JP2017216352A - Thermoelectric conversion device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoelectric conversion device being capable of uniformly diffusing heat on a surface and performing heat insulation between a heat generation end and a heat absorption end of a thermoelectric conversion element couple without generating uneven deformation caused by pressing, and having high durability by being bonded with sheet interposing a thermoelectric conversion chip therebetween with a high strength.SOLUTION: A thermoelectric conversion device 1 comprises: a thermoelectric module layer 20 in which a thermoelectric conversion chip 21 is enclosed by a heat insulation rubber 22 containing a rubber component 22a and hollow fillers 22b forming multiple cavities being independent of each other; an insulation base layer 10 and an insulation intermediate layer 30 that are heat conductive sheets holding the thermoelectric module layer 20 therebetween; a heat diffusion layer 40 overlapping the insulation intermediate layer 30 and having higher heat conduction than the insulation base layer 10 and the insulation intermediate layer 30; and a heat radiation layer 50 overlapping the heat diffusion layer 40 and having heat conductivity. At least a part of the adjacent layers 10, 20, 30, 40 and 50 is bonded via a chemical bond.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a thermoelectric conversion device that includes a thermoelectric module layer having a thermoelectric conversion chip and a heat insulating rubber surrounding the thermoelectric conversion chip and exhibits a Peltier effect and a Seebeck effect.

  A thermoelectric conversion element pair consisting of an n-type semiconductor element and a p-type semiconductor element is applied with a voltage between the two semiconductor elements, thereby generating heat at one end thereof and absorbing heat at the other end, or a thermoelectric conversion element. It is known that the Seebeck effect of generating a voltage is generated due to a temperature difference between one end and the other end of a pair. In particular, a thermoelectric conversion chip configured by sandwiching a plurality of thermoelectric conversion element pairs between substrates utilizes the Peltier effect, for example, heating of equipment and instruments such as a cold storage cabinet and a CPU (Central Processing Unit) cooler. Used as a source or cooling source.

  As an example of such a thermoelectric conversion chip, Patent Document 1 discloses an arrangement in which a large number of thermoelectric conversion element pairs are electrically connected in series on a flexible insulating film such as a polymer film or a rubber sheet as a substrate. And the thermoelectric conversion module which formed the output terminal in the heat generating end which is one end of it, and the heat absorption end which is the other end is disclosed. Since this thermoelectric conversion module can be bent or twisted, it can be mounted on a curved surface as well as a plane of equipment and instruments.

  As an example of using a thermoelectric conversion chip such as the thermoelectric conversion module of Patent Document 1 for a curved surface of a device or the like, in Patent Document 2, a thermoelectric conversion chip is divided and mounted along a ring portion of a steering wheel for an automobile. An example is disclosed. In this steering wheel, the ring part is heated or cooled by a thermoelectric conversion chip, so that the user can grasp and operate the ring part without feeling cold or hot when it is cold or extremely hot. As described above, the flexible thermoelectric conversion chip can be used for a device or the like that is directly touched by a user.

  The thermoelectric conversion chip is incorporated in a thermoelectric conversion device and mounted on a device or instrument. As shown in FIG. 7, the conventional thermoelectric conversion device 60 has a thermoelectric conversion chip 61 disposed between a rubber substrate side sheet 64 and a surface side sheet 65. By fixing the board-side sheet 64 to the equipment substrate 67, the conventional thermoelectric conversion device 60 is attached to the equipment or the like.

  A gap sandwiched between the surface side sheet 65 and the device substrate 67 is a cavity 66. When the heat generated at the heat generation end 62 is conducted to the heat absorption end 63, the thermoelectric conversion element pair 61a not only causes a significant decrease in heat generation / heat absorption efficiency, but also prevents the movement of carriers between the semiconductor elements. Eventually it will be damaged. Therefore, the conventional thermoelectric conversion device 60 insulates the heat generation end 62 and the heat absorption end 63 of the thermoelectric conversion element pair 61 a with the air in the cavity 66. When the surface side sheet 65 on the cavity 66 is pressed as indicated by the white arrow shown in FIG. 7, the surface side sheet 65 is supported by the thermoelectric conversion chip 61 and bends toward the cavity 66. The upper surface of the converter 60 is deformed into an uneven shape.

  When the conventional thermoelectric conversion device 60 is attached to an instrument that is directly touched by the user, such as a ring portion of a steering wheel, this uneven deformation gives the user an unpleasant feeling due to poor touch. Further, each time the surface side sheet 65 is pressed due to the unevenness, stress concentrates on the edge of the thermoelectric conversion chip 61, and the surface side sheet 65 is torn and damaged, or the edge of the thermoelectric conversion chip 61 is crushed and the thermoelectric conversion function. May be damaged. Furthermore, since the rubber-made surface side sheet 65 has poor heat conduction, the heat generated by the thermoelectric conversion chip 61 remains only in the surface side sheet 65 just above the thermoelectric conversion chip 61. For this reason, heat is not uniformly diffused over the entire surface of the front side sheet 65, resulting in an uneven temperature distribution.

JP 2000-286463 A JP 2004-291889 A

  The present invention has been made in order to solve the above-described problems, and can thermally insulate the heat generation end and the heat absorption end of the thermoelectric conversion element pair without causing uneven heat distortion on the surface and without causing uneven deformation due to pressing. An object of the present invention is to provide a thermoelectric conversion device having high durability by being bonded to a sheet sandwiching a conversion chip with high strength.

  The thermoelectric conversion device made to achieve the above object is a thermoelectric module layer in which a heat insulating rubber containing a rubber component and a hollow filler forming a plurality of mutually independent voids surrounds a thermoelectric conversion chip, and An insulating base layer and an insulating intermediate layer, which are heat-conductive insulating sheets, sandwiching the thermoelectric module layer, and overlapping the insulating intermediate layer, and a heat diffusion layer having higher thermal conductivity than the insulating base layer and the insulating intermediate layer, The heat diffusion layer overlaps the heat diffusion layer and has a heat conductivity, and at least a pair of these adjacent layers are bonded via a chemical bond.

  In the thermoelectric conversion device, it is preferable that the hollow filler has a resin shell, and a thermally expandable liquid hydrocarbon is enclosed in the inner space of the shell.

  In the thermoelectric conversion device, the heat insulating rubber and the thermoelectric conversion chip may have the same thickness.

  In the thermoelectric conversion device, the thermal diffusion layer is preferably formed of at least one selected from aluminum, copper, graphite, heat transfer rubber, heat transfer elastomer, and the heat transfer insulating sheet.

  In the thermoelectric conversion device, the thickness of the thermal diffusion layer is preferably 0.01 to 0.5 mm.

  In the thermoelectric conversion device, the thermoelectric conversion chip is bonded to a thermoelectric conversion element pair composed of an n-type semiconductor element and a p-type semiconductor element, an electrode sandwiching the plurality of thermoelectric conversion element pairs, and the electrode overlapping the electrode. It may have an insulating sheet.

  In the thermoelectric converter, the rubber component and the silicone rubber are preferably used, and a silane coupling film is attached to the outer surface of the hollow filler.

  The thermoelectric conversion device may have a circuit layer that is electrically connected to the thermoelectric conversion chip between the thermoelectric module layer and the insulating intermediate layer.

  In the thermoelectric conversion device of the present invention, since the heat insulating rubber having a high heat insulating property by surrounding the hollow filler surrounds the thermoelectric conversion chip, the heat loss generated in the thermoelectric conversion chip is not generated and the high thermoelectric conversion device is used. Has conversion efficiency. In addition, since this thermoelectric conversion device does not have a cavity for heat insulation, even if the thermoelectric conversion device is pressed, the uneven deformation due to the thickness of the thermoelectric conversion chip is caused by the outermost layer of the thermoelectric conversion device. Does not occur on the surface of a heat dissipation layer.

  Since the thermoelectric conversion device has a simple configuration in which a plurality of layers are stacked and joined together, it can be quickly manufactured at a low cost and with a high yield.

  In the thermoelectric conversion device, the heat generated in the thermoelectric conversion chip is diffused in the surface direction by the heat diffusion layer having high thermal conductivity, so that the temperature distribution on the surface of the heat dissipation layer can be made uniform.

  The thermoelectric conversion device has high durability and can be mounted on the curved surface of equipment and instruments without being peeled off between layers by bending or twisting when the bonded surfaces of the laminated layers are firmly bonded by chemical bonding. Yes.

  In the thermoelectric conversion device, when the hollow filler has a resin shell and a thermally expandable liquid hydrocarbon sealed in the inner space thereof, the hollow filler expanded uniformly by heating has a uniform diameter in the heat insulating rubber. Since the gap is formed, uneven distribution of the rubber component in the heat insulating rubber does not occur, and both high heat insulation due to the gap and high strength due to scattering of the rubber component can be achieved.

