric conversion element of <12> as described in <11>, wherein, the loops of the end of substituting group and thick multiring structure closes.
The thermoelectric conversion element of <13> as described in <11> or <12>, wherein, substituting group be alkyl, aryl, heterocyclic radical, alkoxyl, dialkyl amido, alkoxy carbonyl group or complex substituents that they are combined.
The thermoelectric conversion element of <14> according to any one of <1> ~ <13>, wherein, thermoelectric conversion layer contains macromolecular compound.
The thermoelectric conversion element of <15> as described in <14>, wherein, macromolecular compound is be selected from least one macromolecule in the group that is made up of conjugated polymer and non-conjugate high molecular.
The thermoelectric conversion element of <16> as described in <14> or <15>, wherein, macromolecular compound will be for will be selected from by thiophene based compound, azole series compound, aniline based compound, acetylene based compound, to phenylene based compound, to phenylene vinylidene based compound, to phenylene ethynylene based compound, fluorenes based compound, at least one compound polymerization in the group of arylamine based compound and their derivative composition or the conjugated polymer of copolymerization or non-conjugate high molecular.
The thermoelectric conversion element of <17> as described in <15> or <16>, wherein, non-conjugate high molecular is by least one compound polymerization that is selected from the group that is made up of vinyl compound, (methyl) acrylate compounds, carbonate products, ester compounds, amide compound, imide compound and silicone compounds or copolymerization.
The thermoelectric conversion element of <18> according to any one of <15> ~ <17>, wherein, macromolecular compound is the mixture of conjugated polymer and non-conjugate high molecular.
The thermoelectric conversion element of <19> according to any one of <1> ~ <18>, wherein, conductive nano material is nano-carbon material or nano metal material.
The thermoelectric conversion element of <20> according to any one of <1> ~ <19>, wherein, conductive nano material is be selected from least a kind in the group that is made up of carbon nano-tube, carbon nano-fiber, graphite, Graphene, carbon nano-particle and metal nanometer line.
The thermoelectric conversion element of <21> according to any one of <1> ~ <20>, wherein, thermoelectric conversion layer contains dopant.
The thermoelectric conversion element of <22> as described in <21>, wherein, dopant is be selected from least one in the group that is made up of salt compound, oxidant, acid compound and electron acceptor compound.
The thermoelectric conversion element of <23> as described in <21> or <22>, wherein, relative to above-mentioned macromolecular compound 100 mass parts, contain dopant with the ratio more than 0 mass parts and below 60 mass parts.
The thermoelectric conversion element of <24> as described in <22> or <23>, wherein, salt compound irradiates and acidic compound by giving heat or active energy beam.
The thermoelectric conversion element of <25> according to any one of <1> ~ <24>, wherein, base material has pliability.
The thermoelectric conversion element of <26> according to any one of <1> ~ <25>, wherein, the 1st electrode and the 2nd electrode are formed by aluminium, gold, silver or copper independently of one another.
<27> thermoelectric power generation article, it use the thermoelectric conversion element according to any one of <1> ~ <26>.
<28> sensor-use source, it uses the thermoelectric conversion element according to any one of <1> ~ <26>.
<29> thermo-electric converting material for the formation of the thermoelectric conversion layer of thermoelectric conversion element, its low molecule conjugated compound containing conductive nano material and have thick multiring structure, this thick multiring structure is that at least 3 rings be selected from the group that is made up of aromatic hydrocarbon ring and heteroaromatic condense.
The thermo-electric converting material of <30> as described in <29>, it contains macromolecular compound.
The thermo-electric converting material of <31> as described in <29> or <30>, it contains organic solvent.
The thermo-electric converting material of <32> as described in <31>, conductive nano dispersion of materials forms by it in organic solvent.
In the present invention, the numerical value recorded of the front and back using " ~ " number range of representing to refer to be included in " ~ " is as the scope of lower limit and higher limit.
In addition, in the present invention, when being called xxx base about substituting group, this xxx base can have arbitrary substituting group.In addition, when the group represented with prosign is two or more, mutually can be the same or different.
Even if various represented repetitive structure is not identical repetitive structure, as long as in the scope represented by formula, then also different repetitive structures can be comprised.Such as, when repetitive structure has alkyl, various represented repetitive structure can be only the repetitive structure with methyl, also can also comprise the repetitive structure with other alkyl, such as ethyl except the repetitive structure with methyl.
The effect of invention
Concerning thermo-electric converting material of the present invention and thermoelectric conversion element, the favorable dispersibility of conductive nano material, thermoelectricity conversion performance is excellent.
In addition, employ the thermoelectric power generation article of the present invention of thermoelectric conversion element of the present invention and sensor-use source etc. and can play excellent thermoelectricity conversion performance.
Can by following contents and accompanying drawing above and other feature clearly of the present invention and advantage further.
Accompanying drawing explanation
Fig. 1 is the figure in the cross section of the example schematically showing thermoelectric conversion element of the present invention.Arrow in Fig. 1 represents the direction that the temperature difference be endowed when the use of element produces.
Fig. 2 is the figure in the cross section of another example schematically showing thermoelectric conversion element of the present invention.Arrow in Fig. 2 represents the direction that the temperature difference be endowed when the use of element produces.
Embodiment
Thermoelectric conversion element of the present invention has the 1st electrode, thermoelectric conversion layer and the 2nd electrode on base material, thermoelectric conversion layer contains conductive nano material and has the low molecule conjugated compound of thick multiring structure, and this thick multiring structure is that at least 3 rings be selected from the group that is made up of aromatic hydrocarbon ring and heteroaromatic condense.This thermoelectric conversion layer is taken shape on base material by the thermo-electric converting material of the present invention containing conductive nano material and low molecule conjugated compound.
The thermoelectricity conversion performance of thermoelectric conversion element of the present invention can represent with the performance index ZT represented by following formula (A).
Performance index ZT=S 2σ T/ κ (A)
In formula (A), S (V/K): the thermo-electromotive force (Seebeck coefficient) of every 1K absolute temperature
σ (S/m): conductivity
κ (W/mK): conductive coefficient
T (K): absolute temperature
From above-mentioned formula (A), in order to improve thermoelectricity conversion performance, while raising thermo-electromotive force S and conductivityσ, reduce conductive coefficient κ very important.Like this, the factor beyond conductivityσ can have a huge impact thermoelectricity conversion performance, even if be therefore usually considered to the high material of conductivityσ, in fact whether can effectively play function as thermo-electric converting material is also unknown number.
The thermoelectric conversion element of the present invention formed by thermo-electric converting material of the present invention is by the existence of low molecule conjugated compound, thus conductive nano material is disperseed well, and possesses the high thermoelectricity conversion performance being enough to be used as thermo-electric converting material.
In addition, as described later, thermoelectric conversion element of the present invention plays the function temperature difference in thickness direction or direction, face being converted to voltage under being the state that the thickness direction of thermoelectric conversion layer or direction, face produce temperature difference, thus need thermo-electric converting material of the present invention is shaped to the shape of the thickness had to a certain degree and forms thermoelectric conversion layer.Therefore, when forming thermoelectric conversion layer by coating, require that thermo-electric converting material has good coating and film forming.Thermo-electric converting material of the present invention can also meet the requirement relevant with film forming with the dispersiveness of conductive nano material.That is, the favorable dispersibility of the conductive nano material of thermo-electric converting material of the present invention, coating and film forming are also excellent, are suitable for shaping and are processed into thermoelectric conversion layer.
Below thermo-electric converting material of the present invention is described, then thermoelectric conversion element of the present invention etc. is described.
[thermo-electric converting material]
Thermo-electric converting material of the present invention is the thermoelectricity conversion group compound of the thermoelectric conversion layer for the formation of thermoelectric conversion element, and it contains conductive nano material and low molecule conjugated compound.
First, each composition for thermo-electric converting material of the present invention is described.
< conductive nano material >
As long as the size that the length on the conductive nano material used in the present invention at least diameter or 1 limit is nano-scale and there is the material of conductivity, the material with carbon element (being hereinafter sometimes referred to as nano-carbon material) with conductivity that this size is nano-scale can be enumerated, metal material (being hereinafter sometimes referred to as nano metal material) etc. that size is nano-scale.Hereinafter, nano-scale is as defined above.
About the conductive nano material used in the present invention, in nano-carbon material and nano metal material, the nano-carbon material of difference preferred carbon nano-tube described later, carbon nano-fiber, fullerene, graphite, Graphene and carbon nano-particle and metal nanometer line, from the aspect of the dispersiveness improved in conductivity and raising solvent, particularly preferably carbon nano-tube.
About the content of the conductive nano material in thermo-electric converting material, from the viewpoint of the conductivity of the dispersiveness of conductive nano material, thermoelectric conversion element and thermoelectricity conversion performance, in all solids composition of thermo-electric converting material, namely in thermoelectric conversion layer, be preferably 2 quality % ~ 60 quality %, be more preferably 5 quality % ~ 55 quality %, be particularly preferably 10 quality % ~ 50 quality %.
Conductive nano material only can use one separately, also can share two or more.When share two or more as conductive nano material, at least each a kind of nano-carbon material and nano metal material can be share, also can share nano-carbon material or the nano metal material of each two kinds.
1. nano-carbon material
As mentioned above, nano-carbon material is that size is nano-scale and has the material with carbon element of conductivity, if enumerate one example, then for utilizing by the sp of carbon atom 2the carbon-carbon bond that hybridized orbit is formed is by the conductive material etc. of the nano-scale of carbon atom mutual chemical bonding.Specifically, fullerene (comprising endohedral metallofulleren and onion-like fullerene), carbon nano-tube (comprising beanpod structure), the Carbon Nanohorn making the one-sided closed shape of carbon nano-tube, carbon nano-fiber, carbon nm wall, carbon nano wire, carbon nanocoil, vapor grown carbon can be enumerated (also referred to as VGCF.VGCF is the abbreviation of Vapor Grown Carbon Fiber.), graphite, Graphene, carbon nano-particle, nano-sized carbon material etc. in the cup type of the head perforate of carbon nano-tube.In addition, as nano-carbon material, the various carbon blacks demonstrating conductivity with graphite mould crystalline texture can also be used, such as, can enumerate Ketjen black, acetylene black etc., specifically, the carbon blacks such as trade name " Vulcan " can be enumerated.
These nano-carbon materials manufacture by existing manufacture method.Specifically, the contact hydrogen reduction of carbon dioxide, arc discharge method, laser evaporization method, CVD, vapor growth method, Floating method can be enumerated, carbon monoxide is reacted together with iron catalyst carry out the HiPco method, Audit For Process etc. of vapor phase growth at high temperature under high pressure.CVD is the abbreviation of chemical vapour deposition (CVD) Chemical Vapor Deposition.In addition, HiPco is the abbreviation of HighPressure Carbon monoxide (high pressure carbon monoxide).The nano-carbon material produced like this can directly use, and can use in addition and carry out the material after refining by cleaning, centrifugation, filtration, oxidation, chromatography etc.Further, can also use and adopt the ball-type kneading devices such as ball mill, oscillating mill, sand mill, edge runner etc. to pulverize the material obtained as required nano-carbon material; By the material etc. that nano-carbon material cuts off shorter and obtains by chemistry, physical treatment.
As long as the size of the conductive nano material used in the present invention is just not particularly limited for nano-scale.When conductive nano material be carbon nano-tube (being hereinafter also designated as CNT), Carbon Nanohorn, carbon nano-fiber, carbon nano wire, carbon nanocoil, vapor grown carbon (VGCF), cup type nano-sized carbon material etc., especially when CNT, average length is not particularly limited, from aspects such as ease of manufacturing, film forming, conductivity, average length is preferably 0.01 μm ~ 1000 μm, is more preferably 0.1 μm ~ 100 μm.In addition, diameter is not particularly limited, from aspects such as durability, the transparency, film forming, conductivity, is preferably 0.4 μm ~ 100nm, is more preferably below 50nm, more preferably below 15nm.
Carbon nano-tube, carbon nano-fiber, graphite, Graphene and carbon nano-particle during nano-carbon material is preferably above-mentioned, particularly preferably carbon nano-tube.
Below carbon nano-tube (being hereinafter also designated as CNT) is described.CNT comprises the multi-layer C NT that 1 layer of carbon film and graphene film are wound into cylindric individual layer CNT, 2 layer graphene sheets are wound into concentric circles 2 layers of CNT and multi-layer graphene sheet are wound into concentric circles.In the present invention, individual layer CNT, 2 layers of CNT, multi-layer C NT can be used alone respectively, also two or more can be share.Particularly preferably be used in individual layer CNT and the 2 layer CNT that conductivity and characteristic of semiconductor aspect have excellent properties, more preferably use individual layer CNT.
When individual layer CNT, by graphene film based on Graphene hexagonal towards the symmetry of helical structure be called axial chirality, 2 of the datum mark of a certain for the distance on Graphene 6 rings dimension lattice vectors are called chiral vector.(n, the m) of this chiral vector indexation is called chiral index, utilizes this chiral index that individual layer CNT is divided into metallicity and semiconductive.Specifically, n-m is that the CNT of the multiple of 3 demonstrates metallicity, is not that the CNT of the multiple of 3 represents semiconductor.
The individual layer CNT used in the present invention can for the CNT of semiconductive, also for metallic CNT, can also can share both.Further, in CNT can within be surrounded by metal etc., be surrounded by the equimolecular CNT of fullerene in also can using.Particularly the interior CNT being surrounded by fullerene is called beanpod structure.
CNT manufactures by arc discharge method, CVD, laser ablation method etc.The CNT used in the present invention can be the CNT utilizing any one method to obtain, but preferably utilizes arc discharge method and CVD to obtain.
When manufacturing CNT, generate fullerene, graphite, the amorphous carbon as accessory substance simultaneously.In order to remove these accessory substances, can refine.The process for purification of CNT is not particularly limited, and except above-mentioned method for refining, utilizes the acid treatment of nitric acid, sulfuric acid etc., ultrasonic wave process to be also effective for the removal of impurity.Highly purified from the viewpoint of carrying, also more preferably utilize filter to carry out separation in the lump and remove.
After refining, also can directly utilize obtained CNT.In addition, because CNT generates with cord shape usually, thus can cut into desired length to use according to purposes.CNT cuts into short fiber shape by utilizing the acid treatment of nitric acid, sulfuric acid etc., ultrasonic wave process, Freezing smashing method etc.In addition, highly purified from the viewpoint of carrying, also preferably utilize filter to be separated in the lump.
In the present invention, cut-off CNT can not only be used, the CNT making short fiber shape in advance can also be used equally.Such short fiber shape CNT such as can obtain as follows: on substrate, form the catalyst metals such as iron, cobalt, CVD is utilized to carry out the thermal decomposition of carbon compound on its surface at 700 DEG C ~ 900 DEG C, make CNT carry out vapor phase growth, thus obtain this short fiber shape CNT at substrate surface with the shape of carrying out orientation in the vertical direction.The short fiber shape CNT so made can be utilized and obtain from methods such as substrate peel.In addition, for short fiber shape CNT, also can make catalyst metal loadings on the porous support or oxide anodising film of porous silicon and so on, utilize CVD to make CNT in its superficial growth.Following method also can be utilized to make the CNT of the short fiber shape of orientation: using the molecule of the iron-phthalocyanine containing catalyst metals in molecule and so on as raw material, by carrying out CVD in the air-flow of argon/hydrogen, substrate makes CNT.Further, also obtain the short fiber shape CNT of orientation on SiC single crystal surface by epitaxial growth method.
2. nano metal material
Nano metal material is the threadiness or granular metal material etc. of nano-scale, specifically, fibrous metal material (also referred to as metallic fiber), granular metal material (also referred to as metal nanoparticle) etc. can be enumerated.The preferred metal nanometer line described later of nano metal material.
Metallic fiber is preferably solid construction or hollow structure.Be 1nm ~ 1 by average minor axis length, 000nm, average major axis length be 1 μm ~ 100 μm, have the metallic fiber of solid construction is called metal nanometer line, be 1nm ~ 1 by average minor axis length, 000nm, average major axis length are 0.1 μm ~ 1,000 μm, the metallic fiber with hollow structure is called metal nano-tube.
As the material of metallic fiber, as long as be the metal with conductivity, can select according to object is suitable, such as preferably be selected from least one metal in the group be made up of the 4th cycle of the long formula periodic table of elements (IUPAC (IUPAC), 1991 revisions), the 5th cycle and the 6th cycle, be more preferably at least one metal be selected from the 2nd race ~ the 14th race, be more preferably selected from least one metal in the 2nd race, the 8th race, the 9th race, the 10th race, the 11st race, the 12nd race, the 13rd race and the 14th race.
As such metal, such as, can enumerate copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantalum (タ Application テ Le), titanium, bismuth, antimony, lead or their alloy etc.Among them, from the viewpoint of excellent electric conductivity, preferably silver and the alloy with silver.As with the metal used with the alloy form of silver, platinum, osmium, palladium, iridium etc. can be enumerated.Metal can be used alone one, also can share two or more.
About metal nanometer line, as long as be formed as hollow structure by above-mentioned metal, its shape is not particularly limited, can selects according to object is suitable.Cylindric, rectangular-shaped, cross section such as can be taked to be the arbitrary shapes such as polygonal column, increase from the viewpoint of the transparency of thermoelectric conversion layer, preferably polygonal corner angle that are cylindric, cross section become the cross sectional shape justified.The cross sectional shape of metal nanometer line is investigated by utilizing transmission electron microscope (TEM) to observe.
From the viewpoint of identical with above-mentioned conductive nano material, the average minor axis length (being sometimes referred to as " average minor axis footpath " or " average diameter ") of metal nanometer line is preferably below 50nm, is more preferably 1nm ~ 50nm, more preferably 10nm ~ 40nm, is particularly preferably 15nm ~ 35nm.About average minor axis length, such as, can use transmission electron microscope (TEM; Jeol Ltd. manufactures, JEM-2000FX) obtain the minor axis length of 300 metal nanometer lines, calculate their mean value, as average minor axis length.It should be noted that, the minor axis length when minor axis about metal nanometer line is not circular, using the longest minor axis length as minor axis length.
The average major axis length (being sometimes referred to as average length) of metal nanometer line is similarly preferably more than 1 μm, be more preferably 1 μm ~ 40 μm, more preferably 3 μm ~ 35 μm, be particularly preferably 5 μm ~ 30 μm.About average major axis length, such as, can use transmission electron microscope (TEM; Jeol Ltd. manufactures, JEM-2000FX) obtain the long axis length of 300 metal nanometer lines, calculate their mean value, as average major axis length.It should be noted that, when metal nanometer line is bending, the circle that to consider with it be camber line, using the value that calculated by this radius of a circle and flexometer as long axis length.
Metal nanometer line can utilize any manufacture method to manufacture, but preferably record in Japanese Unexamined Patent Publication 2012-230881 publication carry out heating the manufacture method of carrying out the reduction of metal ion in the solvent being dissolved with halide and dispersing additive.The detailed content of halide, dispersing additive and solvent and heating condition etc. is on the books in Japanese Unexamined Patent Publication 2012-230881 publication.In addition, except this manufacture method, such as, also can utilize and be recorded in manufacture method in Japanese Unexamined Patent Publication 2009-215594 publication, Japanese Unexamined Patent Publication 2009-242880 publication, Japanese Unexamined Patent Publication 2009-299162 publication, Japanese Unexamined Patent Publication 2010-84173 publication, Japanese Unexamined Patent Publication 2010-86714 publication etc. respectively to manufacture metal nanometer line.
As long as metal nano-tube is formed as hollow structure by above-mentioned metal, being not particularly limited its shape, can be that individual layer also can for multilayer.From the viewpoint of conductivity and heat conductivity excellence, preferable alloy nanotube is individual layer.
From aspects such as durability, the transparency, film forming, conductivity, the thickness (difference of external diameter and internal diameter) of metal nano-tube is preferably 3nm ~ 80nm, is more preferably 3nm ~ 30nm.From the viewpoint of identical with above-mentioned conductive nano material, the average major axis length of metal nano-tube is preferably 1 μm ~ 40 μm, be more preferably 3 μm ~ 35 μm, more preferably 5 μm ~ 30 μm.The average minor axis length of metal nano-tube is preferably identical with the average minor axis length of metal nanometer line.
Metal nano-tube can utilize any manufacture method to manufacture, such as, the manufacture method etc. recorded in U.S. Patent Application Publication No. 2005/0056118 specification can be utilized to manufacture.
The graininess that as long as metal nanoparticle is above-mentioned metal to be formed or pulverous metal particle; it can be metal particle; can be the surface-coated protectant particulate at metal particle, and then also can for the dispersion that surface-coated microparticulate is obtained in decentralized medium.As the metal used in metal nanoparticle, the silver, copper, gold, palladium, nickel, rhodium etc. in above-mentioned metal preferably can be enumerated.The alloy etc. of alloy, at least one in them and the iron formed by least 2 in them kind can be used in addition.As the alloy formed by 2 kinds, such as, can enumerate platinum-billon, platinum-palldium alloy, gold-silver alloy, silver-palladium alloy, palladium-billon, platinum-billon, rhodium-palldium alloy, silver-rhodium alloy, copper-palldium alloy, nickel-palldium alloy etc.In addition, as the alloy with iron, such as, can enumerate iron-platinum alloy, iron-platinum-copper alloy, iron-platinum-ashbury metal, iron-platinum-bismuth alloy and iron-platinum-lead alloy etc.These metal or alloy can be used alone or two or more combinationally uses.
From the viewpoint of excellent electric conductivity, the average grain diameter (dynamic light scattering method) of metal nanoparticle is preferably 1nm ~ 150nm.
The protective agent of metal particle such as suitably can enumerate the protective agent described in Japanese Unexamined Patent Publication 2012-222055 publication; suitably can enumerate further and there is the protective agent that carbon number is the straight-chain of 10 ~ 20 or the alkyl chain of branched, particularly fatty acid or aliphat amine, analiphatic sulphur alcohols or aliphat alcohols etc.Herein, when carbon number is 10 ~ 20, the storage stability of metal nanoparticle is high and conductivity is also excellent.Fatty acid aliphat amine, analiphatic sulphur alcohols and aliphat alcohols are suitably the material described in Japanese Unexamined Patent Publication 2012-222055 publication.
