JP2015072954A - Thermoelectric conversion element, method for manufacturing the same, article for thermoelectric generation, and power supply for sensor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flexible organic thermoelectric conversion element, high in adhesion with a base material or a metal electrode and capable of preventing an organic thermoelectric conversion layer from being separated during use, and a method for manufacturing the flexible organic thermoelectric conversion element.SOLUTION: A flexible organic thermoelectric conversion element 10 includes: an organic thermoelectric conversion layer 3 including (a) carbon nanotubes, (b) a polymer compound, and (c) a compound represented by the following formula (A), formula (B) and formula (C), and provided in a pattern on a flexible base material 1, on which a metal electrode 2 is provided, so as to correspond with the arrangement of the metal electrode; and an upper electrode 4 provided on the organic thermoelectric conversion layer. Formula (A): R-Y, formula (B): R-Z-C(=S)-Z-R, and formula (C): R-Z-Z-R, where Rrepresents an alkyl group or the like, Y represents -SH, -SCN or the like, Zand Zrepresent a single bond, an oxygen atom, a sulfur atom or the like, Zrepresents a sulfur atom or the like, Rand Rrepresent an alkyl group, an alkenyl group or the like, and R, R, Rand Rrepresent a hydrogen atom, an alkyl group, an aralkyl group or an aryl group.

Description

The present invention relates to a thermoelectric conversion element that converts heat into electricity, a method for manufacturing the thermoelectric conversion element, an article for thermoelectric generation, and a power source for sensors.
In particular, it relates to a thermoelectric conversion element in which an organic thermoelectric conversion layer is produced on a flexible substrate and a method for producing the same, and more specifically, an organic thermoelectric conversion composition containing carbon nanotubes and a polymer compound (for example, a conductive polymer). The present invention relates to a thermoelectric conversion element using a thermoelectric conversion element, a manufacturing method thereof, a thermoelectric power generation article using the thermoelectric conversion element, and a sensor power source.

  Thermoelectric conversion materials that can mutually convert thermal energy and electrical energy are used in thermoelectric conversion elements such as thermoelectric power generation elements and Peltier elements. Thermoelectric power generation using thermoelectric conversion materials and thermoelectric conversion elements can convert heat energy directly into electric power, has the advantage of not requiring moving parts, etc. It is used for remote power and space power.

Conventionally, thermoelectric conversion elements were mainly made of inorganic thermoelectric conversion materials, but in recent years, flexible organic thermoelectric conversion elements made of flexible and lightweight organic thermoelectric conversion materials have attracted attention (for example, Patent Documents 1 and 2).
In addition, Patent Documents 3 to 6 and Non-Patent Documents 1 and 2 relate to organic thermoelectric conversion materials or organic thermoelectric conversion elements.

International Publication No. 2012/121133 Pamphlet JP 2010-199276 A JP 2013-89798 A JP2013-95820A JP 2013-95821 A JP2013-118166A

Nature Materials, Vol. 10,429,2011 J. et al. C. Acs. Nano, Vol. 5,7885,2011

Flexible organic thermoelectric conversion elements can be put to practical use on curved surfaces and uneven surfaces that were difficult with conventional thermoelectric conversion elements made of inorganic thermoelectric conversion materials. It is progressing towards.
However, due to its flexibility, the flexible organic thermoelectric conversion element has insufficient adhesion between the base material or the metal electrode and the organic thermoelectric conversion layer. When used on a curved surface or an uneven surface, the organic thermoelectric conversion layer There was a problem that it was easy to peel off.

The present invention uses a flexible organic thermoelectric conversion element that has high adhesion to a substrate or a metal electrode, and preferably can prevent peeling of the organic thermoelectric conversion layer during use, and a method for manufacturing the same, and the flexible organic thermoelectric conversion element. It is an object to provide an article for thermoelectric power generation and a power source for sensors.
The present invention also provides a flexible organic thermoelectric conversion element having high adhesion to a base material or a metal electrode, excellent conductivity and no decrease in conductivity due to additives or electrode treatment, a method for producing the same, and the flexible organic It is an object of the present invention to provide an article for thermoelectric power generation using a thermoelectric conversion element and a power source for a sensor.

  The present inventors examined the adhesion between the organic thermoelectric conversion layer and the base material or the metal electrode. As a result, the compound having a specific chemical structure has a conductivity of the organic thermoelectric conversion layer containing the carbon nanotube and the polymer compound. It has been found that the adhesion between the organic thermoelectric conversion layer and the base material or the metal electrode can be improved without lowering. The present invention has been completed based on this finding.

That is, said subject was achieved by the following means.
<1> A flexible that includes (a) a carbon nanotube, (b) a polymer compound, and (c) a compound represented by the following formula (A), formula (B), or formula (C) and provided with a metal electrode A flexible organic thermoelectric conversion element having an organic thermoelectric conversion layer provided in a pattern on the base material in accordance with the arrangement of metal electrodes and an upper electrode provided on the organic thermoelectric conversion layer.
Formula ^(A) R 1 -Y
Formula ^{(B) R 1 -Z 1 -C} (= S) -Z 2 -R 2
Formula (C) R ¹ —Z ³ —Z ³ —R ³
(In the formulas (A), (B) and (C), R ¹ represents an alkyl group, an alkenyl group, an aralkyl group or an aryl group. Y represents —SH, —SCN or SiR ⁴ R ⁵ H. Z ¹ and Z ² each independently represents a single bond, an oxygen atom, a sulfur atom or —NR ⁶ —, Z ³ represents a sulfur atom, — (C═S) —S— or —NR ⁷ — (C═ R ² and R ³ each independently represents an alkyl group, an alkenyl group, an aralkyl group or an aryl group, and R ² may combine with R ¹ to form a ring. R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, and R ⁷ may combine with R ¹ or R ³ to form a ring. .)
<2> The flexible organic thermoelectric conversion element according to <1>, wherein R ¹ , R ^2, and R ³ are each independently an alkyl group, an aralkyl group, or an aryl group.
<3> The flexible organic thermoelectric conversion element according to <2>, wherein the alkyl group is a linear alkyl group.
<4> R ¹ , R ² and R ³ each independently have at least one substituent selected from the group consisting of a carboxy group, a hydroxy group, an amide group and a heterocyclic group <1> to <3> The flexible organic thermoelectric conversion element according to any one of the above.
<5> The flexible organic thermoelectric conversion element according to <4>, wherein the heterocyclic group is a 5- or 6-membered heterocyclic group having a nitrogen atom.
<6> The flexible organic thermoelectric conversion element according to any one of <1> to <5>, wherein Y is -SH.
<7> The flexible organic thermoelectric conversion element according to any one of <1> to <5>, wherein at least one of Z ¹ and Z ² is —NR ⁶ —.
The flexible organic thermoelectric conversion element according to any one of <1> to <5>, wherein <8> -Z ³ —Z ³ — includes a disulfide bond.
<9> The flexible organic thermoelectric conversion element according to <8>, wherein Z ³ is a sulfur atom or —NR ⁷ — (C═S) —S—.
<10> The flexible organic thermoelectric conversion element according to any one of <1> to <9>, wherein the content of the compound (c) is 0.1 to 10% by mass with respect to the total solid content of the organic thermoelectric conversion layer. .
<11> The flexible organic thermoelectric conversion element according to any one of <1> to <10>, wherein the compound (c) is a compound having a molecular weight of 1000 or less.
<12> The organic thermoelectric conversion layer according to any one of <1> to <11>, wherein the organic thermoelectric conversion layer includes an organic thermoelectric conversion adhesive composition containing the carbon nanotube (a), the polymer compound (b), and the compound (c). Flexible organic thermoelectric conversion element.
<13> The organic thermoelectric conversion layer is provided with a film made of an organic thermoelectric conversion composition containing the carbon nanotube (a) and the polymer compound (b) on the film made of the compound (c). <11> The flexible organic thermoelectric conversion element according to any one of the above.
<14> The organic thermoelectric conversion adhesive composition or the organic thermoelectric conversion composition further contains (d) an onium salt compound represented by any one of the following general formulas (I) to (V) <12>. Or the flexible organic thermoelectric conversion element as described in <13>.

(In the general formulas (I) to (V), R ^{21 to} R ²³ , R ^{25 to} R ²⁶ and R ^{31 to} R ³³ are each independently an alkyl group, an aralkyl group, an aryl group, or an aromatic heterocyclic group. R ^{27 to} R ³⁰ each independently represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an aromatic heterocyclic group, an alkoxy group, or an aryloxy group, and R ²⁴ represents an alkylene group or an arylene group. .X represents a group ^-. is, ^{R 21} and ^{R 23} in any two groups of ^R 21 ^{to R 23} in an anion of a strong acid formula (I), formula (II), in the general formula (III) R ²⁵ and R ²⁶ , any two groups of R ^{27 to} R ³⁰ in the general formula (IV), and any two groups of R ^{31 to} R ³³ in the general formula (V) are Result To aliphatic ring, may form an aromatic ring, or a heterocyclic ring.)

<15> In the general formulas (I) to (V), X ⁻ represents an anion of an aryl sulfonic acid, an anion of a perfluoroalkyl sulfonic acid, an anion of a perhalogenated Lewis acid, an anion of a perfluoroalkyl sulfonimide, or The flexible organic thermoelectric conversion element according to <14>, which is an alkyl or aryl borate anion.
<16> In the total solid content of the organic thermoelectric conversion adhesive composition, the carbon nanotube (a) is 5 to 60% by mass, the polymer compound (b) is 30 to 80% by mass, and the compound (c) is 0.1%. The flexible organic thermoelectric conversion element as described in <14> or <15> which contains 10-30 mass% and 1-30 mass% of onium salt compounds (d).

<17> An organic thermoelectric conversion adhesive composition containing (a) a carbon nanotube, (b) a polymer compound, and (c) a compound represented by the following formula (A), formula (B) or formula (C) A flexible organic thermoelectric conversion element in which an organic thermoelectric conversion layer is formed on an organic thermoelectric conversion layer by forming a pattern on a flexible base material on which a metal electrode is installed in a pattern according to the arrangement of the metal electrode. Production method.
Formula ^(A) R 1 -Y
Formula ^{(B) R 1 -Z 1 -C} (= S) -Z 2 -R 2
Formula (C) R ¹ —Z ³ —Z ³ —R ³
(In the formulas (A), (B) and (C), R ¹ represents an alkyl group, an alkenyl group, an aralkyl group or an aryl group. Y represents —SH, —SCN or SiR ⁴ R ⁵ H. Z ¹ and Z ² each independently represents a single bond, an oxygen atom, a sulfur atom or —NR ⁶ —, Z ³ represents a sulfur atom, — (C═S) —S— or —NR ⁷ — (C═ R ² and R ³ each independently represents an alkyl group, an alkenyl group, an aralkyl group or an aryl group, and R ² may combine with R ¹ to form a ring. R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, and R ⁷ may combine with R ¹ or R ³ to form a ring. .)

The manufacturing method of the flexible organic thermoelectric conversion element as described in <17> whose content of <18> compound (c) is 0.1-10 mass% with respect to the total solid of an organic thermoelectric conversion adhesive composition.

<19> A surface of at least an organic thermoelectric conversion layer of a flexible substrate provided with a metal electrode is treated with a compound represented by (c) the following formula (A), formula (B) or formula (C) Then, an organic thermoelectric conversion composition containing (a) carbon nanotubes and (b) a polymer compound is provided in a pattern according to the arrangement of the metal electrodes to form an organic thermoelectric conversion layer. The manufacturing method of the flexible organic thermoelectric conversion element which provides an upper electrode.
Formula ^(A) R 1 -Y
Formula ^{(B) R 1 -Z 1 -C} (= S) -Z 2 -R 2
Formula (C) R ¹ —Z ³ —Z ³ —R ³
(In the formulas (A), (B) and (C), R ¹ represents an alkyl group, an alkenyl group, an aralkyl group or an aryl group. Y represents —SH, —SCN or SiR ⁴ R ⁵ H. Z ¹ and Z ² each independently represents a single bond, an oxygen atom, a sulfur atom or —NR ⁶ —, Z ³ represents a sulfur atom, — (C═S) —S— or —NR ⁷ — (C═ R ² and R ³ each independently represents an alkyl group, an alkenyl group, an aralkyl group or an aryl group, and R ² may combine with R ¹ to form a ring. R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, and R ⁷ may combine with R ¹ or R ³ to form a ring. .)

<20> An article for thermoelectric power generation using the flexible organic thermoelectric conversion element according to any one of <1> to <16>.
<21> A power source for sensors using the flexible organic thermoelectric conversion element according to any one of <1> to <16>.

In the present invention, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the present invention, when the xxx group is referred to as a substituent, the xxx group may have an arbitrary substituent. In addition, when there are a plurality of groups indicated by the same reference numerals, they may be the same or different.

According to the present invention, a flexible organic thermoelectric conversion element capable of preventing adhesion of the organic thermoelectric conversion layer at the time of use, and a method for producing the same, and a flexible organic thermoelectric conversion element are provided. The used thermoelectric power generation article and sensor power source can be provided.
In addition, according to the present invention, a flexible organic thermoelectric conversion element having high adhesion to a substrate or a metal electrode and excellent conductivity, a method for producing the same, and a thermoelectric power generation article using the flexible organic thermoelectric conversion element And a power source for the sensor.