  In the thermoelectric conversion device, when the rubber component is silicone rubber, and the silane coupling agent is attached to the outer surface of the hollow filler, the higher strength heat-insulating rubber in which the two are firmly bonded exhibits higher durability. .

  When the thermoelectric conversion device has a circuit layer between the thermoelectric module layer and the insulating intermediate layer, the thermoelectric conversion chip in the thermoelectric module layer is connected to a desired device by connecting a control device to the wiring of the circuit layer. It is possible to control the timing and temperature.

It is a model partially notched perspective view which shows the thermoelectric conversion apparatus to which this invention is applied. It is a schematic cross section which shows the thermoelectric conversion apparatus to which this invention is applied. It is a top view which shows the position of the temperature measurement point in the temperature distribution test using the thermoelectric conversion apparatus to which this invention is applied, and a temperature change test. It is a graph which shows the result of the endothermic control temperature distribution test of the thermoelectric conversion apparatus of the Example to which this invention is applied, and the thermoelectric conversion apparatus of the comparative example which does not apply this invention. It is a graph which shows the result of the thermoelectric conversion apparatus of the Example to which this invention is applied, and the thermoelectric conversion apparatus heat generation control temperature distribution test of the comparative example which does not apply this invention. It is a graph which shows the result of the endothermic control temperature change test of the thermoelectric conversion apparatus of the Example to which this invention is applied, and the thermoelectric conversion apparatus of the comparative example which does not apply this invention, and the exothermic control temperature change test. It is a schematic cross section which shows the conventional thermoelectric conversion apparatus which does not apply this invention.

  Hereinafter, although the form for implementing this invention is demonstrated in detail, the scope of the present invention is not limited to these forms.

  A schematic partially cutaway perspective view of one embodiment of the thermoelectric conversion device 1 of the present invention is shown in FIG. In the thermoelectric conversion device 1, an insulating base layer 10, a thermoelectric module layer 20, an insulating intermediate layer 30, a heat diffusion layer 40, and a heat dissipation layer 50 are stacked in this order. A thermoelectric conversion chip 21 is disposed at the center of the thermoelectric module layer 20.

  A pair of these adjacent layers, that is, the insulating base layer 10 and the thermoelectric module layer 20, the thermoelectric module layer 20 and the insulating intermediate layer 30, the insulating intermediate layer 30 and the heat diffusion layer 40, and the heat diffusion layer 40 and the heat dissipation layer 50 are , Respectively, through chemical bonds. This bonding is extremely strong because the layers are bonded by a covalent bond, which is a chemical bond, unlike those bonded by intermolecular force or physical anchor effect such as adhesives and adhesives. It does not peel off between the layers by pressing, bending or twisting applied to the thermoelectric conversion device 1. Moreover, since the heat generated by the thermoelectric conversion chip 21 moves between layers without using an adhesive or a pressure-sensitive adhesive, no heat loss occurs during the movement of the layers. Therefore, this thermoelectric conversion device 1 has high thermoelectric conversion efficiency.

  The thermoelectric module layer 20 includes a thermoelectric conversion chip 21 and a heat insulating rubber 22 surrounding the side surface of the thermoelectric conversion chip 21. The thermoelectric conversion chip 21 and the heat insulating rubber 22 have the same thickness.

  In FIG. 2, the schematic cross section of the thermoelectric conversion apparatus 1 is shown. The heat insulating rubber 22 includes a rubber component 22a and a hollow filler 22b uniformly dispersed in the rubber component 22a.

  The rubber component 22a is preferably silicone rubber. Silicone rubber has high flexibility and bending fatigue resistance in a wide temperature range such as −40 ° C. to 200 ° C. Therefore, the thermoelectric conversion device 1 can be bent and attached along the curved surface of the device or the like, and expansion due to heat shock can be prevented. The number average molecular weight of the silicone rubber is preferably 10,000 to 1,000,000. The hollow filler 22b has a spherical shape, and has a shell made of a thermoplastic resin that is flexible and has a gas barrier property, such as vinylidene chloride resin and acrylic resin. A small amount of thermally expandable liquid hydrocarbon is sealed in the inner space of the shell.

  Most of the volume of the inner space of the shell constituting the hollow filler 22b is occupied by air. Thereby, since the air gap is formed in the heat insulating rubber 22, the heat insulating rubber 22 has a high heat insulating property comparable to air. Thereby, the heat generated at the heat generating end 23 of the thermoelectric conversion chip 21 is not diffused to the heat insulating rubber 22 but is transmitted through the insulating intermediate layer 30 and the heat diffusion layer 40 and efficiently conducted to the heat radiation layer 50 which is the outermost layer. Therefore, this thermoelectric conversion device 1 can perform thermoelectric conversion with high efficiency.

  As such a hollow filler 22b, a thermally expandable microcapsule is preferable. Specifically, for example, Matsumoto Microsphere (registered trademark) F, FN, FE, F-DE, and MFL (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.) Kureha Microsphere (trade name, manufactured by Kureha Co., Ltd.); Expandel (manufactured by Nihon Ferrite Co., Ltd., registered trademark); ADVANCEL (registered trademark) EM, HB, and NS (manufactured by Sekisui Chemical Co., Ltd., Product name).

  Moreover, since the thermoelectric conversion chip 21 and the heat insulating rubber 22 have the same thickness, the power-extinguishing module layer 20 forms a rectangular parallelepiped with no unevenness on all surfaces. Further, the thermoelectric module layer 20 does not have a cavity around the thermoelectric conversion chip 21. Thereby, even if the heat dissipation layer 50 is pressed, the upper surface of the thermoelectric conversion device 1 is not deformed into an uneven shape unlike the conventional thermoelectric conversion device. Therefore, the pressing force does not concentrate on the edge of the thermoelectric conversion chip 21 and is dispersed, so that the heat dissipation layer 50 arranged on the surface layer is not peeled off and the edge of the thermoelectric conversion chip is not crushed. In addition to this, even if it is attached to the ring part of the steering wheel of an automobile, the user's tactile sensation is not impaired.

  Moreover, since the hollow filler 22b has a shell, the hollow fillers 22b are independent from each other without being combined. That is, the gaps in the heat insulating rubber 22 are not connected and are uniformly dispersed in the rubber component 22 a, so that the distance between the gaps is substantially uniform in the heat insulating rubber 22. As a result, the rubber component 22a can also be present uniformly in the heat insulating rubber 22. Therefore, when the thermoelectric conversion device 1 is bent or pressed, stress dispersion occurs in the rubber component 22a and absorbs the impact. And since the space | gap of the heat insulation rubber 22 is formed of the hollow filler 22b which has a flexible shell, unlike the porous rubber which has many space | gap only, not only the elasticity derived from the rubber component 22a but the hollow filler 22b It also has the flexibility derived from the shell. As a result, coupled with the joining of the rubber component 22a and the hollow filler 22b, the heat insulating rubber 22 does not crack or tear even under external heat such as pressing, bending, or twisting under repeated heat generation / cooling conditions. . Further, since the voids in the heat insulating rubber 22 are formed by the hollow filler 22b, the entry of water from the outside due to the presence of the voids is prevented. As described above, the heat insulating rubber 22 has high strength and waterproofness, and supports the thermoelectric conversion chip 21 by surrounding it, thereby preventing breakage and water immersion. Strength and bending fatigue resistance are imparted.

  A silane coupling film containing a silane coupling agent may be attached to the outer surface of the hollow filler 22b. Accordingly, the rubber component 22a made of silicone rubber and the hollow filler 22b can be firmly bonded by molecular adhesion via the silane coupling agent. Moreover, the hollow filler 22b may contain multiple types from which an average particle diameter, a material, and an expansion coefficient differ.

  The molecular adhesion in which the rubber component 22a and the hollow filler 22b are firmly bonded is shared with the silicone rubber of the rubber component 22a in which the functional group in the molecule of the molecular adhesive such as a silane coupling agent is an adherend. By the chemical reaction by bonding, the rubber component 22a and the hollow filler 22b are bonded through a covalent bond with a single molecule or a multimolecular molecular adhesive molecule. The molecular adhesive has two functional groups and forms a covalent bond by chemically reacting with the rubber component 22a and the hollow filler 22b, and is a generic name for such bifunctional molecules. .