Metal nanoparticle can utilize any manufacture method to manufacture, as manufacture method, such as, can enumerate vapour deposition method, sputtering method, Direct metal forming, colloid method, alkoxide process, coprecipitation method, sluggish precipitation, thermal decomposition method, chemical reduction method, Amine reduction and the solvent evaporated method etc. in gas.These manufacture methods possess distinctive feature respectively, when for the purpose of producing in a large number, particularly preferably use chemical reduction method, Amine reduction.When implementing these manufacture methods, can choice for use is above-mentioned as required protective agent, suitably can use known reducing agent etc. in addition.
< low molecule conjugated compound >
The present invention and above-mentioned conductive nano material together use low molecule conjugated compound.
Low molecule conjugated compound plays function as dispersant, auxiliary, the dispersion of promotion conductive nano material in decentralized medium.Details about its effect is not yet determined, but considers as follows.Namely, the surface of conductive nano material and low molecule conjugated compound pi-conjugated plane produces electro interaction, such as π-π interacts (also referred to as pi-pi accumulation), low molecule conjugated compound is electronically adsorbed to the surface of conductive nano material.This low molecule conjugated compound is higher than conductive nano material with the compatibility of decentralized medium, and owing to being adsorbed in the surface of conductive nano material, therefore the adsorbent of low molecule conjugated compound and conductive nano material is easily scattered in dispersion, as a result, the dispersiveness of conductive nano material improves.
And low molecule conjugated compound has also given play to following function: at the intermolecular structure charge carrier path of conductive nano material, thus improve thermoelectricity conversion performance.
In the past, in order to build the charge carrier path of electronics in the intermolecular movement of conductive nano material, think to intramolecular electronics move favourable, can minority and in electric mode, conductive nano material intermolecular to be linked the macromolecular compound of conductivity connected be favourable and reality.But, although the specific low molecule conjugated compound used in the present invention is to connecting not favourable in electric mode by the intermolecular link of conductive nano material, can at the intermolecular structure charge carrier path of conductive nano material.Details about its effect is not yet determined, but considers as follows.Namely, for the low molecule conjugated compound on surface being adsorbed in conductive nano material as mentioned above, other low molecule conjugated compound carries out arranging (specifically in the mode of intermolecular Orbital Overlap by pi-pi accumulation etc., layered arrangement or the arrangement of catfish bone), by the laminated structure of this low molecule conjugated compound, at the intermolecular structure charge carrier path of conductive nano material.Thus, can promote that the intermolecular electronics of conductive nano material moves, thus thermoelectricity conversion performance improves.
The low molecule conjugated compound used in the present invention has the thick multiring structure that at least 3 rings in the group being selected from and being made up of aromatic hydrocarbon ring and heteroaromatic condense.This thick multiring structure is without particular limitation of the mode condensed at least 3 rings.For aromatic hydrocarbon ring, such as just like polyacene like that with linearity or row condense mode, the mode such as condensed with ring-type as coronene and such as pyrene in the mode etc. that bulk condenses.This low molecule conjugated compound is so long as not the macromolecular compound with repetitive structure, if enumerate an example, the molecular weight of (except substituting group T described later) thick multiring structure is less than 1000.
Low molecule conjugated compound can it be all made up of thick multiring structure, also can have thick multiring structure as basic framework (basic ring structure) in its part.In the present invention, concerning low molecule conjugated compound, the compound be made up of 1 thick multiring structure and the compound that is made up of 1 thick multiring structure and the substituting group that is combined with this thick multiring structure arrange (pi-pi accumulation) due to the easy mode larger with the coincidence of intermolecular orbit, therefore from promoting that the aspect of intermolecular charge carrier movement is preferred.It should be noted that low molecule conjugated compound has thick multiring structure in its part, to there is in its 1 molecule the thick multiring structure of more than 1 or 2, preferably there is 1 thick multiring structure.
From the viewpoint of the conductivity of the dispersiveness of conductive nano material, thermoelectric conversion element and thermoelectricity conversion performance, relative to conductive nano material 100 mass parts, the content of the low molecule conjugated compound in thermo-electric converting material is preferably 1 mass parts ~ 500 mass parts, is more preferably 20 mass parts ~ 200 mass parts.
Low molecule conjugated compound only can use one separately, also can share two or more.
Such low molecule conjugated compound has the thick multiring structure that at least 3 rings in the group being selected from and being made up of aromatic hydrocarbon ring and heteroaromatic condense.
Herein, as aromatic hydrocarbon ring, as long as have the hydrocarbon ring of the monocycle of armaticity, as the ring becoming its basis, phenyl ring can be enumerated.
As heteroaromatic, as long as the heterocycle with the monocycle of armaticity is not particularly limited, can be suitable for enumerating the heteroaromatic of 5 rings or the heteroaromatic of 6 rings.As the heteroaromatic of 5 rings, such as, can enumerate thiphene ring, furan nucleus, pyrrole ring, imidazole ring, pyrazole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, triazole ring, tetrazole ring, furazan ring.As the heteroaromatic of 6 rings, such as, can enumerate pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, triazine ring.Among these, from the viewpoint of the conductivity of the dispersiveness of conductive nano material, thermoelectric conversion element and thermoelectricity conversion performance, the more preferably heteroaromatic of 5 rings, further preferably thiphene ring, furan nucleus, pyrrole ring.
Thick multiring structure is be selected from the structure condensed by the ring of arbitrary more than 3 in above-mentioned aromatic hydrocarbon ring or heteroaromatic, become according to the coincidence at intermolecular orbit the aspect that larger mode arranges (pi-pi accumulation) from easy, the structure that the ring being preferably more than 4 condenses, the structure that the ring being preferably less than 6 in addition condenses.
Low molecule conjugated compound can be compound, i.e. Ppolynuclear aromatic hydrocarbon compound (PAH) compound of the thick multiring structure that the ring with this compound of formation is all made up of aromatic hydrocarbon ring, also can be compound, i.e. the Ppolynuclear aromatic heterocyclic compound (also referred to as Ppolynuclear aromatic heterocyclic compound) with the thick multiring structure at least comprising 1 above-mentioned heteroaromatic.The thick multiring structure that this Ppolynuclear aromatic heterocyclic compound has is according to the structure that at least 3 rings selected by the mode comprising at least 1 heteroaromatic condense from above-mentioned group.
When low molecule conjugated compound is Ppolynuclear aromatic hydrocarbon compound, preferably not there is following structure, that is, each aromatic hydrocarbon ring forming this thick multiring structure condenses the structure of other aromatic hydrocarbon rings of more than 4.Specifically, Ppolynuclear aromatic hydrocarbon compound preferably has that condense with 1 ring, 2 rings or 3 rings, that at least 3 aromatic hydrocarbon rings condense thick multiring structure, namely, the aromatic hydrocarbon ring of the thick multiring structure of preferred formation all condenses with any one in 1 ring ~ 3 ring, more particularly, preferably not there is perylene structure.
When low molecule conjugated compound is Ppolynuclear aromatic heterocyclic compound, there is not as Ppolynuclear aromatic hydrocarbon compound, relevant with the mode that condenses of ring above-mentioned restriction, all rings forming thick multiring structure all can condense mode arbitrarily and condense.In addition, the ring forming Ppolynuclear aromatic heterocyclic compound is heteroaromatic and desired aromatic hydrocarbon ring, and the number of the heteroaromatic comprised in Ppolynuclear aromatic heterocyclic compound is at least 1, also can be whole rings is heteroaromatic.Now, the number of the heteroaromatic of 5 rings in the heteroaromatic comprised in Ppolynuclear aromatic heterocyclic compound is not particularly limited, such as, can be 0, also can be 1, or also can be more than 2, and then can be whole.
From the dispersiveness of conductive nano material, the conductivity of thermoelectric conversion element and the aspect of thermoelectricity conversion performance, low molecule conjugated compound is preferably Ppolynuclear aromatic heterocyclic compound.
No matter low molecule conjugated compound is any one in Ppolynuclear aromatic hydrocarbon compound and Ppolynuclear aromatic heterocyclic compound, all preferably has the thick multiring structure represented by any one formula in following formula (1A) ~ (1D).
Formula (1A) ~ (1D) is respectively the thick multiring structure that 3,4,5 or 6 rings condense in a row ground mode.In above-mentioned formula, for convenience of explanation, be called by the formation ring of thick multiring structure " A ring " ~ " F ring ", these rings can be identical, also can be different.
Thick multiring structure represented by formula (1A) ~ (1D) is made up of " A ring " ~ " the F ring " condensed with 1 ring or 2 rings respectively.Like this, if low molecule conjugated compound has the thick multiring structure that 3 ~ 6 rings condense in the mode of row, then think and easily arrange, the dispersiveness of conductive nano material, the conductivity of thermoelectric conversion element and thermoelectricity conversion performance all can improve further.
At least 1 in thick multiring structure preferred C ring, D ring, E ring and F ring represented by formula (1A) ~ (1D), more preferably all rings condense with the mode that condenses represented by following formula (1-1) and (1-2) and adjacent ring.If C ring, D ring, E ring and F ring condense in this mode that condenses, then think that the thick multiring structure represented by formula (1A) ~ (1D) more easily arranges, the dispersiveness of conductive nano material and the conductivity of thermoelectric conversion element and thermoelectricity conversion performance can be taken into account with higher level.
In formula, X represents carbon atom or hetero-atom, and * 1 represents with * 2 the ring carbons condensed with identical ring respectively.
As long as represent that the hetero-atom of X just can be not particularly limited to the atom of the heterocycle imparting armaticity of 5 rings represented by formula (1-2), preferably sulphur atom, oxygen atom, nitrogen-atoms can be enumerated.
Raise, can improve further the aspect of the dispersiveness of conductive nano material from the compatibility for decentralized medium, low molecule conjugated compound preferably has substituting group.That is, preferably there is substituent Ppolynuclear aromatic heterocyclic compound and in Ppolynuclear aromatic hydrocarbon, imported substituent compound.Particularly, when low molecule conjugated compound has the thick multiring structure represented by above-mentioned formula (1A) ~ (1D), any one ring of these thick multiring structures can have substituting group, from the aspect that the compatibility for decentralized medium is higher, at least one ring preferably in the condensed ring of end, i.e. A ring and B ring has substituting group, and preferred further have substituting group on A ring and B ring.It should be noted that, substituent number is not particularly limited.
Alternatively base, is not particularly limited, such as, can enumerate substituting group T.
Alternatively base T, can enumerate following substituting group.
(preferred carbon number is 1 ~ 20 can to enumerate alkyl, such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, octyl group, decyl etc.), (preferred carbon number is 3 ~ 20 to cycloalkyl, such as, cyclopropyl, cyclopenta, cyclohexyl etc.), (preferred carbon number is 6 ~ 26 to aryl, such as, phenyl, 1-naphthyl etc.), (preferred carbon number is 2 ~ 20 to heterocyclic radical, preferably has at least 1 oxygen atom, sulphur atom (-S-,-SO-,-SO 2-), nitrogen-atoms, the heterocyclic radical of 5 or 6 rings of silicon atom and selenium atom etc., such as, furans cyclic group, thiophene cyclic group, pyridine cyclic group, imidazoles cyclic group, indoles cyclic group, pyrrolidines cyclic group, piperidines cyclic group etc.), (preferred carbon number is 1 ~ 20 to alkoxyl, such as, methoxyl group, ethyoxyl, butoxy, octyloxy, the last of the ten Heavenly stems oxygen base, benzyloxy etc.), (preferred carbon number is 1 ~ 20 for alkyl monosubstituted amino or dialkyl amido, methylamino, ethylamino, hexylamino, N, N-dipropylamino, methylhexyl is amino), (preferred carbon number is 2 ~ 20 to alkoxy carbonyl group, such as, carbonyl octyloxy, 2-ethyl hexyl oxy carbonyl etc.), thioether group, polyethyleneoxy (HO (CH 2cH 2o) n-Ji) (n represents the integer of more than 2).
Herein, as thioether group, as long as by the organic group that sulphur atom is combined with thick multiring structure, such as, (preferred carbon number is 1 ~ 20 can to enumerate alkylthio group, such as, methyl mercapto, ethylmercapto group, isopropyisulfanyl, benzylthio etc.), (preferred carbon number is 3 ~ 20 to cycloalkylthio, such as, ring rosickyite base, ring penta sulfenyl, cyclohexylthio, 4-methyl cyclohexane sulfenyl etc.), (preferred carbon number is 6 ~ 26 to arylthio, such as, thiophenyl, 1-naphthalene sulfenyl, 3-methylphenyl-sulfanyl, 4-Methoxv-phenylsulfanvl etc.).
In addition, substituting group T also can be by the complex substituents of two or more above-mentioned moiety combinations.Such as, the aryl etc. replaced by the alkyl of more than 1 or 2, alkoxyl or alkoxy carbonyl group can be enumerated.
Substituting group T preferred alkyl, aryl, heterocyclic radical, alkoxyl, dialkyl amido, alkoxy carbonyl group, thioether group, polyethyleneoxy and complex substituents, more preferably alkyl, aryl, heterocyclic radical, alkoxyl, dialkyl amido, alkoxy carbonyl group and complex substituents.
Substituting group T is the group of the hydrogen atom replacing thick multiring structure, is not the thick multiring structure group each other of more than 2 that link low molecule conjugated compound has.The thick multiring structure group each other of this link more than 2 can enumerate the substituting group T being at least divalent, such as, be not preferably to comprise the group of P=O, comprise the group of S=O.
The low molecule conjugated compound used in the present invention preferably at least thick multiring structure has symmetry, and the position of substitution and the kind that more preferably comprise substituting group T have symmetry.Like this, if low molecule conjugated compound has symmetry, then easily arrange, the interaction of the electronics on the surface of conductive nano material is excellent.Herein, " symmetry " refers to, low molecule conjugated compound is relative to some rings or condense portion's (point or line) and have chemical constitution for symmetries such as point symmetry, line symmetry, Rotational Symmetries.Such as, refer to by the portion that condenses at the center as thick multiring structure or ring multiple part-structures of splitting there is identical chemical constitution.The portion of condensing refers to, carry out carbon atom that condensation (link) portion of 2 rings of condensation or the ring of more than 2 carry out condensing or hetero-atom, specifically, such as refer to that in the central carbon atom of that alkene structure non-, above-mentioned formula (1B) and formula (1D), C ring and D ring carry out the carbon-to-carbon double bond part etc. condensed.In addition, the C ring etc. in such as formula (1A) and formula (1C) is specifically referred to as the ring at the center of thick multiring structure.
Below, the concrete example of metal complex dye of the present invention is shown, but the present invention is not limited to these.
These low molecule conjugated compounds also can use commercially available product, in addition, also can suitably synthesize as in the embodiment described later.
< macromolecular compound >
Except conductive nano material and low molecule conjugated compound, thermo-electric converting material of the present invention is desirably also containing macromolecular compound.If thermo-electric converting material of the present invention contains macromolecular compound, then the dispersiveness of the conductive nano material in thermo-electric converting material of the present invention and the thermoelectricity conversion performance of thermoelectric conversion element all can improve further.As such macromolecular compound, be not particularly limited, such as, can enumerate conjugated polymer and non-conjugate high molecular.
Therefore, thermo-electric converting material of the present invention preferably containing macromolecular compound, more preferably containing at least one macromolecular compound be selected from the group that is made up of conjugated polymer and non-conjugate high molecular.When containing multiple macromolecular compound, the macromolecular compound of multiple identical type can be contained, also can contain multiple different types of macromolecular compound in addition, preferably contain the mixture of at least one conjugated polymer and at least one non-conjugate high molecular, i.e. conjugated polymer and non-conjugate high molecular.If containing such mixture, then except can improving above-mentioned dispersiveness and thermoelectricity conversion performance, the effect that the thermoelectricity conversion film that also can obtain being easy to prevent from being made up of thermo-electric converting material produces from strippable substrate and crackle.
In the present invention, when macromolecular compound is copolymer, can be block copolymer, random copolymer, alternate copolymer, or also can be graft copolymer etc.
The content of the macromolecular compound in thermo-electric converting material is not particularly limited, from the viewpoint of the conductivity of thermoelectric conversion element and thermoelectricity conversion performance, in the total solid composition of thermo-electric converting material, namely in thermoelectric conversion layer, be preferably 10 quality % ~ 80 quality %, be more preferably 20 quality % ~ 70 quality %, more preferably 30 quality % ~ 60 quality %.
The content of the conjugated polymer in thermo-electric converting material is not particularly limited, from the viewpoint of the conductivity of thermoelectric conversion element and thermoelectricity conversion performance, in the scope of content meeting above-mentioned macromolecular compound, in the total solid composition of thermo-electric converting material, be preferably 15 quality % ~ 70 quality %, be more preferably 25 quality % ~ 60 quality %, more preferably 30 quality % ~ 50 quality %.
Similarly, the content of the non-conjugate high molecular in thermo-electric converting material is not particularly limited, from the viewpoint of the conductivity of thermoelectric conversion element and thermoelectricity conversion performance, in the scope of content meeting above-mentioned macromolecular compound, in the total solid composition of thermo-electric converting material, be preferably 20 quality % ~ 70 quality %, be more preferably 30 quality % ~ 65 quality %, more preferably 35 quality % ~ 60 quality %.
1. conjugated polymer
Just be not particularly limited by the compound of the structure of the lone electron pair generation conjugation of pi-electron or lone pair electrons as long as conjugated polymer has main chain.As such conjugated structure, such as, can enumerate the structure that in the carbon-carbon bond on main chain, singly-bound is alternately connected with double bond.This conjugated polymer is not necessarily high-molecular weight compounds, can be oligomer compounds yet.
As such conjugated polymer, can enumerate: by thiophene based compound, azole series compound, aniline based compound, acetylene based compound, to phenylene based compound, to phenylene vinylidene based compound, to phenylene ethynylene based compound, to fluorenylene vinylene based compound, fluorenes based compound, aromatic polyvalent amine compound (also referred to as arylamine based compound), polyacene based compound, poly-luxuriant and rich with fragrance based compound, metal phthalocyanine based compound, to xylylene based compound, the sulfide-based compound of ethenylidene, metaphenylene based compound, naphthalene ethenylidene based compound, to phenylene oxide based compound, Phenylene Sulfide based compound, furans based compound, selenophen based compound, Azo, metal complex based compound, with in these compounds, imported substituent derivative etc. as monomer, and by the conjugated polymer with the repetitive structure of this monomer of this monomer polymerization or copolymerization.
Among these, from the viewpoint of the dispersiveness of conductive nano material and thermoelectricity conversion performance, preferably will be selected from by thiophene based compound, azole series compound, aniline based compound, acetylene based compound, to phenylene based compound, to phenylene vinylidene based compound, to phenylene ethynylene based compound, fluorenes based compound, this conjugated polymer of conjugated polymer of arylamine based compound and at least one compound polymerization imported group that substituent compound (sometimes also referred to as derivative) forms in these compounds in or copolymerization has the repetitive of above-mentioned monomer.
As the substituting group imported in above-claimed cpd, be not particularly limited, consider and the compatibility of other compositions, the kind etc. of decentralized medium that can use, be preferably suitable for selecting to import the substituting group that can improve the dispersiveness of conjugated polymer in decentralized medium.
An alternatively example of base, when with an organic solvent as decentralized medium, except the alkyl of straight chain, side chain or ring-type, alkoxyl, alkylthio, also preferably can use alkoxyalkylene oxygen base, alkoxyalkylene oxygen base alkyl, crown ether base, aryl etc.These groups can have substituting group further.In addition, substituent carbon number is not particularly limited, is preferably 1 ~ 12, is more preferably 4 ~ 12, particularly preferably carbon number be alkyl, alkoxyl, alkylthio, alkoxyalkylene oxygen base, the alkoxyalkylene oxygen base alkyl of the long-chain of 6 ~ 12.
On the other hand, when using water-medium as decentralized medium, preferably import the hydrophilic radicals such as carboxylic acid group, sulfonic group, hydroxyl, phosphate further at the end of each monomer or above-mentioned substituting group.In addition, can import the alternatively base such as dialkyl amido, alkyl monosubstituted amino, amino, carboxyl, ester group, amide groups, carbamate groups, nitro, cyano group, NCO, isocyano group, halogen atom, perfluoroalkyl, perfluoro alkoxy, be preferred.
The substituent number that can import is not particularly limited, considers dispersiveness and compatibility, the conductivity etc. of conjugated polymer, the substituting group importing more than 1 or 2 can be suitable for.
As the thiophene system conjugated polymer by thiophene based compound and derivative polymerization or copolymerization, as long as there is thiophene based compound or derivatives thereof as repetitive structure, such as can enumerate comprise thiophene as repetitive structure polythiophene, be included in thiphene ring the derivative that is imported with substituent thiophene based compound and there is thiophene based compound containing the thick multiring structure of thiphene ring as the conjugated polymer of repetitive structure as the conjugated polymer of repetitive structure and comprising.
As be included in thiphene ring be imported with substituent thiophene based compound derivative as the conjugated polymer of repetitive structure, can enumerate poly-3 methyl thiophene, poly-3-butyl thiophene, poly-3-hexyl thiophene, poly-3-cyclohexyl thiophene, poly-3-(2 '-ethylhexyl) thiophene, poly-3-octyl thiophene, poly-3-dodecylthiophene, poly-3-(2 '-methoxy ethoxy) methylthiophene, poly-3-(methoxyethoxyethoxy) methylthiophene etc. poly-(alkylated substituted thiazoline fen) is conjugated polymer; Poly-3-methoxythiophene, poly-3-ethoxythiophene, poly-3-own oxygen base thiophene, poly-3-cyclohexyloxy thiophene, poly-3-(2 '-ethyl hexyl oxy) thiophene, poly-3-dodecyl oxygen base thiophene, poly-3-methoxyl group (divinyl oxide base) thiophene, poly-3-methoxyl group (triethylene oxygen base) thiophene, poly-(3,4-ethylene dioxythiophene) etc. poly-(alkoxyl substituted thiophene) are conjugated polymer; Poly-3-methoxyl group-4-methylthiophene, poly-3-own oxygen base-4-methylthiophene, poly-3-dodecyl oxygen base-4-methylthiophene etc. poly-(3-alkoxyl replaces the fen of-4-alkylated substituted thiazoline) are conjugated polymer; Poly-3-sulfo-hexyl thiophene, poly-3-thiocapryl thiophene, poly-3-thiolauryl thiophene etc. poly-(3-alkylthio thiophene) are conjugated polymer.