BRIEF DESCRIPTION OF THE DRAWINGS It is drawing which showed typically the structure of the flexible organic thermoelectric conversion element for describing one Embodiment of this invention, (a) is a top view, (b) is AA in (a) figure. FIG. It is drawing which showed an example of the arrangement | sequence of a flexible organic thermoelectric conversion element, (a) is a top view, (b) is sectional drawing of an arrangement direction. It is the plane surface which showed typically the structure of the flexible organic thermoelectric conversion element for demonstrating another example of this invention. It is the cross-sectional view which showed typically the structure of the flexible organic thermoelectric conversion element for demonstrating another embodiment of this invention.

  The thermoelectric conversion element of the present invention includes one or a plurality of organic thermoelectric conversion layers provided in a pattern on the flexible base material on which one or a plurality of metal electrodes are installed, in accordance with the arrangement of the metal electrodes, and an organic thermoelectric conversion layer And one or a plurality of upper electrodes provided thereon.

  First, the organic thermoelectric conversion composition for forming the organic thermoelectric conversion layer of a flexible organic thermoelectric conversion element is demonstrated.

[Organic thermoelectric conversion composition]
The organic thermoelectric conversion composition used for this invention contains the component which forms a thermoelectric conversion layer. Examples of such components include (a) carbon nanotubes, (b) polymer compounds, (c) compounds represented by the above formula (A), formula (B) or formula (C) (referred to as compound (c)), etc. Is mentioned. In the present invention, the organic thermoelectric conversion composition containing the compound (c) is particularly referred to as an organic thermoelectric conversion adhesive composition.

<(A) Carbon nanotube>
The carbon nanotube (CNT) used in the present invention is a single-walled CNT in which a single carbon film (graphene sheet) is wound in a cylindrical shape, a double-walled CNT in which two graphene sheets are wound concentrically, and There is a multilayer CNT in which a plurality of graphene sheets are concentrically wound. In the present invention, single-walled CNTs, double-walled CNTs, and multilayered CNTs may be used alone, or two or more kinds may be used in combination. In particular, it is preferable to use single-walled CNT and double-walled CNT having excellent properties in terms of conductivity and semiconductor properties, and more preferably single-walled CNT.

In the case of single-walled CNT, the symmetry of the helical structure based on the hexagonal orientation of the graphene sheet graphene is called axial chiral, and the two-dimensional lattice vector from the reference point of the 6-membered ring on the graphene is chiral. It is called a vector. The (n, m) obtained by indexing this chiral vector is called a chiral index, and can be classified into metallic and semiconducting properties by this chiral index. Specifically, a material having nm that is a multiple of 3 indicates metallic properties, and a material that is not a multiple of 3 indicates semiconductor properties.
The single-walled CNT preferably used in the present invention may be semiconductive or metallic, and both may be used in combination. When both semiconducting CNT and metallic CNT are used, the content ratio of both in the composition is not particularly limited, and can be determined as appropriate according to the application. For example, when used as an electrode, it is preferable that the content ratio of metallic CNT is high from the viewpoint of conductivity. When used as a semiconductor application, it is preferable that the content ratio of semiconducting CNT is high from the viewpoint of semiconductor characteristics. The CNT may contain a metal or the like, or may contain a molecule such as fullerene. The organic thermoelectric conversion composition used in the present invention may contain nanocarbons such as carbon nanohorns, carbon nanocoils, and carbon nanobeads in addition to CNTs.

CNT can be produced by an arc discharge method, a chemical vapor deposition method (hereinafter referred to as a CVD method), a laser ablation method, or the like. The CNT used in the present invention may be obtained by any method, but is preferably obtained by an arc discharge method and a CVD method.
When producing CNTs, fullerene, graphite, and amorphous carbon are simultaneously generated as by-products, and catalyst metals such as nickel, iron, cobalt, and yttrium may remain. In order to remove these impurities, purification is preferred. The method for purifying CNTs is not particularly limited, but acid treatment with nitric acid, sulfuric acid, etc., and ultrasonic treatment are effective for removing impurities. In addition, it is more preferable to perform separation and removal using a filter from the viewpoint of improving purity.

After purification, the obtained CNT can be used as it is. In addition, since CNTs are generally obtained in a string shape, they may be cut into a desired length depending on the application. For example, when used for semiconductor applications, it is preferable to use CNT shorter than the distance between the electrodes in order to prevent a short circuit between the electrodes. CNTs can be cut into short fibers by acid treatment with nitric acid, sulfuric acid or the like, ultrasonic treatment, freeze pulverization method or the like. In addition, it is also preferable to perform separation using a filter from the viewpoint of improving purity.
In the present invention, not only cut CNTs but also CNTs produced in the form of short fibers in advance can be used in the same manner. Such short fibrous CNTs form, for example, a catalytic metal such as iron or cobalt on a substrate, and thermally decompose carbon compounds on the surface at 700 to 900 ° C. by CVD to cause vapor growth of the CNTs. Thus, a shape oriented in the direction perpendicular to the substrate surface is obtained. The short fiber CNTs thus produced can be taken out by a method such as peeling off from the substrate. In addition, the short fibrous CNTs can be obtained by supporting a catalytic metal on a porous support such as porous silicon or an anodic oxide film of alumina and growing the CNTs on the surface by the CVD method. Using oriented molecules such as iron phthalocyanine containing a catalytic metal in the molecule as a raw material and producing CNTs on a substrate by performing CVD in an argon / hydrogen gas flow, producing oriented short fiber CNTs You can also. Furthermore, short fiber CNTs oriented on the SiC single crystal surface can be obtained by an epitaxial growth method.

  The average length of the CNTs used in the present invention is not particularly limited and can be appropriately selected according to the use of the composition. For example, when the composition used in the present invention is used for semiconductor applications, the average length of CNTs is 0.01 μm or more and 1000 μm or less from the viewpoint of manufacturability, film formability, conductivity, etc., depending on the distance between electrodes. It is preferable that it is 0.1 micrometer or more and 100 micrometers or less.

  The diameter of the CNT used in the present invention is not particularly limited, but is preferably 0.4 nm or more and 100 nm or less, more preferably 50 nm or less, and still more preferably, from the viewpoint of durability, transparency, film formability, conductivity, and the like. Is 15 nm or less.

<(B) polymer compound>
The polymer compound (b) used in the present invention may be a conductive polymer or a non-conductive polymer.
Here, the conductive polymer is a conjugated polymer compound having a structure in which the main chain is conjugated with π electrons or electrons of a lone electron pair. Examples of the conjugated molecular structure include a structure in which single bonds and double bonds are alternately linked in a carbon-carbon bond on the main chain.
The non-conductive polymer is a non-conjugated polymer compound that does not exhibit conductivity due to the conjugated structure of the polymer main chain. Preferably, the polymer main chain is composed of a ring, group, or atom selected from an aromatic ring (carbocyclic aromatic ring, heteroaromatic ring), an ethynylene bond, an ethenylene bond, and a heteroatom having a lone pair. It is a polymer other than a polymer, or a polymer in which these groups are incorporated without bonding to each other even if these groups are included.

The organic thermoelectric conversion composition contains at least one of a conductive polymer and a non-conductive polymer. By using the polymer compound (b) together with the CNT (a), the CNT (a) is uniformly dispersed without being aggregated in the composition, and the coating property of the composition is improved.
The polymer compound (b) includes an oligomer (for example, a weight average molecular weight of about 1000 to 10,000) in addition to a normal polymer.

  By using a conductive polymer together with the CNT, a highly conductive organic thermoelectric conversion composition can be obtained. This is because the conductive polymer has a long conjugated structure, so that the charge transfer between the polymer and CNT is smooth, and as a result, the original high conductivity and semiconductor characteristics of CNT can be effectively used. This is probably because of this.

  Specific examples of such conductive polymers include thiophene compounds, pyrrole compounds, aniline compounds, acetylene compounds, p-phenylene compounds, p-phenylene vinylene compounds, p-phenylene ethynylene compounds. Compound, p-fluorenylene vinylene compound, fluorene compound, aromatic polyamine compound (also referred to as arylamine compound), polyacene compound, polyphenanthrene compound, metal phthalocyanine compound, p-xylylene compound, vinylene Selected from the group consisting of sulfide compounds, m-phenylene compounds, naphthalene vinylene compounds, p-phenylene oxide compounds, phenylene sulfide compounds, furan compounds, selenophene compounds, azo compounds, and metal complex compounds. Small Conjugated polymer including constituents as repeating structure and the like derived from Kutomo one compound.

Among these, from the viewpoint of thermoelectric conversion performance, thiophene compounds, pyrrole compounds, aniline compounds, acetylene compounds, p-phenylene compounds, p-phenylene vinylene compounds, p-phenylene ethynylene compounds, fluorene compounds, and Preferred is a conjugated polymer containing as a repeating structure a constituent derived from at least one compound selected from the group consisting of arylamine compounds, and more preferred is a conjugated polymer containing as a repeating structure a constituent derived from a thiophene compound. preferable.
The conductive polymer is preferably a linear conjugated polymer.

The conductive polymer used in the present invention may have the above-mentioned repeating unit alone or in combination of two or more. Moreover, in addition to this repeating unit, you may have the repeating unit which has another structure together. In the case of a polymer composed of a plurality of types of repeating units, it may be a block copolymer, a random copolymer, or a graft copolymer.
Other repeating units are not particularly limited as long as they do not impair the conjugated structure of the main chain. Thieno [2,3-c] thiophene group, benzo [1,2-b; 4,5-b ′] dithiophene group, cyclopenta [2,1-b; 3,4-b ′] dithiophene group, pyrrolo [3 , 4-c] pyrrole-1,4 (2H, 5H) -dione group, benzo [2,1,3] thiadiazole-4,8-diyl group, azo group, 1,4-phenylene group, 5H-dibenzo [ b, d] silole group, dithieno [3,2-b; 2 ', 3'-d] silole, thiazole group, imidazole group, pyrrolo [3,4-c] pyrrole-1,4 (2H, 5H)- Dione group, oxadiazole group, thiadiazo Each component derived from a compound having a ru group, a triazole group, or the like.

  The conductive polymer used in the present invention preferably has a total of 50% by mass or more of repeating units derived from at least one compound selected from the above group in the conductive polymer, and is 70% by mass. It is more preferable to have the above, and it is even more preferable to consist only of the above repeating unit.

The substituent introduced into the above repeating unit and the above other repeating unit is not particularly limited, but in consideration of compatibility with other components, the type of dispersion medium that can be used, and the like, a conjugated polymer to the dispersion medium. It is preferable to select and introduce those that can improve the dispersibility of the resin.
As an example of the substituent, when an organic solvent is used as a dispersion medium, a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group, alkoxy group, thioalkyl group, alkoxyalkyleneoxy group, alkoxyalkyleneoxyalkyl group , A crown ether group, an aryl group and the like can be preferably used. These groups may further have a substituent. The number of carbon atoms of the substituent is not particularly limited, but is preferably 1 to 12, more preferably 4 to 12, and particularly a long-chain alkyl group, alkoxy group, thioalkyl group, alkoxyalkylene having 6 to 12 carbon atoms. An oxy group and an alkoxyalkyleneoxyalkyl group are preferable.

  On the other hand, when an aqueous medium is used as the dispersion medium, it is preferable to introduce a hydrophilic group such as a carboxylic acid group, a sulfonic acid group, a hydroxyl group, or a phosphoric acid group at the terminal of each monomer or the above substituent. In addition, dialkylamino group, monoalkylamino group, amino group, carboxyl group, ester group, amide group, carbamate group, nitro group, cyano group, isocyanate group, isocyano group, halogen atom, perfluoroalkyl group, perfluoro An alkoxy group or the like can be introduced as a substituent, which is preferable.

  The number of substituents that can be introduced is not particularly limited, and one or more substituents can be appropriately introduced in consideration of dispersibility, compatibility, conductivity, and the like of the conjugated polymer.

  As the conductive polymer, the “conductive polymer” described in paragraphs [0021] to [0047] of JP2013-118166A can be preferably used, and the contents described in these paragraphs are described in this application. Incorporated in the description.

From the viewpoint of realizing high conductivity, the conductive polymer is preferably one that is not easily decomposed by acid, light, and heat. In order to obtain high conductivity, intramolecular carrier transmission and intermolecular carrier hopping through long conjugated chains of the conductive polymer are required. For this purpose, the molecular weight of the conductive polymer is preferably large to some extent. From this viewpoint, the weight average molecular weight of the conductive polymer used in the present invention is preferably 5000 or more, more preferably 7000 to 300,000, and more preferably 8000. More preferred is ~ 100,000.
The weight average molecular weight can be measured by gel permeation chromatography (GPC). For example, apparatus: “Alliance GPC2000 (manufactured by Waters)”, column: TSKgel GMH ₆ -HT × 2 + TSKgel GMH ₆ -HTL × 2 (both 7.5 mm ID × 30 cm, manufactured by Tosoh Corporation), column temperature: 140 The average molecular weight can be determined by using standard polystyrene, under the conditions and conditions of ° C., detector: differential refractometer, mobile phase: solvent (for example, o-dichlorobenzene).