（化学式(１)中、Ｗは、スペーサ基、例えば置換基を有していてもよいアルキレン基、アミノアルキレン基であってもよく、直接結合であってもよい。Ｙは、ＯＨ基又は加水分解や脱離によりＯＨ基を生成する反応性官能基、例えばトリアルコキシアルキル基である。−Ｚは、−Ｎ_３又は−ＮＲ^１Ｒ^２である（但し、Ｒ^１，Ｒ^２は同一又は異なりＨ又はアルキル基、−Ｒ^３Ｓｉ（Ｒ^４）_ｍ（ＯＲ^５）_３−ｍ[Ｒ^３，Ｒ^４はアルキル基、Ｒ^５はＨ又はアルキル基、ｍは０〜２]。なお、アルキレン基、アルコキシ、アルキル基は、置換基を有していてもよい炭素数１〜１２の直鎖状、分岐鎖状及び／又は環状の炭化水素基である）で表わされるトリアジン化合物；
トリアルコキシシリルアルキル基を有するチオール化合物；
トリアルキルオキシシリルアルキル基を有するエポキシ化合物；
CH₂=CH-Si(OCH₃)₂-O-[Si(OCH₃)₂-O-]_n-Si(OCH₃)₂-CH=CH₂ (n=1.8〜5.7)で例示されるビニルアルコキシシロキサンポリマーのようなシランカップリング剤
が挙げられる。 Specifically, as molecular adhesives,
Amino group-containing compounds such as triethoxysilylpropylamino-1,3,5-triazine-2,4-dithiol (TES), aminoethylaminopropyl trimethoxysilane;
A triazine compound having a trialkoxysilylalkylamino group such as a triethoxysilylpropylamino group and a mercapto group or an azide group, the following chemical formula (1)

(In the chemical formula (1), W may be a spacer group, for example, an alkylene group which may have a substituent, an aminoalkylene group, or a direct bond. A reactive functional group that generates an OH group by decomposition or elimination, such as a trialkoxyalkyl group, -Z is -N ₃ or -NR ¹ R ² (provided that R ¹ and R ² are the same or different. H or an alkyl _{^{group, -R 3 Si (R 4)}} m (oR 5) 3-m [R 3, R 4 is an alkyl group, ^{R 5} is H or an alkyl group, m is 0-2. in addition, an alkylene group , An alkoxy group and an alkyl group are each a linear, branched and / or cyclic hydrocarbon group having 1 to 12 carbon atoms which may have a substituent;
A thiol compound having a trialkoxysilylalkyl group;
An epoxy compound having a trialkyloxysilylalkyl group;
Vinyl represented by CH ₂ = CH-Si (OCH ₃ ) ₂ -O- [Si (OCH ₃ ) ₂ -O-] _n -Si (OCH ₃ ) ₂ -CH = CH ₂ (n = 1.8 to 5.7) Examples include silane coupling agents such as alkoxysiloxane polymers.

  Examples of the silane coupling agent include a silane coupling agent such as a vinylalkoxysiloxane polymer; an amino group-containing silane coupling agent having an alkoxy group. Specific examples of such a silane coupling agent include vinyltriethoxysilane (KBE-1003), N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (KBM-602), N-2- ( Aminoethyl) -3-aminopropyltrimethoxysilane (KBM-603), N-2- (aminoethyl) -3-aminopropyltriethoxysilane (KBE-603), 3-aminopropyltrimethoxysilane (KBM-903) ), 3-aminopropyltriethoxysilane (KBE-903), 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine (KBE-9103), N-phenyl-3-aminopropyltrimethoxy Amino group-containing alkoxysilyl compounds exemplified by silane (KBM-573) and N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride (KBM-575) Company name; product name) and 3-aminopropyltrimeth Xylsilane (Z-6610), 3-aminopropyltrimethoxysilane (Z-6611), 3- (2-aminoethyl) aminopropyltrimethoxysilane (Z-6094), 3-phenylaminopropyltrimethoxysilane (Z- 6883), N- [3- (trimethoxysilyl) propyl] -N '-[(ethenylphenyl) methyl-1,2-ethanediamine hydrochloride (Z-6032) A compound (above, manufactured by Toray Dow Corning Co., Ltd .; product name) can be suitably used.

  The silicone rubber of the rubber component 22a is preferably a three-dimensional silicone rubber, and specific examples include addition-crosslinking silicone rubber, peroxide-crosslinking silicone rubber, and condensation-crosslinking silicone rubber. Further, non-silicone rubber may be used, or a co-blend of silicone rubber and non-silicone rubber may be used. The three-dimensional silicone rubber is obtained by crosslinking these rubber raw material compositions into a molding die.

As the addition-crosslinking silicone rubber of the rubber component 22a, vinylmethylsiloxane / polydimethylsiloxane copolymer synthesized in the presence of a Pt catalyst (molecular weight: 500,000 to 900,000), vinyl-terminated polydimethylsiloxane (molecular weight: 10,000 to 200,000) , Vinyl-terminated diphenylsiloxane / polydimethylsiloxane copolymer (molecular weight: 10,000 to 100,000), vinyl-terminated diethylsiloxane / polydimethylsiloxane copolymer (molecular weight: 10,000 to 50,000), vinyl-terminated trifluoropropylmethylsiloxane / polydimethylsiloxane Copolymer (molecular weight: 10,000 to 100,000), vinyl-terminated polyphenylmethylsiloxane (molecular weight: 10,000 to 10,000), vinylmethylsiloxane / dimethylsiloxane copolymer, trimethylsiloxane-terminated dimethylsiloxane / vinyl Vinyl group-containing polysiloxanes such as tilsiloxane / diphenylsiloxane copolymer, trimethylsiloxane group-terminated dimethylsiloxane / vinylmethylsiloxane / ditrifluoropropylmethylsiloxane copolymer, trimethylsiloxane group-terminated polyvinylmethylsiloxane, and H-terminated polysiloxanes (molecular weight: 0.1%). 050,000 to 100,000), methyl H siloxane / dimethyl siloxane copolymer, polymethyl H siloxane, polyethyl H siloxane, H-terminated polyphenyl (dimethyl H siloxy) siloxane, methyl H siloxane / phenyl methyl siloxane copolymer, methyl H siloxane / octyl methyl siloxane Compositions of H-group-containing polysiloxanes such as copolymers,
Contains amino groups such as aminopropyl-terminated polydimethylsiloxane, aminopropylmethylsiloxane / dimethylsiloxane copolymer, aminoethylaminoisobutylmethylsiloxane / dimethylsiloxane copolymer, aminoethylaminopropylmethoxysiloxane / dimethylsiloxane copolymer, dimethylamino-terminated polydimethylsiloxane Polysiloxanes, epoxypropyl terminated polydimethylsiloxanes, epoxy group containing polysiloxanes such as (epoxycyclohexylethyl) methylsiloxane / dimethylsiloxane copolymers, acid anhydride group containing polysiloxanes such as succinic anhydride terminated polydimethylsiloxanes and Isocyanate group-containing compounds such as toluyl diisocyanate and 1,6-hexamethylene diisocyanate Those obtained from the composition of the like.

  The peroxide-crosslinked silicone rubber of the rubber component 22a is not particularly limited as long as it is synthesized using a silicone raw material compound that can be crosslinked with a peroxide-based crosslinking agent. Specifically, polydimethylsiloxane (molecular weight: 500,000 to 900,000), vinylmethylsiloxane / polydimethylsiloxane copolymer (molecular weight: 500,000 to 900,000), vinyl-terminated polydimethylsiloxane (molecular weight: 10,000 to 200,000), Vinyl-terminated diphenylsiloxane / polydimethylsiloxane copolymer (molecular weight: 10,000 to 100,000), vinyl-terminated diethylsiloxane / polydimethylsiloxane copolymer (molecular weight: 10,000 to 50,000), vinyl-terminated trifluoropropylmethylsiloxane / polydimethylsiloxane copolymer (Molecular weight: 10,000 to 100,000), vinyl-terminated polyphenylmethylsiloxane (molecular weight: 10,000 to 10,000), vinylmethylsiloxane / dimethylsiloxane copolymer, trimethylsiloxane-terminated dimethylsiloxane / vinylmethylsiloxane Copolymer, trimethylsiloxane-terminated dimethylsiloxane / vinylmethylsiloxane / diphenylsiloxane copolymer, trimethylsiloxane-terminated dimethylsiloxane / vinylmethylsiloxane / ditrifluoropropylmethylsiloxane copolymer, trimethylsiloxane-terminated polyvinylmethylsiloxane, methacryloxypropyl-terminated Examples include polydimethylsiloxane, acryloxypropyl group-terminated polydimethylsiloxane, (methacryloxypropyl) methylsiloxane / dimethylsiloxane copolymer, and (acryloxypropyl) methylsiloxane / dimethylsiloxane copolymer.

