Thermoelectric material composition

Abstract

To provide a thermoelectric material composition with which a thermoelectric conversion element low in an electric resistance value and sufficiently high in power generation amount can be obtained.SOLUTION: A thermoelectric material composition contains a polymer (X) including, as constituent monomers, polyepoxyde (A) and polyamine (B), and thermoelectric particles (C). The polymer (X) has a storage modulus (E') at 25°C and at vibration frequency of 10 Hz in dynamic viscoelasticity measurement of 1.0×106-1.0×1010 Pa, and the thermoelectric particles (C) have a volume ratio of 35-65 vol%, based on the total volume of the polymer (X) and the thermoelectric particles (C). The thermoelectric material composition has an electrical resistivity of 0.016-0.100 Ω cm at 25°C.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a thermoelectric material composition. [Background technology]

[0002] Thermoelectric conversion materials have attracted attention as a material that can utilize energy with high efficiency by converting waste heat into electricity, and thermoelectric conversion materials using conductive polymers are known as materials using organic materials. Thermoelectric conversion materials are placed on the surface of a heat source to convert heat into electricity, but since the shape of the surface of the heat source is not uniform, it is difficult to place conductive polymers with low flexibility on the exhaust heat generating parts with curved or uneven surfaces. For this reason, flexible thermoelectric conversion materials that can be placed on surfaces with such shapes are being studied.

[0003] Patent Document 1 describes a thermoelectric material containing a thermoelectric substance and a solvent, the vapor pressure of the solvent at 25° C. being 0 Pa or more and 1.5 Pa or less, and the vapor pressure of the solvent at 25° C. being 1×10 1 Pa or more 4×10 6 The storage modulus G' is in the range of 5 Pa to 4 x 10 6 Thermoelectric materials are disclosed that have a loss modulus G″ in the sub-Pa range. The thermoelectric material of Patent Document 1 contains a thermoelectric substance and a solvent, and is characterized by having viscosity due to this.

[0004] Patent Document 2 discloses a composite thermoelectric material including a binder resin, thermoelectric material particles dispersed in the binder resin, and metal fine particles supported on the surfaces of the thermoelectric material particles. The composite thermoelectric material is said to be capable of being formed into a flexible, thin material while maintaining sufficient thermoelectric properties. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2019 / 017170 [Patent Document 2] Special Publication No. 2012-523121 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the thermoelectric conversion elements using the thermoelectric materials described in Patent Documents 1 and 2 have problems in that the electrical resistance may be high and the amount of power generation is insufficient.

[0007] The present invention has been made to solve the above problems, and has an object to provide a thermoelectric material composition that can provide a thermoelectric conversion element having a low electrical resistance and a sufficiently high amount of power generation. [Means for solving the problem]

[0008] The present inventors conducted extensive research to solve the above problems and arrived at the present invention. The present invention relates to a thermoelectric material composition containing a polymer (X) having constituent monomers of a polyepoxide (A) and a polyamine (B) and thermoelectric particles (C), wherein the polymer (X) has a storage modulus (E') of 1.0×10 at 25° C. and a vibration frequency of 10 Hz as measured by dynamic viscoelasticity measurement. 6 ~1.0×10 10 Pa, the volume ratio of the thermoelectric particles (C) is 35 to 65 vol% with respect to the total volume of the polymer (X) and the thermoelectric particles (C), and the thermoelectric material composition has an electrical resistivity of 0.016 to 0.100 Ω cm at 25°C. Effect of the Invention

[0009] According to the present invention, it is possible to provide a thermoelectric material composition which makes it possible to obtain a thermoelectric conversion element having a low electrical resistance and a sufficiently high amount of power generation. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The present invention relates to a thermoelectric material composition containing a polymer (X) having constituent monomers of a polyepoxide (A) and a polyamine (B) and thermoelectric particles (C), wherein the polymer (X) has a storage modulus (E') of 1.0×10 at 25° C. and a vibration frequency of 10 Hz as measured by dynamic viscoelasticity measurement. 6 ~1.0×10 10 Pa, the volume ratio of the thermoelectric particles (C) is 35 to 65 vol% with respect to the total volume of the polymer (X) and the thermoelectric particles (C), and the thermoelectric material composition has an electrical resistivity of 0.016 to 0.100 Ω cm at 25°C.

[0011] Since the thermoelectric material composition of the present invention is a resin composition and has flexibility, by placing it on a part that generates waste heat and has a curved or uneven surface shape, waste heat can be recovered as electrical energy.

