JP6672562B2 - Peltier cooling element and method of manufacturing the same - Google Patents
Peltier cooling element and method of manufacturing the same Download PDFInfo
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- JP6672562B2 JP6672562B2 JP2015162479A JP2015162479A JP6672562B2 JP 6672562 B2 JP6672562 B2 JP 6672562B2 JP 2015162479 A JP2015162479 A JP 2015162479A JP 2015162479 A JP2015162479 A JP 2015162479A JP 6672562 B2 JP6672562 B2 JP 6672562B2
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- peltier cooling
- cooling element
- thermoelectric
- thermoelectric semiconductor
- heat
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- Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)
Description
本発明は、熱と電気との相互エネルギー変換を行う熱電変換材料を用いたペルチェ冷却素子に関する。 The present invention relates to a Peltier cooling element using a thermoelectric conversion material that performs mutual energy conversion between heat and electricity.
従来から、熱電変換を利用したエネルギー変換技術として、熱電発電技術及びペルチェ冷却技術が知られている。熱電発電技術は、ゼーベック効果による熱エネルギーから電気エネルギーへの変換を利用した技術であり、この技術は、特にビル、工場等で使用される化石燃料資源を使用する機器等から発生する未利用の廃熱エネルギーを電気エネルギーとして回収できる省エネルギー技術として大きな脚光を浴びている。これに対し、ペルチェ冷却技術は、熱電発電の逆で、ペルチェ効果による電気エネルギーから熱エネルギーへの変換を利用した技術であり、この技術は、例えば、ワインクーラー、小型で携帯が可能な冷蔵庫、またコンピュータ等に用いられるＣＰＵ用の冷却、さらに光通信の半導体レーザー発振器の温度制御等の精密な温度制御が必要な部品や装置に用いられている。しかしながら、熱電変換効率が低く、そのため、これら技術の実用化に関しては、上記のように、未だ限定的な分野に留まっている。 Conventionally, a thermoelectric generation technology and a Peltier cooling technology have been known as energy conversion technologies using thermoelectric conversion. Thermoelectric power generation technology is a technology that uses the conversion of heat energy to electric energy by the Seebeck effect.This technology is particularly useful for unused buildings generated from equipment that uses fossil fuel resources used in buildings and factories. It is in the spotlight as an energy-saving technology that can recover waste heat energy as electric energy. In contrast, Peltier cooling technology is a technology that uses the conversion of electric energy to heat energy by the Peltier effect, which is the reverse of thermoelectric power generation.This technology is, for example, a wine cooler, a small and portable refrigerator, It is also used for components and devices that require precise temperature control, such as cooling for a CPU used in a computer or the like, and temperature control of a semiconductor laser oscillator for optical communication. However, the thermoelectric conversion efficiency is low, and as a result, the practical application of these technologies is still limited as described above.
近年、エレクトロニクス機器には、それらの動作や制御に係り半導体素子が実装されることが当たり前のものとなっている中、微細化による半導体素子のさらなる小型化、高性能化等に伴い、半導体素子自体が高温になりかつ多量の熱を放出する発熱体となってきている。このような状況下、半導体素子の発熱を効率良く吸熱する冷却デバイスの小型化が求められている。
その対応方法の一つとして、上述したペルチェ冷却技術を利用した電子冷却があるが、従来のペルチェ素子は、熱電素子として熱電材料の焼結体を用いているため、小型化には機械的強度、また発熱体面への設置形態（屈曲部への実装等）や精度の観点からも限界があることから、印刷などによる塗布プロセスを用いた熱電材料の薄膜化を含むペルチェ素子のシート化、またそれらが屈曲性を有することが望まれている。
In recent years, it has become commonplace for semiconductor devices to be mounted on electronic devices for their operation and control. The heating element itself becomes a high temperature and emits a large amount of heat. Under such circumstances, there is a need for a cooling device that efficiently absorbs heat generated by a semiconductor element.
One method of responding to this is electronic cooling using the Peltier cooling technology described above. However, conventional Peltier elements use a sintered body of a thermoelectric material as a thermoelectric element, so that mechanical strength is required for miniaturization. In addition, since there is a limit in terms of installation form (mounting on a bent portion, etc.) and accuracy on the heating element surface, Peltier elements are sheeted, including thinning of thermoelectric materials using a coating process such as printing. It is desired that they have flexibility.
熱電変換では、上述したように、ゼーベック効果とペルチェ効果といった、材料に固有の物理現象を利用している。そのため、熱電変換の効率を向上させるためには、性能の高い熱電変換材料を開発する必要がある。熱電変換効率は、熱電性能指数Ｚ（Ｚ＝σＳ２／λ＝σΠ２／λＴ２）によって評価することができる。ここで、Ｓはゼーベック係数、Πはペルチェ係数、σは電気伝導率（抵抗率の逆数）、λは熱伝導率、Ｔは接合部の絶対温度である。上記より、冷却の高効率化にあたっては、発電にかかるゼーベック係数Ｓ、冷却にかかるペルチェ係数Π（ペルチェ係数とゼーベック係数とは、上記Ｔを一定とした場合、比例関係にある）、及び電気伝導率σが大きく、熱伝導率λが小さい熱電変換材料を見出すことが重要となる。 As described above, thermoelectric conversion utilizes physical phenomena inherent to materials, such as the Seebeck effect and the Peltier effect. Therefore, in order to improve the efficiency of thermoelectric conversion, it is necessary to develop a thermoelectric conversion material with high performance. The thermoelectric conversion efficiency can be evaluated by a thermoelectric figure of merit Z (Z = σS 2 / λ = σΠ 2 / λT 2 ). Here, S is the Seebeck coefficient, Π is the Peltier coefficient, σ is the electrical conductivity (the reciprocal of the resistivity), λ is the thermal conductivity, and T is the absolute temperature of the junction. From the above, when the cooling efficiency is improved, the Seebeck coefficient S for power generation, the Peltier coefficient for cooling Π (the Peltier coefficient and the Seebeck coefficient are in a proportional relationship when the above T is constant), and the electric conduction. It is important to find a thermoelectric conversion material having a large rate σ and a small thermal conductivity λ.