The conductive polymer can be produced by polymerizing the above repeating unit, which is a structural unit, by an ordinary oxidative polymerization method.
Moreover, a commercial item can also be used, for example, the poly (3-hexyl thiophene-2,5-diyl) regioregular product made from an Aldrich company is mentioned.

  The non-conductive polymer is not particularly limited, and commonly known ones can be used. From the viewpoint of thermoelectric conversion performance, a structure derived from at least one compound selected from the group consisting of vinyl compounds, (meth) acrylate compounds, carbonate compounds, ester compounds, amide compounds, imide compounds, fluorine compounds and siloxane compounds Nonconjugated conjugates containing components as repeating structures are preferred. These compounds may have a substituent, and examples of the substituent include the same as the substituent of the conjugated polymer.

  In the present invention, “(meth) acrylate” represents either or both of acrylate and methacrylate, and includes a mixture thereof.

Specific examples of the vinyl compound include styrene, vinyl pyrrolidone, vinyl carbazole, vinyl pyridine, vinyl naphthalene, vinyl phenol, vinyl acetate, styrene sulfonic acid, vinyl arylamines such as vinyltriphenylamine, and vinyl tributylamine. And trialkylamines.
Specific examples of (meth) acrylate compounds include hydrophobic acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate, 2-hydroxyethyl acrylate, 1-hydroxyethyl acrylate, and 2-hydroxypropyl acrylate. Acrylate monomers such as 3-hydroxypropyl acrylate, 1-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, 2-hydroxybutyl acrylate, 1-hydroxybutyl acrylate, etc. And methacrylate monomers in which the acryloyl group of the monomer is replaced with a methacryloyl group.

Specific examples of polycarbonates containing repeating components derived from carbonate compounds include general-purpose polycarbonates composed of bisphenol A and phosgene, Iupizeta (trade name, manufactured by Mitsubishi Gas Chemical Co., Ltd.), Panlite (trade name, Teijin Chemicals Ltd.) Manufactured) and the like.
Examples of the compound that can constitute the polyester include polyalcohols, polycarboxylic acids, and hydroxy acids such as lactic acid. Specific examples of polyester include Byron (trade name, manufactured by Toyobo Co., Ltd.) and the like.
Specific examples of polyamides containing a structural component derived from an amide compound as a repeating structure include PA-100 (trade name, manufactured by T & K TOKA Corporation).
As a specific example of polyimide containing a constituent component corresponding to an imide compound as a repeating structure, Solpy 6,6-PI (trade name, manufactured by Solpy Kogyo Co., Ltd.) and the like can be given.
Specific examples of the fluorine compound include vinylidene fluoride and vinyl fluoride.
Specific examples of the polysiloxane containing a component derived from a siloxane compound as a repeating structure include polydiphenylsiloxane and polyphenylmethylsiloxane.

The non-conductive polymer may be a homopolymer or a copolymer.
In the present invention, it is more preferable to use a polymer compound obtained by polymerizing a vinyl compound as the non-conductive polymer.

  The nonconductive polymer is preferably hydrophobic, and more preferably has no hydrophilic group such as sulfonic acid or hydroxyl group in the molecule. A non-conductive polymer having a solubility parameter (SP value) of 11 or less is preferable.

  The thermoelectric conversion performance of the organic thermoelectric conversion composition can be improved by including a non-conjugated polymer together with the conjugated polymer in the thermoelectric conversion material.

  The weight average molecular weight of the nonconductive polymer is preferably 5000 to 300,000, and more preferably 10,000 to 150,000. The method for measuring the weight average molecular weight is the same as that for the conductive polymer.

<Compound (c)>
The compound (c) used in the present invention is a compound represented by the following formula (A), formula (B) or formula (C).
Compound (c) can improve the adhesion of the thermoelectric conversion layer to the substrate or the metal electrode. Moreover, it is hard to reduce the electroconductivity of an organic thermoelectric conversion composition and a thermoelectric conversion layer. In particular, the organic thermoelectric conversion adhesive composition and the organic thermoelectric conversion layer are preferably contained in the content described later, from the viewpoint of preventing a decrease in conductivity.

Formula ^(A) R 1 -Y
Formula ^{(B) R 1 -Z 1 -C} (= S) -Z 2 -R 2
Formula (C) R ¹ —Z ³ —Z ³ —R ³

In formula (A), formula (B) and formula (C),
R ¹ represents an alkyl group, an alkenyl group, an aralkyl group or an aryl group.
Y represents —SH, —SCN or SiR ⁴ R ⁵ H.
Z ¹ and Z ² each independently represents a single bond, an oxygen atom, a sulfur atom or —NR ⁶ —.
Z ³ represents a sulfur atom, — (C═S) —S— or —NR ⁷ — (C═S) —S—.
R ² and R ³ each independently represents an alkyl group, an alkenyl group, an aralkyl group or an aryl group. R ² may combine with R ¹ to form a ring.
R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group. R ⁷ may combine with R ¹ or R ³ to form a ring.

R ¹ is preferably an alkyl group, an aralkyl group or an aryl group, more preferably an alkyl group or an aryl group, and still more preferably an alkyl group.
The alkyl group for R ¹ may be linear, branched or cyclic, and is preferably linear.
The number of carbon atoms of the linear alkyl group and the branched alkyl group is not particularly limited, but in the case of the formula (A), 6 or more is preferable, 6 to 20 is more preferable, 1 or more is preferable, 2 or more is more preferable, and 2 to 20 is more preferable. Specific examples include methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, undecane, dodecyl and the like.
The cyclic alkyl group may be monocyclic or polycyclic. The monocyclic alkyl group preferably has 5 or more carbon atoms, more preferably 5 to 10 carbon atoms. Specific examples include cyclopentyl, cyclohexyl, cycloheptyl and the like. The polycyclic alkyl group preferably has 7 or more carbon atoms, more preferably 7 to 20 carbon atoms. Specifically, for example, norbornyl, adamantyl, isobornyl, camphanyl, dicyclopentyl, α-pinel, tricyclodecanyl and the like can be mentioned.

  The alkenyl group may be linear, branched or cyclic. The alkenyl group is preferably an alkenyl group obtained by removing one hydrogen atom from each adjacent carbon atom of the alkyl group.

The aralkyl group is an alkyl group having an aryl group, and the number of carbon atoms is not particularly limited, but is preferably 7 or more, and more preferably 7-17. The alkyl part of the aralkyl group has the same meaning as the above alkyl group, and the aryl group has the same meaning as the aryl group of R ¹ described later, and those satisfying the above carbon number of the aralkyl group are preferable. Specific examples include benzyl, phenethyl, naphthylmethyl, 9-fluorenyl, 9-fluorenylmethyl, 11-phenylundecane, and the like.

  The aryl group preferably has 6 or more carbon atoms, more preferably 6 to 15 carbon atoms. Specific examples include phenyl, naphthyl, anthryl and the like.

The alkyl group, aralkyl group and aryl group of R ⁴ and R ⁵ in SiR ⁴ R ⁵ H have the same meaning as the alkyl group, aralkyl group and aryl group of R ¹ . Preferred alkyl groups are the same as those preferred for R ¹ in formulas (B) and (C), and preferred aralkyl and aryl groups are the same as those for R ¹ . R ⁴ and R ⁵ may be the same or different. R ⁴ and R ⁵ are more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

  Y is preferably -SH or -SCN, more preferably -SH.

In the formula (B), Z ¹ and Z ² each independently represent a single bond, an oxygen atom, a sulfur atom or —NR ⁶ —, preferably a single bond, a sulfur atom or —NR ⁶ —, and Z ¹ and Z More preferably, at least one of ² is —NR ⁶ —. Z ¹ and Z ² may be the same or different from each other.

The alkyl group, aralkyl group and aryl group of R ^{6 have} the same meanings as the alkyl group, aralkyl group and aryl group of R ¹ . Preferred alkyl groups are the same as those preferred for R ¹ in formulas (B) and (C), and preferred aralkyl and aryl groups are the same as those for R ¹ . R ⁶ is more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
R ⁶ may be bonded to R ¹ or R ² to form a ring, and the ring formed by combining R ¹ and R ⁶ or R ² and R ⁶ is R ⁷ and R ¹ described later. Or it is synonymous with the ring formed by combining with R ³ , and the preferred range is also the same.

R ² represents an alkyl group, an alkenyl group, an aralkyl group or an aryl group, preferably an alkyl group, an aralkyl group or an aryl group, and more preferably an alkyl group or an aryl group.
The alkyl group, alkenyl group, aralkyl group and aryl group of R ^{2 have} the same meanings as the alkyl group, alkenyl group, aralkyl group and aryl group of R ¹ . Preferred alkyl groups are the same as those preferred for R ¹ in formulas (B) and (C), and preferred aralkyl, alkenyl and aryl groups are the same as those preferred for R ¹ .
R ² may form a ring with R ^1, as the ring formed by the bonding of R ¹ and R ^2, thioketone group, thioamide group, thiourethane group, such as thiourea group "- A monocyclic or polycyclic aliphatic heterocycle or aromatic ring containing a “Z ¹ —C (═S) —Z ² —” group. Although the number of atoms which comprise this ring is not specifically limited, 5-15 are preferable and 5-8 are more preferable.
R ² may form one aryl group together with R ¹ , for example, a phenylene group.

In the formula (C), Z ³ represents a sulfur atom, — (C═S) —S— or —NR ⁷ — (C═S) —S—, and represents a sulfur atom or —NR ⁷ — (C═S). -S- is preferable, and a sulfur atom is more preferable. Two Z ³ may be the same as or different from each other.
-Z ³ -Z ³ -preferably contains a disulfide (-SS-) bond.

The alkyl group, aralkyl group and aryl group of R ^{7 have} the same meaning as the alkyl group, aralkyl group and aryl group of R ¹ . Preferred alkyl groups are the same as those preferred for R ¹ in formulas (B) and (C), and preferred aralkyl and aryl groups are the same as those for R ¹ . R ⁷ is more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
R ⁷ may combine with R ¹ or R ³ to form a ring. The ring formed by combining R ⁷ and R ¹ or R ³ is an aliphatic or aromatic heterocycle containing a nitrogen atom as a ring constituent atom, and has a heteroatom other than the nitrogen atom. Also good. The number of atoms constituting this ring is not particularly limited, but is preferably 5 to 8, and more preferably 5 to 6.

R ³ represents an alkyl group, an alkenyl group, an aralkyl group or an aryl group, preferably an alkyl group, an aralkyl group or an aryl group, more preferably an alkyl group or an aryl group, and even more preferably an alkyl group.
The alkyl group, alkenyl group, aralkyl group and aryl group of R ^{3 have} the same meanings as the alkyl group, alkenyl group, aralkyl group and aryl group of R ¹ . Preferred alkyl groups are the same as those preferred for R ¹ in formulas (B) and (C), and preferred aralkyl, alkenyl and aryl groups are the same as those preferred for R ¹ . R ³ may be a group different from R ¹ , but is preferably the same group.

R ^{1 to} R ⁷ may have a substituent. It does not specifically limit as a substituent, The following substituent T is mentioned. When it has a substituent, it is sufficient to have at least one.
Examples of the substituent T include the following.
An alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, pentyl, heptyl, 1-ethyl; Pentyl, cyclohexyl), an alkenyl group (preferably a linear, branched or cyclic alkenyl group having 1 to 20 carbon atoms, such as vinyl, allyl, butenyl, cyclohexenyl), an alkynyl group (preferably carbon number) 2-20, for example, ethynyl, butadiynyl, phenylethynyl), an alkoxy group (preferably a linear, branched or cyclic alkoxy group having 1-20 carbon atoms, such as methoxy, ethoxy, propoxy, Butoxy, hydroxyethoxy, hexyloxy), aryl groups (preferably having 6 to 26 carbon atoms, Enyl, 1-naphthyl, 4-methoxyphenyl, 2-chlorophenyl, 3-methylphenyl), halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), hydroxy group, carboxy group, carbamoyl group (preferably carbon A carbamoyl group of 1 to 20 and alkyl, cycloalkyl or aryl is preferable, for example, N, N-dimethylcarbamoyl, N-cyclohexylcarbamoyl, N-phenylcarbamoyl), sulfo group or a salt thereof, sulfamoyl group (preferably carbon A sulfamoyl group of 0 to 20 and alkyl, cycloalkyl or aryl is preferable, for example, N, N-dimethylsulfamoyl, N-cyclohexylsulfamoyl, N-phenylsulfamoyl),