[0012] The thermoelectric material composition of the present invention contains a polymer (X) having polyepoxide (A) and polyamine (B) as constituent monomers, and thermoelectric particles (C). First, the polymer (X) will be described. [Polymer (X)] The polymer (X) is a polymer having a polyepoxide (A) and a polyamine (B) as constituent monomers.

[0013] [Polyepoxide (A)] The polyepoxide (A) has two or more epoxy groups in the molecule. The number of epoxy groups is not particularly limited, but is preferably 2 to 10, and more preferably 2 to 6. The polyepoxide (A) may be used alone or in combination of two or more kinds.

[0014] The number average molecular weight of the polyepoxide (A) [measured by the molecular weight of the compound or by the gel permeation chromatography (GPC) method described below] is preferably 100 to 500, more preferably 120 to 350, from the viewpoints of crosslink density and viscosity. [GPC measurement conditions] Equipment: "HLC-8120" [Tosoh Corporation] Column: "TSK GEL GMH6" [Tosoh Corporation] x 2 Measurement temperature: 40℃ Sample solution: 0.25% by weight tetrahydrofuran solution (undissolved matter was removed by filtration using a glass filter) Solution injection volume: 100μl Detector: Refractive index detector Reference material: 12 standard polystyrenes (TSKstandard POLYSTYRENE) (molecular weight: 500, 1,050, 2,800, 5,970, 9,100, 18,100, 37,900, 96,400, 190,000, 355,000, 1,090,000, 2,890,000) [manufactured by Tosoh Corporation]

[0015] Moreover, the epoxy equivalent of the polyepoxide (A) (the molecular weight per epoxy group) is preferably 100 to 300 / eq, more preferably 100 to 200 / eq, from the viewpoint of crosslink density. It is also preferable that the polyepoxide (A) has a number average molecular weight of 120 to 350 and an epoxy equivalent of 100 to 200 g / eq.

[0016] The viscosity of the polyepoxide (A) is preferably 20 mPa or more and 10,000 mPa or less from the viewpoint of particle dispersion (particle dispersion of the thermoelectric particles (C)). The viscosity of the polyepoxide (A) can be measured, for example, under the following conditions. Equipment: BH type viscometer [model number "TVB-22H", manufactured by Toki Sangyo Co., Ltd.] Measurement temperature: 25℃ Rotation speed: 20 rpm Spindle No.: No. 7

[0017] The SP value of the polyepoxide (A) is preferably 8.0 or more and 11.0 or less. The SP value of the polyepoxide (A) can be calculated by the method by Fedors [Polym. Eng. Sci. 14(2)152, (1974)].

[0018] When the polymer (X) contains two or more kinds of polyepoxides (A), the number average molecular weight and epoxy equivalent of the polyepoxides (A) are defined as weight average values, and the SP value is defined as molar average value. The viscosity is defined as the viscosity of the mixture.

[0019] The polyepoxide (A) includes the following (A1) to (A4), and mixtures of two or more of these.

[0020] (A1) Polyglycidyl ether (A11) Diglycidyl ether of dihydric phenol [carbon number (hereinafter abbreviated as C) 6 to 30] diglycidyl ether of bisphenol (such as bisphenol-F, -A, -B, -AD or S), diglycidyl ether of halogenated bisphenol A (such as tetrachlorobisphenol A), diglycidyl ether of monocyclic dihydric phenol (such as catechol, resorcinol, hydroquinone), diglycidyl ether of condensed polycyclic dihydric phenol (such as 1,5-dihydroxynaphthalene, dihydroxybiphenyl, octachloro-4,4'-dihydroxybiphenyl, 9,9'-bis(4-hydroxyphenyl)fluorene), diglycidyl ether obtained from the reaction of 2 moles of bisphenol A with 3 moles of epichlorohydrin, etc.;

[0021] (A12) Polyglycidyl ether of polyhydric (trihydric to hexahydric or higher) phenols Polyglycidyl ethers of polyhydric phenols (C6 or more and Mn5,000 or less), such as triglycidyl ether of trihydric phenols [pyrogallol, dihydroxynaphthyl cresol, tris(hydroxyphenyl)methane, dinaphthyltriol, p-glycidylphenyldimethyltriyl bisphenol A, etc.], tetraglycidyl ether of tetrahydric phenols [tetrakis(4-hydroxyphenyl)ethane, 4,4'-oxybis(1,4-phenylethyl)tetracresol, bis(dihydroxynaphthalene, etc.)] polyglycidyl ethers of terephthalic acid, phenol or cresol novolac resins (Mn 400-5,000), polyglycidyl ethers of limonene phenol novolac resins (Mn 400-5,000), polyglycidyl ethers of polyphenols (Mn 400-5,000) obtained by the condensation reaction of phenol with glyoxal, glutaraldehyde or formaldehyde, and polyglycidyl ethers of polyphenols (Mn 400-5,000) obtained by the condensation reaction of resorcinol with acetone;