  Examples of peroxide-based crosslinking agents used for crosslinking include ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, and carbonates. Specifically, ketone peroxide, peroxy ketal, hydroperoxide, dialkyl peroxide, peroxy carbonate, peroxy ester, benzoyl peroxide, dicumyl peroxide, dibenzoyl peroxide, t-butyl hydroperoxide, di-t -Butyl hydroperoxide, di (dicyclobenzoyl) peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, 2,5-dimethyl-2,5bis (t-butylperoxide) Shi) hexyne, benzophenone, Mihiraaketon, dimethylaminobenzoic acid ethyl ester, benzoin ethyl ether.

  The amount of the peroxide-based crosslinking agent is appropriately selected according to the type of silicone rubber to be obtained and the required function and characteristics of the heat insulating rubber 22, but 0.01 to 10 mass with respect to 100 parts by mass of the silicone rubber. Part, preferably 0.1 to 2 parts by weight. If it is less than this range, the crosslinking degree is too low to be used as silicone rubber. On the other hand, when it exceeds this range, the degree of cross-linking is too high and the elasticity of the silicone rubber is reduced.

  Silanol-terminated polydimethylsiloxane (molecular weight: 50,000 to 200,000), silanol-terminated polydiphenylsiloxane, silanol-terminated, synthesized in the presence of a tin-based catalyst or a zinc-based catalyst as the condensation-crosslinking silicone rubber of the rubber component 22a Compositions of single condensation components comprising silanol-terminated polysiloxanes such as polytrifluoromethylsiloxane, silanol-terminated diphenylsiloxane / dimethylsiloxane copolymer; these silanol-terminated polysiloxanes with tetraacetoxysilane, triacetoxymethylsilane, di t-butoxydiacetoxysilane, vinyltriacetoxysilane, tetraethoxysilane, trienoxymethylsilane, bis (triethoxysilyl) ethane, tetra-n-propoxysilane, vinyltrimethoxysilane , Methyltris (methylethylketoxime) silane, vinyltris (methylethylketoxyimino) silane, vinyltriisopropenooxysilane, triacetoxymethylsilane, tri (ethylmethyl) oximemethylsilane, bis (N-methylbenzamido) ethoxymethylsilane , Compositions with crosslinkers such as tris (cyclohexylamino) methylsilane, triacetamidomethylsilane, tridimethylaminomethylsilane; these silanol-terminated polysiloxanes, chloro-terminated polydimethylsiloxanes, diacetoxymethyl-terminated polydimethylsiloxanes And those obtained from compositions of terminal block polysiloxanes such as terminal polysiloxanes.

  As the non-silicone rubber of the rubber component 22a, butyl rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, urethane rubber, fluorine rubber, acrylic rubber, butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, chloroprene rubber, isoprene rubber, Examples thereof include natural rubber, 1,2-polybutadiene, styrene-based thermoplastic elastomer, olefin-based thermoplastic elastomer, polyester-based thermoplastic elastomer, and urethane-based thermoplastic elastomer. These may be used alone or in combination.

The thermoelectric conversion chip 21, and the thermoelectric conversion element pairs 21a made of n-type semiconductor element 21a ₁ and the p-type semiconductor element 21a ₂ Prefecture, electrically across both the semiconductor elements _21a 1, 21a ₂ in the their upper and lower ends It has the 1st electrode 21b and the 2nd electrode 21c which are connected, and the insulating sheets 21d and 21e which have overlapped and joined to both the electrodes 21b and 21c, respectively. The n-type semiconductor element 21a ₁ and the p-type semiconductor element 21a _2, are connected while spaced apart from each other, the first electrode 21b at their upper end by soldering. On the other hand, the n-type semiconductor element 21a ₁ of the thermoelectric conversion element pairs 21a, a p-type semiconductor element 21a ₂ of another thermoelectric conversion element pairs 21a neighboring, while spaced from each other, second electrodes 21c at their lower end Are connected by soldering. By repeating these connections, a plurality of thermoelectric conversion element pairs 21a are arranged in a pattern in series.

The thermoelectric conversion element pair 21a and both electrodes 21b and 21c are supported by insulating sheets 21d and 21e. Thus, the n-type semiconductor element 21a ₁ and the p-type semiconductor element 21a ₂ are arranged while having a distance from one another, the insulating sheet 21d, by having a so-called skeleton structure of being supported on the 21e The thermoelectric conversion chip 21 has flexibility. When a voltage is applied to the thermoelectric conversion chip 21, heat is generated at the heat generating end 23 which is the upper end side of the thermoelectric conversion element pair 21a, and the heat absorbing end 24 which is the lower end side is cooled. At this time, the heat generated at the heat generating end 23 and transmitted to the insulating intermediate layer 30 is blocked by the heat insulating rubber 22 having high heat insulating properties and does not move toward the heat absorbing end 24, so this heat is transmitted to the heat absorbing end 24. This prevents the heat generation and heat absorption efficiency from being reduced and the thermoelectric conversion element pair 21a from being damaged. Note that the number of thermoelectric conversion element pairs 21a in the thermoelectric conversion chip 21 can be appropriately increased or decreased according to the size, shape, and output of the thermoelectric conversion device 1, and may be one or more.

Bismutellurium-based thermoelectric conversion materials such as Bi-Sb-Te-Se; silicide-based thermoelectric conversion materials such as Mn-Si and Mg-Si as materials for both semiconductor elements 21a ₁ and 21a ₂ of the thermoelectric conversion element pair 21a Si—Ge-based thermoelectric conversion materials such as Si—Ge; NaCo ₂ O 4, (Ca, Sr, Bi) ₂ Co ₂ O ₅ , (ZnO) ₅ (In—Y) ₂ O ₃ , and (Zn—Al) O Oxide-based thermoelectric conversion material such as PbTe; lead tellurium-based thermoelectric conversion material such as PbTe; TAGS-based thermoelectric conversion material such as GeTe-AgSbTe ₂ ; Ce-Fe-Co-Sb and Yb-Co-ptPb-Sb Such skutterudite-based thermoelectric conversion materials.

  The thickness of the thermoelectric module layer 20 is preferably 0.1 to 5.0 mm, and more preferably 1.0 to 2.0 mm. This thickness is appropriately set according to the thickness of the thermoelectric conversion chip 21. The thermoelectric module layer 20 may have a plurality of thermoelectric conversion chips 21.

  The insulating base layer 10 and the insulating intermediate layer 30 sandwiching the thermoelectric module layer 20 in the thickness direction thereof are formed by a heat conductive insulating sheet having thermal conductivity and electrical insulation. Thereby, heat transfer caused by heat generation and heat absorption generated in the thermoelectric conversion chip 21 of the thermoelectric module layer 20 can be generated with high efficiency, and short-circuiting of both electrodes 21b and 21c and leakage from them are prevented.

  The heat conductive insulating sheet forming the insulating base layer 10 and the insulating intermediate layer 30 is formed of a heat conductive insulating composition having a matrix and a heat conductive filler dispersed in the matrix. The heat conductive insulating sheets of the insulating base layer 10 and the insulating intermediate layer 30 may be the same or different. The thermal conductivity of the heat conductive insulating sheet is preferably 1 W / m · K or more, and specifically 1 to 5 W / m · K. If the thermal conductivity of the heat-conducting insulating sheet is less than 1 W / m · K, the insulating base layer 10 and the insulating intermediate layer 30 having sufficient thermal conductivity cannot be obtained, and the heat generation / heat absorption efficiency of the thermoelectric conversion device 1 is improved. to degrade. The thermal conductivity is a value at 30 ° C.

  The thicknesses of the insulating base layer 10 and the insulating intermediate layer 30 are preferably 0.01 to 10 mm, and more preferably 0.05 to 2 mm. The thicknesses of the insulating base layer 10 and the insulating intermediate layer 30 may be the same as or different from each other within this range. If the thickness is less than 0.01 mm, the strength is not sufficient, and the handleability during manufacture of the thermoelectric conversion device 1 is poor. On the other hand, if the thickness exceeds 10 mm, the flexibility of the thermoelectric conversion device 1 is impaired, and the thermal conductivity becomes poor.

Examples of the matrix of the heat conductive insulating composition of the insulating base layer 10 and the insulating intermediate layer 30 include the same silicone rubber and non-silicone rubber as the rubber component 22a. Further, as the heat conductive filler, magnesium oxide (MgO), aluminum oxide (Al ₂ O ₃ ), aluminum nitride (AlN), boron nitride (BN), silicon nitride (Si ₃ N ₄ ), diamond, carbon, fullerene, and Examples include graphite. Only one kind of heat conductive filler may be used, or a plurality of kinds may be used in combination. The content of the heat conductive filler is preferably 50 to 95% by mass and more preferably 65 to 90% by mass in the heat conductive insulating sheet.