Wherein, preferably poly-(3-alkylthrophene) is conjugated polymer, poly-(3-alkoxy thiophene) be conjugated polymer.About at 3, there is substituent polythiophene system conjugated polymer, by 2 of thiphene ring, the bonding direction of 5 and produce anisotropy.In the polymerization of 3-substituted thiophene, generate mixture, it comprise thiphene ring 2 materials bonded together (HH combination: head head), thiphene ring 2 with the material (HT combination: head is to tail) of 5 bondings, thiphene ring at 5 materials bonded together (TT keyed jointing body: tail tail).From the flatness improving main polymer chain, the aspect that easily forms pi-pi accumulation structure between polymer, make the easy movement of electric charge, thiphene ring is The more the better with the ratio of the material (HT combination) of 5 bondings at 2.The ratio of these bonding pattern by 1h-NMR measures.2 of thiphene ring are preferably more than 50 quality %, more preferably more than 70 quality % with the HT combination ratio in the polymer of 5 bondings, are particularly preferably more than 90 quality %.
More particularly, there is thiophene based compound containing the thick multiring structure of thiphene ring as the conjugated polymer of repetitive structure as being included in thiphene ring the derivative that is imported with substituent thiophene based compound as the conjugated polymer of repetitive structure and comprising, following compd A-1 ~ A-16 can be exemplified.Wherein, in following formula, n represents the integer of more than 10.
As the azole series conjugated polymer by azole series compound and derivative polymerization or copolymerization, as long as there is azole series compound or derivatives thereof as repetitive structure, such as can enumerate comprise pyrroles as repetitive structure polypyrrole, be included in pyrroles the derivative that is imported with substituent azole series compound and there is azole series compound containing the thick multiring structure of pyrrole ring as the conjugated polymer of repetitive structure as the conjugated polymer of repetitive structure and comprising.As azole series conjugated polymer, such as, can exemplify following compd B-1 ~ B-8.It should be noted that, in following formula, n represents the integer of more than 10.
As the aniline system conjugated polymer by aniline based compound and derivative polymerization or copolymerization, as long as there is aniline based compound or derivatives thereof as repetitive structure, such as can enumerate comprise aniline as repetitive structure polyaniline, be included in aniline phenyl ring on be imported with substituent aniline based compound derivative as repetitive structure conjugated polymer and comprise the phenyl ring had containing aniline the aniline based compound of thick multiring structure as the conjugated polymer of repetitive structure.As aniline system conjugated polymer, following Compound C-1 ~ C-8 can be exemplified.It should be noted that, in following formula, n represents the integer of more than 10, and molar ratio y is more than 0 and be less than 1.
As the acetylene system conjugated polymer by acetylene based compound and derivative polymerization or copolymerization, as long as there is acetylene based compound or derivatives thereof as repetitive structure, such as, following Compound D-1 ~ D-3 can be exemplified.It should be noted that, in following formula, n represents the integer of more than 10.
As by phenylene based compound and derivative polymerization or copolymerization to phenylene system conjugated polymer, as long as have to phenylene based compound or derivatives thereof as repetitive structure, such as, can exemplify following compd E-1 ~ E-9.It should be noted that, in following formula, n represents the integer of more than 10.
As by phenylene vinylidene based compound and derivative polymerization or copolymerization to phenylene vinylidene system conjugated polymer, as long as to have phenylene vinylidene based compound or derivatives thereof as repetitive structure, following compound F 17-hydroxy-corticosterone-1 ~ F-3 can be exemplified.It should be noted that, in following formula, n represents the integer of more than 10.
As by phenylene ethynylene based compound and derivative polymerization or copolymerization to phenylene ethynylene system conjugated polymer, as long as to have phenylene ethynylene based compound or derivatives thereof as repetitive structure, following compound G-1 and G-2 can be exemplified.It should be noted that, in following formula, n represents the integer of more than 10.
As the conjugated polymer by compound other than the above and derivative polymerization or copolymerization, as long as there is compound or derivatives thereof other than the above as repetitive structure, following compound H-1 ~ H-13 can be exemplified.It should be noted that, in following formula, n represents the integer of more than 10.
In above-mentioned conjugated polymer, preferably use the conjugated polymer of straight-chain.The conjugated polymer of such straight-chain can such as pass through the thiphene ring of each monomer or pyrrole ring to obtain 2 and 5 bondings respectively when polythiophene system conjugated polymer, polypyrrole system conjugated polymer.When poly base system conjugated polymer, poly (phenylenevinylene) system conjugated polymer, Polyphenylene ethynylene system conjugated polymer, the conjugated polymer of such straight-chain can by obtaining the phenylene of each monomer at contraposition (1 and 4) bonding.
The conjugated polymer used in the present invention can have separately a kind or combination has above-mentioned repetitive of more than two kinds (hereinafter, also will the monomer of this repetitive being provided to be called " the 1st monomer (group) ").In addition, except the repetitive structure derived from the 1st monomer, the repetitive structure derived from the monomer with other structures (hereinafter also referred to as " the 2nd monomer ") can also be had simultaneously.When the conjugated polymer for being made up of multiple repetitive structure, can be block copolymer, random copolymer or graft polymers.
As the repetitive structure with the 2nd monomer of other structures share with above-mentioned 1st monomer, can enumerate there is carbazyl, dibenzo [b, d] thiophene coughs up base, ring five [2,1-b; 3,4-b '] dithienyl, pyrrolo-[3,4-c] pyrroles-1,4 (2H, 5H)-diketo, benzo [2,1,3] thiadiazoles-4,8-bis-base, azo group, 5H-dibenzo [b, d] thiophene are coughed up the compound of base, thiazolyl, imidazole radicals, oxadiazolyl, thiadiazolyl group, triazolyl etc. and be imported with substituent compound further in these compounds.As imported substituting group, the group same with above-mentioned substituting group can be enumerated.
The repetitive structure derived from one or more monomers being selected from the 1st set of monomers in the conjugated polymer used in the present invention adds up to and preferably has more than 50 quality %, more preferably has more than 70 quality % in conjugated polymer, is preferably only made up of the repetitive structure derived from one or more monomers being selected from the 1st set of monomers further.Be particularly preferably the conjugated polymer be only made up of the single repetitive structure being selected from the 1st set of monomers.
In the 1st set of monomers, more preferably use comprise derived from any one in the polythiophene system conjugated polymer of the repetitive structure of thiophene based compound and derivative thereof or both.Particularly preferably there is thiphene ring represented by following structural formula (1) ~ (5) or containing the condensation aromatic ring structure of thiphene ring as the polythiophene system conjugated polymer of repetitive structure.
In structure above (1) ~ (5), R 1~ R 13represent hydrogen atom, halogen atom, alkyl, alkoxyl, perfluoroalkyl, perfluoro alkoxy, amino, alkylthio group, polyalkylene oxide base, acyloxy or alkoxy carbonyl group independently of one another, Y represents carbon atom, nitrogen-atoms or silicon atom, and n represents the integer of 1 or 2.Further, * represents the connecting portion of each repetitive structure.
R 1~ R 13in, as halogen atom, fluorine, chlorine, bromine or iodine atom can be enumerated, preferred fluorine, chlorine.
Alkyl comprises the alkyl of straight chain, side chain, ring-type, preferred carbon number is the alkyl of 1 ~ 14, specifically, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, the tert-butyl group, sec-butyl, n-pentyl, tertiary pentyl, n-hexyl, 2-ethylhexyl, octyl group, nonyl, decyl, dodecyl, myristyl etc. can be enumerated.
As alkoxyl, preferred carbon number is the alkoxyl of 1 ~ 14, specifically, can enumerate methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, tert-butoxy, sec-butoxy, n-pentyloxy, tertiary amoxy, just own oxygen base, 2-ethyl hexyl oxy, octyloxy, the ninth of the ten Heavenly Stems oxygen base, the last of the ten Heavenly stems oxygen base, dodecyl oxygen base, myristyl oxygen base etc.
As perfluoroalkyl, preferred carbon number is the perfluoroalkyl of 1 ~ 10, specifically, can enumerate CF 3base, CF 3cF 2base, positive C 3f 7base, different C 3f 7base, positive C 4f 9base, tertiary C 4f 9base, secondary C 4f 9base, positive C 5f 11base, CF 3cF 2c (CF 3) 2base, positive C 6f 13base, C 8f 17base, C 9f 19base, C 10f 21base, CF 3(CF 2) 2cH 2base, CF 3(CF 2) 4cH 2base, CF 3(CF 2) 5cH 2cH 2base etc.
As perfluoro alkoxy, preferred carbon number is the perfluoro alkoxy of 1 ~ 10, specifically, can enumerate CF 3o base, CF 3cF 2o base, positive C 3f 7o base, different C 3f 7o base, positive C 4f 9o base, tertiary C 4f 9o base, secondary C 4f 9o base, positive C 5f 11o base, CF 3cF 2c (CF 3) 2o base, positive C 6f 13o base, C 8f 17o base, C 9f 19o base, C 10f 21o base, CF 3(CF 2) 2cH 2o base, CF 3(CF 2) 4cH 2o base, CF 3(CF 2) 5cH 2cH 2o base etc.
Amino comprises alkyl amino and arylamino, preferred carbon number is the amino of 0 ~ 16, specifically, amino, single ethylamino, diethylamino, single hexylamino, dihexyl amino, dioctylamino, single dodecylamino can be enumerated, diphenyl amino, two (xylyl) are amino, xylyl is amino, single phenyl amino etc.
As alkylthio group, preferred carbon number is the alkylthio group of 1 ~ 14, specifically, can enumerate CH 3s base, CH 3cH 2s base, positive C 3h 7s base, different C 3h 7s base, positive C 4h 9s base, tertiary C 4h 9s base, secondary C 4h 9s base, positive C 5h 11s base, CH 3cH 2c (CH 3) 2s base, positive C 6h 13s base, c-C 6h 11s base, CH 3(CH 2) 5cH 2cH 2s base, C 6h 13s base, C 8h 17s base, C 9h 19s base, C 10h 21s base, 2-ethyl hexyl sulfenyl etc.
As polyalkylene oxide base, preferred carbon number is the polyalkylene oxide base of 3 ~ 20, specifically, can enumerate polyethyleneoxy, polypropylene oxygen base.
As acyloxy, preferred carbon number is the acyloxy of 1 ~ 14, specifically, such as, can enumerate acetoxyl group, ethyl carbonyl acyloxy, butyl carbonyl acyloxy, octyl group carbonyl acyloxy, dodecyl carbonyl acyloxy, phenyl carbonyl acyloxy etc.
As alkoxy carbonyl group, preferred carbon number is the alkoxy carbonyl group of 1 ~ 14, specifically, methoxycarbonyl, ethoxy carbonyl, positive propoxy carbonyl, isopropoxy carbonyl, n-butoxycarbonyl, tert-butoxycarbonyl, positive hexyloxy carbonyl, dodecyl oxygen base carbonyl etc. can be enumerated.
These groups can be substituted further.
As R 1~ R 13, be preferably alkyl, alkoxyl, amino, alkylthio group, polyalkylene oxide base, hydrogen atom, be more preferably alkyl, alkoxyl, alkylthio group, polyalkylene oxide base, be particularly preferably alkyl, alkoxyl, polyalkylene oxide base.
Y is preferably carbon atom or nitrogen-atoms, is more preferably carbon atom.
As the repetitive structure represented by structure above (1) ~ (5), specifically, following compd A-17 ~ A-25 can be exemplified, but be not limited to these.
Being not particularly limited the molecular weight of above-mentioned each conjugated polymer, can be the material of HMW certainly, also can be the oligomer (such as weight average molecular weight about 1000 ~ 10000) of molecular weight lower than this molecular weight.
From the viewpoint of realizing high conductivity, conjugated polymer is preferably difficult to by acid, light, thermal decomposition.In order to obtain high conductivity, the long conjugated chain by conjugated polymer is needed to carry out intramolecular charge carrier transmission and the jump of intermolecular charge carrier.In order to reach this object, the molecular weight of preferred conjugated polymer is large to a certain extent.From then on viewpoint is set out, and the molecular weight of the conjugated polymer used in the present invention is preferably more than 5000 with Weight-average molecular gauge, is more preferably 7000 ~ 300,000, more preferably 8000 ~ 100,000.Weight average molecular weight can utilize gel permeation chromatography (GPC) to measure.
These conjugated polymers can utilize common oxidative polymerization method to make the above-mentioned monomer as construction unit carry out being polymerized manufacturing.
In addition, also can use commercially available product, such as, can enumerate poly-(3-hexyl thiophene-2,5-bis-base) stereoregular product that Aldrich society manufactures.
As the conjugated polymer used in the present invention, except above-mentioned each conjugated polymer, the fluorene structured conjugated polymer as repetitive structure at least comprised represented by following general formula (1A) or (1B) can also be enumerated.
(in formula, R 1Aand R 2Arepresent substituting group independently of one another.R 3Aand R 4Arepresent aromatic cyclic hydrocarbon group, aromatic heterocycle, alkyl or alkoxyl independently of one another.Herein, R 3Awith R 4Acan bonding and form ring mutually.N11 and n12b represents the integer of 0 ~ 3 independently of one another, and n12 represents the integer of 0 ~ 2.L arepresent the linking group be selected from by the moiety combinations in the group of singly-bound ,-N (Ra1)-or the aromatic cyclic hydrocarbon group of divalent, the aromatic heterocycle of divalent and N (Ra1)-form.L brepresent singly-bound, divalent aromatic cyclic hydrocarbon group, divalent aromatic heterocycle ,-N (Ra1)-or by the linking group of these moiety combinations.Herein, Ra1 represents substituting group.X brepresent 3 valency aromatic cyclic hydrocarbon groups, 3 valency aromatic heterocycle or >N-.* bonding position is represented.)
As R 1A, R 2Ain substituting group, following substituting group W1 can be enumerated.
(substituting group W1)
Alternatively base W1, halogen atom can be enumerated, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl group, aryl, aryl boryl, hydrogenation boryl, heterocyclic radical (comprises heteroaryl, as ring member nitrogen atoms, preferred oxygen atom, sulphur atom, nitrogen-atoms, silicon atom, boron atom), alkoxyl, aryloxy group, alkylthio group, arylthio, the sulfonyl of alkyl or aryl, the phosphinyl (ス Off ィ ニ Le) of alkyl or aryl, amino (comprises amino, alkyl amino, arylamino, heterocyclic amino group), acylamino-, the sulfoamido of alkyl or aryl, the carbamoyl of alkyl or aryl, the sulfamoyl of alkyl or aryl, the sulfoamido of alkyl or aryl, acyl group, alkoxy carbonyl group, aryloxycarbonyl, acyloxy, urea groups, carbamate groups, imide, hydroxyl, cyano group, nitro etc.
Among them, optimization aromatic hydrocarbon cyclic base, aromatic heterocycle, alkyl, alkoxyl, alkylthio group, amino, hydroxyl, more preferably aromatic cyclic hydrocarbon group, aromatic heterocycle, alkyl, alkoxyl, hydroxyl, further optimization aromatic hydrocarbon cyclic base, aromatic heterocycle, alkyl, alkoxyl, particularly preferably alkyl.
R 1A, R 2Awhen for alkylthio group, carbon number is preferably 1 ~ 24, is more preferably 1 ~ 20, more preferably 6 ~ 16.Alkylthio group can have substituting group, as this substituting group, can enumerate above-mentioned substituting group W1.
As alkylthio group, such as, can enumerate methyl mercapto, ethylmercapto group, isopropyisulfanyl, tertiary butylthio, just own sulfenyl, n-octyl sulfenyl, 2-ethyl hexyl sulfenyl, n-octadecane base sulfenyl.
R 1A, R 2Awhen for amino, this amino comprises amino, alkyl amino, arylamino, and carbon number is preferably 0 ~ 24, is more preferably 1 ~ 20, more preferably 1 ~ 16.Alkyl amino, arylamino or heterocyclic amino group can have substituting group, alternatively base, can enumerate above-mentioned substituting group W1.
As amino, such as, can enumerate amino, methylamino, N, N-diethylamino, phenyl amino, N-methyl-N-phenyl, preferred alkyl amino, arylamino.
R 1A, R 2Awhen for aromatic cyclic hydrocarbon group, aromatic heterocycle, alkyl, alkoxyl, R described later can be enumerated 3A, R 4Ain aromatic cyclic hydrocarbon group, aromatic heterocycle, alkyl, alkoxyl.
It should be noted that, the preferred carbon number of alkyl, alkoxyl is 1 ~ 18, is more preferably 1 ~ 12, more preferably 1 ~ 8.
It should be noted that, the preferable range of aromatic cyclic hydrocarbon group, aromatic heterocycle and R 3A, R 4Aidentical.
N11, n12 are preferably 0 or 1.
R 3A, R 4Ain the carbon number of aromatic hydrocarbon ring of aromatic cyclic hydrocarbon group be preferably 6 ~ 24, be more preferably 6 ~ 20, more preferably 6 ~ 18.Aromatic hydrocarbon ring can enumerate phenyl ring, naphthalene nucleus, and these rings can be condensed by rings such as aromatic hydrocarbon ring, aliphatic hydrocarbon ring, heterocycles.Further, aromatic cyclic hydrocarbon group can have substituting group, alternatively base, can enumerate above-mentioned substituting group W1.As this substituting group, preferred alkyl, alkoxyl, alkylthio group, amino, hydroxyl, more preferably alkyl, alkoxyl, hydroxyl, further preferred alkyl, alkoxyl.
R 3A, R 4Ain the carbon number of heteroaromatic of aromatic heterocycle be preferably 2 ~ 24, be more preferably 3 ~ 20, more preferably 3 ~ 18.The one-tenth ring hetero atom of heteroaromatic is preferably nitrogen-atoms, oxygen atom, sulphur atom, is preferably 5 or 6 rings.This heteroaromatic can be condensed by rings such as aromatic hydrocarbon ring, aliphatic hydrocarbon ring, heterocycles.In addition, aromatic cyclic hydrocarbon group can have substituting group, alternatively base, can enumerate above-mentioned substituting group W1.As this substituting group, preferred alkyl, alkoxyl, alkylthio group, more preferably alkyl, alkoxyl, further preferred alkyl.
As heteroaromatic, pyrrole ring can be enumerated, thiphene ring, imidazole ring, pyrazole ring, thiazole ring, isothiazole ring, pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, triazine ring, indole ring, iso-indoles ring, quinoline ring, isoquinolin ring, quinazoline ring, phthalazines ring, pteridine ring, coumarin ring, chromone ring, 1, 4-benzene diazacyclo (ゼ Application ゾ ジ ア ゼ ピ ン Ring), benzimidazole ring, benzofuran ring, purine ring, acridine ring, phenoxazine ring, phenthazine ring, furan nucleus, selenophen ring, tellurium fen ring, oxazole ring, isoxazole ring, pyridone-2-ketone ring, seleno pyranoid ring (セ レ ノ ピ ラ ン Ring), telluro pyranoid ring (テ Le ロ ピ ラ ン Ring) etc., preferred thiphene ring, pyrrole ring, furan nucleus, imidazole ring, pyridine ring, quinoline ring, indole ring.
R 3A, R 4Ain the carbon number of alkyl be preferably 1 ~ 24, be more preferably 1 ~ 20, more preferably 6 ~ 16.Alkyl can be straight-chain, branched or ring-type, also can have substituting group further, alternatively base, can enumerate above-mentioned substituting group W1.
As alkyl, such as, can enumerate methyl, ethyl, isopropyl, the tert-butyl group, n-hexyl, n-octyl, 2-ethylhexyl, n-octadecane base.
R 3A, R 4Ain the carbon number of alkoxyl be preferably 1 ~ 24, be more preferably 1 ~ 20, more preferably 6 ~ 16.Alkoxyl can have substituting group, alternatively base, can enumerate above-mentioned substituting group W1.
As alkoxyl, such as, can enumerate methoxyl group, ethyoxyl, isopropoxy, tert-butoxy, just own oxygen base, n-octyloxy, 2-ethyl hexyl oxy, n-octadecane base oxygen base.
R 3Aand R 4Aat least one party be preferably aromatic cyclic hydrocarbon group or aromatic heterocycle.
R 3Aand R 4Amutually can form ring by bonding, as ring, be preferably 3 ~ 7 rings, can be saturated hydrocarbons ring, unsaturated hydrocarbons ring, aromatic hydrocarbon ring, heterocycle (comprising heteroaromatic), and the ring formed can be monocycle, also can be thick combined into many rings.Further, the ring formed can have substituting group, alternatively base, can enumerate substituting group W1.
In the present invention, the ring that they are formed is preferably fluorenes ring, preferably 9 for spirane structure, be following structure material.
Herein, R 1A, R 2A, R in n11 and n12 and above-mentioned general formula (1A) or (1B) 1A, R 2A, n11 with n12 implication is identical, preferred scope is also identical.
R 1A', R 2A' and n12 ' and R 1A, R 2A, n12 implication is identical, preferred scope is also identical.N11 ' represents the integer of 0 ~ 4.
About Rx, when general formula (1A) (when namely utilizing 2 of fluorenes ring phenyl ring to be connected in main polymer chain), Rx represents associative key; When general formula (1B) (when namely 1 phenyl ring is combined with main polymer chain), Rx represents hydrogen atom or substituting group.As the substituting group in Rx, above-mentioned substituting group W1 can be enumerated, wherein optimization aromatic hydrocarbon cyclic base, aromatic heterocycle, alkyl, alkoxyl, alkylthio group, amino, hydroxyl, more preferably alkyl, alkoxyl, hydroxyl, further preferred alkyl.
Rx ' represents hydrogen atom or substituting group.As the substituting group in Rx ', above-mentioned substituting group W1 can be enumerated, wherein optimization aromatic hydrocarbon cyclic base, aromatic heterocycle, alkyl, alkoxyl, alkylthio group, amino, hydroxyl, more preferably alkyl, alkoxyl, hydroxyl, further preferred alkoxyl.
L aand L bin the carbon number of aromatic hydrocarbon ring of divalent aromatic cyclic hydrocarbon group be preferably 6 ~ 24, be more preferably 6 ~ 20, more preferably 6 ~ 18.Aromatic hydrocarbon ring can enumerate phenyl ring, naphthalene nucleus, and these rings can be condensed by rings such as aromatic hydrocarbon ring, aliphatic hydrocarbon ring, heterocycles.Further, aromatic cyclic hydrocarbon group can have substituting group, alternatively base, can enumerate above-mentioned substituting group W1.As this substituting group, preferred alkyl, alkoxyl, alkylthio group, amino, hydroxyl, more preferably alkyl, alkoxyl, hydroxyl, further preferred alkyl, alkoxyl.
Above-mentioned aromatic hydrocarbon ring is preferably phenyl ring, naphthalene nucleus, fluorenes ring.
L aand L bin the carbon number of heteroaromatic of divalent aromatic heterocycle be preferably 2 ~ 24, be more preferably 3 ~ 20, more preferably 3 ~ 18.The one-tenth ring hetero atom of heteroaromatic is preferably nitrogen-atoms, oxygen atom, sulphur atom, is preferably 5 or 6 rings.Heteroaromatic can be condensed by rings such as aromatic hydrocarbon ring, aliphatic hydrocarbon ring, heterocycles.Further, aromatic cyclic hydrocarbon group can have substituting group, alternatively base, can enumerate above-mentioned substituting group W1.As this substituting group, preferred alkyl, alkoxyl, alkylthio group, more preferably alkyl, alkoxyl, further preferred alkyl.
Above-mentioned heteroaromatic such as can enumerate thiazole ring, pyrrole ring, furan nucleus, pyrazole ring, imidazole ring, imidazole ring, triazole ring, Thiadiazole, oxadiazole rings, pyridine ring, pyrimidine ring, pyrimidine ring, pyridazine ring, triazine ring, benzothiazole ring, indole ring, diazosulfide ring, quinoxaline ring, phenoxazine ring, dibenzofurans ring, bisbenzothiazole ring, dibenzo silane cyclopentadiene ring (ジ ベ Application ゾ シ ラ ノ シ Network ロ ペ Application タ ジ エ ン Ring), carbazole ring, phenthazine ring, thiphene ring, isothiazole ring, indole ring, iso-indoles ring, quinoline ring, isoquinolin ring, quinazoline ring, phthalazines ring, pteridine ring, coumarin ring, chromone ring, Isosorbide-5-Nitrae-benzene diazacyclo (ゼ Application ゾ ジ ア ゼ ピ ン Ring), benzimidazole ring, benzofuran ring, purine ring, acridine ring, phenoxazine ring, phenthazine ring, furan nucleus, selenophen ring, tellurium fen ring, oxazole ring, isoxazole ring, pyridone-2-ketone ring, seleno pyranoid ring (セ レ ノ ピ ラ ン Ring), telluro pyranoid ring (テ Le ロ ピ ラ ン Ring) etc.
L aand L bin-N (Ra1)-Ra1 represent substituting group, as this substituting group, above-mentioned substituting group W1 can be enumerated.
Ra1 is preferably alkyl, aryl, heterocyclic radical, and these each groups can further with substituting group.For the substituting group that can replace on above-mentioned each group, above-mentioned substituting group W1 can be enumerated.
The carbon number of the alkyl in Ra1 is preferably 1 ~ 18.The carbon number of the aryl in Ra1 is preferably 6 ~ 24, is more preferably 6 ~ 20, more preferably 6 ~ 12.
Heterocyclic radical optimization aromatic heterocyclic radical in Ra1, preferred R 3A, R 4Ain aromatic heterocycle.
L aand L bin by divalent aromatic cyclic hydrocarbon group, divalent aromatic heterocycle or-N (Ra) as long as-linking group that combines for by these groups more than 2 groups combined, can combine by any-mode.
Such as can enumerate-divalent aromatic cyclic hydrocarbon group-divalent aromatic cyclic hydrocarbon group-,-divalent aromatic heterocycle-divalent aromatic heterocycle-,-divalent aromatic cyclic hydrocarbon group-divalent aromatic heterocycle-,-divalent aromatic cyclic hydrocarbon group-N (Ra1)-,-divalent aromatic cyclic hydrocarbon group-N (Ra1)-divalent aromatic cyclic hydrocarbon group-,-divalent aromatic heterocycle-N (Ra1)-divalent aromatic cyclic hydrocarbon group-,-divalent aromatic heterocycle-divalent aromatic heterocycle-divalent aromatic heterocycle-,-divalent aromatic cyclic hydrocarbon group-N (Ra1)-divalent aromatic cyclic hydrocarbon group-N (Ra1)-divalent aromatic cyclic hydrocarbon group-,-divalent aromatic cyclic hydrocarbon group-N (Ra1)-divalent aromatic cyclic hydrocarbon group-divalent aromatic cyclic hydrocarbon group-N (Ra1)-divalent aromatic cyclic hydrocarbon group-.
L abe preferably the linking group be selected from more than 2 by the moiety combinations in the group of divalent aromatic cyclic hydrocarbon group, divalent aromatic heterocycle and above-mentioned-N (Ra1)-form.
L bbe preferably divalent aromatic cyclic hydrocarbon group, divalent aromatic heterocycle or-N (Ra1)-or by the linking group of these moiety combinations.
L abe preferably following formula (a) or the linking group represented by (b).
(in formula, X a0represent singly-bound, divalent aromatic cyclic hydrocarbon group or divalent aromatic heterocycle, X a1and X a2represent divalent aromatic cyclic hydrocarbon group or divalent aromatic heterocycle independently of one another.R a0represent substituting group, n a0represent the integer of 0 ~ 5.)
X a0, X a1, X a2in divalent aromatic cyclic hydrocarbon group, divalent aromatic heterocycle and L ain divalent aromatic cyclic hydrocarbon group, divalent aromatic heterocycle implication identical, preferred scope is also identical.