[0022] (A13) Diglycidyl ether of aliphatic diol diglycidyl ethers of aliphatic diols (dihydric alcohols (e.g., ethylene glycol, propylene glycol, tetramethylene glycol, neopentyl glycol, 1,6-hexanediol (hereinafter abbreviated as EG, PG, TMG, NPG, and 1,6-HD, respectively), polyalkylene glycols (e.g., polyethylene glycol (hereinafter abbreviated as PEG, having a molecular weight of 106 or more and Mn of 4,000 or less), polypropylene glycol (hereinafter abbreviated as PPG, having a molecular weight of 134 or more and Mn of 5,000 or less), polytetramethylene glycol (hereinafter abbreviated as PTMG, having a molecular weight of 162 or more and Mn of 5,000 or less)), etc.), preferably diglycidyl ethers of neopentyl glycol (e.g., Denacol EX-211, manufactured by Nagase ChemteX Corp.) or diglycidyl ethers of polypropylene glycol (e.g., Denacol EX-931, manufactured by Nagase ChemteX Corp.); (A13) preferably has C2 or more and Mn of 5,000 or less.

[0023] (A14) Polyglycidyl ether of aliphatic poly(trihydric to hexahydric or higher)ol aliphatic polyols (polyglycidyl ethers of polyhydric (3-6) alcohols (trimethylolpropane, glycerin, pentaerythritol, sorbitol (hereinafter abbreviated as TMP, GR, PE, SO, etc.), intramolecular or intermolecular dehydration products of polyhydric alcohols (poly(n=2-5)GR), and alkylene oxides (hereinafter abbreviated as AO, C2-6, for example, ethylene oxide, 1,2-propylene oxide (hereinafter abbreviated as EO, PO, etc.) adducts of these polyhydric alcohols), preferably polyglycidyl ethers of glycerol (e.g., Denacol EX-314, manufactured by Nagase ChemteX Corporation); (A14) preferably has C6 or more and Mn of 10,000 or less.

[0024] (A15) Polyglycidyl ether of alicyclic ring-containing poly(dihydric to tetrahydric or higher)ol those with C3 or more and Mn of 5,000 or less, for example, polyglycidyl ethers such as 1,2-cyclopropanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-cyclohexanediol, hydrogenated bisphenol A, 1,2,3-cyclopropanetriol, 1,3,5-cyclohexanetriol, sucrose, and AO (1 to 20 mol) adducts thereof;

[0025] (A16) Polyglycidyl ether of aromatic ring-containing polyhydric (dihydric to tetrahydric or higher) alcohol polyglycidyl ethers such as those having an Mn of 8 or more and an Mn of 5,000 or less, AO (1 to 20 mol) adducts of bisphenol A, m- or p-xylylene glycol, benzenediethanol, 1,2-diphenylethane-1,2-diol, 1,1,2,2,-tetraphenylethane-1,2-diol, and AO (1 to 20 mol) adducts thereof;

[0026] (A2) Polyglycidyl ester (A21) Glycidyl esters of aromatic polyvalent (divalent to hexavalent or higher) carboxylic acids Polyglycidyl esters of aromatic polycarboxylic acids (C6 to C20 or more), such as diglycidyl esters of aromatic dicarboxylic acids (such as ortho-, iso-, or terephthalic acid), triglycidyl esters of aromatic tricarboxylic acids (such as trimellitic acid); (A22) Polyglycidyl esters of aliphatic or alicyclic polycarboxylic acids (C6 to C20 or more) For example, aliphatic dicarboxylic acids (oxalic acid, maleic acid, succinic acid, glutaric acid, adipic acid, diglycidyl esters of aliphatic tricarboxylic acids (such as tricarballylic acid, pimelic acid), triglycidyl esters of aliphatic tricarboxylic acids (such as tricarballylic acid), (co)polymers of glycidyl (meth)acrylate (degree of polymerization being 2 to 10), polyglycidyl esters of alicyclic-containing polycarboxylic acids (such as dimer acid), and nuclear hydrogenations of the above (A21);