Cyano group, acyl group (preferably having 1 to 20 carbon atoms, for example, acetyl, propanoyl, cyclohexylcarbonyl, benzoyl), acyloxy group (preferably having 1 to 20 carbon atoms, for example, acetyloxy, propanoyloxy, cyclohexylcarbonyl) Oxy, benzoyloxy), alkoxycarbonyl groups (preferably having 2 to 20 carbon atoms, for example, ethoxycarbonyl, ethoxycarbonyl, propoxycarbonyl), cycloalkoxycarbonyl groups (preferably having 4 to 20 carbon atoms, for example, cyclopropyloxy Carbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl), an aryloxycarbonyl group (preferably having 6 to 20 carbon atoms, for example, phenyloxycarbonyl, naphthyloxycarbonyl), Mino group or a salt thereof (preferably having 0 to 20 carbon atoms, including alkylamino group, alkenylamino group, alkynylamino group, cycloalkylamino group, cycloalkenylamino group, arylamino group, heterocyclic amino group, Amino, N, N-dimethylamino, N, N-diethylamino, N-ethylamino, N-allylamino, N- (2-propynyl) amino, N-cyclohexylamino, N-cyclohexenylamino, anilino, pyridylamino, imidazolylamino , Benzimidazolylamino, thiazolylamino, benzothiazolylamino, triazinylamino, 5-indazoleamino), heterocyclic groups (including aliphatic heterocyclic groups and aromatic heterocyclic groups, preferably having 1 to 20 carbon atoms) , At least one oxygen atom, sulfur atom, nitrogen A 5- or 6-membered heterocyclic group having a child is more preferable, for example, 1-morpholine ring group, pyrrole ring group, pyridine ring group, imidazole ring group, benzopyrrole ring group, benzimidazole ring group, thiazole ring group Oxazole ring group), nitro group,

Linear and branched alkylthio groups (preferably having 1 to 20 carbon atoms, such as methylthio, ethylthio, isopropylthio, benzylthio), cyclic alkylthio groups (preferably having 3 to 20 carbon atoms, such as cyclopropylthio, for example) , Cyclopentylthio, cyclohexylthio, 4-methylcyclohexylthio), an arylthio group (preferably having 6 to 26 carbon atoms, such as phenylthio, 1-naphthylthio, 3-methylphenylthio, 4-methoxyphenylthio), an amide group, Phosphate group, oxo group (═O), formyl group, polyalkylene oxide group (for example, polyethylene glycol group),

Alkenyloxy group (preferably having 2 to 20 carbon atoms, for example, vinyloxy, allyloxy), alkynyloxy group (preferably having 2 to 20 carbon atoms, for example, 2-propynyloxy, 4-butynyloxy), cycloalkyloxy group ( Preferably having 3 to 20 carbon atoms, for example, cyclopropyloxy, cyclopentyloxy, cyclohexyloxy, 4-methylcyclohexyloxy), aryloxy groups (preferably having 6 to 26 carbon atoms, such as phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy), a heterocyclic oxy group (for example, imidazolyloxy, benzoimidazolyloxy, thiazolyloxy, benzothiazolyloxy, triazinyloxy, purinyloxy),

An acylamino group (preferably an acylamino group having 1 to 20 carbon atoms such as acetylamino, cyclohexylcarbonylamino, benzoylamino), a sulfonamide group (preferably an alkyl, cycloalkyl or aryl sulfonamide group having 0 to 20 carbon atoms) For example, methanesulfonamide, benzenesulfonamide, N-methylmethanesulfonamide, N-cyclohexylsulfonamide, N-ethylbenzenesulfonamide), alkyl, cycloalkyl or arylsulfonyl groups (preferably having 1 to 20 carbon atoms) , For example, methylsulfonyl, ethylsulfonyl, cyclohexylsulfonyl, benzenesulfonyl), silyl group (preferably having 1 to 20 carbon atoms, alkyl, aryl, alkoxy and aryloxy Substituted silyl groups are preferable, for example, triethylsilyl, triphenylsilyl, diethylbenzylsilyl, dimethylphenylsilyl), silyloxy groups (preferably having 1 to 20 carbon atoms, substituted with alkyl, aryl, alkoxy and aryloxy) For example, triethylsilyloxy, triphenylsilyloxy, diethylbenzylsilyloxy, dimethylphenylsilyloxy), phosphonyl group, phosphoryl group, boric acid group and the like.

  Of these, a carboxy group, a hydroxy group, an amide group or a heterocyclic group is preferable.

  Each of these groups may further have a substituent, and examples of the substituent include the substituent T. For example, the hydroxyalkyl group etc. which the hydroxy group substituted by the alkyl group are mentioned.

  When a compound or a substituent includes an alkyl group, an alkenyl group, etc., these may be linear or branched, and may be substituted or unsubstituted. In addition, when an aryl group, a heterocyclic group and the like are included, they may be monocyclic or condensed, and may be substituted or unsubstituted.

  Although the specific example of a compound (c) is shown below, this invention is not limited to these by this.

  The compound (c) is preferably a low molecular compound in terms of conductivity, and the molecular weight thereof is not particularly limited, but is preferably 1000 or less, and preferably 150 to 700.

  Compound (c) may be a commercially available product or may be synthesized as appropriate. For example, it can synthesize | combine by the method according to the method described in well-known organic synthesis academic books, such as Organic Syntheses.

  Compound (c) can be used alone or in combination of two or more.

<(D) Onium salt compound>
The onium salt (d) used in the present invention is a compound represented by any one of the following general formulas (I) to (V).

With such an onium salt compound, the conductivity can be dramatically improved. The details of the mechanism by which the conductivity is improved are not yet clear, but the onium compound is activated by applying energy such as light and heat from the outside to the CNT and / or conductive polymer as it is. Oxidizing ability is expressed in the state of oxidization. It is considered that an acid is generated during the oxidation process, and the generated acid acts as a dopant. The dopant improves the conductivity because the conductive polymer and the charge transfer between the conductive polymer and the CNT become smoother.
In the conventional doping technique, since an acid such as a protonic acid or a Lewis acid is used as a dopant, the CNT and the conductive polymer are aggregated, precipitated, and precipitated when the acid is added to the composition. Such a composition is inferior in coating property and film forming property, and as a result, conductivity is also lowered.

  However, the onium salt compound (d) is neutral and does not aggregate, precipitate, or precipitate CNTs or conductive polymers. Further, it is a compound that generates an acid when energy such as light or heat is applied, and the start timing of acid generation can be controlled. The composition can be prepared under conditions that do not generate acid to prevent aggregation, and the composition can be molded while maintaining good dispersibility and coating properties. Therefore, high conductivity can be imparted by appropriately applying energy after molding and film formation.

  The organic thermoelectric conversion composition used in the present invention realizes improvement in dispersibility of CNT (a) by the polymer compound (b), but the onium salt compound (d) is good even when used together with these. Dispersibility and applicability can be maintained. The film quality after coating is also good, and the CNT (a), polymer compound (b), and onium salt compound (d) are uniformly dispersed, so that external energy such as heat and light is applied after coating as necessary. Thus, high conductivity is exhibited.

  For the above reasons, the onium salt compound (d) used in the present invention is preferably a compound having an oxidizing ability with respect to the CNT (a) and / or the polymer compound (b). Furthermore, the onium salt compound (d) used in the present invention is preferably a compound (acid generator) that generates an acid upon application of energy such as light or heat. Examples of the energy application method include irradiation with active energy rays and heating.

  Examples of such onium salt compounds (d) include sulfonium salts, iodonium salts, ammonium salts, carbonium salts, phosphonium salts, and the like. Of these, sulfonium salts, iodonium salts, ammonium salts and carbonium salts are preferable, sulfonium salts, iodonium salts and carbonium salts are more preferable, and sulfonium salts and iodonium salts are particularly preferable. Examples of the anion moiety constituting the salt include a strong acid counter anion.

  Specifically, compounds represented by the following general formulas (I) and (II) are used as sulfonium salts, compounds represented by the following general formula (III) are used as iodonium salts, and the following general formulas are used as ammonium salts. Examples of the compound represented by (IV) and the carbonium salt include compounds represented by the following general formula (V), which are preferably used in the present invention.

(In the general formulas (I) to (V), R ^{21 to} R ²³ , R ^{25 to} R ²⁶ and R ^{31 to} R ³³ are each independently an alkyl group, an aralkyl group, an aryl group, or an aromatic heterocyclic group. R ^{27 to} R ³⁰ each independently represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an aromatic heterocyclic group, an alkoxy group, or an aryloxy group, and R ²⁴ represents an alkylene group or an arylene group. R ^{21 to} R ³³ may have a substituent, and X ⁻ represents a strong acid anion.
Any two groups of R ^{21 to} R ²³ in the general formula (I), R ²¹ and R ^{23 in} the general formula (II), R ²⁵ and R ^{26 in} the general formula (III), R ²⁷ in the general formula (IV) Any two groups of -R ³⁰ and any two groups of R ³¹ -R ³³ in the general formula (V) are bonded to each other in the general formula to form an aliphatic ring, an aromatic ring, or a heterocyclic ring May be formed.

In R ^{21 to} R ²³ and R ^{25 to} R ³³ , the alkyl group may be linear, branched or cyclic. As the linear or branched alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable, and specific examples include those represented by R ¹ above. As the cyclic alkyl group, an alkyl group having 3 to 20 carbon atoms is preferable, and specific examples include a cyclopropyl group, a bicyclooctyl group, and the like in addition to those represented by R ¹ above.
As the aralkyl group, an aralkyl group having 7 to 15 carbon atoms is preferable, and specific examples include those represented by R ¹ above.
As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, and specific examples include phenacyl, pyrenyl and the like in addition to those represented by R ¹ above.
The aromatic heterocyclic group is not particularly limited. For example, in addition to those exemplified for the substituent T, a pyrazole ring group, an indole ring group, a quinoline ring group, an isoquinoline ring group, a purine ring group, and a pyrimidine ring group. And thiazine ring group.

In R ^{27 to} R ³⁰ , the alkoxy group is preferably a linear or branched alkoxy group having 1 to 20 carbon atoms, and specific examples include those exemplified for the substituent T above.
As the aryloxy group, an aryloxy group having 6 to 20 carbon atoms is preferable, and specific examples include those exemplified for the substituent T above.

In R ²⁴ , the alkylene group may be linear, branched or cyclic. The linear or branched alkylene group is preferably an alkylene group having 2 to 20 carbon atoms, and specific examples include an ethylene group, a propylene group, a butylene group, and a hexylene group. The cyclic alkylene group is preferably a cyclic alkylene group having 3 to 20 carbon atoms, and specific examples include a cyclopentylene group, cyclohexylene, bicyclooctylene group, norbornylene group, adamantylene group and the like.
As the arylene group, an arylene group having 6 to 20 carbon atoms is preferable, and specific examples include a phenylene group, a naphthylene group, and an anthranylene group.

When R ^{21 to} R ³³ further have a substituent, the substituent is preferably an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom (a fluorine atom, a chlorine atom, an iodine atom), Aryl group having 6 to 10 carbon atoms, aryloxy group having 6 to 10 carbon atoms, alkenyl group having 2 to 6 carbon atoms, cyano group, hydroxyl group, carboxy group, acyl group, alkoxycarbonyl group, alkylcarbonylalkyl group, aryl Examples thereof include a carbonylalkyl group, a nitro group, an alkylsulfonyl group, a trifluoromethyl group, -S- ^{R41, and the} like. R ⁴¹ has the same meaning as R ²¹ described above.

X ⁻ is preferably an anion of an aryl sulfonic acid, an anion of a perfluoroalkyl sulfonic acid, an anion of a perhalogenated Lewis acid, an anion of a perfluoroalkylsulfonimide, a perhalogenate anion, or an alkyl or aryl borate anion. These may further have a substituent, and examples of the substituent include a fluoro group.
Specific examples of anions of aryl sulfonic acids include p-CH ₃ C ₆ H ₄ SO ₃ ⁻ , PhSO ₃ ⁻ , naphthalene sulfonic acid anions, naphthoquinone sulfonic acid anions, naphthalenedisulfonic acid anions, anthraquinone sulfonic acid anions Is mentioned.
Specific examples of the anion of perfluoroalkylsulfonic acid include CF ₃ SO ₃ ⁻ , C ₄ F ₉ SO ₃ ⁻ , and C ₈ F ₁₇ SO ₃ ^— .
Specific examples of the anion of the perhalogenated Lewis acid include PF ₆ ⁻ , SbF ₆ ⁻ , BF ₄ ⁻ , AsF ₆ ⁻ , and FeCl ₄ ⁻ .
Specific examples of the anion of perfluoroalkylsulfonimide include CF ₃ SO ₂ —N ^— SO ₂ CF ₃ and C ₄ F ₉ SO ₂ —N ^— SO ₂ C ₄ F ₉ .
Specific examples of the perhalogenate anion include ClO ₄ ⁻ , BrO ₄ ⁻ and IO ₄ ⁻ .
Specific examples of the alkyl or aryl borate anion include (C ₆ H ₅ ) ₄ B ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , (p-CH ₃ C ₆ H ₄ ) ₄ B ⁻ , (C ₆ H _{4 F)} 4 B ^-, and the like.
X ^- is more preferably an anion of perhalogenated Lewis acid, a fluoro group is an alkyl or aryl borate anions were replaced, more preferably fluoro substituted aryl borate anions, particularly preferably a pentafluorophenyl borate anion.

  Specifically, as the onium salt compound, the onium salt compounds described in paragraphs [0048] to [0079] of JP2013-118166A can be preferably used, and the contents described in these paragraphs are described in this application. Incorporated in the description.

  An onium salt compound can be used alone or in combination of two or more.