  The thermal diffusion layer 40 laminated on the insulating intermediate layer 30 has higher thermal conductivity than the insulating base layer 10 and the insulating intermediate layer 30. Therefore, the heat diffusion layer 40 is generated at the heat generating end 23 of the thermoelectric conversion chip 21, and the heat transferred to the insulating intermediate layer 30 is efficiently and quickly moved in the horizontal direction, and is uniformly diffused throughout the heat dissipation layer 50. Can be made. Thereby, the temperature of the surface of the heat-dissipating layer 50 rises uniformly without unevenness.

  Examples of the material of the thermal diffusion layer 40 include aluminum (270 W / m · K (30 ° C.)), copper (400 W / m · K (30 ° C.)), and graphite (130 W / m · K (30 ° C., plane direction)). ) And high heat transfer rubber / high heat transfer elastomer (5 to 10 W / m · K (30 ° C.)). Further, as a material of the thermal diffusion layer 40, a heat conductive insulating sheet that is a material of the insulating base layer 10 and the insulating intermediate layer 30 may be used. These materials may be used alone or may be used by overlapping or arranging a plurality of types. The thickness of the thermal diffusion layer 40 is preferably 0.01 to 0.5 mm, and more preferably 0.05 to 0.3 mm. When the thermal diffusion layer 40 is formed of a metal material such as aluminum or copper, if the thickness is within this range, each layer 10, depending on the rigidity of the metal material without impairing the flexibility of the thermoelectric conversion device 1. 20, 30, 50 can be supported, and the bending fatigue resistance of the thermoelectric converter 1 can be improved.

  The heat dissipation layer 50 laminated on the heat diffusion layer 40 moves the heat transferred from the heat diffusion layer 40 to the object to be heated. Therefore, it is preferable that the material of the heat dissipation layer 50 has high thermal conductivity, and specific examples include a heat transfer insulating composition that is a material of the insulating base layer 10 and the insulating intermediate layer 30. Since the heat dissipation layer 50 is exposed on the surface of the device or instrument or directly touched by the user of the device, the material is easy to process and does not impair the design of the device or the user's tactile sensation. Preferably there is. Examples of the material for the heat radiation layer 50 include resins such as polyethylene, polypropylene, and polyurethane, woven fabrics, non-woven fabrics, woods, and leathers in addition to the heat conductive insulating composition.

  The thermoelectric conversion device 1 is manufactured as follows.

  First, a rubber raw material composition to be the rubber component 22a of the heat insulating rubber 22 and a hollow filler 22b whose outer surface is covered with a molecular adhesive by previously applying a molecular adhesive or immersing it in this are kneaded. The hollow filler 22b before heating has a sharp particle size distribution in the range of an average particle size of 5 to 50 μm, and its outer shape is almost a sphere. Since the hollow filler 22b has a uniform particle size and outer shape, it diffuses uniformly into the rubber raw material composition by kneading. In the heat insulating rubber 22, the content of the hollow filler 22b is preferably 5 to 60% by mass, more preferably 15 to 50% by mass, and still more preferably 20 to 30% by mass. If the content of the hollow filler 22b is too low, the heat insulating rubber 22 having sufficient heat insulating properties and flexibility cannot be obtained. On the other hand, when the content rate of the hollow filler 22b is too high, the strength of the heat insulating rubber 22 is lowered, and cracks and tears are likely to occur.

  Next, a predetermined amount of the kneaded material is placed in a mold kept at a predetermined temperature and heated for a predetermined time so that the thickness after molding is the same as that of the thermoelectric conversion chip 21. Thereby, the rubber raw material composition is cured by crosslinking. At this time, the shell of the hollow filler 22b formed of a flexible thermoplastic resin is softened by heating. Further, the thermally expandable liquid hydrocarbon sealed in the inner space thereof is changed into a gas to increase the volume, and the internal pressure of the hollow filler 22b exceeds its external pressure. The hollow filler 22b has a volume ratio of 50 to 50%. It expands 100 times, as if it were a balloon. The hollow filler 22b has a uniform expansion rate because the shells are all formed with the same thickness, and the shell is a true sphere, so that the pressure of the vaporized thermally expandable liquid hydrocarbon is low. Hang evenly across the shell. As a result, it is possible to form voids having a uniform shape and diameter, unlike bubbles having irregular shapes and diameters formed by foaming of a foaming agent contained in a rubber component, for example. In addition, although conditions, such as heating temperature and a heating time, change with kinds and characteristics of addition reaction, it is preferable to heat at 0-200 degreeC for 1 minute-24 hours.

  After a predetermined time has passed, the cured product is taken out from the mold and cooled. Thereby, while the thermally expansible liquid hydrocarbon of the hollow filler 22b returns to a liquid, its shell maintains the size at the time of expansion. In this manner, the heat insulating rubber 22 having a uniform diameter and uniformly dispersed voids is molded. A predetermined position of the heat insulating rubber 22 is cut out to a size in which the thermoelectric conversion chip 21 fits using a laser cutter. A thermoelectric module layer 20 is obtained by fitting the thermoelectric conversion chip 21 there.

  A heat conductive filler is added to the rubber raw material composition and kneaded, and the insulating base layer 10, the insulating intermediate layer 30, and the heat dissipation layer 50 are molded in the same manner as the method for manufacturing the heat insulating rubber 22.

  The aluminum sheet is cut out with a cutter so as to have the same outer shape as each of the layers 10, 20, 30, 50, and the thermal diffusion layer 40 is formed.

  One surface of the insulating base layer 10 and both surfaces of the thermoelectric module layer 20 are subjected to surface activation treatment such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment or excimer treatment, and hydroxy groups are made reactive on these surfaces. It is newly generated, amplified and exposed as a functional group. Hydroxy groups, which are reactive functional groups, are scattered on these bonding surfaces together with the hydroxy groups originally exposed on the bonding surfaces of the insulating base layer 10 and the thermoelectric module layer 20. The surfaces of both layers 10 and 20 are fixed and aligned with a jig (not shown) while facing each other, and are brought into contact with each other. They are pressed and crimped at high temperatures. As a result, the hydroxyl groups form a direct ether bond by dehydration, and the surfaces of the two layers 10 and 20 are chemically bonded to bond the two layers 10 and 20 together.

When the two layers 10 and 20 are joined, they may be covalently bonded under normal pressure, but may be covalently bonded under reduced pressure or increased pressure. The proximity of reactive groups such as hydroxy groups in both layers 10 and 20 is reduced or reduced under vacuum, for example, 50 torr or less, more specifically, reduced pressure from 50 to 10 torr, or less than 10 torr, more specifically, By removing the gaseous medium at the contact interface under vacuum conditions of less than 10 torr to 1 × 10 ⁻³ torr, preferably less than 10 torr to 1 × 10 ⁻² torr, or stress (load) on the contact interface, for example It is accelerated by adding 10-200 kgf and further heating the contact interface.

  As corona discharge treatment applied to both layers 10 and 20, for example, using an atmospheric pressure corona surface reformer (manufactured by Shinko Electric Measurement Co., Ltd., product name: Corona Master), for example, power supply: AC100V, output voltage: 0-20kV Oscillation frequency: 0 to 40 kHz, 0.1 to 60 seconds, temperature 0 to 60 ° C. Such a corona discharge treatment may be performed in a state of being wet with water, alcohols, acetones, esters, or the like.

  The surface activation treatment may be atmospheric pressure plasma treatment. In this case, for example, using an atmospheric pressure plasma generator (manufactured by Panasonic Corporation, product name: Aiplasma), for example, plasma processing speed 10 to 100 mm / s, power source: 200 or 220 V AC (30 A), compressed air: 0. It is performed under the conditions of 5 MPa (1 NL / min), 10 kHz / 300 W to 5 GHz, power: 100 W to 400 W, and irradiation time: 0.1 to 60 seconds.

The surface activation treatment may be an ultraviolet irradiation treatment (a general UV treatment or excimer UV treatment that generates ozone by UV irradiation). The ultraviolet irradiation process is performed using an excimer lamp light source (manufactured by Hamamatsu Photonics Co., Ltd., product name: L11751-01), for example, with an integrated light amount of 50 to 1500 mJ / cm ² .

  The surface activation treatment may be performed on both surfaces of the layers 10 and 20 to be joined, or may be performed only on one side.