[0027] (A3) Glycidyl amine of polyamine (C6-C20 or more and having 2-10 or more active hydrogen atoms directly bonded to nitrogen atoms) (A31) Polyglycidylamines of aromatic amines For example, N,N-diglycidylaniline, N,N-diglycidyltoluidine, N,N,N',N'-tetraglycidyldiaminodiphenylmethane, N,N,N',N'-tetraglycidyldiaminodiphenylsulfone, N,N,N',N'-tetraglycidyldiaminoethylphenylmethane, and N,N,O-triglycidylaminophenol; (A32) Polyglycidylamines of Aliphatic Amines For example, N,N,N',N'-tetraglycidylxylylenediamine, N,N,N',N'-tetraglycidylhexamethylenediamine; (A33) Polyglycidylamines containing alicyclic or heterocyclic rings (C6-C20 or more and having 2-10 or more active hydrogen atoms directly bonded to nitrogen atoms) Polyglycidylamines of alicyclic ring-containing amines (e.g. hydrogenated N,N,N',N'-tetraglycidylxylylenediamine), polyglycidylamines of heterocyclic ring-containing amines (e.g. trisglycidylmelamine);

[0028] (A4) Other polyepoxides (A41) Aliphatic poly(2-6 or more) epoxides C6 or more and Mn2,500 or less, e.g., epoxidized polybutadiene, epoxidized soybean oil; (A42) Alicyclic poly(divalent to tetravalent or higher) epoxide Those with C6 or more and Mn of 2,500 or less, such as vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis(2,3-epoxycyclopentyl)ether, ethylene glycol bisepoxydicyclopentyl ether, 3,4-epoxy-6-methylcyclohexylmethyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, and bis(3,4-epoxy-6-methylcyclohexylmethyl)butylamine.

[0029] Of these (A), (A1) is preferred, (A13) or (A14) is more preferred, and diglycidyl ether of neopentyl glycol, diglycidyl ether of polypropylene glycol, and polyglycidyl ether of glycerol are particularly preferred.

[0030] [Polyamine (B)] The polyamine (B) has two or more active hydrogens directly bonded to a nitrogen atom, and preferably has two or more amino groups, and more preferably has three or more amino groups. The polyamine (B) may be used alone or in combination of two or more kinds.

[0031] The number average molecular weight of the polyamine (B) [measured by the molecular weight of the compound or the above-mentioned GPC method] is preferably 80 to 300 from the viewpoint of crosslink density.

[0032] The active hydrogen equivalent of the polyamine (B) (the molecular weight per active hydrogen) is preferably 100 / eq or less from the viewpoint of crosslink density.

[0033] The total amine value of the polyamine (B) is preferably 1200 to 2100 mgKOH / g from the viewpoint of crosslink density.

[0034] The viscosity of the polyamine (B) is preferably 20 mPa or more and 700 mPa or less from the viewpoint of particle dispersion (particle dispersion of the thermoelectric particles (C)). The viscosity of the polyamine (B) can be measured under the same conditions as those for the viscosity of the polyepoxide (A).

[0035] The SP value of the polyamine (B) is preferably 10.5 or more and 11.5 or less. The SP value of the polyamine (B) can be calculated in the same manner as the SP value of the polyepoxide (A).

[0036] When multiple types of polyamine (B) are contained in polymer (X), the number average molecular weight, active hydrogen equivalent, and total amine value of polyamine (B) are defined as weight average values, and the SP value is defined as molar average value. The viscosity is defined as the viscosity of the mixture.

[0037] The polyamine (B) includes the following (B1) to (B9), and mixtures of two or more of these.

[0038] (B1) Aliphatic poly(2-7)amines those with C2 or more and Mn500 or less, such as C2-10 alkylenediamines (ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.), polyalkylene (C2-10) poly(trivalent to hexavalent or higher) amines [diethylenetriamine, iminobispropylamine, bis(hexamethylene)triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.], as well as their alkyl (C1-4) or hydroxyalkyl (C2-4) substituted derivatives, such as dialkyl (C1-3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2,5-hexamethylenediamine, methyliminobispropylamine, N,N'-di-n-butyl-1,6-hexanediamine;

[0039] (B2) Alicyclic-containing poly(di- or trivalent)amine C4-15, such as 1,3-diaminocyclohexane, 1,3-bisaminomethylcyclohexane, isophoronediamine, menthenediamine, 4,4'-methylenedicyclohexanediamine (hydrogenated methylenedianiline);