このような中、特許文献１には、発電効率の向上及び効率よく製造することを目的として、支持体上に、絶縁体を有し、ｐ型、ｎ型有機半導体素子の材料となる溶液を用いて塗布又は印刷後に、乾燥する工程を経ることにより作製した熱電変換素子の製造方法が開示されている。また、非特許文献１には、熱電変換材料として、ビスマステルライドをエポキシ樹脂に分散した組成物とし、それらを塗布により成膜することで、薄膜型熱電変換素子を作製する検討がなされている。さらに、特許文献２では、ポリチオフェンもしくはその誘導体などの有機熱電材料と、無機熱電材料とが分散状態で一体化されている熱電材料が検討されている。さらにまた、特許文献３では、図３に示すように、Ｐ型熱電素子４１、Ｎ型熱電素子４２の薄膜に備わる電極４３が薄膜の長さ方向の少なくとも両端に配置された熱電変換モジュール（以下、「Ｉｎ−ｐｌａｎｅ型熱電変換モジュール」という。）を用いた場合の熱電素子両端部間（両電極間）の温度差の付与について、両端の電極４３から効率良く熱起電力を取り出すために、熱伝導率の異なる材料で構成された柔軟性を有するフィルム状基板４４、４５を用い、フィルム状基板４４、４５の厚さ方向の温度勾配をフィルム状基板４４、４５の面内方向の温度勾配に変換する検討がなされている。 Under such circumstances, Patent Literature 1 discloses a solution having an insulator on a support and serving as a material for a p-type or n-type organic semiconductor element for the purpose of improving power generation efficiency and manufacturing efficiently. A method for manufacturing a thermoelectric conversion element manufactured by performing a coating and printing process and then a drying step is disclosed. In addition, Non-Patent Document 1 discusses manufacturing a thin-film thermoelectric conversion element by forming a composition in which bismuth telluride is dispersed in an epoxy resin as a thermoelectric conversion material and forming a film by coating. Further, Patent Document 2 studies a thermoelectric material in which an organic thermoelectric material such as polythiophene or a derivative thereof and an inorganic thermoelectric material are integrated in a dispersed state. Further, in Patent Document 3, as shown in FIG. 3, a thermoelectric conversion module (hereinafter referred to as a thermoelectric conversion module) in which electrodes 43 provided on a thin film of a P-type thermoelectric element 41 and an N-type thermoelectric element 42 are arranged at least at both ends in the longitudinal direction of the thin film. , "In-plane type thermoelectric conversion module"), the temperature difference between both ends of the thermoelectric element (between both electrodes) is given in order to efficiently extract thermoelectromotive force from the electrodes 43 at both ends. Using the flexible film substrates 44 and 45 made of materials having different thermal conductivities, the temperature gradient in the thickness direction of the film substrates 44 and 45 is reduced in the in-plane direction of the film substrates 44 and 45. Consideration has been given to converting to.
しかしながら、特許文献１では、熱電材料として、ｐ型、ｎ型有機半導体素子を用いており、熱電変換特性が十分ではなかった。また、非特許文献１の薄膜型熱電変換素子では、バインダー樹脂の分解温度以上の高温で加熱処理を行うため、ビスマステルライドのみを成膜した場合と同程度の屈曲性しか得られず、しかも熱電変換特性が十分ではなかった。さらに、特許文献２の熱電材料は、熱電変換特性をより向上させるために、熱電材料の薄膜を形成した後に有機熱電材料の分解温度以上の高温で加熱処理を行った場合、有機熱電材料が消失してしまい、熱電変換特性が低下するおそれがあった。さらにまた、特許文献３では、フィルム状基板をＩｎ−ｐｌａｎｅ型熱電変換モジュールに用いた場合の温度差の付与が十分ではなく、該フィルム状基板を、ペルチェ素子を構成する、Ｉｎ−ｐｌａｎｅ型熱電変換モジュールの放熱フィルム（以下、「熱伝導性フィルム」ということがある。）として用いた場合においても、熱電性能（冷却効果）が十分得られないおそれがあった。 However, in Patent Document 1, p-type and n-type organic semiconductor elements are used as thermoelectric materials, and thermoelectric conversion characteristics are not sufficient. Further, in the thin-film thermoelectric conversion element of Non-Patent Document 1, since the heat treatment is performed at a high temperature higher than the decomposition temperature of the binder resin, only the same degree of flexibility as when only bismuth telluride is formed can be obtained. The conversion characteristics were not sufficient. Further, the thermoelectric material of Patent Document 2 loses the organic thermoelectric material when a heat treatment is performed at a high temperature equal to or higher than the decomposition temperature of the organic thermoelectric material after forming a thin film of the thermoelectric material in order to further improve the thermoelectric conversion characteristics. As a result, the thermoelectric conversion characteristics may be reduced. Furthermore, in Patent Literature 3, when a film-shaped substrate is used for an In-plane type thermoelectric conversion module, the temperature difference is not sufficiently imparted, and the film-shaped substrate is used as an In-plane type thermoelectric conversion module that constitutes a Peltier element. Even when used as a heat dissipation film (hereinafter sometimes referred to as a “heat conductive film”) of the conversion module, there is a possibility that sufficient thermoelectric performance (cooling effect) cannot be obtained.
本発明は、上記状況を鑑み、熱電性能及び屈曲性に優れ、簡便に低コストで製造可能であるペルチェ冷却素子を提供することを課題とする。 The present invention has been made in view of the above circumstances, and has as its object to provide a Peltier cooling element that is excellent in thermoelectric performance and flexibility and can be easily manufactured at low cost.