  In the same manner as described above, after surface activation treatment is performed on both surfaces of the insulating intermediate layer 30, the insulating intermediate layer 30 is stacked and pressure-bonded so that the thermoelectric module layer 20 is sandwiched between the insulating base layer 10. Join. The thermal diffusion layer 40 and the heat dissipation layer 50 are bonded in the same manner to obtain the thermoelectric conversion device 1.

  Although direct chemical bonding by performing surface activation treatment was shown as bonding between adjacent layers 10, 20, 30, 40, 50, this bonding may be indirect via a molecular adhesive. Good.

  As this molecular adhesive, the same silane coupling agent as that applied to the outer surface of the hollow filler 22b can be used. In this case, a molecular adhesive is sprayed or applied to the surfaces to be joined of the respective layers 10, 20, 30, 40, 50, or the respective layers 10, 30, 40, 50 and the heat insulating rubber 22 are made into a molecular adhesive solution. This can be applied by dipping.

（化学式（２）中、ｐ及びｑは０又は２〜２００の数でｒは０又は２〜１００の数であってｐ＋ｑ＋ｒ＞２である。-Ａ^１，-Ａ^２及び-Ａ^３は、-ＣＨ_３、-Ｃ_２Ｈ_５、-ＣＨ＝ＣＨ_２、-ＣＨ(ＣＨ_３)_２、-ＣＨ_２ＣＨ(ＣＨ_３)_２、-Ｃ(ＣＨ_３)_３、-Ｃ_６Ｈ_５又は-Ｃ_６Ｈ_１２と、-ＯＣＨ_３、-ＯＣ_２Ｈ_５、-ＯＣＨ＝ＣＨ_２、-ＯＣＨ(ＣＨ_３)_２、-ＯＣＨ_２ＣＨ(ＣＨ_３)_２、-ＯＣ(ＣＨ_３)_３、-ＯＣ_６Ｈ_５及び-ＯＣ_６Ｈ_１２から選ばれヒドロキシ基と反応し得る反応性基との何れかである。-Ｂ^１及び-Ｂ^２は、-Ｎ(ＣＨ_３)ＣＯＣＨ_３又は-Ｎ(Ｃ_２Ｈ_５)ＣＯＣＨ_３と、-ＯＣＨ_３、-ＯＣ_２Ｈ_５、-ＯＣＨ＝ＣＨ_２、-ＯＣＨ(ＣＨ_３)_２、-ＯＣＨ_２ＣＨ(ＣＨ_３)_２、-ＯＣ(ＣＨ_３)_３、-ＯＣ_６Ｈ_５、-ＯＣ_６Ｈ_１２、-ＯＣＯＣＨ_３、-ＯＣＯＣＨ(Ｃ_２Ｈ_５)Ｃ_４Ｈ_９、-ＯＣＯＣ_６Ｈ_５、-ＯＮ＝Ｃ(ＣＨ_３)_２及び-ＯＣ(ＣＨ_３)＝ＣＨ_２から選ばれヒドロキシ基と反応し得る反応性基との何れかである。ｐ，ｑ及びｒを正数とする-{Ｏ-Ｓｉ(-Ａ^１)(-Ｂ^１)}_p-と-{Ｏ-Ｔｉ(-Ａ^２)(-Ｂ^２)}_ｑ-と-{Ｏ-Ａｌ(-Ａ^３)}_ｒ-との繰返単位中の-Ａ^１，-Ａ^２，-Ａ^３，-Ｂ^１及び-Ｂ^２の少なくとも何れかが前記反応性基であり、各層１０，２０，３０，４０，５０の接合の際、表面のヒドロキシ基と反応するものである）で模式的に示される反応性基含有ポリシロキサン化合物が挙げられる。この化合物は、繰返単位が、ブロック共重合、又はランダム共重合したものであってもよい。 As another example of this molecular adhesive, the following chemical formula (2)

(In the chemical formula (2), p and q are 0 or a number from 2 to 200, r is 0 or a number from 2 to 100, and p + q + r> 2. -A ¹ , -A ² and -A ³ are _{-CH 3, -C 2 H 5,} -CH = CH 2, -CH (CH 3) 2, -CH 2 CH (CH 3) 2, -C (CH 3) 3, -C 6 H 5 or -C and _{6 H 12, -OCH 3, -OC} 2 H 5, -OCH = CH 2, -OCH (CH 3) 2, -OCH 2 CH (CH 3) 2, -OC (CH 3) 3, -OC 6 It is either a reactive group selected from H ₅ and —OC ₆ H ₁₂ and capable of reacting with a hydroxy group, —B ¹ and —B ² are —N (CH ₃ ) COCH ₃ or —N (C ₂ H ₅₎ and _{COCH 3, -OCH 3, -OC 2} H 5, -OCH = CH 2, -OCH (CH 3) 2, -OCH 2 CH (CH 3) 2, -OC (CH 3) 3, - OC ₆ H ₅ , -OC ₆ H ₁₂ , -OCOCH ₃ , -OCOCH (C ₂ H ₅ ) C ₄ H ₉ , -OCOC ₆ H ₅ , -ON = C (CH ₃ ) ₂ and -OC (CH ₃ ) = CH ₂ Any one of the reactive groups that can react with the hydroxy group, and-{O-Si (-A ¹ ) (-B ¹ )} _p -and-{O with p, q, and r as positive numbers. -Ti (-A ² ) (-B ² )} _q -and-{O-Al (-A ³ )} _r- in repeating units -A ¹ , -A ² , -A ³ , -B ^At least ^{one of 1} and -B ² is the reactive group, and reacts with the hydroxy group on the surface when the layers 10, 20, 30, 40, 50 are bonded). And a functional group-containing polysiloxane compound. In this compound, the repeating unit may be one obtained by block copolymerization or random copolymerization.

  In this case, each layer 10, 30, 40, 50 and the heat insulating rubber 22 can be attached by immersing each layer 10, 30, 40, 50 and the heat insulating rubber 22 in a solution of a reactive group-containing polysiloxane that reacts with a hydroxy group. Further, this solution is applied or sprayed on the outer surfaces of the insulating sheets 21 d and 21 e of the thermoelectric conversion chip 21. After that, by carrying out heat treatment, the reactive group-containing polysiloxane is bonded to the hydroxy groups on the surfaces of the respective layers 10, 20, 30, 40, 50 to form a single-layer molecular film. And the reactive group is amplified. The hydroxy group on one surface of each layer 10, 20, 30, 40, 50 is chemically bonded to the reactive group-containing polysiloxane, so that the hydroxy group of each layer 10, 20, 30, 40, 50 is a reactive group. The layers 10, 20, 30, 40, and 50 are bonded to each other by indirectly bonding via the contained polysiloxane. When the reactive group-containing polysiloxane compound is attached to the thermoelectric conversion chip 21 and the heat insulating rubber 22 at the same time, instead of the dipping process, the reactive group-containing polysiloxane solution is sprayed, subsequently dried, and heated as necessary. It is preferable to process. You may attach this reactive group containing polysiloxane compound to the outer surface of the hollow filler 22b as a silane coupling membrane.

  In addition, when the heating / cooling effect by the heat generation / heat absorption of the thermoelectric conversion chip 21 does not need to be expressed on the insulating base layer 10 side, the insulating base layer 10 may be formed of a heat insulating material, or may be insulated. The base layer 10 and the thermoelectric module layer 20 may be joined via an adhesive or a pressure-sensitive adhesive.

  When the thermoelectric conversion chip 21 and the heat insulating rubber 22 are different in thickness, the thermoelectric conversion chip 21 and the heat insulating rubber 22 may have the same thickness by overlapping spacers on the insulating sheets 21d and 21e.

  The thermoelectric conversion device 1 is used as a heating source for a steering heater or a thermal seat, for example, by being mounted in a ring portion of a steering wheel of an automobile or a seat surface of a seat so that the heat radiation layer 50 faces outward. In addition, by attaching the thermoelectric conversion device 1 to the inside of a helmet or protective clothing, the inside of the cold clothing can be warmed rapidly, thus reducing the physical burden on the user working in a cold place such as a freezer. Can do.

  The thermoelectric conversion device 1 may cause a cooling phenomenon on the surface of the heat dissipation layer 50 by disposing the thermoelectric conversion chip 21 with the heat absorption end 24 facing the heat dissipation layer 50. In this case, by attaching the thermoelectric conversion device 1 in the ring part of the steering wheel and inside the helmet and protective clothing, temperature rise in the helmet and protective clothing is prevented in summer and hot places, and it is used due to heat and heat. Can reduce the physical burden on the person and prevent burns and heat stroke.