[0040] (B3) Heterocycle-containing poly(di- or trivalent)amine those with C4-15, such as piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 1,4-bis(2-amino-2-methylpropyl)piperazine;

[0041] (B4) Aromatic ring-containing polyamine C8-15, such as xylylenediamine, tetrachloro-p-xylylenediamine, reaction products of xylylenediamine with styrene;

[0042] (B5) Polyamide polyamine Those having a molecular weight of 200 or more and Mn of 1,000 or less, such as polyamidepolyamines obtained by condensation of a dicarboxylic acid (dimer acid, etc.) with an excess of [2 or more equivalents of the above (B1) or the like per equivalent of carboxyl group];

[0043] (B6) Polyether polyamine Those with a molecular weight of 100 or more and Mn of 1,000 or less, such as hydrogenated cyanoethylated polyether polyols (such as the above-mentioned polyalkylene glycols);

[0044] (B7) Epoxy-added polyamine Those having a molecular weight of 100 or more and Mn of 1,000 or less, for example, a reaction product of 1 mole of an epoxy compound with 1 to 30 moles of the (B1) [a reaction product of 1 mole of an epoxy compound [the polyepoxide (A) and a monoepoxide (butyl glycidyl ether, phenyl glycidyl ether, etc.)] with 1 to 30 moles of the aliphatic polyamine (B1) (molecular weight of 100 or more and Mn of 1,000 or less), etc.];

[0045] (B8) Cyanoethylated polyamines Molecular weight of 100 or more and Mn of 500 or less, for example, acrylonitrile and the above (B1) Reactants of (biscyanoethyldiethylenetriamine, etc.);

[0046] (B9) Other polyamines (B91) Hydrazine compounds (those with molecular weight of 32 or more and Mn of 500 or less, such as hydrazine and monoalkylhydrazine) (B92) Dihydrazide compounds [those with molecular weight of 74 or more and Mn of 1,000 or less, such as dihydrazides of acids (succinic acid, adipic acid, isophthalic acid, terephthalic acid, etc.)] (B93) Guanidine compounds (those with a molecular weight of 59 or more and Mn of 500 or less, such as butylguanidine and 1-cyanoguanidine).

[0047] Of these (B), (B1) is preferred, and pentaethylenehexamine and diethylenetriamine are more preferred.

[0048] The polymer (X) has a storage modulus (E') of 1.0 x 10 at 25°C and a vibration frequency of 10 Hz in dynamic viscoelasticity measurement. 6 ~1.0×10 10Pa. Preferably 1.0×10 8 ~5.0×10 9 Pa, more preferably 5.0×10 8 ~3.0×10 9 It is Pa. When the storage modulus is within this range, the flexibility of the thermoelectric material composition is in an appropriate range, and the thermoelectric material composition has improved conformability when placed on an exhaust heat generating part having a curved or uneven surface shape.

[0049] The weight ratio (A / B) of the polyepoxide (A) and the polyamine (B) constituting the polymer (X) is preferably 0.9 / 0.1 to 0.75 / 0.25. By blending polyepoxide (A) and polyamine (B) in a specific blend ratio and crosslinking them, it becomes easy to obtain a polymer (X) having a storage modulus within a certain range.

[0050] The polymer (X) may contain other constituent monomers in addition to the polyepoxide (A) and the polyamine (B). The other constituent monomers include polycarboxylic acids.

[0051] Next, the thermoelectric particles (C) will be explained. [Thermoelectric particles (C)] Thermoelectric particles are particles of a material that converts heat into electrical energy via the Seebeck effect (or creates a temperature difference when a voltage is applied via the Peltier effect).

[0052] Thermoelectric particles may include elemental metals, intermetallic compounds, or semi-metals. The metal element includes bismuth, antimony, lead, tellurium, etc. The intermetallic compound or metalloid is preferably selected from the group consisting of tellurium compounds, silicide compounds, antimony compounds, gallium compounds, aluminum compounds, sulfides, and rare earth compounds.