本発明者らは、上記課題を解決すべく鋭意検討を重ねた結果、支持体上に、熱伝導率の低下に寄与する微粒子化した熱電半導体、耐熱性樹脂、及び微粒子間の空隙部での電気伝導率の低下を抑制するイオン液体を含む熱電半導体組成物からなる薄膜を有する熱電変換材料を用いて構成したペルチェ冷却素子、さらに放熱フィルムとして該薄膜の片面又は両面に高熱伝導部と低熱伝導部とを備えた熱伝導性フィルムを貼付したペルチェ冷却素子が、従来の上記熱電変換材料及び放熱フィルムを用いたペルチェ冷却素子と比べ、高い熱電性能すなわちペルチェ素子として高い冷却性能を有し、かつ屈曲性に優れることを見出し、本発明を完成した。
すなわち、本発明は、以下の（１）〜（１２）を提供するものである。
（１）支持体上に、熱電半導体微粒子、耐熱性樹脂及びイオン液体を含む熱電半導体組成物からなる薄膜を有する熱電変換材料を用いたペルチェ冷却素子であって、該ペルチェ冷却素子が、該薄膜の片面又は両面に高熱伝導部と低熱伝導部とを備えた熱伝導性フィルムを含む、ペルチェ冷却素子。
（２）前記ペルチェ冷却素子の前記薄膜に電極が備わり、該電極が該薄膜の長さ方向の両端部に少なくとも一つ以上備わる、上記（１）に記載のペルチェ冷却素子。
（３）前記熱伝導性フィルムが接着層を含む、上記（１）に記載のペルチェ冷却素子。
（４）前記イオン液体の配合量が、前記熱電半導体組成物中０．０１〜５０質量％である、上記（１）に記載のペルチェ冷却素子。
（５）前記イオン液体のカチオン成分が、ピリジニウムカチオン及びその誘導体、イミダゾリウムカチオン及びその誘導体から選ばれる少なくとも１種を含む、上記（１）に記載のペルチェ冷却素子。
（６）前記イオン液体のアニオン成分が、ハロゲン化物アニオンを含む、上記（１）に記載のペルチェ冷却素子。
（７）前記ハロゲン化物アニオンが、Ｃｌ−、Ｂｒ−及びＩ−から選ばれる少なくとも１種を含む、上記（６）に記載のペルチェ冷却素子。
（８）前記耐熱性樹脂が、ポリアミド樹脂、ポリアミドイミド樹脂、ポリイミド樹脂及びエポキシ樹脂から選ばれる少なくとも１種である、上記（１）に記載のペルチェ冷却素子。
（９）前記熱電半導体微粒子の配合量が、前記熱電半導体組成物中３０〜９９質量％である、上記（１）に記載のペルチェ冷却素子。
（１０）前記熱電半導体微粒子の平均粒径が、１０ｎｍ〜２００μｍである、上記（１）〜（９）のいずれか１項に記載のペルチェ冷却素子。
（１１）前記熱電半導体微粒子が、ビスマス−テルル系熱電半導体材料の微粒子である、上記（１）〜（１０）のいずれか１項に記載のペルチェ冷却素子。
（１２）支持体上に、熱電半導体微粒子、耐熱性樹脂及びイオン液体を含む熱電半導体組成物からなる薄膜を有する熱電変換材料を用いたペルチェ冷却素子の製造方法であって、支持体上に、熱電半導体微粒子、耐熱性樹脂及びイオン液体を含む熱電半導体組成物を塗布し、乾燥し、薄膜を形成する工程、該薄膜をアニール処理する工程、さらに高熱伝導部と低熱伝導部とを備えた熱伝導性フィルムを片面又は両面に貼付する工程を含む、ペルチェ冷却素子の製造方法。
The present inventors have conducted intensive studies to solve the above-described problems, and as a result, on the support, a finely divided thermoelectric semiconductor that contributes to a decrease in thermal conductivity, a heat-resistant resin, and a void between the fine particles. A Peltier cooling element composed of a thermoelectric conversion material having a thin film made of a thermoelectric semiconductor composition containing an ionic liquid that suppresses a decrease in electrical conductivity, and a high heat conducting portion and low heat conduction on one or both surfaces of the thin film as a heat dissipation film Peltier cooling element to which a heat conductive film having a part is attached, compared to the conventional Peltier cooling element using the thermoelectric conversion material and the heat dissipation film, has high thermoelectric performance, that is, high cooling performance as a Peltier element, and The inventors have found that the present invention has excellent flexibility, and have completed the present invention.
That is, the present invention provides the following (1) to (12).
(1) A Peltier cooling element using a thermoelectric conversion material having a thin film made of a thermoelectric semiconductor composition containing thermoelectric semiconductor fine particles, a heat-resistant resin and an ionic liquid on a support, wherein the Peltier cooling element is formed of the thin film A Peltier cooling element comprising a heat conductive film provided with a high heat conduction part and a low heat conduction part on one or both sides of the Peltier cooling element.
(2) The Peltier cooling element according to (1), wherein the thin film of the Peltier cooling element is provided with an electrode, and at least one of the electrodes is provided at both ends in the longitudinal direction of the thin film.
(3) The Peltier cooling device according to (1), wherein the heat conductive film includes an adhesive layer.
(4) The Peltier cooling element according to the above (1), wherein the compounding amount of the ionic liquid is 0.01 to 50% by mass in the thermoelectric semiconductor composition.
(5) The Peltier cooling element according to (1), wherein the cation component of the ionic liquid includes at least one selected from a pyridinium cation and a derivative thereof, and an imidazolium cation and a derivative thereof.
(6) The Peltier cooling device according to (1), wherein the anion component of the ionic liquid includes a halide anion.
(7) The Peltier cooling element according to (6), wherein the halide anion contains at least one selected from Cl − , Br − and I − .
(8) The Peltier cooling element according to (1), wherein the heat-resistant resin is at least one selected from a polyamide resin, a polyamide-imide resin, a polyimide resin, and an epoxy resin.
(9) The Peltier cooling element according to the above (1), wherein the compounding amount of the thermoelectric semiconductor fine particles is 30 to 99% by mass in the thermoelectric semiconductor composition.