<(E) Solvent>
The organic thermoelectric conversion composition used in the present invention preferably contains a solvent. As the solvent, any conventionally known solvent can be appropriately used as long as it dissolves or is compatible with organic substances such as the polymer compound (b) and the compound (c) and disperses the CNT (a).

  Examples of the solvent include known organic solvents such as aromatic hydrocarbon solvents, alcohol solvents, ketone solvents, aliphatic hydrocarbon solvents, amide solvents, and halogen solvents.

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene, trimethylbenzene, tetramethylbenzene, cumene, ethylbenzene, methylpropylbenzene, methylisopropylbenzene, tetrahydronaphthalene, xylene, cumene, trimethylbenzene, Tetramethylbenzene and tetrahydronaphthalene are preferred.
Examples of the alcohol solvent include methanol, ethanol, butanol, benzyl alcohol, and cyclohexanol, and benzyl alcohol and cyclohexanol are preferable.
Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, 2-butanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, and phenyl. Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetyl acetone, acetonyl acetone, ionone, diacetonyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, isophorone, and propylene carbonate are preferable, and methyl isobutyl ketone and propylene carbonate are preferable.

Examples of the aliphatic hydrocarbon solvent include pentane, hexane, octane, decane, and tetralin, and octane and decane are preferable.
Examples of the amide solvent include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, and 1,3-dimethyl-2-imidazolidinone. N-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone are preferred.
Examples of the halogen solvent include chloroform, chlorobenzene, and dichlorobenzene, and chlorobenzene and dichlorobenzene are preferable.
The said solvent may be used independently and may use 2 or more types together.

<(F) Other ingredients>
The organic thermoelectric conversion composition used in the present invention may contain other components in addition to the above components.
For example, in order to improve the dispersion stability, lithium hydroxide, ammonium persulfate, an ultraviolet absorber and the like can be contained. From the viewpoint of increasing the film strength, inorganic fine particles, polymer fine particles, silane coupling agents, etc., from the viewpoint of increasing the transparency by lowering the refractive index, from the viewpoint of preventing unevenness at the time of coating with a fluorine-based compound, etc. Can contain a fluorine-based surfactant or the like according to the intended use.
The content of these components is preferably about 0.1 to 5% by mass relative to the total mass of the composition.

  The organic thermoelectric conversion composition used in the present invention is preferably a CNT dispersion or CNT dispersion paste in which CNT (a) is dispersed in a solvent (e).

  The organic thermoelectric conversion composition can control the electrical conductivity and semiconductor characteristics of the composition by changing the content of CNT (a). The content of CNT (a), polymer compound (b), compound (c) and onium salt compound (d) in the composition depends on the use of the composition, properties such as conductivity and transparency required for the use. Depending on the situation, it can be appropriately selected and determined.

5-60 mass% is preferable, as for content of CNT in a composition, 5-40 mass% is more preferable, and 10-30 mass% is further more preferable.
30-80 mass% is preferable, as for content of the high molecular compound in a composition, 35-75 mass% is more preferable, and 40-70 mass% is further more preferable. When a conductive polymer and a non-conductive polymer are used in combination as the polymer compound, the non-conductive polymer is preferably 10 to 1500 parts by mass, and 30 to 1200, with respect to 100 parts by mass of the conductive polymer. A mass part is more preferable and 80-1000 mass parts is especially preferable.
When the compound (c) is contained, the content of the compound (c) in the composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 7% by mass, and further preferably 1 to 5% by mass. preferable.
When the onium salt compound (d) is contained, the content of the onium salt compound (d) in the composition is preferably 1 to 30% by mass, more preferably 3 to 20% by mass. More preferably, it is -15 mass%.
When the solvent (e) is contained, the content of the solvent is preferably 60 to 99.9% by mass with respect to the total solid content of the organic thermoelectric conversion composition and the total mass of the solvent (e), and is preferably 70 to 99. 5 mass% is more preferable, and 80-99 mass% is further more preferable.

The organic thermoelectric conversion composition used in the present invention can be prepared by mixing the above components. Preferably, each component is added to the solvent (e), and these are dispersed and dissolved by a usual method. The order of addition and mixing of each component is not particularly limited. Moreover, there is no restriction | limiting in particular in a preparation method, A normal method can be applied. For example, a dispersion method such as a mechanical homogenizer method, a jaw crusher method, an ultracentrifugation method, a cutting mill method, an automatic mortar method, a disk mill method, a ball mill method, or an ultrasonic dispersion method can be used. If necessary, two or more of these methods may be used in combination.
Moreover, when using onium salt compound (d), it is preferable to prepare an organic thermoelectric conversion composition in the state which shielded the radiation, electromagnetic waves, etc. under the temperature which does not produce | generate an acid. Aggregation by an acid or the like can be prevented, and uniform dispersibility or solubility of each component in the organic thermoelectric conversion composition can be maintained during the preparation and storage of the organic thermoelectric conversion composition.

[Thermoelectric conversion element]
The thermoelectric conversion element of the present invention is a flexible element having the above structure.
In the thermoelectric conversion element of the present invention, “flexible” means the flexibility of the thermoelectric conversion element. The flexible organic thermoelectric conversion element is a polymer film substrate such as PET or PEN, or a metal such as aluminum having a thickness of 1 mm or less. An element in which a thermoelectric conversion layer or the like is formed on a substrate or paper.

A preferred embodiment of the thermoelectric conversion element of the present invention will be described in detail with reference to FIGS.
Note that this description is not construed as being limited by the description of the following embodiments.

As shown in FIG. 1, the flexible organic thermoelectric conversion element 10 of the present embodiment includes a portion 2 a in which a plurality of metal electrodes 2 are arranged on the main surface of a resin base material 1 and wiring of the metal electrodes 2 is connected. A plurality of organic thermoelectric conversion layers 3 that individually cover the metal electrodes 2 are provided. The organic thermoelectric conversion layer 3 may be provided on the surface of the metal electrode 2 in the same number as the metal electrode 2 so as to overlap the metal electrode 2 in accordance with the arrangement of the metal electrode 2. Is preferably provided also on the base material 1 around the metal electrode 2 excluding the portion 2a to which the is connected.
Moreover, the upper part which electrically connects the organic thermoelectric conversion layer 3 and the part (not shown) to which the wiring of another electrode adjacent to the metal electrode 2 (21) coat | covered with this organic thermoelectric conversion layer 3 is connected. An electrode 4 is provided. The upper electrode 4 is provided so as not to be connected to the metal electrode 2 (21). The illustrated upper electrode 4 is narrower than the metal electrode 2 or the organic thermoelectric conversion layer 3, but may be equal to or wider than the metal electrode 2 or the organic thermoelectric conversion layer 3. Thus, the flexible organic thermoelectric conversion element 10 is provided on the base material 1 on which the metal electrode 2 is installed in accordance with the arrangement of the metal electrode 2, that is, in the same pattern as the arrangement of the metal electrode 3. 3 and an upper electrode 4 provided on the organic thermoelectric conversion layer 3.

The flexible organic thermoelectric conversion element 10 is used with the upper electrode 4 side on the organic thermoelectric conversion layer 3 as a high temperature side and the metal electrode 2 side as a low temperature side, and between the upper electrode 4 and the metal electrode 2 Electric energy is generated according to the temperature difference.
That is, in the organic thermoelectric conversion layer 3, a positive charge (hole) moves from the high temperature upper electrode 4 side to the low temperature metal electrode 2 side, thereby generating a potential difference and generating a thermoelectromotive force. The electromotive phenomenon is called the Seebeck effect.

The surface on the base material 1 on which the organic thermoelectric conversion layer 3 is preferably provided is not particularly limited in shape and area as long as it is a place other than the portion 2a to which the wiring of the metal electrode 2 is connected. For example, in the rectangular (quadrangle) metal electrode 2 illustrated in FIG. 1, any one of three surrounding sides excluding the portion 2 a to which the wiring of the metal electrode 2 is connected, any two sides, or The region of the substrate 1 in contact with the three sides may be used as the region 3a where the organic thermoelectric conversion layer 3 is provided. From the viewpoint of improving adhesion, the region of the substrate 1 in contact with any two sides or the three sides is described above. It is preferable to use as the region 3a, and it is more preferable to use all of the region of the base material 1 in contact with the three sides. The organic thermoelectric conversion layer 3 is preferably in close contact with the base material 1 around the metal electrode 2 at least below the upper electrode 4 connected to the organic thermoelectric conversion layer 3. By providing the close contact portion in this manner, the close contact between the organic thermoelectric conversion layer 3 and the substrate 1 becomes stronger.
Further, if the organic thermoelectric conversion layer 3 is not short-circuited to the upper electrode 4 connected to the metal electrode 2, the region of the base material 1 that is in contact with the side of the metal electrode 2 on the side to which the upper electrode 4 is connected is also an adhesion portion. It is good. By providing the close contact portion in this manner, the close contact between the organic thermoelectric conversion layer 3 and the substrate 1 is further strengthened.
The width w of the region 3a is not particularly limited as long as there is no short circuit with the adjacent thermoelectric conversion layer, electrode, or wiring.
In addition, even if the shape of the metal electrode 2 is a triangle, a polygon, a circle, or a rounded quadrangle (having corners having a curvature), the portion other than the portion excluding the portion 2a to which the wiring of the metal electrode 2 is connected. It can be used as the region 3 a of the organic thermoelectric conversion layer 3 in the region of the base material 1 in contact with the side or a part of the side.

Moreover, by providing the area | region 3a in which the organic thermoelectric conversion layer 3 is provided in the base material 1 under the upper electrode 4 connected to the organic thermoelectric conversion layer 3, the upper electrode 4 and the metal electrode 2 on the base material 1 are short-circuited. Can be prevented, and recombination of electrons generated by the Seebeck effect inside the upper electrode 4 and holes generated by the Seebeck effect inside the organic thermoelectric conversion layer 3 can be suppressed, and an effect of increasing output power is expected. it can.
At this time, it is preferable that the organic thermoelectric conversion layer 3 is in close contact with the base material 1 around the metal electrode 2 at least below the upper electrode 4 connected to the organic thermoelectric conversion layer 3, and the width w of the region 3a is In addition, the thickness is preferably equal to or larger than the thickness t of the organic thermoelectric conversion layer 3, and more preferably twice or more than the thickness t from the viewpoint of achieving both increase in output voltage and adhesion.

Also, in FIG. 2, a plurality of organic thermoelectric conversion units 5 including a metal electrode 2, an organic thermoelectric conversion layer 3, and an upper electrode 4 are electrically arranged in series in a single row on the substrate 1. The thermoelectric power generation article 20 using the flexible organic thermoelectric conversion elements 10 connected by the above is shown.
FIG. 3 shows a flexible organic thermoelectric conversion element according to another example of the present invention. FIG. 3 shows a thermoelectric power generation article 20 using a flexible organic thermoelectric conversion element 10 in which organic thermoelectric conversion units 5 are arranged vertically and horizontally on a substrate 1 and electrically connected in series with an upper electrode 4 in order. Has been. In other words, each organic thermoelectric conversion unit 5 is electrically connected in series in the form of a polygonal line pattern. The number of arrangements of the organic thermoelectric conversion units 5 shown in FIG. 3 is an example, and the organic thermoelectric conversion unit 5 is determined by the electromotive force per one of the organic thermoelectric conversion units 5 and the electromotive force as the thermoelectric power generation article 20. The number of sequences is appropriately determined.
2 and 3, both ends of the organic thermoelectric conversion units 5 connected in series become output terminals 51 and 52, and output wirings 53 and 54 are connected thereto. As the output terminals 51 and 52, the metal electrode 2, the upper electrode 4, or the metal electrode 23 connected to the upper electrode 4 of the organic thermoelectric conversion unit 5 can be used.

Since the organic thermoelectric conversion units 5 are connected in series in this way, a current flows in one direction, the thermoelectromotive force generated in each organic thermoelectric conversion unit 5 is added, and the desired value is obtained by taking this out to the outside. Electricity can be generated.
Here, the number, size, installation position, arrangement, etc. of the pattern in which the metal electrodes 2 and the like are arranged are not particularly limited as long as the current flows in one direction. For example, as shown in FIGS. Although a pattern can be illustrated, it is not limited to this.

Examples of the substrate 1 include a substrate such as a plastic film having flexibility. A plastic film is preferable because it is inexpensive and flexible.
In the present invention, the “flexible substrate” means a substrate having flexibility.
From such a viewpoint, the base material 1 includes polyethylene terephthalate, polyethylene isophthalate, polyethylene naphthalate, polybutylene terephthalate, poly (1,4-cyclohexylenedimethylene terephthalate), polyethylene-2,6-phthalenedicarboxylate. Polyester resin such as polyimide, polycarbonate, polypropylene, polyether sulfone, cycloolefin polymer, polyether ether ketone (PEEK), plastic film (resin film) such as triacetyl cellulose (TAC), glass epoxy, liquid crystalline polyester, etc. preferable.

  Of these, easy availability, economical viewpoint and no solvent dissolution, as a substrate capable of printing, polyether ether ketone, polyethylene terephthalate, polyethylene naphthalate, polyimide, glass epoxy, liquid crystalline polyester is preferable, In particular, polyethylene terephthalate, polyethylene naphthalate, polyimide, glass epoxy, and liquid crystalline polyester are preferable.