R a0in substituting group can enumerate above-mentioned substituting group W1, preferred alkyl, alkoxyl, alkylthio group, acyl group, alkoxy carbonyl group, halogen atom, particularly preferably alkoxy carbonyl group.
N a0be preferably 0 or 1.
For X bin 3 valency aromatic cyclic hydrocarbon groups in aromatic hydrocarbon ring, can L be enumerated aand L bin aromatic hydrocarbon ring, preferred scope is also identical.
Wherein preferred phenyl ring, the phenyl ring of preferred fluorenes ring is combined in 5 of the phenylene being made up of main polymer chain 1,3-phenylene.
For X bin 3 valency aromatic heterocycles in heteroaromatic, can L be enumerated aand L bin heteroaromatic, preferred scope is also identical.
Wherein preferably the phenyl ring of fluorenes ring is combined in 10 of phenoxazine ring, 10,9 of carbazole ring, 1 of pyrroles of phenthazine ring.
X bin, preferred X batom be formed aromatic hydrocarbon ring carbon atom or form the carbon atom of heteroaromatic or nitrogen-atoms or X bfor >N-, particularly preferably X bfor >N-.
The weight average molecular weight (polystyrene conversion GPC measured value) of the fluorene structured conjugated polymer as repetitive structure at least comprised represented by general formula (1A) or (1B) is not particularly limited, is preferably 4000 ~ 100000, is more preferably 6000 ~ 80000, is particularly preferably 8000 ~ 50000.
The end group at least comprising the fluorene structured conjugated polymer as repetitive structure represented by general formula (1A) or (1B) such as be positioned at the repetitive represented by above-mentioned general formula (1A) or (1B) parantheses outside with the substituting group of repetitive structure bonding.Substituting group as this end group changes by high molecular synthetic method, can be the halogen atom (such as fluorine, chlorine, bromine, iodine) in synthesis material source, hydrogen, boracic substituting group and the hydrogen atom replaced, the phosphorous substituting group that derives from catalyst ligand as the side reaction of polymerization reaction.Also preferably end group is made to be hydrogen atom or aryl by reduction reaction, substitution reaction after polymerisation.
Fluorene structured concrete example represented by general formula (1A) or (1B) is shown, but the present invention is not limited thereto below.In following concrete example, * represents bonding position.
Me as follows represents methyl, Pr represents propyl group.
The fluorene structured conjugated polymer as repetitive structure at least comprised represented by general formula (1A) or (1B) such as can utilize Chem.Rev., 2011,111 volumes, the known method recorded in pp.1417 etc., utilize common coupling polymerization method to carry out being polymerized manufacturing.
As the conjugated polymer used in the present invention, except above-mentioned each conjugated polymer, can also enumerate and at least comprise the conjugated polymer of the structure represented by following general formula (1) as repetitive structure.
(in general formula (1), Ar 1Band Ar 12represent arlydene or heteroarylidene independently of one another.Ar 13represent aryl or heteroaryl.R 1B, R 2Band R 3Brepresent substituting group independently of one another.Herein, R 1Bwith R 2B, R 1Bwith R 3B, R 2Bwith R 3Bcan bonding and form ring mutually.L represents the linking group represented by any same form of singly-bound or following formula (l-1) ~ (l-4).N1B, n2B and n3B represent the integer of 0 ~ 4 independently of one another, n 1represent the integer of more than 5.)
(in formula, Ar 14and Ar 16represent arlydene or heteroarylidene independently of one another, Ar 15represent aryl or heteroaryl.R 4B~ R 6Brepresent substituting group independently of one another.Herein, R 4Bwith R 2B, R 5Bwith R 2B, R 6Bwith R 2B, R 5Bwith R 6Bcan bonding and form ring mutually.N4B ~ n6B represents the integer of 0 ~ 4 independently of one another.X 1represent arlydene carbonyl arlydene or arlydene sulfonyl arlydene, X 2the linking group representing arlydene, heteroarylidene or they are combined.)
Ar 11and Ar 12represent arlydene or heteroarylidene, Ar independently of one another 13represent aryl or heteroaryl, aromatic rings, the assorted aromatic rings of these groups are preferably following ring.
The carbon number of aromatic rings is preferably 6 ~ 50, is more preferably 6 ~ 40, more preferably 6 ~ 20.Aromatic nucleus is as enumerated phenyl ring, naphthalene nucleus, anthracene nucleus, phenanthrene ring, indacene (Indacene) ring, fluorenes ring, and these rings can be monocycle, also can be condensed by other ring.As the ring that can carry out condensing, aromatic rings, alicyclic ring, assorted aromatic rings, non-aromatic heterocyclic can be enumerated.
The carbon number of assorted aromatic rings is preferably 2 ~ 50, be more preferably 2 ~ 40, more preferably 2 ~ 20, be particularly preferably 3 ~ 20.One-tenth ring hetero atom in assorted aromatic rings is preferably oxygen atom, sulphur atom, nitrogen-atoms, silicon atom.Assorted aromatic rings can be condensed by other ring.As the ring that can carry out condensing, aromatic rings, alicyclic ring, assorted aromatic rings, non-aromatic heterocyclic can be enumerated.As assorted aromatic rings, such as, can enumerate thiphene ring, furan nucleus, pyrrole ring, imidazole ring, pyridine ring, oxazole ring, thiazole ring, Thiadiazole and their fused benzo ring body (such as benzothiophene) or dibenzo two condensed ring body (such as dibenzothiophenes, carbazole).
R 1B, R 2Band R 3Brepresent substituting group W2, as this substituting group W2, the above-mentioned substituting group W1 except aryl boryl and hydrogenation boryl can be enumerated.
R 1B, R 2Band R 3Bbe preferably alkyl, aryl, heterocyclic radical, alkoxyl, alkylthio group, amino, acyl group, acylamino-, the sulfoamido of alkyl or aryl, alkoxy carbonyl group, the carbamoyl of alkyl or aryl, the sulfamoyl of alkyl or aryl.
Herein, the aromatic rings in aryl is preferably phenyl ring, naphthalene nucleus, fluorenes ring, and the heterocycle in heterocyclic radical is preferably carbazole ring, dibenzothiophenes ring, 9-silicon heterofluorene ring.
L represents the linking group represented by any same form of singly-bound or above-mentioned formula (l-1) ~ (l-4), is preferably the linking group represented by any same form of above-mentioned formula (l-1) ~ (l-4).
Ar 14and Ar 16with Ar 11, Ar 12implication is identical, and preferred scope is also identical.Ar 15with Ar 13implication is identical, and preferred scope is also identical.R 4B~ R 6Bwith R 1B~ R 3Bimplication is identical, and preferred scope is also identical.
X 1represent arlydene carbonyl arlydene or arlydene sulfonyl arlydene, be expressed as-Ar a-C (=O)-Ar b-,-Ar a-SO 2-Ar b-form.Ar herein a, Ar brepresent arlydene independently of one another, this arlydene can have substituting group.As this substituting group, substituting group W2 can be enumerated.Aromatic rings in arlydene can enumerate above-mentioned Ar 11in aromatic rings.Ar a, Ar bpreferred phenylene, more preferably Isosorbide-5-Nitrae-phenylene.
X 2the linking group representing arlydene, heteroarylidene or they combined, the ring of these groups can enumerate above-mentioned Ar 11in the ring enumerated, preferred scope also with Ar 11identical.
R 1Bwith R 2B, R 1Bwith R 3B, R 2Bwith R 3B, R 4Bwith R 2B, R 5Bwith R 2B, R 6Bwith R 2B, R 5Bwith R 6Bcan bonding and form ring mutually.As the ring formed by them, can be aromatic rings, also can be assorted aromatic rings, such as, can enumerate naphthalene nucleus, fluorenes ring, carbazole ring, dibenzothiophenes ring, 9-silicon heterofluorene ring.
Herein, preferred R 1Bwith R 3B, R 2Bwith R 4Bor R 5Bmutual bonding forms ring, and the ring formed is preferably carbazole ring.
In the group of the carbazole ring formed, preferred following radicals.
Herein, Ra and R 2B~ R 3Bimplication is identical, and preferred scope is also identical.Na and n1B ~ n3B implication is identical, and preferred scope is also identical.
Na is preferably 0 or 1, be more preferably 1, Ra is preferably alkyl.
N1B, n2B, n3B are the integer of 0 ~ 4, are preferably 0 ~ 2, are more preferably 0 ~ 1.N1B, n2B, n3B can be identical or different, preferably different.
Herein, about Ar 11, X 2, particularly preferably basic framework is the situation of following radicals.It should be noted that, these rings can have substituting group.
Herein, Z represents-C (Rb) 2-,-Si (Rb) 2-, Rb represents alkyl.
Among repetitive structure represented by above-mentioned general formula (1), the structure represented by any same form of preferred following general formula (2) ~ (6).
(in general formula (2) ~ (6), Ar 11~ Ar 16, R 1B~ R 6B, n1B ~ n6B, X 1and X 2with the Ar in above-mentioned general formula (1) 11~ Ar 16, R 1B~ R 6B, n1B ~ n6B, X 1and X 2implication is identical.)
Among repetitive structure represented by above-mentioned general formula (2) ~ (6), preferred above-mentioned general formula (4), (5) or the structure represented by (6), the structure represented by especially preferred above-mentioned general formula (5).
N 1it is the integer of more than 5, its preferred scope changes according to the molecular weight of repetitive structure, and the conjugated polymer with this repetitive structure is preferably 5000 ~ 100000 in weight average molecular weight (polystyrene conversion GPC measured value), is more preferably 8000 ~ 50000, is particularly preferably 10000 ~ 20000.
The end group of conjugated polymer be the repetitive structure be positioned at represented by general formula (1) ~ (6) parantheses outside with the substituting group of repetitive structure bonding.Substituting group as this end group can be changed by high molecular synthetic method, can be the halogen atom (such as fluorine, chlorine, bromine, iodine) in synthesis material source, hydrogen, boracic substituting group and the hydrogen atom replaced, the phosphorous substituting group that derives from catalyst ligand as the side reaction of polymerization reaction.Also preferably end group is made to be hydrogen atom or aryl by reduction reaction, substitution reaction after polymerisation.
The concrete example of the repetitive structure of the conjugated polymer formed represented by general formula (1) is shown, but the present invention is not limited to these below.In following concrete example, * represents bonding position.
Et as follows represents ethyl, Bu (n) represents normal-butyl, Ph represents phenyl (-C 6h 5).
Common oxidative polymerization method or coupling polymerization method can be utilized to make one or more the starting compound of part or all with the structure represented by general formula (1) carry out being polymerized manufacturing using the structure represented by above-mentioned general formula (1) as the conjugated polymer of repetitive structure.
The synthesis of starting compound can be carried out according to general known method.Among raw material of the present invention, cannot synthesize by the amination of aryl compound by buying the raw material obtained, the reaction technology by traditional ullmann reaction and periphery thereof synthesizes.In recent years, use the aryl amination of palladium complex catalyst very flourishing, the reaction technology by Buchwald-Hartwig reaction and periphery thereof synthesizes.The typical example of Buchwald-Hartwig reaction can enumerate Organic Synthesis 78 volume 23 pages, Journal of American Chemical Society 116 volume in 1994 7901 pages.
2. non-conjugate high molecular
As long as macromolecular compound, i.e. main chain that non-conjugate high molecular does not have the molecular structure that conjugation occurs do not utilize the macromolecule of the lone electron pair generation conjugation of pi-electron or lone pair electrons to be just not particularly limited.Such non-conjugate high molecular is not necessarily high-molecular weight compounds, can be oligomer compounds yet.
As such non-conjugate high molecular, be not particularly limited, known non-conjugate high molecular can be used usually.As non-conjugate high molecular, from the viewpoint of the dispersiveness of conductive nano material and thermoelectricity conversion performance, the non-conjugated high score with the repetitive structure of monomer by least one compound polymerization that is selected from the group that is made up of vinyl compound, (methyl) acrylate compounds, carbonate products, ester compounds, amide compound, imide compound and silicone compounds or copolymerization suitably can be enumerated.These compounds can have substituting group, alternatively base, can enumerate the group that substituting group high molecular with conjugation is same.
In the present invention, " (methyl) acrylate " represent both acrylate and methacrylate or any one, also comprise their mixture.
As the high molecular vinyl compound of formation polyethylene base system, specifically, the vinyl such as ethenyl aromatic yl amine, the vinyl tri-n-butylamine trialkyl amines etc. such as styrene, vinyl pyrrolidone, vinylcarbazole, vinylpyridine, vinyl naphthalene, vinylphenol, vinyl acetate, styrene sulfonic acid, vinyl triphenylamine can be enumerated.
As (methyl) acrylate compounds forming poly-(methyl) acrylate, specifically, the acrylic ester monomers such as hydroxyalkyl acrylates such as the hydrophobic alkyl acrylate such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acrylic acid-2-hydroxyl ethyl ester, acrylic acid-1-hydroxyl ethyl ester, 2-hydroxypropyl acrylate, acrylic acid-3-hydroxypropyl acrylate, acrylic acid-1-hydroxypropyl acrylate, acrylic acid-4-hydroxy butyl ester, acrylic acid-3-hydroxy butyl ester, acrylic acid-2-hydroxy butyl ester, acrylic acid-1-hydroxy butyl ester can be enumerated; The acryloyl group of these monomers is changed into the methacrylate ester monomer etc. of methacryl.
As the concrete example of Merlon, the general Merlon, Iupizeta (trade name, Mitsubishi Gas Chemical Co., Ltd manufacture), Panlite (trade name, Teijin Chemicals, Ltd. manufacture) etc. that are formed by bisphenol-A photoreactive gas can be enumerated.
As the compound forming polyester, polyalcohol and the carboxylic acid such as polybasic carboxylic acid, lactic acid can be enumerated.As the concrete example of polyester, Vylon (trade name, Japan spin Co., Ltd. manufacture) etc. can be enumerated.
As the concrete example of polyamide, PA-100 (trade name, Co., Ltd. T & K TOKA manufacture) etc. can be enumerated.
As the concrete example of polyimides, Sorupi 6,6-PI (trade name, Sorupi Industry Co., Ltd. manufacture) etc. can be enumerated.
As polysiloxanes, specifically, polydiphenylsiloxane, polyphenyl methyl siloxane etc. can be enumerated.
About non-conjugate high molecular, as possible, can be homopolymers, also can be the copolymer with above-mentioned each compound etc.
In the present invention, as non-conjugate high molecular, more preferably use the polyethylene-based macromolecule of polymerization of vinyl compound.
Non-conjugate high molecular is preferably hydrophobicity, does not more preferably have the hydrophilic radical such as sulfonic acid, hydroxyl in molecule.In addition, preferred dissolution degree parameter (SP value) is the non-conjugate high molecular of less than 11.In the present invention, solubility parameter represents the SP value of Hildebrand, adopts the value of the predication method based on Fedors.
If thermo-electric converting material of the present invention contains conjugated polymer and non-conjugate high molecular, then can improve dispersiveness and the thermoelectricity conversion performance of conductive nano material further.Be still not clear about its mechanism, but be by inference due to: the gap (band gap) between the HOMO energy level of (1) non-conjugate high molecular and lumo energy is wide, thus from can appropriateness be low keeps the aspect of the carrier concentration conjugated polymer to consider, compared with the system not containing non-conjugate high molecular, Seebeck coefficient can be kept with high level; (2) on the other hand, except utilizing above-mentioned low molecule conjugated compound except the charge carrier path of the intermolecular formation of conductive nano material, by coexisting of conjugated polymer and conductive nano material, the transmission path of charge carrier can be formed further, thus can high conductivity be kept.Namely, by these three kinds of compositions of at least one in the conductive nano material that coexists in the material, low molecule conjugated compound and non-conjugate high molecular and conjugated polymer, thus both Seebeck coefficient and conductivity can be improved, its result, thermoelectricity conversion performance (ZT value) significantly improves.
1 kind or combinationally use above-mentioned non-conjugate high molecular of more than two kinds is can be used alone in thermo-electric converting material of the present invention.
< decentralized medium >
Thermo-electric converting material of the present invention contains decentralized medium, is dispersed with conductive nano material in this decentralized medium.
As long as decentralized medium can dispersing Nano carbon tubes, water, organic solvent and their mixed solvent can be used.Be preferably organic solvent, the aliphat such as preferred alcohols, chloroform halogen series solvent; The polar solvent of the aprotic such as DMF (DMF), METHYLPYRROLIDONE (NMP), dimethyl sulfoxide (DMSO) (DMSO); The aromatic series series solvents such as chlorobenzene, dichloro-benzenes, benzene,toluene,xylene, trimethylbenzene, tetrahydronaphthalene, durol, pyridine; The ketone series solvents such as cyclohexanone, acetone, methyl ethyl ketone; The ether series solvents etc. such as diethyl ether, oxolane (THF), t-butyl methyl ether, dimethoxy-ethane, diethylene glycol dimethyl ether, more preferably the halogen series solvent such as chloroform; The polar solvent of the aprotic such as DMF, NMP; The aromatic series series solvents such as dichloro-benzenes, dimethylbenzene, tetrahydronaphthalene, durol; The ether series solvents etc. such as THF.
1 kind or combinationally use decentralized medium of more than two kinds is can be used alone in thermo-electric converting material of the present invention.
In addition, decentralized medium preferably carries out degassed in advance.Dissolved oxygen concentration in decentralized medium is preferably below 10ppm.As degassed method, the method etc. of under reduced pressure irradiating hyperacoustic method, making the bubbling inert gas such as argon can be enumerated.
And then decentralized medium preferably dewaters in advance.Water content in decentralized medium is preferably below 1000ppm, is more preferably below 100ppm.As the dewatering of decentralized medium, the known method such as method, distillation utilizing molecular sieve can be used.
Relative to the total amount of thermo-electric converting material, the decentralized medium amount in thermo-electric converting material is preferably 25 quality % ~ 99.99 quality %, is more preferably 30 quality % ~ 99.95 quality %, more preferably 30 quality % ~ 99.9 quality %.
< dopant >
When thermo-electric converting material of the present invention contains above-mentioned conjugated polymer, when further containing dopant, can improve the conductivity of thermoelectric conversion layer further due to the increase of carrier concentration, be preferred from this viewpoint.
Dopant is be doped to the compound in above-mentioned conjugated polymer, if can by by protonated for this conjugated polymer or remove from the pi-conjugated system of conjugated polymer electronics and with positive charge doping (p-type doping) this conjugated polymer.Specifically, following salt compound, oxidant, acid compound, electron acceptor compound etc. can be used.
1. salt compound
The salt compound used as dopant is given and acidic compound (acid agent, acid precursors) preferably by the irradiation of active energy beam (radioactive ray or electromagnetic wave etc.), the imparting homenergic of heat.As such salt compound, sulfonium salt, salt compounded of iodine, ammonium salt, carbon Yan, phosphonium salt etc. can be enumerated.Wherein preferred sulfonium salt, salt compounded of iodine, ammonium salt, carbon salt, more preferably sulfonium salt, salt compounded of iodine, carbon salt, particularly preferably sulfonium salt, salt compounded of iodine.As the anionicsite forming these salt, the counter anion of strong acid can be enumerated.
Specifically, as sulfonium salt, following general formula (I) or the compound represented by (II) can be enumerated; As salt compounded of iodine, the compound represented by following general formula (III) can be enumerated; As ammonium salt, the compound represented by following general formula (IV) can be enumerated; As carbon salt, can enumerate the compound represented by following general formula (V), they can preferably use in the present invention.
In above-mentioned general formula (I) ~ (V), R 21~ R 23, R 25~ R 26and R 31~ R 33represent alkyl, aralkyl, aryl, aromatic heterocycle independently of one another.R 27~ R 30represent hydrogen atom, alkyl, aralkyl, aryl, aromatic heterocycle, alkoxyl, aryloxy group independently of one another.R 24represent alkylidene, arlydene.R 21~ R 33substituting group can be substituted base further and replaced.X -represent the anion of strong acid.
R in general formula (I) 21~ R 23in any 2 groups, R in general formula (II) 21and R 23, R in general formula (III) 25and R 26, R in general formula (IV) 27~ R 30in any 2 groups, R in general formula (V) 31~ R 33in any 2 groups can form aliphat ring, aromatic rings, heterocycle by bonding respectively.
R 21~ R 23, R 25~ R 33in, alkyl comprises the alkyl of straight chain, side chain, ring-type, and as the alkyl of straight or branched, preferred carbon number is the alkyl of 1 ~ 20, specifically, methyl, ethyl, propyl group, normal-butyl, sec-butyl, the tert-butyl group, hexyl, octyl group, dodecyl etc. can be enumerated.
As cyclic alkyl, preferred carbon number is the alkyl of 3 ~ 20, specifically, can enumerate cyclopropyl, cyclopenta, cyclohexyl, bicyclooctyl, norborny, adamantyl etc.
As aralkyl, preferred carbon number is the aralkyl of 7 ~ 15, specifically, can enumerate benzyl, phenethyl etc.
As aryl, preferred carbon number is the aryl of 6 ~ 20, specifically, can enumerate phenyl, naphthyl, anthryl, phenanthryl, pyrenyl etc.
As aromatic heterocycle, pyridine cyclic group, pyrazoles cyclic group, imidazoles cyclic group, benzimidazole cyclic group, indoles cyclic group, quinoline cyclic group, isoquinolin cyclic group, purine cyclic group, pyrimidine cyclic group, oxazole cyclic group, thiazole cyclic group, thiazine cyclic group etc. can be enumerated.
R 27~ R 30in, as alkoxyl, preferred carbon number is the alkoxyl of the straight or branched of 1 ~ 20, specifically, can enumerate methoxyl group, ethyoxyl, isopropoxy, butoxy, own oxygen base etc.
As aryloxy group, preferred carbon number is the aryloxy group of 6 ~ 20, specifically, can enumerate phenoxy group, naphthoxy etc.
R 24in, alkylidene comprises the alkylidene of straight chain, side chain, ring-type, and preferred carbon number is the alkylidene of 2 ~ 20.Specifically, ethylidene, propylidene, butylidene, hexylidene etc. can be enumerated.As cyclic alkylidene, preferred carbon number is the cyclic alkylidene of 3 ~ 20, specifically, can enumerate cyclopentylene, cyclohexylidene, two sub-ring octyl groups, sub-norborny, sub-adamantyl etc.
As arlydene, preferred carbon number is the arlydene of 6 ~ 20, specifically, can enumerate phenylene, naphthylene, anthrylene etc.
R 21~ R 33substituting group there is substituent situation further under; alternatively base, preferably can enumerate carbon number be 1 ~ 4 alkyl, carbon number be 1 ~ 4 alkoxyl, halogen atom (fluorine atom, chlorine atom, atomic iodine), the carbon number aryl that is 6 ~ 10, the carbon number aryloxy group that is 6 ~ 10, carbon number be 2 ~ 6 alkenyl, cyano group, hydroxyl, carboxyl, acyl group, alkoxy carbonyl group, Alkylcarbonylalkyl, aryl carbonyl, aryl alkyl carbonyl, nitro, alkyl sulphonyl, trifluoromethyl ,-S-R 41deng.It should be noted that, R 41substituting group and above-mentioned R 21implication is identical.
As X -, the anion of preferred aryl groups sulfonic acid, the anion of perfluoro alkyl sulfonic acid, the excessively lewis acidic anion of halogenation, the anion of per-fluoroalkyl sulfonyl imines, high hydracid anion or alkyl or aryl borate anion.They can have substituting group further, alternatively base, can enumerate fluorine-based.
As the anion of aryl sulfonic acid, specifically, p-CH can be enumerated 3c 6h 4sO 3 -, C 6h 5sO 3 -, the anion of naphthalene sulfonic acids, the anion of naphthoquinone sulfonic acid, the anion of naphthalenedisulfonic acid, the anion of anthraquinone sulfonic acid.
As the anion of perfluoro alkyl sulfonic acid, specifically, CF can be enumerated 3sO 3 -, C 4f 9sO 3 -, C 8f 17sO 3 -.
As crossing the lewis acidic anion of halogenation, specifically, PF can be enumerated 6 -, SbF 6 -, BF 4 -, AsF 6 -, FeCl 4 -.
As the anion of per-fluoroalkyl sulfonyl imines, specifically, CF can be enumerated 3sO 2-N --SO 2cF 3, C 4f 9sO 2-N --SO 2c 4f 9.
As high hydracid anion, specifically, ClO can be enumerated 4 -, BrO 4 -, IO 4 -.
As alkyl or aryl boric acid salt anionic, specifically, (C can be enumerated 6h 5) 4b -, (C 6f 5) 4b -, (p-CH 3c 6h 4) 4b -, (C 6h 4f) 4b -.
The concrete example of salt is shown, but the present invention is not limited to these below.
It should be noted that, the X in above-mentioned concrete example -represent PF 6 -, SbF 6 -, CF 3sO 3 -, p-CH 3c 6h 4sO 3 -, BF 4 -, (C 6h 5) 4b -, RfSO 3 -, (C 6f 5) 4b -, or anion represented by following formula, Rf represents perfluoroalkyl.
In the present invention, particularly preferably following general formula (VI) or the salt compound represented by (VII).
In general formula (VI), Y represents carbon atom or sulphur atom, Ar 1represent aryl, Ar 2~ Ar 4represent aryl, aromatic heterocycle independently of one another.Ar 1~ Ar 4base can be substituted further replaced.
As Ar 1, the aryl being preferably fluorine substituted aryl or being replaced by least 1 perfluoroalkyl, the phenyl being more preferably pentafluorophenyl group or being replaced by least 1 perfluoroalkyl, is particularly preferably pentafluorophenyl group.
Ar 2~ Ar 4aryl, aromatic heterocycle and above-mentioned R 21~ R 23, R 25~ R 33aryl, aromatic heterocycle implication identical, be preferably aryl, be more preferably phenyl.These groups can be substituted base further and replaced, and alternatively base, can enumerate above-mentioned R 21~ R 33substituting group.
In general formula (VII), Ar 1represent aryl, Ar 5and Ar 6represent aryl, aromatic heterocycle independently of one another.Ar 1, Ar 5and Ar 6base can be substituted further replaced.