(10) The Peltier cooling device according to any one of (1) to (9), wherein the thermoelectric semiconductor fine particles have an average particle size of 10 nm to 200 μm.
(11) The Peltier cooling element according to any one of (1) to (10), wherein the thermoelectric semiconductor fine particles are fine particles of a bismuth-tellurium-based thermoelectric semiconductor material.
(12) A method of manufacturing a Peltier cooling element using a thermoelectric conversion material having a thin film made of a thermoelectric semiconductor composition containing thermoelectric semiconductor fine particles, a heat-resistant resin, and an ionic liquid on a support, the method comprising: A step of applying a thermoelectric semiconductor composition containing thermoelectric semiconductor fine particles, a heat-resistant resin and an ionic liquid, drying and forming a thin film, a step of annealing the thin film, and a heat treatment comprising a high heat conduction part and a low heat conduction part. A method for manufacturing a Peltier cooling element, comprising a step of attaching a conductive film to one or both surfaces.
本発明によれば、熱電性能及び屈曲性に優れ、簡便に低コストで製造可能であるペルチェ冷却素子を提供することができる。 According to the present invention, it is possible to provide a Peltier cooling element which is excellent in thermoelectric performance and flexibility and can be easily manufactured at low cost.
［ペルチェ冷却素子］
本発明のペルチェ冷却素子は、支持体上に、熱電半導体微粒子、耐熱性樹脂及びイオン液体を含む熱電半導体組成物からなる薄膜を有する熱電変換材料を用いたペルチェ冷却素子であって、該ペルチェ冷却素子が、該薄膜の片面又は両面に高熱伝導部と低熱伝導部とを備えた熱伝導性フィルムを含むことを特徴とする。
ペルチェ冷却素子では、通常、ｐ型熱電素子とｎ型熱電素子とを電極を介し直列に接続し、ｐｎ接合部に電流を流すことにより、ペルチェ効果により、ｎ→ｐ接合部分（矢印の方向へ電流が流れる）では吸熱現象が、ｐ→ｎ接合部分（矢印の方向へ電流が流れる）では放熱現象が発生する。これにより、熱を低温側（吸熱側）から高温側（発熱側）へ輸送することができる。
また、ペルチェ冷却素子は、高温側と低温側の温度差が大きくなると、高温側から低温側に素子の内部を通って熱の逆流が増加（増加分＝モジュールの熱伝導率×温度差の増加分）することから、発熱側と吸熱側との温度差が小さいほど、冷却効果が高くなる。
[Peltier cooling element]
The Peltier cooling element of the present invention is a Peltier cooling element using a thermoelectric conversion material having a thin film made of a thermoelectric semiconductor composition containing thermoelectric semiconductor fine particles, a heat-resistant resin and an ionic liquid on a support, wherein the Peltier cooling element is used. The element is characterized by including a heat conductive film having a high heat conductive portion and a low heat conductive portion on one or both surfaces of the thin film.
In a Peltier cooling element, usually, a p-type thermoelectric element and an n-type thermoelectric element are connected in series via an electrode, and a current is caused to flow through a pn junction, so that an n → p junction (in the direction of the arrow) is formed by the Peltier effect. In this case, an endothermic phenomenon occurs in a p-n junction (current flows in the direction of the arrow). Thereby, heat can be transported from the low temperature side (endothermic side) to the high temperature side (heat generation side).
In the Peltier cooling element, when the temperature difference between the high temperature side and the low temperature side increases, the backflow of heat increases from the high temperature side to the low temperature side through the inside of the element (increase = thermal conductivity of module x increase in temperature difference) Therefore, the smaller the temperature difference between the heat generation side and the heat absorption side, the higher the cooling effect.
図１（ａ）において、Ｉｎ−ｐｌａｎｅ型熱電変換モジュール１は、支持体２上に、薄膜のｐ型熱電素子３及びｎ型熱電素子４が電極５ｂ、５ｃ、５ｄを介し、電気的に直列に接続されている。また、図１（ｂ）において、Ｉｎ−ｐｌａｎｅ型ペルチェ冷却素子１０は、高熱伝導部７及び低熱伝導部８からなる熱伝導性フィルム６Ａ及び６Ｂが、Ｉｎ−ｐｌａｎｅ型熱電変換モジュール１の薄膜の両面に接着剤層９を介し配置され、構成されている。
前記薄膜に備わる電極は、薄膜の長さ方向の両端部にそれぞれ少なくとも一つ以上備わることが好ましく、効率的に温度差を得る観点から、例えば、図１（ａ）のように対向する端部同士に備わることがより好ましい。
ここで、熱伝導性フィルム（詳細は後述する）は、例えば、ペルチェ冷却素子を構成するＩｎ−ｐｌａｎｅ型熱電変換モジュール１の電極５ａ、５ｅ間に電圧を印加した時に、ｐ型熱電素子３及びｎ型熱電素子４の接合部を交互に高温部又は低温部にし、熱伝導性フィルムの外面間に効率良く温度差を発生させるために用いられる。熱伝導性フィルムとＩｎ−ｐｌａｎｅ型熱電変換モジュールとの配置は、具体的には、図１（ｂ）のように、薄膜の両面同士では高熱伝導部７と低熱伝導部８が向かい合うように対向させ、さらにそれらと電極の接合部との位置関係等を、適宜調整することが必要である。
本発明は、熱伝導率の低下に寄与する微粒子化した熱電半導体、耐熱性樹脂、及び微粒子間の空隙部での電気伝導率の低下を抑制するイオン液体を含む熱電半導体組成物からなる薄膜の片面又は両面に高熱伝導部と低熱伝導部とを備えた熱伝導性フィルムを貼付してなるＩｎ−ｐｌａｎｅ型ペルチェ冷却素子である。
In FIG. 1A, an In-plane thermoelectric conversion module 1 is configured such that a thin-film p-type thermoelectric element 3 and an n-type thermoelectric element 4 are electrically connected in series on a support 2 via electrodes 5b, 5c, and 5d. It is connected to the. In FIG. 1B, in the In-plane type Peltier cooling element 10, the heat conductive films 6A and 6B including the high heat conductive portion 7 and the low heat conductive portion 8 are formed of the thin film of the In-plane type thermoelectric conversion module 1. It is arranged on both sides with an adhesive layer 9 interposed therebetween.