  Moreover, as long as the effect as a base material is not impaired, the copolymer of the said resin, the blended material of these resins, and another kind of resin, etc. can be used.

  Furthermore, in the resin film, a small amount of inorganic or organic fine particles, for example, inorganic fillers such as titanium oxide, calcium carbonate, silica, barium sulfate, silicone, acrylic, benzoguanamine, Teflon ( (Registered trademark), an organic filler such as epoxy, polyethylene glycol (PEG), and an adhesion improver such as sodium dodecylbenzenesulfonate and an antistatic agent can be contained.

  As a method for producing each resin film, known methods and conditions can be appropriately selected and used. For example, the polyester film can be formed by melt-extrusion of the above-described polyester resin into a film shape, orientation crystallization by longitudinal and transverse biaxial stretching, and crystallization by heat treatment.

  There is no restriction | limiting in particular in the thickness of the base material 1 used here, Usually, the thing of the thickness of 5 micrometers-1000 micrometers is used for the resin film used as a base material, and the thing of 10 micrometers-500 micrometers is used from a flexible viewpoint. It is preferable to use those of 10 μm or more and 250 μm or less.

  It is preferable that the base material 1 contains additives, such as a ultraviolet absorber, from a viewpoint of preventing further deterioration of the base material. As the ultraviolet absorber, an oxazole, triazine, stilbene, or coumarin absorber can be suitably used.

  As the metal electrode 2, any one of known metals such as a metal electrode such as copper, silver, gold, platinum, nickel, chromium, and a copper alloy, a transparent electrode such as indium tin oxide (ITO), and zinc oxide (ZnO) is used. Use. Preferably, any of copper, gold, platinum, nickel, copper alloy, etc. is used, and more preferably, any of gold, platinum, nickel is used. Or you may use what solidified the metal paste which atomized the said metal and added the binder and the solvent.

The organic thermoelectric conversion layer 3 is formed of the organic thermoelectric conversion composition, and has the same composition as the solid content composition of the organic thermoelectric conversion composition.
The layer thickness of the organic thermoelectric conversion layer 3 is preferably 0.1 to 1000 μm, and more preferably 1 to 100 μm. By setting the film thickness within this range, it is easy to impart a temperature difference and increase in resistance within the film can be prevented.

The upper electrode 4 is formed using either a conductive paste in which conductive fine particles such as silver and carbon are dispersed or a conductive paste containing metal nanowires such as silver, copper and aluminum. Can do.
By using conductive paste, it is possible to follow the step between the upper surface of the thermoelectric conversion layer and the electrode on the substrate, connect without disconnection or contact failure, high output power, and reliability A highly functional module can be formed.
In addition, by combining sputtering, vacuum deposition and metal mask methods, known conductive materials such as metals such as gold, silver, copper and nickel, alloy materials thereof, and oxide semiconductor materials such as indium tin oxide (ITO) Therefore, wiring may be performed.

The organic thermoelectric conversion layer 3 is formed as a single layer. However, in the present invention, the organic thermoelectric conversion layer is not limited to a single layer, but includes a multilayer.
As a flexible organic thermoelectric conversion element or an organic thermoelectric conversion unit provided with the organic thermoelectric conversion layer which consists of a multilayer, what is shown by FIG. 4 is mentioned, for example. This flexible organic thermoelectric conversion element 10A is the same as the flexible organic thermoelectric conversion element 10 shown in FIG. 1 except that the organic thermoelectric conversion layer 3A is composed of multiple layers. Therefore, the thermoelectric power generation article 20 shown in FIG. 2 or FIG. 3 can be formed using the flexible organic thermoelectric conversion element 10A.
The organic thermoelectric conversion layer 3A is made of an organic thermoelectric conversion composition containing a carbon nanotube (a) and a polymer compound (b) on a film 6A made of the compound (c), for example, a monomolecular film (SAM film). The structure is provided with a film 6B. In FIG. 4, the film 6A is shown with an emphasis on thickness.

In the flexible organic thermoelectric conversion element of the present invention, the organic thermoelectric conversion layer contains the compound (c), or the organic thermoelectric conversion layer includes a film made of the compound (c). Or the adhesiveness with an electrode is improving. This is considered to be due to the interaction between the compound (c) contained in the organic thermoelectric conversion layer or the compound (c) forming a film and the base material or the metal electrode.
The flexible organic thermoelectric conversion element 10 and the article 20 for thermoelectric power generation shown in FIGS. 1 to 3 are preferably formed by an organic thermoelectric conversion adhesive composition in which the organic thermoelectric conversion layer 3 contains a compound (c), and organic thermoelectric conversion. The adhesion between the layer 3 and the substrate 1 and the metal electrode 2 is high.
Moreover, the flexible organic thermoelectric conversion element 10A shown in FIG. 4 includes a film 6A in which the organic thermoelectric conversion layer 3A is made of the compound (c), and the adhesion between the organic thermoelectric conversion layer 3A, the substrate 1, and the metal electrode 2 Is high.

  In these flexible organic thermoelectric conversion elements 10, 10 </ b> A and thermoelectric power generation article 20, the organic thermoelectric conversion layers 3, 3 </ b> A are provided not only on the metal electrode 2 but also on the base material 1, and the adhesion is further enhanced. Therefore, the flexible organic thermoelectric conversion elements 10 and 10A are preferably prevented from peeling off the organic thermoelectric conversion layers 3 and 3A even during use. As a result, durability against bending can be obtained, and it can withstand repeated use. Moreover, the organic thermoelectric conversion layers 3 and 3A can also be manufactured by application | coating so that it may mention later. Thereby, it can manufacture by making adhesiveness with the base material 1 stronger, without giving the base material 1 damage.

  In the flexible organic thermoelectric conversion elements 10 and 10A and the thermoelectric power generation article 20, the organic thermoelectric conversion layers 3 and 3A are formed of an organic thermoelectric conversion composition containing CNT (a) and a polymer compound (b). The conductivity exhibited by a) and the polymer compound (b) can be maintained. Therefore, even if the flexible organic thermoelectric conversion elements 10 and 10A and the thermoelectric power generation article 20 have high adhesion to the base material 1 and the metal electrode 2, they exhibit excellent conductivity.

  The flexible organic thermoelectric conversion element of the present invention provides an organic thermoelectric conversion composition on a flexible substrate on which a metal electrode is installed in a pattern according to the arrangement of the metal electrode, thereby forming an organic thermoelectric conversion layer. Can be manufactured.

  A method for forming a metal electrode in a desired pattern on a flexible substrate is not particularly limited. For example, a plating method, a patterning method by etching, a sputtering method using a lift-off method, an ion plating method, or a metal mask is used. Examples thereof include a sputtering method and an ion plating method. Moreover, it can also form using the metal paste which atomized the metal mentioned above and added the binder and the solvent. When using a metal paste, a screen printing method or a printing method by a dispenser method can be used. After printing, heating for drying and heat treatment for decomposition of the binder and sintering of the metal may be performed.

In this way, the organic thermoelectric conversion layer is provided in a pattern on the flexible substrate on which the metal electrode is installed in accordance with the arrangement of the metal electrode.
A method of providing the organic thermoelectric conversion layer in a pattern is not particularly limited, but a method of applying an organic thermoelectric conversion composition is preferable. For example, a metal mask printing method for printing an organic thermoelectric conversion composition using a metal mask, an ink jet printing method for printing by ejecting an ink jet coating liquid composed of an organic thermoelectric conversion composition by an ink jet method, printing such as screen printing The method is preferred.
The screen printing method involves patterning exposure of a photosensitive resin onto a normal mesh made of stainless steel, nylon, or polyester, developing it to produce a plate, printing, and printing a plate from an etched metal mask. And printing methods.
The metal mask printing method will be described in detail later in Examples.

  After apply | coating an organic thermoelectric conversion composition, Preferably, a heating process and a drying process are provided and a solvent etc. are distilled off. For example, the solvent can be volatilized and the coating film of the organic thermoelectric conversion composition can be dried by heat drying or blowing hot air.

  In the case where the organic thermoelectric conversion composition contains an onium salt compound (d), after the film formation, the film is heated or the film is irradiated with active energy rays to perform doping treatment to improve conductivity. preferable. By this treatment, an acid is generated from the onium salt compound (d), and this acid protonates the conductive polymer, thereby doping the conductive polymer with a positive charge (p-type doping).

Active energy rays include radiation and electromagnetic waves, and radiation includes particle beams (high-speed particle beams) and electromagnetic radiation. Particle rays include alpha rays (α rays), beta rays (β rays), proton rays, electron rays (which accelerates electrons with an accelerator regardless of nuclear decay), charged particle rays such as deuteron rays, Examples of the electromagnetic radiation include gamma rays (γ rays) and X-rays (X rays, soft X rays). Examples of the electromagnetic wave include radio waves, infrared rays, visible rays, ultraviolet rays (near ultraviolet rays, far ultraviolet rays, extreme ultraviolet rays), X-rays, gamma rays, and the like. The line type used in the present invention is not particularly limited. For example, an electromagnetic wave having a wavelength near the maximum absorption wavelength of the onium salt compound (acid generator) to be used may be appropriately selected.
Among these active energy rays, ultraviolet rays, visible rays, and infrared rays are preferable from the viewpoint of doping effect and safety, specifically, 240 to 1100 nm, preferably 240 to 850 nm, and more preferably 240 to 670 nm. It is a light beam having an emission wavelength.

For irradiation with active energy rays, a radiation or electromagnetic wave irradiation device is used. The wavelength of the radiation or electromagnetic wave to be irradiated is not particularly limited, and a radiation or electromagnetic wave in a wavelength region corresponding to the sensitive wavelength of the onium salt compound to be used may be selected.
Examples of devices that can irradiate radiation or electromagnetic waves include LED lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, deep UV lamps, low-pressure UV lamps and other mercury lamps, halide lamps, xenon flash lamps, metal halide lamps, ArF excimer lamps, and KrF excimer lamps. There are exposure apparatuses using a light source such as an excimer lamp, an extreme ultraviolet light lamp, an electron beam, or an X-ray lamp. The ultraviolet irradiation can be performed using a normal ultraviolet irradiation apparatus, for example, a commercially available ultraviolet irradiation apparatus for curing / adhesion / exposure (USHIO INC. SP9-250UB, etc.).

The exposure time and the amount of light may be appropriately selected in consideration of the type of onium salt compound to be used and the doping effect. Specifically, the light intensity is 10 mJ / cm ^{2 to} 10 J / cm ² , preferably 50 mJ / cm ^{2 to 5} J / cm ² .

  When doping is performed by heating, the formed film may be heated above the temperature at which the onium salt compound generates an acid. The heating temperature is preferably 50 to 200 ° C, more preferably 70 to 150 ° C. The heating time is preferably 1 to 60 minutes, more preferably 3 to 30 minutes.

  The timing of the doping treatment is not particularly limited, but it is preferably performed after processing the organic thermoelectric conversion composition such as film formation.

Next, an upper electrode is provided on the organic thermoelectric conversion layer. The upper electrode is provided by a coating method using the conductive paste, a sputtering method using the conductive material, a method combining a vacuum deposition method and a metal mask method, or the like.
Thus, a flexible organic thermoelectric conversion element can be manufactured.

Here, the flexible organic thermoelectric conversion element provided with the organic thermoelectric conversion layer containing CNT (a), a high molecular compound (b), and a compound (c), for example, the flexible organic thermoelectric conversion element 10 shown in FIGS. 1-3, is manufactured. When doing, the organic thermoelectric conversion adhesive composition containing CNT (a), a high molecular compound (b), and a compound (c) is used as an organic thermoelectric conversion composition.
The flexible organic thermoelectric conversion element thus manufactured includes a base material, one or more metal electrodes provided on the base material, and one or more organic thermoelectric elements provided in a pattern according to the arrangement of the metal electrodes. It has a conversion layer.

On the other hand, when manufacturing a flexible organic thermoelectric conversion element having an organic thermoelectric conversion layer having a film made of the compound (c), for example, the flexible organic thermoelectric conversion element 10A shown in FIG. 4, CNT (a) and a polymer compound The organic thermoelectric conversion composition containing (b) is used.
In this flexible organic thermoelectric conversion element, a surface of at least an organic thermoelectric conversion layer of a flexible base material provided with a metal electrode is surface-treated with the compound (c), and then the carbon nanotube (a) and the polymer compound (b ) Containing the organic thermoelectric conversion composition is provided in a pattern according to the arrangement of the metal electrodes to form an organic thermoelectric conversion layer, and the upper electrode is provided on the organic thermoelectric conversion layer.
In this production method, at least the surface on which the organic thermoelectric conversion layer is provided in the flexible substrate on which the metal electrode is installed as described above, for example, the surface of the metal electrode and preferably the substrate is surface-treated with the compound (c). . Examples of the surface treatment method include a method in which a solution containing the compound (c) and preferably a solvent or the like is applied to a predetermined surface and preferably dried. The application method is not particularly limited, and examples thereof include the same method as the application method of the organic thermoelectric conversion composition. Thereby, a film made of the compound (c), for example, a monomolecular film (SAM film) is formed on a predetermined surface. In the present invention, the film made of the compound (c) may be provided on the surface on which the organic thermoelectric conversion layer is provided, but may be provided on a surface other than the surface on which the organic thermoelectric conversion layer is provided.