Ar 1with the Ar of above-mentioned general formula (VI) 1implication is identical, and preferred scope is also identical.
Ar 5and Ar 6with the Ar of above-mentioned general formula (VI) 2~ Ar 4implication is identical, and preferred scope is also identical.
Above-mentioned salt compound can utilize common chemical synthesis to manufacture.Commercially available reagent etc. can be used in addition.
As an execution mode of the synthetic method of salt compound, triphenylsulfonium four (pentafluorophenyl group) boratory synthetic method is shown, but the present invention is not limited to this below.About other salt, also can profit use the same method to synthesize.
Triphenyl phosphonium bromide sulfonium (Tokyo changes into manufacture) 2.68g, four (pentafluorophenyl group) lithium borate-etherate (Tokyo changes into manufacture) 5.00g and ethanol 146ml are encased in the there-necked flask of 500ml capacity, at room temperature stir after 2 hours, adding pure water 200ml, getting separated out white solid matter by filtering to divide.Utilized by this white solid pure water and ethanol to carry out cleaning and vacuumize, thus obtain triphenylsulfonium four (pentafluorophenyl group) the borate 6.18g as salt.
2. oxidant, acid compound, electron acceptor compound
About in the present invention as the oxidant that dopant uses, halogen (Cl can be enumerated 2, Br 2, I 2, ICl, ICl 3, IBr, IF), lewis acid (PF 5, AsF 5, SbF 5, BF 3, BCl 3, BBr 3, SO 3), transistion metal compound (FeCl 3, FeOCl, TiCl 4, ZrCl 4, HfCl 4, NbF 5, NbCl 5, TaCl 5, MoF 5, MoCl 5, WF 6, WCl 6, UF 6, LnCl 3(group of the lanthanides such as Ln=La, Ce, Pr, Nd, Sm) and O 2, O 3, XeOF 4, (NO 2 +) (SbF 6 -), (NO 2 +) (SbCl 6 -), (NO 2 +) (BF 4 -), FSO 2oOSO 2f, AgClO 4, H 2irCl 6, La (NO 3) 36H 2o etc.
As acid compound, can enumerate illustrate below polyphosphoric acid, hydroxy compounds, carboxyl compound or sulfoacid compound, Bronsted acid (HF, HCl, HNO 3, H 2sO 4, HClO 4, FSO 3h, CISO 3h, CF 3sO 3h, various organic acid, amino acid etc.).
As electron acceptor compound, TCNQ (four cyano quinone bismethane) can be enumerated, tetrafluoro quinone bismethane, halogenation four cyano quinone bismethane, 1, 1-dicyano acetylene (ジ シ ア ノ PVC ニ レ Application), 1, 1, 2-tricyano acetylene, benzoquinones, Pentafluorophenol, dicyano Fluorenone, cyano group-fluoro-alkyl sulfonyl-Fluorenone, pyridine, pyrazine, triazine, tetrazine, pyrido-pyrazine, diazosulfide, heterocycle thiadiazoles, porphyrin, phthalocyanine, boron quinoline based compound, boron diketonate based compound, boron two iso-indoles methylene based compound, carborane based compound, the compound of other boracic atoms, or Chemistry Letters, 1991, p.1707-1710 the electronic acceptance compound etc. recorded in.
-polyphosphoric acid-
Polyphosphoric acid comprises diphosphonic acid, pyrophosphoric acid, triphosphoric acid, four phosphoric acid, metaphosphoric acid and polyphosphoric acid and their salt.Also can be their mixture.In the present invention, polyphosphoric acid is preferably diphosphonic acid, pyrophosphoric acid, triphosphoric acid, polyphosphoric acid, is more preferably polyphosphoric acid.Polyphosphoric acid is by by H 3pO 4with the P of abundance 4o 10(anhydrous phosphoric acid) carries out heating to synthesize or pass through H together 3pO 4carry out heating and synthesize except anhydrating.
-hydroxy compounds-
As long as hydroxy compounds, for having the compound of at least 1 hydroxyl, preferably has phenolic hydroxyl group.As hydroxy compounds, the compound represented by preferred following general formula (VIII).
In general formula (VIII), R represents sulfo group, halogen atom, alkyl, aryl, carboxyl, alkoxy carbonyl group, and n represents that 1 ~ 6, m represents 0 ~ 5.
As R, preferred sulfo group, alkyl, aryl, carboxyl, alkoxy carbonyl group, more preferably sulfo group.
N is preferably 1 ~ 5, is more preferably 1 ~ 4, more preferably 1 ~ 3.
M is 0 ~ 5, is preferably 0 ~ 4, is more preferably 0 ~ 3.
-carboxyl compound-
As carboxyl compound, as long as the compound for having at least 1 carboxyl, preferred following general formula (IX) or the compound represented by (X).
HOOC-A-COOH general formula (IX)
In general formula (IX), A represents divalent linker.As divalent linker, the combination of preferred alkylidene, arlydene or alkylene group and oxygen atom, sulphur atom or nitrogen-atoms, the more preferably combination of alkylidene or arlydene and oxygen atom or sulphur atom.It should be noted that, when divalent linker is the combination of alkylidene and sulphur atom, this compound is also equivalent to sulfide compound.Such sulfide compound is used also to be applicable.
When divalent linker represented by A contains alkylidene, this alkylidene can with substituting group.As this substituting group, preferred alkyl, more preferably has carboxyl alternatively base.
In general formula (X), R represents sulfo group, halogen atom, alkyl, aryl, hydroxyl, alkoxy carbonyl group, and n represents that 1 ~ 6, m represents 0 ~ 5.
As R, preferred sulfo group, alkyl, aryl, hydroxyl, alkoxy carbonyl group, more preferably sulfo group, alkoxy carbonyl group.
N is preferably 1 ~ 5, is more preferably 1 ~ 4, more preferably 1 ~ 3.
M is 0 ~ 5, is preferably 0 ~ 4, is more preferably 0 ~ 3.
-sulfoacid compound-
Sulfoacid compound is the compound with at least 1 sulfo group, preferably has the compound of more than 2 sulfo groups.As sulfoacid compound, preferably by aryl, alkyl replace, more preferably replace by aryl.
It should be noted that, in the hydroxy compounds and carboxyl compound of above-mentioned explanation, the compound with sulfo group alternatively base is classified in hydroxy compounds and carboxyl compound as mentioned above.Thus sulfoacid compound does not comprise the hydroxy compounds and carboxyl compound with sulfo group.
In the present invention, use these dopants to be not necessary, but when using dopant, can be expected by the raising of conductivity that thermoelectricity transfer characteristic further improves, for preferably.When using dopant, can be used alone one or combinationally using two or more.From the aspect controlling best carrier concentration, relative to above-mentioned macromolecular compound 100 mass parts, dopant, preferably being greater than 0 mass parts and be that the ratio of below 60 mass parts uses, more preferably using 2 mass parts ~ 50 mass parts, further preferably uses 5 mass parts ~ 40 mass parts.
Improve from the viewpoint of the dispersiveness of thermo-electric converting material or film forming, in above-mentioned dopant, preferably use salt compound.Salt compound is neutral releasing under the state before acid, is given and decomposes generation acid, show doping effect by this acid by the energy of light or heat etc.Therefore, can be penetrated etc. by illumination after being desired shape by thermo-electric converting material processing and forming and adulterate, thus show doping effect.In addition, owing to being neutral before acid is released, thus can not there is cohesion precipitation etc. in above-mentioned conjugated polymer, can make each composition uniform dissolution or dispersion in thermo-electric converting material such as conjugated polymer and conductive nano material.By uniform dissolution or the dispersiveness of this thermo-electric converting material, can give play to excellent conductivity after doping, and then can obtain good coating and film forming, therefore the molding processibility of thermoelectric conversion layer etc. is also excellent.
< excites adjuvant >
When thermo-electric converting material of the present invention contains above-mentioned conjugated polymer, can further improve thermoelectricity transfer characteristic containing exciting during adjuvant further, is preferred from this respect.
Thermal excitation adjuvant has the poor MO material of particular level relative to the MO energy level of above-mentioned conjugated polymer, by using together with conjugated polymer, can improve thermal excitation efficiency, improves the thermo-electromotive force of thermoelectric conversion layer.
The thermal excitation adjuvant used in the present invention refers to LUMO (the LowestUnoccupied Molecular Orbital compared to above-mentioned conjugated polymer; Lowest unoccupied molecular orbital) there is the compound of the low LUMO of energy level, it is the compound not forming doped energy-band in conjugated polymer.Above-mentioned dopant is the compound forming doped energy-band in conjugated polymer, no matter all forms doped energy-band with or without thermal excitation adjuvant.
In conjugated polymer, whether form doped energy-band can utilize the mensuration of absorption spectrum to evaluate, and the compound of the formation doped energy-band in the present invention and the compound not forming doped energy-band refer to the compound carrying out as follows evaluating.
-with or without formed doped energy-band evaluation assessment-
By conjugated polymer A and other composition B before doping in mass ratio 1:1 mix, the absorption spectrum of the sample of filming is observed.Its result, in the following cases, be judged as creating doped energy-band: create the new absworption peak different from the absworption peak of independent conjugated polymer A or independent composition B, and with the absorption maximum wave appearance ratio of conjugated polymer A, this new absorption peak wavelength is positioned at long wavelength side.In this case, composition B is defined as dopant.On the other hand, when there is not new absworption peak in the absorption spectrum of sample, composition B is defined as and excites adjuvant.
The energy level of the LUMO of thermal excitation adjuvant lower than the energy level of the LUMO of above-mentioned conjugated polymer, as HOMO (the Highest Occupied Molecular Orbital by conjugated polymer; The highlyest being occupied) acceptor level of thermal excitation electronics that produces plays function.
Further, when the absolute value of the absolute value of the energy level of the HOMO of above-mentioned conjugated polymer and the lumo energy of thermal excitation adjuvant is in the relation meeting following mathematical expression (I), thermo-electric converting material possesses excellent thermo-electromotive force.
Mathematical expression (I)
0.1eV≤| the LUMO|≤1.9eV of the HOMO|-| thermal excitation adjuvant of conjugated polymer
Above-mentioned mathematical expression (I) represents the LUMO of thermal excitation adjuvant and the energy difference of the high molecular HOMO of conjugation, (situation of energy level lower than the energy level of the HOMO of conjugated polymer of the LUMO of thermal excitation adjuvant is comprised) when it is less than 0.1eV, the activation energy of the electronics movement between the HOMO (donor) of conjugated polymer and the LUMO (acceptor) of thermal excitation adjuvant becomes very little, thus can produce redox reaction between conjugated polymer and thermal excitation adjuvant, condense.Its result can cause the deterioration of material filming or the deterioration of conductivity.Otherwise when the energy difference of two tracks is greater than 1.9eV, the energy difference of two tracks, much larger than thermal-excitation energy, thus produces thermal excitation charge carrier hardly, does not namely almost have the additive effect of thermal excitation adjuvant.In order to improve the thermo-electromotive force of thermoelectric conversion element, the energy difference of two tracks is preferably made to be in the scope of above-mentioned mathematical expression (I).
Like this, in the present invention, thermal excitation adjuvant and conjugated polymer utilize the absolute value of the energy level of LUMO to distinguish, specifically, thermal excitation adjuvant be the absolute value with energy level lower than conjugated polymer LUMO, preferably there is the compound of the LUMO meeting above-mentioned mathematical expression (I), " conjugated polymer " is the compound (not comprising the material suitable with thermal excitation adjuvant) with the high LUMO of energy level.
It should be noted that, in the energy level of HOMO and LUMO of conjugated polymer and thermal excitation adjuvant, about HOMO energy level, the independent coated film of each composition (glass substrate) can be made respectively, utilize photoelectron spectroscopy to measure HOMO energy level.About lumo energy, ultraviolet-uisible spectrophotometer can be utilized to measure band gap, be added in afterwards on the HOMO energy of said determination, thus calculate LUMO energy.The value that the HOMO of the conjugated polymer in the present invention and thermal excitation adjuvant and lumo energy use measure and calculation according to the method described above to obtain.
When using thermal excitation adjuvant, thermal excitation efficiency improves, and thermal excitation carrier number increases, and therefore the thermo-electromotive force of thermoelectric conversion element improves.It is different from the method utilizing the doping effect of conjugated polymer to improve thermoelectricity conversion performance that the thermo-electromotive force that such thermal excitation adjuvant produces improves effect.
From above-mentioned formula (A), in order to improve the thermoelectricity conversion performance of thermoelectric conversion element, as long as increase the absolute value of Seebeck coefficient S of thermoelectric conversion layer and conductivityσ, reduction conductive coefficient κ.It should be noted that, Seebeck coefficient is the thermo-electromotive force of every 1K absolute temperature.
Thermal excitation adjuvant is the material improving thermoelectricity conversion performance by improving Seebeck coefficient.When using thermal excitation adjuvant, the electronics produced by thermal excitation is existed in the LUMO of the thermal excitation adjuvant as acceptor level, and the electronics on the hole thus on conjugated polymer and thermal excitation adjuvant is in physically opposing liftoff existence.Therefore, the doped energy-band of conjugated polymer is not easily saturated by the electron institute produced by thermal excitation, can improve Seebeck coefficient.
As thermal excitation adjuvant, be preferably containing the macromolecular compound being selected from diazosulfide skeleton, benzothiazole skeleton, two thieno thiophenes cough up at least one structure in skeleton, ring penta 2 thiophene skeleton, thienothiophene skeleton, thiophene skeleton, fluorene skeleton and phenylene vinylidene skeleton; Fullerene based compound; Phthalocyanine based compound; Perylene dicarboximide based compound; Or four cyano quinone bismethane based compound, is more preferably containing the macromolecular compound being selected from diazosulfide skeleton, benzothiazole skeleton, two thieno thiophenes cough up at least one structure in skeleton, ring penta 2 thiophene skeleton and thienothiophene skeleton; Fullerene based compound; Phthalocyanine based compound; Perylene dicarboximide based compound; Or four cyano quinone bismethane based compound.
As the concrete example of thermal excitation adjuvant meeting above-mentioned feature, following substances can be exemplified, but the present invention is not limited to these.It should be noted that, in following exemplary compounds, n represents the integer integer of more than 10 (be preferably), Me represents methyl.
From the viewpoint of the conductivity of thermoelectric conversion element and thermoelectricity conversion performance, in the total solid composition of thermo-electric converting material, namely in thermoelectric conversion layer, the content of the thermal excitation adjuvant in thermo-electric converting material is preferably 0 ~ 35 quality %, is more preferably 3 quality % ~ 25 quality %, is particularly preferably 5 quality % ~ 20 quality %.
In addition, relative to conjugated polymer 100 mass parts, the thermal excitation adjuvant preferably use 0 ~ 100 mass parts, more preferably using 5 mass parts ~ 70 mass parts, preferably use 10 mass parts ~ 50 mass parts further.
Thermal excitation adjuvant can be used alone a kind or combinationally use two or more.
< metallic element >
From the viewpoint of improving further thermoelectricity transfer characteristic, thermo-electric converting material of the present invention preferably contains the metallic element of the form such as simple substance, ion.Metallic element can be used alone a kind or combinationally use two or more.
It is believed that, if thermo-electric converting material contains metallic element, then in formed thermoelectric conversion layer, metallic element promotes the transmission of electronics, and thus thermoelectricity transfer characteristic improves.Metallic element is not particularly limited, and from the viewpoint of thermoelectricity transfer characteristic, preferred atomic weight is the metallic element of 45 ~ 200, further preferably transition metal, particularly preferably zinc, iron, palladium, nickel, cobalt, molybdenum, platinum, tin.About the addition of metallic element, if addition is very few, then fully can not show the raising effect of thermoelectricity transfer characteristic; If otherwise too much, then the physical strength of thermoelectric conversion layer reduces, crackle etc. occurs, and makes thermoelectricity transfer characteristic reduce.
From the viewpoint of the thermoelectricity transfer characteristic of thermoelectric conversion layer, in the total solid composition of ready-mixed thing, the composite rate of metallic element is preferably 50ppm ~ 30000ppm, is more preferably 100ppm ~ 10000ppm, more preferably 200ppm ~ 5000ppm.About the metallic element concentration in dispersion, such as, undertaken quantitatively by known analytic approachs such as ICP mass spectrometer (such as Shimadzu Scisakusho Ltd manufactures " ICPM-8500 " (trade name)), energy dispersion type fluorescent x-ray analyzers (such as Shimadzu Scisakusho Ltd manufactures " EDX-720 " (trade name)).
In the total solid composition of ready-mixed thing, the composite rate of other compositions is preferably below 5 quality %, more preferably 0 ~ 2 quality %.
Other compositions of < >
In thermo-electric converting material of the present invention, in addition to the aforementioned ingredients, also antioxidant, resistance to light stabilizer, heat-resisting stabilizing agent, plasticizer etc. can be contained.
As antioxidant, IRGANOX 1010 (Japanese Ciba-Geigy manufactures), SumilizerGA-80 (Sumitomo Chemical Company Ltd's manufacture), Sumilizer GS (Sumitomo Chemical Company Ltd's manufacture), Sumilizer GM (Sumitomo Chemical Company Ltd's manufacture) etc. can be enumerated.As resistance to light stabilizer, TINUVIN234 (BASF manufacture), CHIMASSORB 81 (BASF manufacture), Cyasorb UV-3853 (Sun Chemical manufactures) etc. can be enumerated.As heat-resisting stabilizing agent, IRGANOX 1726 (BASF manufacture) can be enumerated.As plasticizer, ADEKA CIZER RS (ADEKA manufacture) etc. can be enumerated.
In the total solid composition of ready-mixed thing, the composite rate of other compositions is preferably below 5 quality %, more preferably below 2 quality %.
The preparation > of < thermo-electric converting material
Thermo-electric converting material of the present invention is by preparing above-mentioned each composition mixing.Preferably, in decentralized medium, mix conductive nano material, low molecule conjugated compound desirably mix each composition, each component dissolves or dispersion are prepared.Now, in each composition in thermo-electric converting material, preferred conductive nano material be other compositions such as dispersity, low molecule conjugated compound, conjugated polymer for dispersing or dissolving state, the composition more preferably beyond conductive nano material is dissolved state.If the composition beyond conductive nano material is dissolved state, then the effect of the conductivity reduction that is inhibited by grain boundary, thus preferably.It should be noted that, above-mentioned dispersity refer to have that long-time even if (be more than 1 month as benchmark) preserve also can not the Set Status of the molecule of the particle diameter of the degree of sedimentation in a solvent, in addition, dissolved state refers to the state that solvation occurs in a solvent under 1 molecular state.
The preparation method of thermo-electric converting material is not particularly limited, common mixing arrangement etc. can be used to carry out at normal temperatures and pressures.Such as, each composition carried out in a solvent stir, vibrate, mixing, make it dissolve or disperse to be prepared.In order to promote to dissolve, disperse, ultrasonic wave process can be carried out.
In addition, by above-mentioned dispersion step by more than solvothermal to room temperature and for the temperature below boiling point, extend jitter time or improve stir, soak into, the applying intensity etc. of mixing, ultrasonic wave etc., the dispersiveness of conductive nano material can be improved.
[thermoelectric conversion element]
Thermoelectric conversion element of the present invention has the 1st electrode, thermoelectric conversion layer and the 2nd electrode on base material, and thermoelectric conversion layer contains conductive nano material and low molecule conjugated compound.
As long as thermoelectric conversion element of the present invention has the 1st electrode, thermoelectric conversion layer and the 2nd electrode on base material, to position relationship of the 1st electrode and the 2nd electrode and thermoelectric conversion layer etc., other form and are not particularly limited.In thermoelectric conversion element of the present invention, the mode that thermoelectric conversion layer connects with the 1st electrode and the 2nd electrode according to its at least one face configures.Such as, the mode that can be clipped in the middle by the 1st electrode and the 2nd electrode for thermoelectric conversion layer, namely thermoelectric conversion element of the present invention can for sequentially having the mode of the 1st electrode, thermoelectric conversion layer and the 2nd electrode on base material.In addition also can fetch with the 1st electrode and the 2nd electrode the mode be configured for a face of thermoelectric conversion layer mutually, namely thermoelectric conversion element of the present invention can be the mode forming the 1st electrode and the 2nd electrode with mutually separating on base material and have the thermoelectric conversion layer of lamination on the 1st electrode and the 2nd electrode.
As an example of the structure of thermoelectric conversion element of the present invention, the structure of the element shown in Fig. 1 and Fig. 2 can be enumerated.In Fig. 1 and Fig. 2, the direction of generation temperature difference when arrow represents that thermoelectric conversion element uses.
Thermoelectric conversion element 1 shown in Fig. 1 possesses the pair of electrodes comprising the 1st electrode 13 and the 2nd electrode 15 and the thermoelectric conversion layer 14 formed by thermo-electric converting material of the present invention between the 1st electrode 13 and the 2nd electrode 15 on the 1st base material 12.Arrange the 2nd base material 16 on another surface of the 2nd electrode 15, arrange metallic plate 11 and 17 opposed to each other in the outside of the 1st base material 12 and the 2nd base material 16.
In thermoelectric conversion element of the present invention, preferably on base material, arrange thermoelectric conversion layer across electrode by thermo-electric converting material of the present invention with film (film) shape, this base material plays function as the 1st base material.That is, thermoelectric conversion element 1 is preferably following structure: arrange the 1st electrode 13 or the 2nd electrode 15 on the surface (forming surface of thermoelectric conversion layer 14) of 2 plate substrates 12 and 16, between these the 1st electrode 13 and the 2nd electrodes 15, have the thermoelectric conversion layer 14 formed by thermo-electric converting material of the present invention.
Thermoelectric conversion element 2 shown in Fig. 2 arranges the 1st electrode 23 and the 2nd electrode 25 on the 1st base material 22, arranges the thermoelectric conversion layer 24 formed by thermo-electric converting material of the present invention thereon.
In the thermoelectric conversion layer 14 of thermoelectric conversion element 1, from the aspect of protection thermoelectric conversion layer 14, preferably a surface is covered by the 1st base material 12 across the 1st electrode 13, also crimps the 2nd base material 16 across the 2nd electrode 15 on another surface.In addition, in the thermoelectric conversion layer 24 of thermoelectric conversion element 2, from the aspect of protection thermoelectric conversion layer 24, preferably surface is covered by the 1st electrode 23 and the 2nd electrode 25 and the 1st base material 22, also crimps the 2nd base material 26 on another surface.In addition, preferably on the surface of the 2nd base material 16 or the electrolysis of thermoelectric conversion layer 14 of thermoelectric conversion element 1, the 2nd electrode 15 is being pre-formed with.In addition, in thermoelectric conversion element 1 and 2, from the aspect improving adaptation, electrode is preferably heated to 100 DEG C ~ about 200 DEG C carry out with crimping of thermoelectric conversion layer.
The 1st base material 12 in the base material of thermoelectric conversion element of the present invention, thermoelectric conversion element 1 and the 2nd base material 16 can use the base materials such as glass, transparent ceramic, metal, plastic film.In thermoelectric conversion element of the present invention, preferred substrates has pliability, and specifically, the number of times of the resistance to bending MIT preferably had based on the determination method specified in ASTM D2176 is the above pliability that circulates for 10,000 times.There is so flexible base material and be preferably plastic film, specifically, can enumerate: PETG, polyethylene glycol isophthalate, PEN, polybutylene terephthalate (PBT), poly-(1,4-cyclohexene dimethylene terephthalate), the polyester film such as the polyester film of polyethylene-2,6-naphthalene (Off タ レ Application) dicarboxylic ester, bisphenol-A and M-phthalic acid and terephthalic acid (TPA); The poly-cycloolefin film such as ZEONOR film (trade name, Japanese Zeon society manufacture), ARTON film (trade name, JSR society manufacture), SUMILITFS1700 (trade name, SUMITOMO BAKELITE society manufacture); The polyimide films such as KAPTON (trade name, society of Dong Li Du Pont manufacture), Apical (trade name, Kaneka society manufacture), Upilex (trade name, Yu Buxingchan society manufacture), Pomiran (trade name, waste river chemistry society manufacture); The polyether-ether-ketone film such as polycarbonate membrane, SUMILIT FS1100 (trade name, SUMITOMO BAKELITE society manufacture) of Pureace (trade name, Supreme Being people change into society and manufacture), Elmec (trade name, Kaneka society manufacture) etc.; The polyphenylene sulfide films etc. such as Torelina (trade name, Dong Li society manufacture).Can be suitable for selecting according to service condition, environment, from the easiness obtained, be preferably the thermal endurance of more than 100 DEG C, the aspect of economy and effect, preferably commercially available PETG, PEN, various polyimides or polycarbonate membrane etc.