It is preferable that at least one or more electrodes provided on the thin film are provided at both ends in the longitudinal direction of the thin film, and from the viewpoint of efficiently obtaining a temperature difference, for example, opposite end portions as shown in FIG. More preferably, they are provided with each other.
Here, for example, when a voltage is applied between the electrodes 5a and 5e of the In-plane type thermoelectric conversion module 1 constituting the Peltier cooling element, the heat conductive film (which will be described in detail later), The junction of the n-type thermoelectric element 4 is alternately set to a high-temperature portion or a low-temperature portion, and is used to efficiently generate a temperature difference between the outer surfaces of the heat conductive film. Specifically, as shown in FIG. 1B, the arrangement of the heat conductive film and the In-plane type thermoelectric conversion module is opposite such that the high heat conductive portion 7 and the low heat conductive portion 8 face each other on both surfaces of the thin film. In addition, it is necessary to appropriately adjust the positional relationship between them and the joints of the electrodes.
The present invention provides a thin film of a thermoelectric semiconductor composition containing a thermoelectric semiconductor that is made into fine particles that contribute to a decrease in thermal conductivity, a heat-resistant resin, and an ionic liquid that suppresses a decrease in electrical conductivity in voids between the particles. This is an In-plane type Peltier cooling element in which a heat conductive film having a high heat conductive part and a low heat conductive part is attached to one or both surfaces.
＜熱電変換材料＞
本発明のペルチェ冷却素子に用いた熱電変換材料は、支持体上に、熱電半導体微粒子、耐熱性樹脂及びイオン液体を含む熱電半導体組成物からなるものである。
本発明のペルチェ冷却素子に用いる熱電変換材料は、冷却能力及び冷却効率の観点から、ｐ型及びｎ型熱電素子を交互に配列し、かつ電気的には直列に接続し、熱的には接合部の温度が、高温部と低温部とが交互になるようにして用いることが好ましく、冷却効果が損なわれない範囲で、それらを複数個使用してもよい。
<Thermoelectric conversion material>
The thermoelectric conversion material used for the Peltier cooling element of the present invention is composed of a thermoelectric semiconductor composition containing thermoelectric semiconductor fine particles, a heat-resistant resin and an ionic liquid on a support.
The thermoelectric conversion material used in the Peltier cooling element of the present invention is obtained by alternately arranging p-type and n-type thermoelectric elements, electrically connecting them in series, and thermally joining them from the viewpoint of cooling capacity and cooling efficiency. It is preferable that the temperature of the part is such that the high temperature part and the low temperature part are alternately used, and a plurality of them may be used as long as the cooling effect is not impaired.
（支持体）
支持体としては、熱電変換材料の電気伝導率の低下、熱伝導率の増加に影響を及ぼさないものであれば、特に制限されず、例えば、ガラス、シリコン、プラスチックフィルム等が挙げられる。なかでも、屈曲性に優れるという点から、プラスチックフィルムが好ましい。
プラスチックフィルムとしては、具体的には、ポリエチレンテレフタレートフィルム、ポリエチレンナフタレートフィルム、ポリイミドフィルム、ポリアミドフィルム、ポリエーテルイミドフィルム、ポリアラミドフィルム、ポリアミドイミドフィルム、ポリエーテルケトンフィルム、ポリエーテル・エーテルケトンフィルム、ポリフェニレンサルファイドフィルム、ポリ（４−メチルペンテン−１）フィルム等が挙げられる。また、これらフィルムの積層体であってもよい。
これらの中でも、熱電半導体組成物からなる薄膜をアニール処理した場合でも、支持体が熱変形することなく、熱電変換材料の性能を維持することができ、耐熱性及び寸法安定性が高いという点から、ポリイミドフィルム、ポリアミドフィルム、ポリエーテルイミドフィルム、ポリアラミドフィルム、ポリアミドイミドフィルムが好ましく、さらに、汎用性が高いという点から、ポリイミドフィルムが特に好ましい。
(Support)
The support is not particularly limited as long as it does not affect the decrease in the electrical conductivity of the thermoelectric conversion material and the increase in the thermal conductivity, and examples thereof include glass, silicon, and plastic films. Among them, a plastic film is preferable because of its excellent flexibility.
As the plastic film, specifically, a polyethylene terephthalate film, a polyethylene naphthalate film, a polyimide film, a polyamide film, a polyetherimide film, a polyaramid film, a polyamideimide film, a polyetherketone film, a polyetheretherketone film, Examples include a polyphenylene sulfide film, a poly (4-methylpentene-1) film, and the like. Further, a laminate of these films may be used.
Among these, even when a thin film made of a thermoelectric semiconductor composition is annealed, the performance of the thermoelectric conversion material can be maintained without thermal deformation of the support, and heat resistance and dimensional stability are high. , A polyimide film, a polyamide film, a polyether imide film, a polyaramid film, and a polyamide imide film are preferable, and a polyimide film is particularly preferable because of high versatility.
前記支持体の厚さは、屈曲性、耐熱性及び寸法安定性の観点から、１〜１０００μｍが好ましく、１０〜５００μｍがより好ましく、２０〜１００μｍがさらに好ましい。
また、上記プラスチックフィルムは、分解温度が３００℃以上であることが好ましい。
From the viewpoints of flexibility, heat resistance and dimensional stability, the thickness of the support is preferably from 1 to 1000 μm, more preferably from 10 to 500 μm, and still more preferably from 20 to 100 μm.
The plastic film preferably has a decomposition temperature of 300 ° C. or higher.