  As described above, the adjacent layers 10, 20, 30, 40, 50 are firmly bonded to each other by chemical bonding in the thermoelectric conversion device 1. Therefore, even if bent, no separation occurs between the layers, and the thermoelectric conversion chip 21. Is surrounded by the heat insulating rubber 22 having the same thickness as this, so that no space is required for heat insulation, so that the surface of the heat radiating layer 50 may be deformed into an uneven shape by the pressing force applied to the heat radiating layer 50, or the thermoelectric conversion chip 21 Does not cause damage. Therefore, the thermoelectric conversion device 1 can be suitably used for instruments such as a steering wheel and protective clothing, and does not impair the tactile sensation of these users.

  The thermoelectric conversion device 1 may be used not only as a heating source or a cooling source but also to generate a voltage using the Seebeck effect. In this case, the heat dissipation layer 50 on the heat generating end 23 side is brought into contact with the high temperature member, and the insulating base layer 10 on the heat absorbing end 24 side is brought into contact with the low temperature member. The thermoelectric conversion chip 21 generates a voltage due to a temperature difference between the high temperature member and the low temperature member.

  The thermoelectric conversion device 1 may have a circuit layer between the thermoelectric module layer 20 and the insulating intermediate layer 30. The circuit layer includes wiring that electrically relays the thermoelectric conversion chip 21 and, for example, a control device provided outside the thermoelectric conversion device 1. A part of the wiring of the circuit layer is joined to the electrodes 21b and 21c of the thermoelectric conversion chip 21 so as to be conductive, for example, by soldering, and another part of the wiring is electrically connected to the control device. In this case, the thermoelectric conversion device 1 can be operated at a desired timing and temperature by a signal generated from the control device. The circuit layer is formed by attaching a conductor such as copper to the surface of the insulating intermediate layer 30 facing the thermoelectric module layer 20 using a printing method such as screen printing, flexographic printing, ink jet printing, and offset printing. Can be formed.

  Examples of the present invention will be described in detail below, but the scope of the present invention is not limited to these forms.

Example 1
100 parts by mass of dimethyl silicone rubber (manufactured by Asahi Kasei Wacker Silicone Co., Ltd., product name: 3320-20) as the rubber component 22a, and thermally expandable microcapsules (manufactured by Matsumoto Yushi Seiyaku Co., Ltd., product name: Matsumoto Micro) as the hollow filler 22a 20 parts by mass of Sphere F-36-D (average particle diameter 13 μm) and 40 parts by mass of F-36LVD (average particle diameter 16 μm), and a curing accelerator a (Asahi Kasei Wacker Silicone Co., Ltd.) And 0.1 part by mass of product name: Cat. Ep) were kneaded and cured by pressurization and heating with a compression molding machine, and the cured product was cut out with a laser cutter. Thereby, a heat insulating rubber 22 having a square of 50 × 50 mm and a thickness of 2 mm was obtained. The central portion of the heat insulating rubber 22 was cut into a 4 × 4 mm square, and a hole for fitting the thermoelectric conversion chip 21 was formed. The heat conductivity of the heat insulating rubber 22 was measured by a heat conductivity meter (product name: QTM-500, manufactured by Kyoto Electronics Co., Ltd.) in accordance with JIS R2616-2000, and found to be 0.44 W / m · K. .

  An aluminum sheet having a thickness of 0.1 mm was cut into a 50 × 50 mm square with a cutter to form a heat diffusion layer 40.

Magnesium oxide (MgO) and aluminum oxide (Al ₂ O ₃ ) as heat conductive fillers are dispersed in dimethyl silicone rubber to form a flexible 0.5 mm thick sheet made of heat conductive rubber, A composition for the insulating base layer 10, the insulating intermediate layer 30, the heat dissipation layer 50, and the insulating sheets 21d and 21e was obtained. This was heated under pressure and cured, and the cured product was cut out with a laser cutter. As a result, a 50 × 50 mm square, 0.5 mm thick insulating base layer 10, insulating intermediate layer 30, and heat dissipation layer 50 were obtained. Similarly, 4 × 4 mm square and 0.5 mm thick insulating sheets 21d and 21e were obtained. It was 3.0 W / m * K when the heat conductivity of each layer 10,30,50 and the insulating sheets 21d and 21e was measured similarly to the heat insulation rubber 22. FIG.

  Applying an ethanol solution of vinyltriethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd., product name: KBE-1003) as a molecular adhesive to the outer surfaces of insulating sheets 21d and 21e sandwiching a plurality of thermoelectric conversion element pairs 21a, After heating, it was washed with ethanol. Thereby, the thermoelectric conversion chip 21 in which the outer surfaces of the insulating sheets 21d and 21e were modified was obtained.

  The thermoelectric conversion chip 21 whose surface was modified was fitted into the hole of the heat insulating rubber 22 to produce the thermoelectric module layer 20. Corona discharge treatment was performed on the surfaces to be joined of the respective layers 10, 20, 30, 40, and 50 to generate hydroxy groups. The layers 10, 20, 30, 40, and 50 were stacked in order, the hydroxy group generation surfaces were brought into contact with each other, and sandwiched between jigs. At this time, the thermoelectric module layer 20 was arranged so that the endothermic end 24 of the thermoelectric conversion chip 21 was located on the insulating intermediate layer 30 side, and was joined by a molecular adhesive. Thereby, a thermoelectric conversion device 1 (length × width × thickness = 50 × 50 × 2 mm) as shown in FIGS. 1 and 2 was obtained.

(Comparative Example 1)
The insulating base layer, the thermoelectric conversion chip, and the heat dissipation layer are the same as in Example 1 except that the heat insulating rubber is not disposed in the thermoelectric module layer and the intermediate insulating layer 30 and the heat diffusion layer 40 are not stacked. Were joined by molecular adhesion. Thereby, the thermoelectric conversion apparatus (length × width × thickness = 50 × 50 × 2 mm) of Comparative Example 1 was obtained.

  Table 1 shows the structures of the thermoelectric conversion devices of Example 1 and Comparative Example 1.

(Endothermic control temperature distribution test)
As shown in FIG. 3, thermocouples were attached to the positions of measurement points A to C which are the surface of the heat dissipation layer 50 of the thermoelectric conversion device 1 of Example 1. The position coordinates of each point are measurement point A: x, y = 25, 25 mm, measurement point B: x, y = 15, 15 mm, and measurement point C: x, y = 5, 5 mm. Measurement point A is directly above the thermoelectric conversion chip. Using a direct current stabilized power supply, a voltage of 0.45 V was applied to the thermoelectric conversion chip 21 to cool the endothermic end 24 side. The temperature at each measurement point was recorded using a data logger. The temperature distribution test of Comparative Example 1 was performed in the same manner as Example 1. FIG. 4 is a graph showing the change over time of the temperature difference ΔT (° C.) between Example 1 and Comparative Example 1. The temperature difference ΔT (° C.) is a difference between the temperature at each measurement point and room temperature, and is represented by the following formula (1).
ΔT (° C.) = (Temperature of each measurement point) − (room temperature) (1)

  4A shows Example 1, and FIG. 4B shows Comparative Example 1. The horizontal axis of the graph indicates time (minutes), and the vertical axis indicates temperature difference ΔT (° C.). Yes. Table 2 shows the temperature after 5 minutes from the start of voltage application.

  The thermoelectric conversion device of Example 1 showed a uniform temperature distribution with a smaller temperature difference between the points than that of Comparative Example 1. Since the thermoelectric conversion device of Example 1 has a thermal diffusion layer, it is excellent in thermoelectric conversion efficiency and temperature distribution uniformity.

(Example 2)
A thermoelectric conversion device of Example 2 was produced in the same manner as in Example 1 except that the thermoelectric module layer 20 was produced so that the heat generating end 23 of the thermoelectric conversion chip 21 was positioned on the insulating intermediate layer 30 side.

(Comparative Example 2)
The thermoelectric conversion device of Comparative Example 1 was turned over, and a thermocouple was attached to the surface of the insulating base layer on the heat generating end side of the thermoelectric conversion chip, whereby the thermoelectric conversion device of Comparative Example 2 was obtained.

  Table 3 shows the structures of the thermoelectric converters of Example 2 and Comparative Example 2.

(Heat control temperature distribution test)
By operating in the same manner as the endothermic control temperature distribution test, a voltage is applied to the thermoelectric conversion chip of Example 2, the heat generation end 23 side is heated, the temperature at each measurement point is measured, and the temperature difference ΔT according to Equation (1) (° C.) was determined. The thermoelectric conversion chip of Comparative Example 2 was also measured in the same manner as in Example 1. The result of Example 2 is shown in FIG. 5A, and the result of Comparative Example 2 is shown in FIG. 5B. Table 4 shows the temperature after 5 minutes from the start of voltage application.