[0053] Tellurium compounds include PbTe and Bi 2 Te 3 , Bi 0.3 Sb 1.7 Te3 , Bi 2 Te 3 -Ru(99.75:0.25wt%), AgSbTe 2 , GeTe, Sb 2 Te 3 Silicide compounds include SiGe, β-FeSi 2 , B.A. 8 S 46 , Mg 2 Si, MnSi 1.73 , Ce-Al-Si, Ba-Ga-Al-Si clathrate compounds, etc. Antimony compounds include ZnSb, Zn 4 Sb 3 , CeFe 3 CoSb 12 , LaF 3 CoSb 12 Gallium compounds include Ba-Ga-Sn and Ga-In-Sb. Aluminum compounds include NiAl and Fe-V-Al Heusler compounds. Sulfides include TiS 2 , TiS 3 Examples of rare earth compounds include CeRhAs. The thermoelectric particles may be p-type thermoelectric particles or n-type thermoelectric particles.

[0054] The purity of the thermoelectric particles is not particularly limited, and for example, a 3N (99.9%) purity product can be used. In addition, a part of the thermoelectric particles may be gold plated.

[0055] The thermoelectric particles may be particles synthesized by a hot pressing method, crushed and classified by sieving, or may be particles plated with gold by a displacement plating method.

[0056] The average particle size of the thermoelectric particles (C) is preferably 10 to 300 μm. The average particle size of the thermoelectric particles (C) can be measured by a particle size measuring device using a laser diffraction method.

[0057] The volume ratio of the thermoelectric particles (C) is 35 to 65 vol% with respect to the total volume of the polymer (X) and the thermoelectric particles (C). The volume ratio of the thermoelectric particles (C) is preferably 40 to 60 vol%, and more preferably 42 to 55 vol%. When the volume fraction of the thermoelectric particles is 35 vol% or more, the amount of thermoelectric particles is sufficient, so that the thermoelectromotive force is sufficiently high when used as a thermoelectric conversion element. When the volume fraction of the thermoelectric particles is 65 vol% or less, the amount of polymer (X) is sufficient to maintain the bond with the surroundings, so that the electrical resistance value can be reduced when used as a thermoelectric conversion element.

[0058] The thermoelectric material composition of the present invention has an electrical resistivity at 25°C of 0.016 to 0.100 Ω·cm. The electrical resistivity of the thermoelectric material composition can be measured by an AC four-terminal method. The electrical resistance value of a thermoelectric conversion element using a thermoelectric material composition is measured, and the value is multiplied by the surface area of ​​the thermoelectric conversion element and divided by the thickness, to obtain the electrical resistivity of the thermoelectric material composition.

[0059] The thermoelectric material composition may contain other components in addition to the polymer (X) and the thermoelectric particles (C), such as conductive particles.

[0060] The thermoelectric material composition of the present invention is preferably obtained by mixing polyepoxide (A), polyamine (B) and thermoelectric particles (C) and reacting the polyepoxide (A) with polyamine (B) in a state in which the thermoelectric particles (C) are mixed to form a polymer (X). For example, polyepoxide (A) and thermoelectric particles (C) may be mixed to obtain a mixture, and polyamine (B) may be added to the mixture. Alternatively, polyamine (B) and thermoelectric particles (C) may be mixed to obtain a mixture, and polyepoxide (A) may be added to the mixture.

[0061] The thermoelectric material composition of the present invention can be cured to form a thermoelectric conversion element, and then by connecting leads to both ends of the element and applying a potential difference, the element can be used as an element that generates a temperature difference by utilizing the potential difference. In addition, after hardening it into a thermoelectric conversion element, it can be used as an element in which electrodes are provided on both ends, with one electrode in contact with a high-temperature part and the other electrode in contact with a low-temperature part, generating a potential difference (voltage) between the electrodes.

[0062] The present specification discloses the following:

[0063] The present disclosure (1) relates to a thermoelectric material composition containing a polymer (X) having a polyepoxide (A) and a polyamine (B) as constituent monomers, and thermoelectric particles (C), The polymer (X) has a storage modulus (E') of 1.0 x 10 at 25°C and a vibration frequency of 10 Hz in dynamic viscoelasticity measurement. 6 ~1.0×10 10 Pa, the volume ratio of the thermoelectric particles (C) is 35 to 65 vol% with respect to the total volume of the polymer (X) and the thermoelectric particles (C); This thermoelectric material composition has an electrical resistivity of 0.016 to 0.100 Ω·cm at 25°C.

[0064] The present disclosure (2) is the thermoelectric material composition according to the present disclosure (1), wherein the thermoelectric particles (C) have an average particle size of 10 to 300 μm.

[0065] The present disclosure (3) relates to a method for producing the thermoelectric particles (C) of Bi 0.3 Sb 1.7 Te 3 The thermoelectric material composition according to the present disclosure (1) or (2),

[0066] The present disclosure (4) is the thermoelectric material composition according to any one of the present disclosures (1) to (3), wherein a weight ratio (A / B) of the polyepoxide (A) and the polyamine (B) constituting the polymer (X) is 0.9 / 0.1 to 0.75 / 0.25.