（熱電半導体微粒子）
熱電変換材料に用いる熱電半導体微粒子は、熱電半導体材料を、微粉砕装置等により、所定のサイズまで粉砕することにより得られる。
(Thermoelectric semiconductor particles)
The thermoelectric semiconductor fine particles used for the thermoelectric conversion material are obtained by crushing the thermoelectric semiconductor material to a predetermined size using a fine crusher or the like.
前記熱電半導体材料としては、特に制限されず、例えば、ｐ型ビスマステルライド、ｎ型ビスマステルライド、Ｂｉ２Ｔｅ３等のビスマス−テルル系熱電半導体材料；ＧｅＴｅ、ＰｂＴｅ等のテルライド系熱電半導体材料；アンチモン−テルル系熱電半導体材料；ＺｎＳｂ、Ｚｎ３Ｓｂ２、Ｚｎ４Ｓｂ３等の亜鉛−アンチモン系熱電半導体材料；ＳｉＧｅ等のシリコン−ゲルマニウム系熱電半導体材料；Ｂｉ２Ｓｅ３等のビスマスセレナイド系熱電半導体材料；β―ＦｅＳｉ２、ＣｒＳｉ２、ＭｎＳｉ１．７３、Ｍｇ２Ｓｉ等のシリサイド系熱電半導体材料；酸化物系熱電半導体材料；ＦｅＶＡｌ、ＦｅＶＡｌＳｉ、ＦｅＶＴｉＡｌ等のホイスラー材料、ＴｉＳ２等の硫化物系熱電半導体材料等が用いられる。 As the thermoelectric semiconductor material is not particularly limited, for example, p-type bismuth telluride, n-type bismuth telluride, bismuth such as Bi 2 Te 3 - telluride thermoelectric semiconductor material; GeTe, Telluride based thermoelectric semiconductor materials such as PbTe; antimony - tellurium based thermoelectric semiconductor material; ZnSb, Zn 3 Sb 2, Zn 4 zinc Sb 3 etc. - antimony thermoelectric semiconductor material; silicon such as SiGe - germanium thermoelectric semiconductor material; Bi bismuth selenide-based thermoelectric such as 2 Se 3 Semiconductor materials; silicide-based thermoelectric semiconductor materials such as β-FeSi 2 , CrSi 2 , MnSi 1.73 , and Mg 2 Si; oxide-based thermoelectric semiconductor materials; Heusler materials such as FeVAl, FeVAlSi, FeVTiAl, and sulfides such as TiS 2 A thermoelectric semiconductor material or the like is used.
これらの中でも、本発明に用いる前記熱電半導体材料は、ｐ型ビスマステルライド又はｎ型ビスマステルライド、Ｂｉ２Ｔｅ３等のビスマス−テルル系熱電半導体材料であることが好ましい。
前記ｐ型ビスマステルライドは、キャリアが正孔で、ゼーベック係数が正値であり、例えば、ＢｉＸＴｅ３Ｓｂ２−Ｘで表わされるものが好ましく用いられる。この場合、Ｘは、好ましくは０＜Ｘ≦０．８であり、より好ましくは０．４≦Ｘ≦０．６である。Ｘが０より大きく０．８以下であるとゼーベック係数と電気伝導率が大きくなり、ｐ型熱電変換材料としての特性が維持されるので好ましい。
また、前記ｎ型ビスマステルライドは、キャリアが電子で、ゼーベック係数が負値であり、例えば、Ｂｉ２Ｔｅ３−ＹＳｅＹで表わされるものが好ましく用いられる。この場合、Ｙは、好ましくは０≦Ｙ≦３であり、より好ましくは０≦Ｙ≦２．７である。Ｙが０以上３以下であるとゼーベック係数と電気伝導率が大きくなり、ｎ型熱電変換材料としての特性が維持されるので好ましい。
Among them, the thermoelectric semiconductor material used in the present invention, p-type bismuth telluride or an n-type bismuth telluride, bismuth such as Bi 2 Te 3 - preferably a telluride thermoelectric semiconductor material.
The p-type bismuth telluride, the carrier is in the hole, the Seebeck coefficient is a positive value, for example, those represented by Bi X Te 3 Sb 2-X is preferably used. In this case, X preferably satisfies 0 <X ≦ 0.8, and more preferably 0.4 ≦ X ≦ 0.6. When X is greater than 0 and 0.8 or less, the Seebeck coefficient and the electrical conductivity increase, and the characteristics as a p-type thermoelectric conversion material are preferably maintained.
Further, the n-type bismuth telluride, the carrier is an electron, the Seebeck coefficient is negative value, for example, those represented by Bi 2 Te 3-Y Se Y is preferably used. In this case, Y is preferably 0 ≦ Y ≦ 3, more preferably 0 ≦ Y ≦ 2.7. When Y is 0 or more and 3 or less, the Seebeck coefficient and the electric conductivity increase, and the characteristics as an n-type thermoelectric conversion material are preferably maintained.
熱電半導体微粒子の前記熱電半導体組成物中の配合量は、好ましくは、３０〜９９質量％である。より好ましくは、５０〜９６質量％であり、さらに好ましくは、７０〜９５質量％である。熱電半導体微粒子の配合量が、上記範囲内であれば、ゼーベック係数すなわちペルチェ係数の絶対値が大きく、また電気伝導率の低下が抑制され、熱伝導率のみが低下するため高い熱電性能を示すとともに、十分な皮膜強度、屈曲性を有する膜が得られ好ましい。 The blending amount of the thermoelectric semiconductor fine particles in the thermoelectric semiconductor composition is preferably 30 to 99% by mass. More preferably, it is 50 to 96% by mass, and still more preferably 70 to 95% by mass. If the blending amount of the thermoelectric semiconductor fine particles is within the above range, the absolute value of the Seebeck coefficient, that is, the Peltier coefficient is large, and a decrease in the electric conductivity is suppressed, and a high thermoelectric performance is exhibited because only the heat conductivity decreases. It is preferable because a film having sufficient film strength and flexibility can be obtained.