Particularly preferably be used in the base material being provided with electrode with the electrolysis of thermoelectric conversion layer.As the electrode material for the formation of the 1st electrode be located on this base material and the 2nd electrode, the transparency electrode such as tin indium oxide (ITO), zinc oxide (ZnO) can be used; The metal electrodes such as silver, copper, gold, aluminium; The material with carbon element such as CNT, Graphene; The organic materials such as poly-(3,4-ethylene dioxythiophene) poly-(styrene sulfonate) (PEDOT:PSS); Be dispersed with the conductive paste of the electrically conductive microparticle such as silver, carbon; Conductive paste etc. containing metal nanometer lines such as silver, copper, aluminium.Among them, preferred aluminium, gold, silver or copper.Now, thermoelectric conversion element 1 is formed according to the order of base material 12, the 1st electrode 13, thermoelectric conversion layer 14 and the 2nd electrode 15, the 2nd base material 16 can be had adjacent in the outside of the 2nd electrode 15, the 2nd base material 16 also can not be set and make the 2nd electrode 15 for outmost surface and expose in atmosphere.And, thermoelectric conversion element 2 is formed according to the order of base material 22, the 1st electrode 23 and the 2nd electrode 25, thermoelectric conversion layer 24, the 2nd base material 26 can be had in the outside of thermoelectric conversion layer 24 adjacent, the 2nd base material 26 also can not be set and make thermoelectric conversion layer 24 for outmost surface and expose in atmosphere.
From the viewpoint of treatability, durability etc., the thickness of base material is preferably 30 μm ~ 3000 μm, be more preferably 50 μm ~ 1000 μm, more preferably 100 μm ~ 1000 μm, be particularly preferably 200 μm ~ 800 μm.If base material is blocked up, then conductive coefficient reduces; If cross thin, then the easy film that makes due to external impact is impaired.
The thermoelectric conversion layer of thermoelectric conversion element of the present invention is formed by thermo-electric converting material of the present invention, in addition, preferably also contain at least one of above-mentioned non-conjugate high molecular and thermal excitation adjuvant, also can contain dopant or its analyte, metallic element, other compositions.These compositions in thermoelectric conversion layer and content described above.
The thickness of thermoelectric conversion layer is preferably 0.1 μm ~ 1000 μm, is more preferably 1 μm ~ 100 μm.When thickness is thinner, is not easy to give resistance in temperature difference, layer and increases, thus not preferred.
Usually, for thermoelectric conversion element, compared with the photo-electric conversion elements such as organic thin film solar cell element, element can be manufactured easily.Particularly when using thermo-electric converting material of the present invention, compared with organic thin film solar cell element, without the need to considering efficiency of light absorption, thus can carry out the thick-film of about 100 ~ 1000 times, the chemical stability for the oxygen in air or moisture improves.
The film build method of thermoelectric conversion layer is not particularly limited, such as, can uses the known coating process such as spin coating, extrusion die painting, scraper plate coating, rod painting, silk screen printing, hole version (stencil) printing, roller coat, curtain coating, spraying, dip coated.Wherein, particularly consider in the excellent adhesion of thermoelectric conversion layer on electrode, particularly preferably silk screen printing.
After coating, drying process is carried out as required.Such as, make solvent evaporates by heat drying, blowing hot air, carry out drying.
(utilizing the doping that energy is given)
When thermo-electric converting material contains above-mentioned salt compound as dopant, preferably after film forming, active energy beam irradiated to formed film or carry out heating to carry out doping treatment, improving conductivity.By this process, from salt compound, produce acid, this acid by protonated for above-mentioned conjugated polymer, thus makes conjugated polymer carry out adulterate (p-type doping) with positive charge.
Comprise radioactive ray, electromagnetic wave in active energy beam, in radioactive ray, comprise the particle beams (high velocity beam) and electromagnetic radiation line.As the particle beams, the charge-particle beams such as alpha ray (alpha ray), β ray (beta ray), proton beam, electron ray (refer to and do not rely on nuclear disintegration and utilize accelerator using the ray of Accelerating electron), deuteron ray, neutron ray, cosmic ray etc. as non-charge-particle beam can be enumerated; As electromagnetic radiation line, gamma-rays (gamma ray), X ray (Aix-en-Provence ray, soft Aix-en-Provence ray) can be enumerated.As electromagnetic wave, electric wave, infrared ray, luminous ray, ultraviolet (near ultraviolet ray, far ultraviolet, extreme ultraviolet line), X ray, gamma-rays etc. can be enumerated.The ray type used in the present invention is not particularly limited, such as the suitable electromagnetic wave selecting the wavelength had near the maximum absorption wavelength of used salt compound (acid agent).
Among these active energy beams, from the aspect of adulterate effect and fail safe, preferred ultraviolet, luminous ray, infrared ray, specifically at 240nm ~ 1100nm, preferably at 240nm ~ 850nm, the light more preferably at 240nm ~ 670nm with very big emission wavelength.
Radioactive ray or electromagnetic wave irradiation device is used in the irradiation of active energy beam.The radioactive ray irradiated or electromagnetic wavelength are not particularly limited, select to irradiate the radioactive ray of the wavelength region may corresponding with the induction wavelength of used salt compound or electromagnetic wavelength.
As radioactive ray or electromagnetic device can be irradiated, there are the Excimer lamps such as mercury lamp, halide lamp, xenon flash lamp, metal halide lamp, ArF (argon fluoride) Excimer lamp, KrF (KrF) Excimer lamp such as LED (light-emitting diode: the abbreviation of Light Emitting Diode) lamp, high-pressure mercury lamp, ultrahigh pressure mercury lamp, Deep UV (far ultraviolet) lamp, low pressure UV (ultraviolet) lamp, extreme ultraviolet light modulation, electron beam, an exposure device that is light source with X ray lamp.Ultraviolet radiation can use common ultraviolet lamp, such as use commercially available solidification/bonding/exposure ultraviolet lamp (USHIO INC. Co., Ltd. SP9-250UB etc.) to carry out.
About time for exposure and light quantity, consider that the kind of the salt compound used and doping effect are suitable for selecting.Specifically, can enumerate with light quantity is 10mJ/cm 2~ 10J/cm 2, be preferably 50mJ/cm 2~ 5J/cm 2condition carry out.
When utilizing heating to adulterate, more than the acidic temperature of salt compound, the film after film forming is heated.As heating-up temperature, be preferably 50 DEG C ~ 200 DEG C, be more preferably 70 DEG C ~ 150 DEG C.Be preferably 1 minute ~ 60 minutes heating time, be more preferably 3 minutes ~ 30 minutes.
The period of doping treatment is not particularly limited, preferably carries out after thermo-electric converting material of the present invention being carried out to the processing process such as film forming.
The thermoelectric conversion layer (also referred to as thermoelectricity conversion film) formed by thermo-electric converting material of the present invention and thermoelectric conversion element of the present invention have high thermoelectricity conversion performance index ZT, the thermoelectricity conversion performance at initial stage is excellent, even and if under hot and humid and so on severe rugged environment, the ageing stability of thermoelectricity conversion performance is also good, can the thermoelectricity conversion performance at long term maintenance higher initial stage.
Therefore, thermoelectric conversion element of the present invention can suitably use as the generating element of thermoelectric power generation article.As such generating element, specifically, the generators such as hot spring generator, solar thermal power generation machine, waste-heat power generation machine, wrist-watch power supply, semiconductor driving power, (small-sized) sensor-use source etc. can be enumerated.
In addition, thermo-electric converting material of the present invention and the thermoelectric conversion layer formed by thermo-electric converting material of the present invention are suitable for being used as thermoelectric conversion element of the present invention, thermoelectric generation elements material, thermoelectric power generation film or various conductive film, specifically, the suitable thermo-electric converting material as above-mentioned generating element or thermoelectric power generation film etc.
Embodiment
Illustrate in greater detail the present invention by the following examples, but the present invention is not limited thereto.
Employ following low molecule conjugated compound 1 ~ 8, macromolecular compound 1 ~ 7 and PEDOT:PSS.
Low molecule conjugated compound 3 and macromolecular compound 2 synthesize as follows.
(synthesis example of low molecule conjugated compound 3)
By 4-hexyl benzene ylboronic acid (4-hexylphenylboronic acid) (2.40g, 11.6mmol), 3,7-bis-bromo-2,8-dimethyl dibenzo [b, d] thiophene (3,7-dibromo-2,8-dimethyldibenzo [b, d] thiophene) (4.31g, 11.6mmol), two (dibenzalacetone) palladium (0) (67.0mg, 0.117mmol), 2-dicyclohexyl phosphino--2 ', 6 '-dimethoxy-biphenyl (47.8mg, 24.5mmol) imports in the flask of 300mL, carries out nitrogen replacement in container.Utilize syringe to be added into as the oxolane (65mL) of solvent and water (13mL) after in this container, utilize the oil bath of 110 DEG C to add thermal agitation in a nitrogen atmosphere 9 hours, make it react.After reactant liquor is cooled to room temperature, remove insoluble composition by diatomite filtration.For obtained filtrate, utilize ethyl acetate and water, by extraction and isolation organic layer.For this organic layer, utilize rotary evaporator to distill except after desolventizing, utilize silica gel column chromatography to refine, obtain the low molecule conjugated compound 3 (output 3.29g, yield 78%) as target.
(synthesis example of macromolecular compound 2)
By 9, two (the 2-ethylhexyl)-2 of 9-, two (the tributylestannyl)-9H-fullerene (9 of 7-, 9-Bis (2-ethylhexyl)-2, 7-bis (trimethylstannyl)-9H-fluorene) (3.08g, 4.38mmol), 3-(two (4-bromine hexyl) is amino) methyl benzoate (methyl 3-(bis (4-bromophenyl) amino) benzoate) (2.02g, 4.38mmol), tetrakis triphenylphosphine palladium (253mg, 0.219mmol) import in the flask of 200mL, nitrogen replacement is carried out in container.Utilize syringe to be added into as the toluene (35mL) of solvent and DMF (9mL) after in this container, utilize the oil bath of 120 DEG C to add thermal agitation in a nitrogen atmosphere 24 hours, make it react.After reactant liquor is cooled to room temperature, by the insoluble composition of diatomite filtration removing solution.Obtained filtrate being dropped in methyl alcohol bit by bit, after solid matter is separated out, getting solid matter by filtering to divide.Utilize tetrahydrofuran solvent to divide the solid matter got to carry out 10 hours heated wash to use apparatus,Soxhlet's, impurity is removed.Finally, under vacuo by the solid matter drying after cleaning 10 hours, the macromolecular compound 2 (output 2.21g, yield 73%) as target is obtained thus.
In the following repetitive structure of macromolecular compound 1 ~ 6 and PEDOT:PSS, * represents the connecting portion of repetitive structure.
The macromolecular compound 1 ~ 6 used and the molecular weight of PEDOT:PSS as described below.
Macromolecular compound 1: weight average molecular weight=53000
Macromolecular compound 2: weight average molecular weight=20000
Macromolecular compound 3: weight average molecular weight=19000
Macromolecular compound 4: weight average molecular weight=41000
Macromolecular compound 5: weight average molecular weight=34000
Macromolecular compound 6: weight average molecular weight=26000
PEDOT:PSS: poly-(3,4-ethylenedioxy thiophene) poly-(styrene sulfonate), the manufacture of H.C.Starck society, the water dispersion of trade name " Baytron P ", PEDOT/PSS about 1.3 quality %), EDOT (3,4-ethylene dioxythiophene)/PSS (poly-(styrene sulfonate)) (mass ratio)=1/2.5
Polystyrene: Aldrich society manufacture 430102, weight average molecular weight=192000
Dopant uses following compound 1 ~ 4.
Embodiment 1
By 2mg low molecule conjugated compound 3,4mg individual layer CNT, (ASP-100F, Hanwha Nanotech society manufactures, the average length of dispersion (CNT concentration 60 quality %), CNT: about 5 μm ~ 20 μm, average diameter: about 1.0nm ~ 1.2nm, volume mean diameter (D50): 50nm), 4mg macromolecular compound 1 is added in o-dichlorohenzene 4.0ml, utilizes ultrasound bath to disperse 70 minutes.Utilize silk screen print method to be applied to by this dispersion liquid, in single side surface, there is gold (thickness 20nm, wide: 5mm) as electrode 12 surface of the glass baseplate 11 (thickness: 0.8mm) of the 1st electrode 13,80 DEG C of heating 45 minutes, except desolventizing.Thereafter, under room temperature in vacuo, drying 10 hours, forms the thermoelectric conversion layer 14 of thickness 1.9 μm, size 8mm × 8mm thus.Thereafter, at 80 DEG C, there is gold as the glass baseplate 16 (thickness of the width of the thickness of electrode 15: 20nm, electrode 15: 5mm, glass baseplate 16: 0.8mm) of the 2nd electrode 15 on the top of thermoelectric conversion layer 14 according to the mode that the 2nd electrode 15 is opposed with thermoelectric conversion layer 14 evaporation of fitting, make the thermoelectric conversion element of the present invention 101 as the thermoelectric conversion element 1 shown in Fig. 1.
Except changing the presence or absence of low molecule conjugated compound and kind, the presence or absence of CNT, the presence or absence of macromolecular compound and kind and electrode material as described in Table 1, make thermoelectric conversion element 102 ~ 114 of the present invention and compare with thermoelectric conversion element c01 ~ c07 in the same manner as thermoelectric conversion element 101.It should be noted that, macromolecular compound used is identical with the material used in embodiment 3.
About each thermoelectric conversion element, evaluate the dispersiveness (being designated as in table 1 " dispersiveness ") of pyroelecthc properties value (thermo-electromotive force S) and conductive nano material by the following method.Result is shown in table 1.
[mensuration of pyroelecthc properties value (thermo-electromotive force S)]
1st electrode 13 of each thermoelectric conversion element is arranged on the heating plate of maintenance uniform temperature, amber ear note (Peltier) element that set temperature controls on the 2nd electrode 15.While the temperature of heating plate is kept certain (100 DEG C), reduce the temperature of amber ear note (Peltier) element, thus between two electrodes, give temperature difference (more than 0K and be the scope of below 4K).Now, by by the thermo-electromotive force produced between two electrodes (μ V) divided by the specified temp difference (K) produced between two electrodes, calculate the thermo-electromotive force S (μ V/K) of per unit temperature difference, using the pyroelecthc properties value of this value as thermoelectric conversion element.Calculated pyroelecthc properties value is listed in table 1 with the form of the relative value relative to the calculated value compared with thermoelectric conversion element c01.
[the dispersiveness evaluation of CNT]
As follows the CNT dispersiveness in the dispersion liquid after ultrasonic wave dispersion obtained above is evaluated.
Use the day Microtrack MT3300 type laser diffraction and scattering formula particle size distribution device that manufactures of machine dress (strain) society to measure the scope of 0.1 μm ~ 2000 μm, calculate the volume average particle size (D50) when being 50% cumulative frequency.As follows CNT dispersiveness is categorized into the grade of following A ~ E according to the value of this volume average particle size.Preferably meet the benchmark of A ~ C in practical.
It should be noted that, substantially do not disperse at CNT, represent with "-" when cannot evaluate dispersiveness.
A: volume average particle size (D50) is less than 150nm
B: volume average particle size (D50) is for more than 150nm and be less than 300nm
C: volume average particle size (D50) is for more than 300nm and be less than 600nm
D: volume average particle size (D50) is more than 600nm, but do not observe sediment or condensation product by visual.
E: by being visually observed sediment or condensation product.
[table 1]
Table 1
As shown in Table 1, containing all not relying on the presence or absence of macromolecular compound and the kind of electrode material as the CNT of conductive nano material and the thermoelectric conversion element 101 ~ 114 of above-mentioned low molecule conjugated compound, CNT excellent dispersion and pyroelecthc properties value are also more than about 2 times of the thermoelectric conversion element of thermoelectric conversion element c01, are excellent.
On the other hand, not containing the dispersed inequality of CNT of the comparison thermoelectric conversion element c01 ~ c07 of at least one in CNT and above-mentioned low molecule conjugated compound, pyroelecthc properties value is also low.Particularly, the thermo-electromotive force S not containing the thermoelectric conversion element c05 ~ c07 of CNT is below detectability, and thermoelectricity capability is very low.
Embodiment 2
The kind of change macromolecular compound as shown in table 2 and the kind of conductive nano material, make thermoelectric conversion element 201 ~ 209 of the present invention in addition and compare with thermoelectric conversion element c21 and c22 in the same manner as thermoelectric conversion element 101, evaluating dispersiveness and the pyroelecthc properties value (relative value relative to the calculated value of thermoelectric conversion element c101) of conductive nano material similarly to Example 1.Result is shown in table 2.
Conductive nano materials'use following substances.
Graphite: AGB-5 (trade name, Ito Graphite Co., Ltd. manufacture)
Carbon nano-fiber: VGCF-X (trade name, Showa Denko K. K manufacture)
Graphene: F-GF1205-AB (trade name, SPI Supplies society manufacture)
Carbon black: Ketjen black EC600JD (trade name, LION Co., Ltd. manufacture)
Carbon nano-particle: Nano diamond PL-D-G (trade name, PlasmaChem society manufacture)
Nano silver wire: based on the nano silver wire made by the preparation method 2 recorded in Japanese Unexamined Patent Publication 2012-230881 publication
Nickel nanotubes: the Nickel nanotubes made by method utilizing the embodiment 1 recorded based on Japan Patent No. 4374439 publication
Gold nano grain: 636347 (product coding, SIGMA-ALDRICH society manufacture)
Fullerene: nanom purple ST (trade name, Frontier Carbon Corporation manufacture)
[table 2]
Table 2
As shown in Table 2, the CNT of the thermoelectric conversion element of the present invention 201 ~ 209 containing conductive nano material and above-mentioned low molecule conjugated compound is dispersed all excellent, and thermo-electromotive force value is higher compared with thermoelectric conversion element c01.
On the other hand, not containing the dispersed inequality of CNT of comparison thermoelectric conversion element c21 and c22 of above-mentioned low molecule conjugated compound.
Embodiment 3
3mg low molecule conjugated compound 1,2mg CNT (manufacture of ASP-100F, Hanwha Nanotech society), 2mg dopant 1 and 2.5mg are added in o-dichlorohenzene 5ml as the polystyrene (Aldrich society manufacture 430102) of non-conjugate high molecular and 2.5mg macromolecular compound 1, utilize ultrasound bath to disperse 70 minutes.After using this dispersion liquid to form thermoelectric conversion layer similarly to Example 1, utilize ultraviolet irradiation machine (Eyegraphics Co., Ltd. manufactures, ECS-401GX) irradiation ultraviolet radiation (light quantity: 1.06J/cm 2), adulterate.Thereafter, the 2nd electrode of fitting similarly to Example 1, makes thermoelectric conversion element 301 of the present invention.
The kind of the presence or absence of the presence or absence of change low molecule conjugated compound as shown in table 3 and kind, macromolecular compound and kind, dopant, makes thermoelectric conversion element 302 ~ 310 of the present invention in addition, compares with thermoelectric conversion element c31 and c32 in the same manner as thermoelectric conversion element 301.
It should be noted that, in thermoelectric conversion element 302,305 and 310, do not utilize Ultraviolet radiation to carry out doping treatment.
In addition, the material that the polymethyl methacrylate illustrated in table 3 as non-conjugate high molecular uses Wako Pure Chemical Industries, Ltd. to manufacture, the material that polyvinyl acetate uses Wako Pure Chemical Industries, Ltd. to manufacture, PLA uses PLA-0015 (trade name, pharmaceutical worker industry pure with light), the material that PVP uses Wako Pure Chemical Industries, Ltd. to manufacture, imide compound uses Sorupi 6, 6-PI (trade name, Sorupi Industry Co., Ltd. manufacture), and carbonate products uses IupizetaPCZ-300 (trade name, Mitsubishi Gas Chemical Co., Ltd manufactures).
About each thermoelectric conversion element, have rated dispersiveness and the pyroelecthc properties value of conductive nano material similarly to Example 1.Result is shown in table 3.It should be noted that, the pyroelecthc properties value shown in table 3 is the relative value of the calculated value relative to the comparison thermoelectric conversion element c01 made in embodiment 1.
[table 3]
Table 3
As shown in Table 3, the thermoelectric conversion element of the present invention 301 ~ 310 also containing dopant except CNT and above-mentioned low molecule conjugated compound all demonstrates more excellent pyroelecthc properties value.
On the other hand, even if containing dopant but not containing the CNT bad dispersibility of thermoelectric conversion element c31 and c32 of above-mentioned low molecule conjugated compound.
Embodiment 4
As the 1st base material 12 with the 1st electrode 13, do not use glass and use the PETG film (thickness: 125 μm) with pliability (number of times of the resistance to bending MIT of the above-mentioned determination method based on specifying in ASTM D2176 is more than 50,000 circulations); Use has the 2nd base material (glass manufacture) 16 of the 2nd electrode 15 formed by copper thickener (trade name: ACP-080, Co., Ltd. Asahi chemical research are manufactured), in addition, the thermoelectric conversion element of the present invention 401 as thermoelectric conversion element 1 is made in the same manner as the thermoelectric conversion element 101 of embodiment 1.Between the 2nd base material 16 and the 2nd electrode 15, give the temperature difference of 3 DEG C at the 1st base material (PETG film) 12 with the 1st electrode 13, result utilizes potentiometer to confirm the thermo-electromotive force creating 230 μ V between two electrodes.
The thermo-electric converting material made in the thermoelectric conversion element c01 of embodiment 1 is used as thermo-electric converting material, in addition, comparison thermoelectric conversion element c41 in the same manner as above-mentioned thermoelectric conversion element 401.Between the 2nd base material and the 2nd electrode, give the temperature difference of 3 DEG C at the 1st base material with the 1st electrode, result utilizes potentiometer to confirm the thermo-electromotive force creating 93 μ V between two electrodes.
From above result, with not containing above-mentioned low molecule conjugated compound comparison thermoelectric conversion element c41 compared with, the thermo-electromotive force that the thermoelectric conversion element 401 containing CNT and above-mentioned low molecule conjugated compound produces is large.
Embodiment 5
The slaine shown in table 4 is added according to the addition shown in table 4 in low molecule conjugated compound 3 and individual layer CNT, in addition, make thermoelectric conversion element 501 ~ 504 of the present invention in the same manner as thermoelectric conversion element 101, evaluate dispersiveness and the pyroelecthc properties value (relative value relative to the calculated value of thermoelectric conversion element c101) of conductive nano material similarly to Example 1.Result is shown in table 4.
[table 4]
Table 4
As shown in Table 4, except CNT and above-mentioned low molecule conjugated compound, also dispersed the and pyroelecthc properties value of the CNT taken into account with high level is all demonstrated containing the thermoelectric conversion element of the present invention 501 ~ 504 of metallic element.
Although describe the present invention in conjunction with its execution mode, but applicant thinks, as long as no special declaration, then the present invention is at any details place illustrated all not circumscribeds, should carry out wide in range explanation under the condition not violating the invention spirit and scope shown in claims.
The application advocates the priority based on carrying out the Japanese Patent Application 2013-063577 of patent submission on March 26th, 2013 in Japan, it the part of its content as this specification contents to be introduced with reference to this.
The explanation of symbol
1,2 thermoelectric conversion elements
11,17 metallic plates
12,22 the 1st base materials
13,23 the 1st electrodes
14,24 thermoelectric conversion layer
15,25 the 2nd electrodes
16,26 the 2nd base materials