  On the film | membrane which consists of a compound (c), an organic thermoelectric conversion composition is provided in a pattern shape according to arrangement | positioning of this film | membrane, ie, arrangement | positioning of a metal electrode. Although the method is not specifically limited, The method of apply | coating an organic thermoelectric conversion composition is preferable. The application method is as described above. The organic thermoelectric conversion composition used here may or may not contain the compound (c), and preferably does not contain it. After applying the organic thermoelectric conversion composition, as described above, a heating process or a drying process is preferably performed to distill off the solvent and the like, and when the onium salt compound (d) is contained, a doping treatment is preferably performed. In this way, the organic thermoelectric conversion layer can be provided in a desired pattern.

  Subsequently, a flexible organic thermoelectric conversion element is manufactured by providing an upper electrode on an organic thermoelectric conversion layer as mentioned above.

  The flexible organic thermoelectric conversion element manufactured in this way includes a base material, one or more metal electrodes provided on the base material, and one or more compounds provided in a pattern according to the arrangement of the metal electrodes. And an organic thermoelectric conversion layer provided with a film made of (c). This organic thermoelectric conversion layer contains CNT (a) and a polymer compound (b).

The article for thermoelectric power generation of the present invention uses the flexible organic thermoelectric conversion element of the present invention as a thermoelectric power generation element. Specifically, the flexible organic thermoelectric conversion element of the present invention is used for applications such as hot spring thermal power generators, solar thermal power generators, waste heat power generators, wristwatch power supplies, semiconductor drive power supplies, and (small) sensor power supplies. Is preferred.
In particular, since the flexible organic thermoelectric conversion element of the present invention is excellent in flexibility and the organic thermoelectric conversion layer is hardly peeled off, the thermoelectric power generation article of the present invention is suitably used for curved surfaces and uneven surfaces. . Specifically, it is used for housing and office lighting, electronic equipment, solar cells (photoelectric conversion and thermoelectric conversion hybrid power generation), waste heat recovery from piping such as factory steam and cooling water, and sensor networks and health monitors. It is preferably used for micro power generation. Examples of the health monitor include an electrocardiogram monitor device, a pulse meter, a blood pressure monitor, and a pedometer.

  Hereinafter, although an example and a comparative example explain the present invention in more detail, the present invention is not limited to them.

The polymer compound (b) used in each example is shown below.
Conductive polymer 1: poly (3-octyl) thiophene (manufactured by Sigma-Aldrich), weight average molecular weight 35,000
Conductive polymer 2: poly (3-hexyl) thiophene (manufactured by Sigma-Aldrich), weight average molecular weight 50,000
Conductive polymer 3: Polymer having the following repeating unit (weight average molecular weight 39,000)
Conductive polymer 4: Polymer having the following repeating unit (weight average molecular weight: 27,000)
Non-conductive polymer A: polystyrene (manufactured by Kanto Chemical Co., degree of polymerization 2000)
Non-conductive polymer B: PC-Z type polycarbonate “Panlite TS-2020” (trade name, manufactured by Teijin Chemicals Ltd.)
In the following repeating units, * represents a bonding position.

<Synthesis of conductive polymer 3>
The conductive polymer 3 was synthesized as follows.
2,5-dibromothieno [3,2-b] thiophene (1.10 g, 3.68 mmol), (4,4′-didodecyl- [2,2′-bithiophene] -5,5′-diyl) bis (trimethylstanne) ) (3.14 g, 3.79 mmol) and tetrakistriphenylphosphine palladium (170 mg, 0.147 mmol) were introduced into a 100 mL flask, and the inside of the container was purged with nitrogen. To this container, toluene (29 mL) and N, N-dimethylformamide (7 mL) were added as a solvent using a syringe, and the mixture was reacted by heating and stirring in a 120 ° C. oil bath for 26 hours in a nitrogen atmosphere. It was. After cooling the reaction solution at room temperature, insoluble components were removed from the solution by Celite filtration. The obtained solid was sequentially extracted by Soxhlet extraction (methanol 12 hours, acetone 3 hours, hexane 3 hours) to remove impurities, and then extracted with chlorobenzene. The chlorobenzene extract solution was concentrated, dissolved in chlorobenzene, crystallized with methanol, and collected by filtration. Finally, the solid was dried under vacuum for 10 hours to obtain the target conductive polymer 3 (yield 1.69 g, yield 72%).

<Synthesis of conductive polymer 4>
The conductive polymer 4 was synthesized as follows.
2,6-dibromo-4,4-dihexyl-4H-silolo [3,2-b: 4,5-b ′] dithiophene (2.28 g, 4.38 mmol), 2,5-bis (trimethylstannyl) -3 -Hexylthiophene (2.23 g, 4.51 mmol) and tetrakistriphenylphosphine palladium (253 mg, 0.219 mmol) were introduced into a 200 mL flask, and the inside of the container was purged with nitrogen. After adding toluene (35 mL) and N, N-dimethylformamide (9 mL) as a solvent in this container using a syringe, the mixture was reacted by heating and stirring for 31 hours in a 120 ° C. oil bath in a nitrogen atmosphere. It was. After cooling the reaction solution at room temperature, insoluble components were removed from the solution by Celite filtration. The obtained filtrate was added dropwise to methanol little by little to precipitate a solid, and the solid was collected by filtration. The obtained solid was sequentially extracted by Soxhlet extraction (methanol 12 hours, acetone 3 hours, hexane 3 hours) to remove impurities, and then extracted with chlorobenzene. The chlorobenzene extract solution was concentrated, dissolved in chlorobenzene, crystallized with methanol, and collected by filtration. Finally, the solid was dried under vacuum for 10 hours to obtain the target conductive polymer 4 (yield 1.63 g, yield 84%).

<Measurement of weight average molecular weight>
The weight average molecular weight of the polymer compound was determined as a polystyrene equivalent value by gel permeation chromatography (GPC).
Specifically, o-dichlorobenzene was added to the polymer compound, dissolved at 145 ° C., filtered through a 1.0 μm sintered filter to prepare a 0.15 w / v% sample solution, and measured under the following conditions. did.
Apparatus: “Alliance GPC2000 (Waters)”
Column: “TSKgel GMH ₆ -HT” — “TSKgel GMH ₆ —HT” — “TSKgel GMH ₆ —HTL” — “TSKgel GMH ₆ —HTL” (all 7.5 mm ID × 30 cm, manufactured by Tosoh Corporation)
Column temperature: 140 ° C
Detector: differential refractometer Mobile phase: o-dichlorobenzene

The onium salt compound (d) used in the examples is shown below. In the following formula, X is B (C ₆ F ₅ ) ₄ .

(Example 1)
The electrical conductivity of the thermoelectric conversion layer provided according to manufacture of the flexible organic thermoelectric conversion element 10 as shown in FIG. 1 was measured using the CNT dispersion liquid prepared as the organic thermoelectric conversion adhesive composition.

  10 mg of tetrahydronaphthalene (manufactured by Kanto Chemical) is added to 25 mg of conductive polymer 1 (poly (3-octyl) thiophene) as the polymer compound (b), and an ultrasonic cleaner “US-2” (trade name, Iuchi) A polythiophene solution was prepared using Seieido Co., Ltd., output 120 W, indirect irradiation. Furthermore, 25 mg of ASP-100F (manufactured by Hanwha Nanotech, 95% purity) was added as a single-walled CNT (a), a mechanical homogenizer “T10 basic ULTRA-TURRAX” (trade name, manufactured by IKA Work), an ultrasonic homogenizer “VC” -750 "(trade name, manufactured by SONICS & MATERIALS. Inc.), taper microtip (probe diameter 6.5 mm), ultrasonic dispersion at 30 ° C. for 30 minutes at 50 W output, direct irradiation, duty ratio 50%. It was. To this, 4 mg of compound (c) (C-7) was added to prepare CNT dispersion 101.

The CNT dispersion liquid 102 was the same as the CNT dispersion liquid 101 except that the types and presence of the compound (c), the polymer compound (b) and the onium salt compound (d) were changed as shown in Table 1 below. ˜108 and comparative CNT dispersions c101 and c102 were prepared.
In addition, 10 mg of onium salt compounds (d) were added to the CNT dispersion.

Using the prepared CNT dispersions 101 to 108 and the comparative CNT dispersions c101 and c102, respectively, a metal electrode 2, an organic thermoelectric conversion layer 3 and an upper electrode 4 are provided on the substrate 1, The flexible organic thermoelectric conversion elements 102 to 108 of the invention and the flexible organic thermoelectric conversion elements c101 and c102 as comparative examples were produced.
The electrical conductivity of the thermoelectric conversion layer of the manufactured flexible organic thermoelectric conversion element was evaluated by the electrical conductivity of the thermoelectric conversion layer provided on the glass substrate as described below using the CNT dispersion.

[Measurement of conductivity]
As a substrate, a glass substrate having a thickness of 1.1 mm and a size of 40 × 50 mm was ultrasonically cleaned in acetone and then subjected to UV-ozone treatment for 10 minutes. Each of the CNT dispersions 101 to 108 and c101 and c102 was applied onto this glass substrate with a spin coater and then dried at room temperature under vacuum conditions for 3 hours to form an organic thermoelectric conversion layer having a thickness of about 1 μm. .
Thereafter, the organic thermoelectric conversion layer to which the onium salt is added is irradiated with ultraviolet rays (light quantity: about 500 mJ / cm ² ) by an ultraviolet irradiator “ECS-401GX” (trade name, manufactured by Eye Graphics Co., Ltd.). Heat treatment was performed at 80 ° C. for 2 hours.
The conductivity of the obtained organic thermoelectric conversion layer was measured as a conductivity σ (unit: S / cm) at 100 ° C. using a thermoelectric property measuring device “RZ2001i” (trade name, manufactured by Ozawa Science Co., Ltd.). The results are shown in Table 1.

As is clear from Table 1, the flexible organic thermoelectric conversion elements 101 to 108 of the present invention having the organic thermoelectric conversion layer containing CNT (a), the polymer compound (b), and the compound (c) are all highly conductive. The rate σ is shown.
In particular, sample no. 101, sample c101, and sample no. Comparing the sample 102 and the sample c102, it can be seen that even when the compound (c) is contained, the conductivity of the organic thermoelectric conversion layer not containing the compound (c) does not decrease and is improved.
Furthermore, it turns out that electrical conductivity becomes still higher when onium salt compound (d) is contained.

Example 2
A CNT dispersion paste was prepared as an organic thermoelectric conversion adhesive composition to produce a flexible organic thermoelectric conversion element 10 as shown in FIG.

Silica fine particles “JA-244” (manufactured by Jujo Chemical) 3 g was added to 27 g of non-conductive polymer A (polystyrene), and the silica fine particles were dispersed in polystyrene with a two-roll mill heated to 180 ° C. Polystyrene was produced.
Next, to 9.7 g of the CNT dispersion 101 prepared in Example 1, 1.0 g of silica-dispersed polystyrene, 1.0 g of non-conductive polymer B (PC-Z type polycarbonate “Panlite TS-2020”), And dissolved in a 50 ° C. warm bath, and then stirred with a self-revolving stirrer “ARE-250” (trade name, manufactured by Sinky Corporation) at a rotation speed of 2200 rpm and a stirring time of 15 minutes. A dispersion paste 201 was prepared.

As a base material 1, an A6 size (Japanese Industrial Standard), 188 μm thick PET film with an opening 6 × 9 mm metal mask formed by etching is used to make chromium 100 nm by ion plating and then gold A metal electrode 2 was formed by forming a 200 nm thick film.
Next, using a metal mask having 80 openings 8 × 9 mm formed by laser processing and having a thickness of 2 mm, CNT dispersion paste 201 was injected and flattened with a squeegee. At this time, the CNT dispersion paste 201 was printed on the metal electrode 2 in an arrangement as shown in FIG.
The organic thermoelectric conversion layer 3 (thickness of about 20 μm) was provided on the metal electrode 2 by heating and drying the PET film on an 80 ° C. hot plate.
A silver paste “FA-333” (trade name, manufactured by Fujikura Kasei Co., Ltd.) is applied to each of the eight organic thermoelectric conversion layers 3 arranged in a straight line in the organic thermoelectric conversion layer 3 and wired in series. The upper electrode 4 was provided by drying on a hot plate at 0 ° C. for 1 hour. In this way, the flexible organic thermoelectric conversion element 201 of the present invention having 10 lines in which eight of the organic thermoelectric conversion units 5 are electrically connected in series was manufactured. Note that the output terminals 51 and 52 and the output wirings 53 and 54 shown in FIG. 3 are provided by known materials and methods.

The flexible organic thermoelectric conversion element 201 except that the type and presence of the compound (c), the polymer compound (b) and the onium salt compound (d) used in the CNT dispersion were changed as shown in Table 2 below. Similarly, flexible organic thermoelectric conversion elements 202 to 208 of the present invention and flexible organic thermoelectric conversion elements c201 and c202 as comparative examples were produced.
In addition, 10 mg of onium salt compounds (d) were added to the CNT dispersion.