熱電半導体微粒子の平均粒径は、好ましくは、１０ｎｍ〜２００μｍ、より好ましくは、１０ｎｍ〜３０μｍ、さらに好ましくは、５０ｎｍ〜１０μｍ、特に好ましくは、１〜６μｍである。上記範囲内であれば、均一分散が容易になり、電気伝導率を高くすることができる。
前記熱電半導体材料を粉砕して熱電半導体微粒子を得る方法は特に限定されず、ジェットミル、ボールミル、ビーズミル、コロイドミル、コニカルミル、ディスクミル、エッジミル、製粉ミル、ハンマーミル、ペレットミル、ウィリーミル、ローラーミル等の公知の微粉砕装置等により、所定のサイズまで粉砕すればよい。
なお、熱電半導体微粒子の平均粒径は、レーザー回折式粒度分析装置（ＣＩＬＡＳ社製、１０６４型）にて測定することにより得られ、粒径分布の中央値とした。
The average particle size of the thermoelectric semiconductor fine particles is preferably 10 nm to 200 μm, more preferably 10 nm to 30 μm, further preferably 50 nm to 10 μm, and particularly preferably 1 to 6 μm. Within the above range, uniform dispersion becomes easy, and electric conductivity can be increased.
The method of pulverizing the thermoelectric semiconductor material to obtain thermoelectric semiconductor fine particles is not particularly limited, and a jet mill, a ball mill, a bead mill, a colloid mill, a conical mill, a disc mill, an edge mill, a milling mill, a hammer mill, a pellet mill, a wheely mill, a roller What is necessary is just to grind | pulverize to a predetermined | prescribed size with well-known fine grinding | pulverization apparatuses, such as a mill.
The average particle size of the thermoelectric semiconductor particles was obtained by measuring with a laser diffraction particle size analyzer (manufactured by CILAS, Model 1064), and was defined as the median value of the particle size distribution.
また、熱電半導体微粒子は、アニール処理（以下、「アニール処理Ａ」ということがある。）されたものであることが好ましい。アニール処理Ａを行うことにより、熱電半導体微粒子は、結晶性が向上し、さらに、熱電半導体微粒子の表面酸化膜が除去されるため、熱電変換材料のゼーベック係数すなわちペルチェ係数が増大し、熱電性能指数をさらに向上させることができる。アニール処理Ａは、特に限定されないが、熱電半導体組成物を調製する前に、熱電半導体微粒子に悪影響を及ぼすことがないように、ガス流量が制御された、窒素、アルゴン等の不活性ガス雰囲気下、同じく水素等の還元ガス雰囲気下、または真空条件下で行うことが好ましく、不活性ガス及び還元ガスの混合ガス雰囲気下で行うことがより好ましい。具体的な温度条件は、用いる熱電半導体微粒子に依存するが、通常、微粒子の融点以下の温度で、かつ１００〜１５００℃で、数分〜数十時間行うことが好ましい。 Further, it is preferable that the thermoelectric semiconductor fine particles have been subjected to an annealing treatment (hereinafter, sometimes referred to as “annealing treatment A”). By performing the annealing treatment A, the crystallinity of the thermoelectric semiconductor particles is improved, and furthermore, since the surface oxide film of the thermoelectric semiconductor particles is removed, the Seebeck coefficient, that is, the Peltier coefficient of the thermoelectric conversion material increases, and the thermoelectric performance index increases. Can be further improved. Annealing treatment A is not particularly limited, but before preparing the thermoelectric semiconductor composition, under an inert gas atmosphere such as nitrogen or argon, the gas flow rate is controlled so as not to adversely affect the thermoelectric semiconductor particles. Similarly, it is preferably performed in an atmosphere of a reducing gas such as hydrogen or under vacuum conditions, and more preferably in an atmosphere of a mixed gas of an inert gas and a reducing gas. The specific temperature condition depends on the thermoelectric semiconductor fine particles to be used, but it is usually preferable to perform the heating at a temperature equal to or lower than the melting point of the fine particles and at 100 to 1500 ° C. for several minutes to tens of hours.
（イオン液体）
本発明で用いるイオン液体は、カチオンとアニオンとを組み合わせてなる溶融塩であり、−５０〜５００℃の幅広い温度領域において液体で存在し得る塩をいう。イオン液体は、蒸気圧が極めて低く不揮発性であること、優れた熱安定性及び電気化学安定性を有していること、粘度が低いこと、かつイオン伝導度が高いこと等の特徴を有しているため、導電補助剤として、熱電半導体微粒子間の電気伝導率の低減を効果的に抑制することができる。また、イオン液体は、非プロトン性のイオン構造に基づく高い極性を示し、耐熱性樹脂との相溶性に優れるため、熱電変換材料の電気伝導率を均一にすることができる。
(Ionic liquid)
The ionic liquid used in the present invention is a molten salt obtained by combining a cation and an anion, and refers to a salt that can exist as a liquid in a wide temperature range of −50 to 500 ° C. Ionic liquids have features such as extremely low vapor pressure, non-volatility, excellent thermal stability and electrochemical stability, low viscosity, and high ionic conductivity. Therefore, as a conductive auxiliary agent, it is possible to effectively suppress a decrease in electric conductivity between the thermoelectric semiconductor particles. In addition, the ionic liquid has a high polarity based on the aprotic ionic structure and has excellent compatibility with the heat-resistant resin, so that the electric conductivity of the thermoelectric conversion material can be made uniform.