Claims (32)

1. a thermoelectric conversion element, it is the thermoelectric conversion element on base material with the 1st electrode, thermoelectric conversion layer and the 2nd electrode, wherein,
Described thermoelectric conversion layer contains conductive nano material and has the low molecule conjugated compound of thick multiring structure, and this thick multiring structure is that at least 3 rings be selected from the group that is made up of aromatic hydrocarbon ring and heteroaromatic condense.
2. thermoelectric conversion element as claimed in claim 1, wherein, described low molecule conjugated compound has the thick multiring structure that 3 ~ 6 rings be selected from described group condense.
3. thermoelectric conversion element as claimed in claim 1 or 2, wherein, the Ppolynuclear aromatic hydrocarbon compound that at least 3 rings that described low molecule conjugated compound is the Ppolynuclear aromatic heterocyclic compound that condenses according at least 3 rings selected by the mode comprising at least 1 described heteroaromatic from described group or described aromatic hydrocarbon ring condense.
4. the thermoelectric conversion element according to any one of claims 1 to 3, wherein, described Ppolynuclear aromatic hydrocarbon compound is the Ppolynuclear aromatic hydrocarbon compound except the Ppolynuclear aromatic hydrocarbon compound with perylene structure.
5. the thermoelectric conversion element according to any one of Claims 1 to 4, wherein, described Ppolynuclear aromatic hydrocarbon compound is except having the Ppolynuclear aromatic hydrocarbon compound condensed on 1 ring except the Ppolynuclear aromatic hydrocarbon compound of the structure of the ring of more than 4.
6. the thermoelectric conversion element according to any one of Claims 1 to 5, wherein, described Ppolynuclear aromatic hydrocarbon compound has that condense with 1 ring, 2 rings or 3 rings, that at least 3 aromatic hydrocarbon rings condense thick multiring structure.
7. the thermoelectric conversion element according to any one of claim 1 ~ 6, wherein, described heteroaromatic is 5 rings or 6 rings.
8. thermoelectric conversion element as claimed in claim 7, wherein, described heteroaromatic is thiphene ring, furan nucleus or pyrrole ring.
9. the thermoelectric conversion element according to any one of claim 1 ~ 8, wherein, described low molecule conjugated compound has the thick multiring structure in following formula (1A) ~ (1D) represented by any one formula,
10. thermoelectric conversion element as claimed in claim 9, wherein, at least 1 person in the C ring ~ F ring of described formula (1A) ~ (1D) represented by following formula (1-1) or (1-2),
In formula, X represents carbon atom or hetero-atom, and * 1 represents with * 2 the ring carbons condensed with identical ring respectively.
11. thermoelectric conversion elements according to any one of claim 1 ~ 10, wherein, described thick multiring structure has at least 1 substituting group.
12. thermoelectric conversion elements as claimed in claim 11, wherein, the loops of the end of described substituting group and described thick multiring structure closes.
13. thermoelectric conversion elements as described in claim 11 or 12, wherein, described substituting group is alkyl, aryl, heterocyclic radical, alkoxyl, dialkyl amido, alkoxy carbonyl group or the complex substituents that they combined.
14. thermoelectric conversion elements according to any one of claim 1 ~ 13, wherein, described thermoelectric conversion layer contains macromolecular compound.
15. thermoelectric conversion elements as claimed in claim 14, wherein, described macromolecular compound is be selected from least one macromolecule in the group that is made up of conjugated polymer and non-conjugate high molecular.
16. thermoelectric conversion elements as described in claims 14 or 15, wherein, described macromolecular compound is to be selected from by thiophene based compound, azole series compound, aniline based compound, acetylene based compound, to phenylene based compound, to be polymerized at least one compound in phenylene vinylidene based compound, the group that forms phenylene ethynylene based compound, fluorenes based compound, arylamine based compound and their derivative or the conjugated polymer of copolymerization or non-conjugate high molecular.
17. thermoelectric conversion elements as described in claim 15 or 16, wherein, described non-conjugate high molecular is by least one compound polymerization that is selected from the group that is made up of vinyl compound, (methyl) acrylate compounds, carbonate products, ester compounds, amide compound, imide compound and silicone compounds or copolymerization.
18. thermoelectric conversion elements according to any one of claim 15 ~ 17, wherein, described macromolecular compound is the mixture of described conjugated polymer and described non-conjugate high molecular.
19. thermoelectric conversion elements according to any one of claim 1 ~ 18, wherein, described conductive nano material is nano-carbon material or nano metal material.
20. thermoelectric conversion elements according to any one of claim 1 ~ 19, wherein, described conductive nano material is be selected from least a kind in the group that is made up of carbon nano-tube, carbon nano-fiber, graphite, Graphene, carbon nano-particle and metal nanometer line.
21. thermoelectric conversion elements according to any one of claim 1 ~ 20, wherein, described thermoelectric conversion layer contains dopant.
22. thermoelectric conversion elements as claimed in claim 21, wherein, described dopant is be selected from least one in the group that is made up of salt compound, oxidant, acid compound and electron acceptor compound.
23. thermoelectric conversion elements as described in claim 21 or 22, wherein, relative to described macromolecular compound 100 mass parts, contain described dopant with the ratio more than 0 mass parts and below 60 mass parts.
24. thermoelectric conversion elements as described in claim 22 or 23, wherein, described salt compound is by giving heat or active energy beam irradiates and acidic compound.
25. thermoelectric conversion elements according to any one of claim 1 ~ 24, wherein, described base material has pliability.
26. thermoelectric conversion elements according to any one of claim 1 ~ 25, wherein, described 1st electrode and described 2nd electrode are formed by aluminium, gold, silver or copper independently of one another.
27. 1 kinds of thermoelectric power generation article, it use the thermoelectric conversion element according to any one of claim 1 ~ 26.
28. 1 kinds of sensor-use sources, it use the thermoelectric conversion element according to any one of claim 1 ~ 26.
29. 1 kinds of thermo-electric converting materials for the formation of the thermoelectric conversion layer of thermoelectric conversion element, its low molecule conjugated compound containing conductive nano material and have thick multiring structure, this thick multiring structure is that at least 3 rings be selected from the group that is made up of aromatic hydrocarbon ring and heteroaromatic condense.
30. thermo-electric converting materials as claimed in claim 29, it contains macromolecular compound.
31. thermo-electric converting materials as described in claim 29 or 30, it contains organic solvent.
32. thermo-electric converting materials as claimed in claim 31, described conductive nano dispersion of materials forms by it in described organic solvent.
CN201480005086.5A 2013-03-26 2014-03-19 Thermoelectric conversion material, thermoelectric conversion element, and thermoelectric power generation article and sensor power source using thermoelectric conversion element Pending CN104937734A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2013-063577 2013-03-26
JP2013063577A JP5951539B2 (en) 2013-03-26 2013-03-26 Thermoelectric conversion material, thermoelectric conversion element, article for thermoelectric power generation using the same, and power source for sensor
PCT/JP2014/057508 WO2014156872A1 (en) 2013-03-26 2014-03-19 Thermoelectric conversion material, thermoelectric conversion element, and thermoelectric power generation article and sensor power source using thermoelectric conversion element