  The thermoelectric conversion device of Example 2 showed a uniform temperature distribution with a smaller temperature difference between the points than that of Comparative Example 2. Since the thermoelectric conversion device of Example 2 has a thermal diffusion layer, it is excellent in thermoelectric conversion efficiency and temperature distribution uniformity. On the other hand, in Comparative Example 1, only the measurement point A directly above the thermoelectric conversion chip showed a local temperature rise, and no uniform temperature distribution was observed.

(Comparative Example 3)
The thermoelectric of Comparative Example 3 in which molecular adhesion is not applied in the same manner as in Example 1 except that a thermoelectric module layer having a thermoelectric conversion chip that is not surface-modified is used and each layer is bonded with an acrylic adhesive. A conversion device was produced (length × width × thickness = 50 × 50 × 2 mm).

(Comparative Example 4)
In the same manner as in Example 1 except that the heat insulating rubber was not used for the thermoelectric module layer produced in Example 1, the thermoelectric conversion device of Comparative Example 4 in which air was surrounded by the thermoelectric conversion chip instead of the heat insulating rubber (vertical) X horizontal x thickness = 50 x 50 x 2 mm).

  Table 5 shows the structures of the thermoelectric conversion devices of Example 1 and Comparative Examples 3 and 4.

(Endothermic control temperature change test)
Except that the applied voltage was 0.6 V, the heat dissipation layer of the thermoelectric conversion device of Example 1 and Comparative Examples 3 and 4 was cooled by operating in the same manner as in the endothermic control temperature distribution test, and each measurement point A to For C, the temperature difference ΔT (° C.) 5 minutes after the start of voltage application was determined according to the equation (1). The results are shown in FIG. As can be seen from FIG. 5A, the temperature of Example 1 is greatly reduced compared to Comparative Example 3 in which molecular adhesion is not applied. It was found that the conversion efficiency can be improved. Moreover, since Example 1 showed higher cooling than the comparative example 4 which does not have heat insulation rubber, it turned out that heat insulation rubber has the heat insulation effect equivalent to or more than air.

(Comparative Example 5)
The thermoelectric of Comparative Example 5 in which molecular adhesion is not applied in the same manner as in Example 2 except that a thermoelectric module layer having a thermoelectric conversion chip that is not surface-modified is used and each layer is bonded with an acrylic adhesive. A conversion device was produced (length × width × thickness = 50 × 50 × 2 mm).

(Comparative Example 6)
In the same manner as in Example 1 except that the heat insulating rubber was not used for the thermoelectric module layer produced in Example 2, the thermoelectric conversion device of Comparative Example 6 in which air was surrounded by the thermoelectric conversion chip instead of the heat insulating rubber (vertical) X horizontal x thickness = 50 x 50 x 2 mm).

  Table 6 shows the structures of the thermoelectric conversion devices of Example 2 and Comparative Examples 5 and 6.

(Exothermic control temperature change test)
By operating in the same manner as the endothermic control temperature change test, the heat dissipation layer of the thermoelectric conversion device of Example 2 and Comparative Examples 5 and 6 is heated, and the temperature after 5 minutes from the start of voltage application is measured for each measurement point A to C. The temperature difference ΔT (° C.) was determined according to the equation (1). The results are shown in FIG. According to FIG. 5B, there was almost no difference between Example 2 and Comparative Example 5 where molecular adhesion was not applied.

While there was a difference in the endothermic controlled temperature change test for the presence or absence of molecular adhesion, there was no difference in the exothermic controlled temperature change test. This is thought to be due to the following reason. First, the following formula (2) is established in the thermoelectric converter.
Q _H > Q _C (2)
Here, Q _H is the amount of heat generated at the heat dissipation layer, Q _C is the amount of heat absorption in the heat dissipation layer. Q _H and Q _C is at least the amount of heat generated by the internal resistance of the thermoelectric conversion element pairs (Q _r), and the heat loss quantity (Q _lambda) respectively comprise by heat transfer resistance between the layers. Since _Qr shows a large value at a high temperature and a small value at a low temperature, Expression (2) always holds. On the other hand, Q _λ has a lower temperature dependency than Q _r and can be regarded as constant.

In the endothermic control temperature change test, since Q _r <Q _λ holds, Q _λ contributes more to Q _C than Q _r , that is, molecular adhesion that reduces heat loss due to heat transfer resistance between each layer. the difference in _{Q C} is caused by the presence or absence. On the other hand, in the heat generation control temperature change test, Q _r> Q _{for lambda} is established, Q _H Q _r contributes greater than Q _lambda, ie the amount of heat generated by the internal resistance of the thermoelectric conversion element pairs in each layer heat for over a heat loss due to transfer resistance, a difference in Q _H hardly occurs by the presence or absence of molecular adhesion.

  As can be seen from FIG. 6 (b), Example 2 having the heat insulating rubber exhibits heat generation equivalent to that of Comparative Example 6 not having the heat insulating rubber. Therefore, the heat insulating rubber has a heat insulating effect equivalent to or higher than that of air. I found out.

  Since the thermoelectric conversion device of the present invention does not cause irregular deformation on the surface due to pressing, bending, and twisting, it can be suitably used as a heat pump by being attached to the curved surface of a device or instrument that the user directly touches.

  The thermoelectric conversion device uses a Peltier effect that generates heat at one end of the thermoelectric conversion element pair and generates heat at the other end by applying a voltage to the thermoelectric conversion chip. It can be used as a heating source or cooling source for such devices and instruments.

  The thermoelectric conversion device can be used for power generation of a device driven by a small amount of electric power such as a wristwatch by utilizing the Seebeck effect of generating a voltage by providing a temperature difference at both ends of the thermoelectric conversion chip.

1 is a thermoelectric conversion device, 10 is an insulating base layer, 20 is a thermoelectric module layer, 21 is a thermoelectric conversion chip, 21a is a thermoelectric conversion element pair, 21a ₁ is an n-type semiconductor element, 21a ₂ is a p-type semiconductor element, and 21b is a first 1 electrode, 21 c is the second electrode, 21 d and 21 e are insulating sheets, 22 is a heat insulating rubber, 22 a is a rubber component, 22 b is a hollow filler, 23 is a heat generating end, 24 is a heat absorbing end, 30 is an insulating intermediate layer, and 40 is heat Diffusion layer, 50 is a heat dissipation layer, 60 is a conventional thermoelectric conversion device, 61 is a thermoelectric conversion chip, 61a is a thermoelectric conversion element pair, 62 is a heat generation end, 63 is a heat absorption end, 64 is a substrate side sheet, 65 is a surface side sheet , 66 are cavities, 67 is an instrument substrate, and A, B, and C are measurement points.

Claims (8)

A heat insulating rubber containing a rubber component and a hollow filler forming a plurality of mutually independent voids, and a thermoelectric module layer surrounding the thermoelectric conversion chip;
Sandwiching the thermoelectric module layer, an insulating base layer and an insulating intermediate layer, which are heat conductive insulating sheets,
A thermal diffusion layer that overlies the insulating intermediate layer and has a higher thermal conductivity than the insulating base layer and the insulating intermediate layer;
The heat diffusion layer overlaps the heat diffusion layer, and has a heat dissipation layer,
A thermoelectric conversion device, wherein at least a pair of these adjacent layers are bonded via a chemical bond.   The thermoelectric conversion device according to claim 1, wherein the hollow filler has a resin shell, and thermally expandable liquid hydrocarbons are sealed in the inner space of the shell.   The thermoelectric conversion device according to claim 1, wherein the heat insulating rubber and the thermoelectric conversion chip have the same thickness.   4. The heat diffusion layer is formed of at least one selected from aluminum, copper, graphite, heat transfer rubber, heat transfer elastomer, and the heat transfer insulating sheet. 5. Thermoelectric conversion device.   The thermoelectric conversion device according to any one of claims 1 to 4, wherein a thickness of the heat diffusion layer is 0.01 to 0.5 mm.   The thermoelectric conversion chip includes a thermoelectric conversion element pair composed of an n-type semiconductor element and a p-type semiconductor element, an electrode sandwiching the plurality of thermoelectric conversion element pairs, and an insulating sheet that is overlapped and bonded to the electrode The thermoelectric conversion device according to claim 1, wherein the thermoelectric conversion device is provided.   The thermoelectric conversion device according to any one of claims 1 to 6, wherein the rubber component is silicone rubber, and a silane coupling film is attached to the outer surface of the hollow filler.   The thermoelectric conversion device according to any one of claims 1 to 7, further comprising a circuit layer electrically connected to the thermoelectric conversion chip between the thermoelectric module layer and the insulating intermediate layer.

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