[0067] The present disclosure (5) is the thermoelectric material composition according to any one of the present disclosures (1) to (4), wherein the polyepoxide (A) has a number average molecular weight of 120 to 350 and an epoxy equivalent of 100 to 200 g / eq.

[0068] The present disclosure (6) is the thermoelectric material composition according to any one of the present disclosures (1) to (5), wherein the polyamine (B) has a total amine value of 1200 to 2100 mgKOH / g. EXAMPLES

[0069] The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples as long as they do not deviate from the gist of the present invention. In addition, unless otherwise specified, parts means parts by weight and % means % by weight.

[0070] The materials used are as follows: Polyepoxide (A) (A-1) Neopentyl glycol diglycidyl ether (Denacol EX-211, Nagase ChemteX Corporation) Epoxy equivalent: 138 / eq, SP value: 9.60, viscosity: 20 mPa·s (25°C), number average molecular weight: 216 (A-2) Glycerol polyglycidyl ether (Denacol EX-314, Nagase ChemteX Corporation) Epoxy equivalent: 141 / eq, SP value: 10.89, viscosity: 170 mPa·s (25°C), number average molecular weight: 204 (A-3) Glycidyl ether of bisphenol A (JER825, manufactured by Mitsubishi Chemical Corporation) Epoxy equivalent 175 / eq, SP value 10.84, viscosity 12,000mPa·s, number average molecular weight 340 (A-4) Glycidyl ether of bisphenol F (JER806, manufactured by Mitsubishi Chemical Corporation) Epoxy equivalent 170 / eq, SP value 10.86, viscosity 3800mPa·s, number average molecular weight 312

[0071] Polyamine (B) (B-1) Pentaethylenehexamine Amine value 1450mgKOH / g, SP value 10.90, viscosity 382mPa·s, number average molecular weight 232 (B-2) Gascamine 240 (reaction product of metaxylylenediamine and styrene, manufactured by Mitsubishi Gas Chemical Co., Ltd.) Amine value 403mgKOH / g, SP value 10.86, viscosity 66mPa·s, number average molecular weight 198 (B-3) Diethylenetriamine Amine value 1633mgKOH / g, SP value 10.89, viscosity 103, number average molecular weight 103

[0072] Thermoelectric particles (C) (C-1) p-type thermoelectric particle Bi 0.3 Sb 1.7 Te 3 Average particle size 250μm (C-2) p-type thermoelectric particle Bi 0.3 Sb 1.7 Te 3 Average particle size 120μm (C-3) p-type thermoelectric particle Bi 0.3 Sb 1.7 Te 3 Average particle size 10μm (C-4) p-type thermoelectric particle Bi 0.3 Sb 1.7 Te 3 Average particle size 5μm Both are non-gold plated thermoelectric particles (manufactured by Toshima Manufacturing Co., Ltd., purity 3N (99.9%)).

[0073] Example 1 Into a screw tube (volume 9 mL), 10.6 parts of neopentyl glycol diglycidyl ether (A-1) and 86.8 parts of thermoelectric particles (C-1) were placed and stirred for 10 minutes at 2000 rpm with a stirrer (Thinky Corporation, Awatori Rentaro ARE-310). 2.6 parts of pentaethylenehexamine (B-1) was added to the stirred mixture, and the mixture was stirred again at 2000 rpm for 5 minutes to prepare a thermoelectric material composition (S-1).

[0074] (Examples 2 to 9, Comparative Examples 1 to 5) In the same manner as in Example 1, thermoelectric material compositions (S-2) to (S-9) and (T-1) to (T-5) were prepared according to the formulations shown in Table 1.

[0075] [Measurement of storage modulus of polymer (X)] A resin composition was prepared from only the polymer (X) portion of the thermoelectric material composition of each Example and Comparative Example, excluding the thermoelectric particles (C), and this resin composition was cured and molded to a length of 35 mm, width of 5 mm, and thickness of 1 mm to prepare a test piece of the polymer (X). A 10 Hz sine wave was applied to this test piece using a dynamic viscoelasticity measuring device, and the storage modulus E' was measured from -20°C to 150°C.

[0076] Table 1 shows the volume fraction (vol %) of the thermoelectric particles (C) and the storage modulus of the polymer (X).