Publications (1)

Publication Number Publication Date
CN104937734A true CN104937734A (en) 2015-09-23

Family

ID=51623851

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201480005086.5A Pending CN104937734A (en) 2013-03-26 2014-03-19 Thermoelectric conversion material, thermoelectric conversion element, and thermoelectric power generation article and sensor power source using thermoelectric conversion element

Country Status (3)

Country Link
JP (1) JP5951539B2 (en)
CN (1) CN104937734A (en)
WO (1) WO2014156872A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109786542A (en) * 2019-01-23 2019-05-21 深圳大学 A kind of porphyrin/carbon nano-tube composite heat electric material and preparation method thereof
CN110300727A (en) * 2017-01-09 2019-10-01 加拿大国家研究委员会 Decomposable S- tetrazine quasi polymer for single-walled carbon nanotube application
CN114008147A (en) * 2019-06-26 2022-02-01 日产化学株式会社 Charge-transporting varnish

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6499450B2 (en) * 2015-01-07 2019-04-10 株式会社日本触媒 Graphene oxide composite composition
WO2016195091A1 (en) * 2015-06-05 2016-12-08 富士フイルム株式会社 Thermoelectric conversion element
KR102628850B1 (en) * 2016-03-07 2024-01-25 삼성디스플레이 주식회사 Condensed cyclic compound and organic light emitting device comprising the same
CN110268535A (en) * 2017-02-10 2019-09-20 国立大学法人奈良先端科学技术大学院大学 N-shaped conductive material and its manufacturing method
JP2019179845A (en) * 2018-03-30 2019-10-17 株式会社Ｎｂｃメッシュテック Thermoelectric element and manufacturing method therefor
JP2019212823A (en) * 2018-06-06 2019-12-12 株式会社Ｎｂｃメッシュテック Thermoelectric element and manufacturing method therefor
JP7451932B2 (en) 2019-10-17 2024-03-19 ａｒｔｉｅｎｃｅ株式会社 Thermoelectric conversion materials and thermoelectric conversion elements using the same
JP6845521B1 (en) * 2020-09-30 2021-03-17 株式会社Ｇｃｅインスティチュート Power generation elements, power generation equipment, electronic devices, and methods for manufacturing power generation elements
JP6944168B1 (en) * 2021-05-31 2021-10-06 国立大学法人九州大学 Manufacturing methods for thermoelectric elements, power generators, electronic devices, and thermoelectric elements
JP7011361B1 (en) 2021-09-10 2022-01-26 株式会社Ｇｃｅインスティチュート Manufacturing method of power generation element, power generation element, power generation device, and electronic device

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101257054A (en) * 2007-07-02 2008-09-03 兰州理工大学 Solar cell structure and preparing method thereof
CN101573404A (en) * 2006-10-11 2009-11-04 佛罗里达大学研究基金公司 Electroactive polymers containing pendant pi-interacting/binding substituents, their carbon nanotube composites, and processes to form the same
WO2012133314A1 (en) * 2011-03-28 2012-10-04 富士フイルム株式会社 Conductive composition, conductive film using conducive composition, and method for manufacturing conductive film

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060060839A1 (en) * 2004-09-22 2006-03-23 Chandross Edwin A Organic semiconductor composition
JP2008305831A (en) * 2007-06-05 2008-12-18 Tokyo Gas Chemicals Co Ltd Thermoelectric conversion material
JP5453869B2 (en) * 2009-03-25 2014-03-26 東レ株式会社 Organic semiconductor composite and organic field effect transistor using the same
JP2011126727A (en) * 2009-12-16 2011-06-30 Toray Ind Inc Carbon nanotube composite, carbon nanotube composite dispersion, carbon nanotube composite-dispersed film and field effect transistor
JP5734575B2 (en) * 2010-03-02 2015-06-17 株式会社リコー Organic laminated film
JP5578665B2 (en) * 2010-05-19 2014-08-27 国立大学法人九州大学 Thermoelectric conversion element and manufacturing method thereof
JP2012089604A (en) * 2010-10-18 2012-05-10 Nec Corp Thermoelectric conversion device, method of manufacturing the same, and thermoelectric conversion unit
JP5652767B2 (en) * 2010-11-09 2015-01-14 独立行政法人産業技術総合研究所 Photothermal power generation element and photothermal power generation method using the photothermal power generation element
US9892817B2 (en) * 2011-05-25 2018-02-13 Nissan Chemical Industries, Ltd. Conductive composition, and conductive complex
JP2013008722A (en) * 2011-06-22 2013-01-10 Toyota Motor Corp Nanocomposite thermoelectric conversion material and manufacturing method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101573404A (en) * 2006-10-11 2009-11-04 佛罗里达大学研究基金公司 Electroactive polymers containing pendant pi-interacting/binding substituents, their carbon nanotube composites, and processes to form the same
CN101257054A (en) * 2007-07-02 2008-09-03 兰州理工大学 Solar cell structure and preparing method thereof
WO2012133314A1 (en) * 2011-03-28 2012-10-04 富士フイルム株式会社 Conductive composition, conductive film using conducive composition, and method for manufacturing conductive film

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110300727A (en) * 2017-01-09 2019-10-01 加拿大国家研究委员会 Decomposable S- tetrazine quasi polymer for single-walled carbon nanotube application
CN109786542A (en) * 2019-01-23 2019-05-21 深圳大学 A kind of porphyrin/carbon nano-tube composite heat electric material and preparation method thereof
CN114008147A (en) * 2019-06-26 2022-02-01 日产化学株式会社 Charge-transporting varnish

Also Published As

Publication number Publication date
JP2014192190A (en) 2014-10-06
WO2014156872A1 (en) 2014-10-02
JP5951539B2 (en) 2016-07-13

Similar Documents

Publication Publication Date Title
CN104937734A (en) Thermoelectric conversion material, thermoelectric conversion element, and thermoelectric power generation article and sensor power source using thermoelectric conversion element
CN105103316B (en) Thermo-electric converting material, thermoelectric conversion element, thermoelectric power generation article and sensor-use source
CN103828081B (en) Thermo-electric converting material and thermoelectric conversion element
CN105103317A (en) Method for manufacturing thermoelectric conversion element and method for producing dispersion for thermoelectric conversion layers
CN103907212B (en) Thermoelectric conversion material and thermoelectric conversion element
CN103477397B (en) Conductive composition, the conductive film using described compositions and manufacture method thereof
JP6047468B2 (en) Thermoelectric conversion materials, thermoelectric conversion elements, articles for thermoelectric power generation, and power supplies for sensors
JP2013098299A (en) Thermoelectric conversion material and thermoelectric conversion element
CN104919609B (en) Thermo-electric converting material, thermoelectric conversion element and the thermoelectric power generation article using it and sensor-use source
WO2014119468A1 (en) Thermoelectric conversion material, thermoelectric conversion element, article for thermoelectric power generation using thermoelectric conversion element, and power supply for sensors using thermoelectric conversion element
JP5931763B2 (en) Thermoelectric conversion material, thermoelectric conversion element, article for thermoelectric power generation using the same, and power supply for sensor
CN104919608A (en) Thermoelectric conversion material, thermoelectric conversion element, article for thermoelectric power generation using thermoelectric conversion element, and power supply for sensors using thermoelectric conversion element
Bolognesi et al. From block copolymers to end-capped polymers: A suitable method to control the electro-optical properties of polymeric materials
TW201229200A (en) Organic electroluminescence element and light-emitting device
Yang et al. Emission-tunable multicolor graphene molecules with controllable synthesis, excellent optical properties, and specific applications
Chen et al. Synthesis and Characterization of Polycyclic Aromatic Hydrocarbons with Different Spatial Constructions Based on Hexaphenylbenzene Derivatives
Botiz et al. Structural Control in Polymeric Semiconductors: Application to the Manipulation of Light-emitting Properties
Lee Thermodynamic Synthesis of Ladder-Type Functional Organic Materials
STINGELIN Structural Control in Polymeric Semiconductors: Application to the Manipulation of Light-emitting Properties
Keita White-Emitting Conjugated Polymer Nanoparticles: Tuning Emission Via Förster Resonance Energy Transfer in Nanostructures Assembled Through Click Reactions

Legal Events

Date Code Title Description
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20150923

RJ01 Rejection of invention patent application after publication