[Evaluation of adhesion by tape peeling test]
Cello tape (registered trademark) (width 12 mm) “CT-12” (manufactured by Nichiban) was attached to the organic thermoelectric conversion layer 3 before the flexible organic thermoelectric conversion elements 201 to 208 and the upper electrode 4 in c201 and c202 were provided. At the time of peeling, the angle of the substrate 1 and the tape was set to 135 degrees, and the tape was peeled off. The state of the organic thermoelectric conversion layer after tape peeling was evaluated based on the following criteria for the adhesion of the organic thermoelectric conversion layer. The results are shown in Table 2.
A: Peeling of the organic thermoelectric conversion layer is not observed. B: Peeling is observed in a part of the organic thermoelectric conversion layer, but it is practically usable. The organic thermoelectric conversion layer is completely peeled off

As is clear from Table 2, the flexible organic thermoelectric conversion elements 201 to 208 of the present invention having the organic thermoelectric conversion layer containing CNT (a), the polymer compound (b) and the compound (c) are all base materials. And the adhesiveness with a metal electrode was high.
On the other hand, flexible organic thermoelectric conversion elements c201 and c202 as comparative examples having an organic thermoelectric conversion layer containing no compound (c) have low adhesion to the substrate and the metal electrode.

Example 3
Similar to the flexible organic thermoelectric conversion element 201, a CNT dispersion paste was prepared to produce a flexible organic thermoelectric conversion element 10 as shown in FIG.
That is, as described above, the metal electrode 2 is formed on a PET film having an A6 size (Japanese Industrial Standard) and a thickness of 188 μm, and the CNT dispersion paste 301 prepared in the same manner as the CNT dispersion paste 201 is printed at 80 ° C. The organic thermoelectric conversion layer 3 was provided on the metal electrode 2 by heating and drying on the hot plate.
A silver paste “FA-333” (trade name, manufactured by Fujikura Kasei Co., Ltd.) is applied to each of the eight organic thermoelectric conversion layers 3 arranged in a straight line in the organic thermoelectric conversion layer 3 and wired in series. The upper electrode 4 was provided by drying on a hot plate at 0 ° C. for 1 hour. In this way, the flexible organic thermoelectric conversion element 301 of the present invention having 10 lines in which eight of the organic thermoelectric conversion units 5 are electrically connected in series was manufactured. Note that the output terminals 51 and 52 and the output wirings 53 and 54 shown in FIG. 3 are provided by known materials and methods.

The flexible organic thermoelectric conversion element 301 except that the type and presence of the compound (c), the polymer compound (b) and the onium salt compound (d) used in the CNT dispersion were changed as shown in Table 3 below. Similarly, flexible organic thermoelectric conversion elements 302 to 308 of the present invention and flexible organic thermoelectric conversion elements c301 and c302 as comparative examples were produced.
In addition, 10 mg of onium salt compounds (d) were added to the CNT dispersion.

[Heating and bending resistance test]
A 60 W incandescent bulb was lit at the center of the inside of an ABS resin pipe having an outer diameter of 35 mm and an inner diameter of 25 mm. At this time, the ambient temperature was 25 ° C. and the pipe surface temperature was 45 ° C. After winding the flexible organic thermoelectric conversion elements 301 to 308 and c301 and c302 around this pipe and holding for 3 minutes, the resistance value was measured and the resistance change rate was calculated from the following equation. Moreover, the state of the organic thermoelectric conversion layer was confirmed visually. The resistance change rate was an average value of 10 lines.

  Resistance change rate (increase rate) = [(resistance value after resistance test) − (resistance value before resistance test)] / (resistance value before resistance test) × 100 (%)

In the heating and bending resistance test, the resistance change rate and the state of the organic thermoelectric conversion layer were evaluated according to the following criteria.
A: The resistance change rate is less than ± 2% and the organic thermoelectric conversion layer is not peeled. B: The resistance change rate is ± 2% or more and less than 10%, and the organic thermoelectric conversion layer is not peeled. C: Resistance The rate of change is ± 10% or more and cracks are observed in the organic thermoelectric conversion layer. D: The resistance value cannot be measured, and the organic thermoelectric conversion layer is peeled off.

As is clear from Table 3, the flexible organic thermoelectric conversion elements 301 to 308 of the present invention having the organic thermoelectric conversion layer containing CNT (a), the polymer compound (b) and the compound (c) are all base materials. In addition, the adhesiveness with the metal electrode was high, the resistance change rate was small in the heating and bending resistance test assuming actual use, and peeling of the organic thermoelectric conversion layer was not observed.
On the other hand, flexible organic thermoelectric conversion elements c301 and c302 as comparative examples having an organic thermoelectric conversion layer containing no compound (c) were not able to measure resistance values, and peeling of the organic thermoelectric conversion layer was observed.

DESCRIPTION OF SYMBOLS 1 Base material 2, 23 Metal electrode 2a The part to which an upper electrode is connected 3, 3A Organic thermoelectric conversion layer 3a Area | region in which the organic thermoelectric conversion layer 3 is provided 4 Upper electrode 5, 5A Organic thermoelectric conversion unit 6A It consists of a compound (c) Film 6B Film made of organic thermoelectric conversion composition 10, 10A Flexible organic thermoelectric conversion element 20 Thermoelectric power generation article 51, 52 Output terminal 53, 54 Output wiring

Claims (21)

(A) A flexible base material including a carbon nanotube, (b) a polymer compound, and (c) a compound represented by the following formula (A), formula (B), or formula (C) and provided with a metal electrode The flexible organic thermoelectric conversion element which has the organic thermoelectric conversion layer provided in the pattern shape according to arrangement | positioning of the said metal electrode, and the upper electrode provided on this organic thermoelectric conversion layer.
Formula ^(A) R 1 -Y
Formula ^{(B) R 1 -Z 1 -C} (= S) -Z 2 -R 2
Formula (C) R ¹ —Z ³ —Z ³ —R ³
(In the formulas (A), (B) and (C), R ¹ represents an alkyl group, an alkenyl group, an aralkyl group or an aryl group. Y represents —SH, —SCN or SiR ⁴ R ⁵ H. Z ¹ and Z ² each independently represents a single bond, an oxygen atom, a sulfur atom or —NR ⁶ —, Z ³ represents a sulfur atom, — (C═S) —S— or —NR ⁷ — (C═ R ² and R ³ each independently represents an alkyl group, an alkenyl group, an aralkyl group or an aryl group, and R ² may combine with R ¹ to form a ring. R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, and R ⁷ may combine with R ¹ or R ³ to form a ring. .) The flexible organic thermoelectric conversion element according to claim ¹ , wherein R ¹ , R ^2, and R ³ are each independently an alkyl group, an aralkyl group, or an aryl group.   The flexible organic thermoelectric conversion element according to claim 2, wherein the alkyl group is a linear alkyl group. The R ¹ , the R ^2, and the R ³ each independently have at least one substituent selected from the group consisting of a carboxy group, a hydroxy group, an amide group, and a heterocyclic group. The flexible organic thermoelectric conversion element of Claim 1.   The flexible organic thermoelectric conversion element according to claim 4, wherein the heterocyclic group is a 5- or 6-membered heterocyclic group having a nitrogen atom.   Said Y is -SH, The flexible organic thermoelectric conversion element of any one of Claims 1-5. 6. The flexible organic thermoelectric conversion element according to claim 1, wherein at least one of Z ¹ and Z ² is —NR ⁶ —. The flexible organic thermoelectric conversion element according to claim 1, wherein the —Z ³ —Z ³ — includes a disulfide bond. The flexible organic thermoelectric conversion element according to claim 8, wherein Z ³ is a sulfur atom or —NR ⁷ — (C═S) —S—.   The flexible organic thermoelectric conversion element according to any one of claims 1 to 9, wherein the content of the compound (c) is 0.1 to 10% by mass with respect to the total solid content of the organic thermoelectric conversion layer.   The flexible organic thermoelectric conversion element according to any one of claims 1 to 10, wherein the compound (c) is a compound having a molecular weight of 1000 or less.   The organic thermoelectric conversion layer is composed of an organic thermoelectric conversion adhesive composition containing the carbon nanotube (a), the polymer compound (b), and the compound (c). The flexible organic thermoelectric conversion element as described.   The organic thermoelectric conversion layer is formed by providing a film made of an organic thermoelectric conversion composition containing the carbon nanotube (a) and the polymer compound (b) on a film made of the compound (c). The flexible organic thermoelectric conversion element of any one of -11. The organic thermoelectric conversion adhesive composition or the organic thermoelectric conversion composition further contains (d) an onium salt compound represented by any one of the following general formulas (I) to (V): 13. The flexible organic thermoelectric conversion element according to 13.

(In the general formulas (I) to (V), R ^{21 to} R ²³ , R ^{25 to} R ²⁶ and R ^{31 to} R ³³ are each independently an alkyl group, an aralkyl group, an aryl group, or an aromatic heterocyclic group. R ^{27 to} R ³⁰ each independently represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an aromatic heterocyclic group, an alkoxy group, or an aryloxy group, and R ²⁴ represents an alkylene group or an arylene group. .X represents a group ^-. is, ^{R 21} and ^{R 23} in any two groups of ^R 21 ^{to R 23} in an anion of a strong acid formula (I), formula (II), in the general formula (III) R ²⁵ and R ²⁶ , any two groups of R ^{27 to} R ³⁰ in the general formula (IV), and any two groups of R ^{31 to} R ³³ in the general formula (V) are Result To aliphatic ring, may form an aromatic ring, or a heterocyclic ring.) In the general formulas (I) to (V), X ⁻ represents an anion of an aryl sulfonic acid, an anion of a perfluoroalkyl sulfonic acid, an anion of a perhalogenated Lewis acid, an anion of a perfluoroalkyl sulfonimide, or an alkyl or The flexible organic thermoelectric conversion element according to claim 14, which is an aryl borate anion.   In the total solid content of the organic thermoelectric conversion adhesive composition, 5 to 60% by mass of the carbon nanotube (a), 30 to 80% by mass of the polymer compound (b), and 0. The flexible organic thermoelectric conversion element according to claim 14 or 15, comprising 1 to 10% by mass and 1 to 30% by mass of the onium salt compound (d). An organic thermoelectric conversion adhesive composition containing (a) a carbon nanotube, (b) a polymer compound, and (c) a compound represented by the following formula (A), formula (B) or formula (C): A method for producing a flexible organic thermoelectric conversion element in which an organic thermoelectric conversion layer is formed on a flexible base material on which a metal electrode is provided in a pattern according to the arrangement of the metal electrode, and an upper electrode is provided on the organic thermoelectric conversion layer .
Formula ^(A) R 1 -Y
Formula ^{(B) R 1 -Z 1 -C} (= S) -Z 2 -R 2
Formula (C) R ¹ —Z ³ —Z ³ —R ³
(In the formulas (A), (B) and (C), R ¹ represents an alkyl group, an alkenyl group, an aralkyl group or an aryl group. Y represents —SH, —SCN or SiR ⁴ R ⁵ H. Z ¹ and Z ² each independently represents a single bond, an oxygen atom, a sulfur atom or —NR ⁶ —, Z ³ represents a sulfur atom, — (C═S) —S— or —NR ⁷ — (C═ R ² and R ³ each independently represents an alkyl group, an alkenyl group, an aralkyl group or an aryl group, and R ² may combine with R ¹ to form a ring. R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, and R ⁷ may combine with R ¹ or R ³ to form a ring. .)   The method for producing a flexible organic thermoelectric conversion element according to claim 17, wherein the content of the compound (c) is 0.1 to 10% by mass with respect to the total solid content of the organic thermoelectric conversion adhesive composition. The surface on which at least the organic thermoelectric conversion layer of the flexible substrate provided with the metal electrode is provided is (c) surface-treated with a compound represented by the following formula (A), formula (B) or formula (C), and thereafter , (A) an organic thermoelectric conversion composition containing carbon nanotubes and (b) a polymer compound is provided in a pattern according to the arrangement of the metal electrodes to form an organic thermoelectric conversion layer, and the organic thermoelectric conversion layer is formed on the organic thermoelectric conversion layer. The manufacturing method of the flexible organic thermoelectric conversion element which provides an electrode.
Formula ^(A) R 1 -Y
Formula ^{(B) R 1 -Z 1 -C} (= S) -Z 2 -R 2
Formula (C) R ¹ —Z ³ —Z ³ —R ³
(In the formulas (A), (B) and (C), R ¹ represents an alkyl group, an alkenyl group, an aralkyl group or an aryl group. Y represents —SH, —SCN or SiR ⁴ R ⁵ H. Z ¹ and Z ² each independently represents a single bond, an oxygen atom, a sulfur atom or —NR ⁶ —, Z ³ represents a sulfur atom, — (C═S) —S— or —NR ⁷ — (C═ R ² and R ³ each independently represents an alkyl group, an alkenyl group, an aralkyl group or an aryl group, and R ² may combine with R ¹ to form a ring. R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, and R ⁷ may combine with R ¹ or R ³ to form a ring. .)   The article for thermoelectric power generation using the flexible organic thermoelectric conversion element of any one of Claims 1-16. The power supply for sensors using the flexible organic thermoelectric conversion element of any one of Claims 1-16.

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