[0077] [Table 1]

[0078] (Examples 10 to 18, Comparative Examples 6 to 10) The thermoelectric material compositions prepared in each of the Examples and Comparative Examples were used as Peltier elements to measure the electrical resistance, Seebeck coefficient, thermoelectromotive force, electrical resistivity, and power generation amount. The results are shown in Table 2.

[0079] [Measurement of electrical resistance and electrical resistivity] The thermoelectric material composition of each Example and Comparative Example was filled into a cylindrical hole with a diameter of 3 mm and a height of 1 mm, sealed with a substrate, and thermally cured to form a Peltier element. Copper wires (diameter 0.8 mm, length 1 cm) were soldered to both ends of the substrate part of the fabricated Peltier element, and the resistance value between the filled elements was measured with a Battery HiTester (BT3562A, manufactured by Hioki E.E. Corporation) to obtain the electrical resistance value (Ω). The obtained electrical resistance value was multiplied by the surface area of ​​the test piece and divided by the height of the test piece to obtain the electrical resistivity (Ω·cm). The electrical resistance value was measured at 25°C. The obtained electrical resistivity is the same as the electrical resistivity of the thermoelectric material composition used in each of the Examples and Comparative Examples.

[0080] [Seebeck coefficient measurement] Temperature sensors were attached to the top and bottom of the Peltier element prepared in the above [Measurement of electrical resistance value], and the bottom was heated to 25°C, 40°C, and 60°C with an air-cooled hot / cold plate (CHP-77HI, manufactured by Sensor Controls, Inc.). The temperature difference and the voltage generated in the Peltier element were measured, and the Seebeck coefficient was determined as the slope of the approximation line when the temperature difference (K) during measurement was plotted on the horizontal axis and the electromotive voltage (mV) on the vertical axis. (Seebeck coefficient (mV / K) = electromotive force (mV) / temperature difference (K))

[0081] [Measurement of thermoelectric power] Temperature sensors were attached to the upper and lower surfaces of the Peltier element prepared in the above [Measurement of electrical resistance value], and the lower surface was heated to 25°C, 40°C, and 60°C using an air-cooled hot / cold plate (CHP-77HI, manufactured by Sensor Controls, Inc.). The electromotive voltage generated during this process was measured with a Battery HiTester (BT3562A, manufactured by Hioki E.E. Corporation) in the same manner as the electrical resistance value, and was taken as the thermoelectromotive force (mV).

[0082] [Measurement of power generation amount] The amount of power generation was calculated from the electrical resistance value and thermoelectromotive force obtained from a battery high tester during the thermoelectromotive force measurement using the following formula. Power generation (μW) = (electromotive force (mV)) 2 ÷Electrical resistance value (Ω)

[0083] [Table 2]

[0084] As shown in Table 2, the electrical resistance of the Peltier element using the thermoelectric material composition of each Example was lower than that of the Peltier element using the thermoelectric material composition of each Comparative Example, and the amount of power generation was higher than that of the Comparative Examples.

Claims

1. A thermoelectric material composition comprising a polymer (X) having polyepoxide (A) and polyamine (B) as constituent monomers, and thermoelectric particles (C), The polymer (X) has a storage modulus (E′) of 1.0×10 at 25° C. and a vibration frequency of 10 Hz in dynamic viscoelasticity measurement. ６ ~1.0 x 10 １０ Pa, the volume ratio of the thermoelectric particles (C) is 35 to 65 vol % with respect to the total volume of the polymer (X) and the thermoelectric particles (C); A thermoelectric material composition having an electrical resistivity of 0.016 to 0.100 Ω·cm at 25° C.

2. 2. The thermoelectric material composition according to claim 1, wherein the average particle size of the thermoelectric particles (C) is 10 to 300 μm.

3. The thermoelectric particles (C) are Bi ０．３ Sb １．７ Te ３ The thermoelectric material composition according to claim 1 or 2,

4. 3. The thermoelectric material composition according to claim 1, wherein a weight ratio (A / B) of the polyepoxide (A) and the polyamine (B) constituting the polymer (X) is 0.9 / 0.1 to 0.75 / 0.

25.

5. 3. The thermoelectric material composition according to claim 1, wherein the polyepoxide (A) has a number average molecular weight of 120 to 350 and an epoxy equivalent of 100 to 200 g / eq.

6. 3. The thermoelectric material composition according to claim 1, wherein the polyamine (B) has a total amine value of 1200 to 2100 mg KOH / g.

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