イオン液体は、公知または市販のものが使用できる。例えば、ピリジニウム、ピリミジニウム、ピラゾリウム、ピロリジニウム、ピペリジニウム、イミダゾリウム等の窒素含有環状カチオン化合物及びそれらの誘導体；テトラアルキルアンモニウムのアミン系カチオン及びそれらの誘導体；ホスホニウム、トリアルキルスルホニウム、テトラアルキルホスホニウム等のホスフィン系カチオン及びそれらの誘導体；リチウムカチオン及びその誘導体等のカチオン成分と、Ｃｌ−、ＡｌＣｌ４ −、Ａｌ２Ｃｌ７ −、ＣｌＯ４ −等の塩化物イオン、Ｂｒ−等の臭化物イオン、Ｉ−等のヨウ化物イオン、ＢＦ４ −、ＰＦ６ −等のフッ化物イオン、Ｆ（ＨＦ）ｎ −等のハロゲン化物アニオン、ＮＯ３ −、ＣＨ３ＣＯＯ−、ＣＦ３ＣＯＯ−、ＣＨ３ＳＯ３ −、ＣＦ３ＳＯ３ −、（ＦＳＯ２）２Ｎ−、（ＣＦ３ＳＯ２）２Ｎ−、（ＣＦ３ＳＯ２）３Ｃ−、ＡｓＦ６ −、ＳｂＦ６ −、ＮｂＦ６ −、ＴａＦ６ −、Ｆ（ＨＦ）ｎ−、（ＣＮ）２Ｎ−、Ｃ４Ｆ９ＳＯ３ −、（Ｃ２Ｆ５ＳＯ２）２Ｎ−、Ｃ３Ｆ７ＣＯＯ−、（ＣＦ３ＳＯ２）（ＣＦ３ＣＯ）Ｎ−等のアニオン成分とから構成されるものが挙げられる。 Known or commercially available ionic liquids can be used. For example, nitrogen-containing cyclic cation compounds such as pyridinium, pyrimidinium, pyrazolium, pyrrolidinium, piperidinium, imidazolium and derivatives thereof; amine cations of tetraalkylammonium and derivatives thereof; phosphines such as phosphonium, trialkylsulfonium and tetraalkylphosphonium systems cations and their derivatives; and cationic components, such as lithium cations and derivatives thereof, Cl -, AlCl 4 -, Al 2 Cl 7 -, ClO 4 - chloride or ion, Br -, etc. of bromide ion, I -, etc. , Fluoride ions such as BF 4 − and PF 6 − , halide anions such as F (HF) n − , NO 3 − , CH 3 COO − , CF 3 COO − , CH 3 SO 3 − , CF 3 SO 3 -, FSO 2) 2 N -, ( CF 3 SO 2) 2 N -, (CF 3 SO 2) 3 C -, AsF 6 -, SbF 6 -, NbF 6 -, TaF 6 -, F (HF) n -, (CN) 2 N -, C 4 F 9 SO 3 -, (C 2 F 5 SO 2) 2 N -, C 3 F 7 COO -, (CF 3 SO 2) (CF 3 CO) N - like anion And a component.
上記のイオン液体の中で、高温安定性、熱電半導体微粒子及び樹脂との相溶性、熱電半導体微粒子間隙の電気伝導率の低下抑制等の観点から、イオン液体のカチオン成分が、ピリジニウムカチオン及びその誘導体、イミダゾリウムカチオン及びその誘導体から選ばれる少なくとも１種を含むことが好ましい。イオン液体のアニオン成分が、ハロゲン化物アニオンを含むことが好ましく、Ｃｌ−、Ｂｒ−及びＩ−から選ばれる少なくとも１種を含むことがさらに好ましい。 Among the above ionic liquids, the cation component of the ionic liquid is a pyridinium cation and a derivative thereof from the viewpoints of high-temperature stability, compatibility with the thermoelectric semiconductor fine particles and the resin, and suppression of a decrease in the electric conductivity of the gap between the thermoelectric semiconductor fine particles. , And at least one selected from imidazolium cations and derivatives thereof. The anion component of the ionic liquid preferably contains a halide anion, and more preferably contains at least one selected from Cl − , Br − and I − .
カチオン成分が、ピリジニウムカチオン及びその誘導体を含むイオン液体の具体的な例として、４−メチル−ブチルピリジニウムクロライド、３−メチル−ブチルピリジニウムクロライド、４−メチル−ヘキシルピリジニウムクロライド、３−メチル−ヘキシルピリジニウムクロライド、４−メチル−オクチルピリジニウムクロライド、３−メチル−オクチルピリジニウムクロライド、３、４−ジメチル−ブチルピリジニウムクロライド、３、５−ジメチル−ブチルピリジニウムクロライド、４−メチル−ブチルピリジニウムテトラフルオロボレート、４−メチル−ブチルピリジニウムヘキサフルオロホスフェート、１-ブチル-４-メチルピリジニウムブロミド、１-ブチル-４-メチルピリジニウムヘキサフルオロホスファート、１-ブチル-４-メチルピリジニウムヨージド等が挙げられる。この中で、１−ブチル−４−メチルピリジニウムブロミド、１−ブチル−４−メチルピリジニウムヘキサフルオロホスファート、１-ブチル-４-メチルピリジニウムヨージドが好ましい。 Specific examples of the ionic liquid in which the cation component contains a pyridinium cation and a derivative thereof include 4-methyl-butylpyridinium chloride, 3-methyl-butylpyridinium chloride, 4-methyl-hexylpyridinium chloride, and 3-methyl-hexylpyridinium. Chloride, 4-methyl-octylpyridinium chloride, 3-methyl-octylpyridinium chloride, 3,4-dimethyl-butylpyridinium chloride, 3,5-dimethyl-butylpyridinium chloride, 4-methyl-butylpyridinium tetrafluoroborate, 4- Methyl-butylpyridinium hexafluorophosphate, 1-butyl-4-methylpyridinium bromide, 1-butyl-4-methylpyridinium hexafluorophosphate, 1-butyl-4-methyl Lupi lysine iodide and the like. Among them, 1-butyl-4-methylpyridinium bromide, 1-butyl-4-methylpyridinium hexafluorophosphate, and 1-butyl-4-methylpyridinium iodide are preferred.
また、カチオン成分が、イミダゾリウムカチオン及びその誘導体を含むイオン液体の具体的な例として、［１−ブチル−３−（２−ヒドロキシエチル）イミダゾリウムブロミド］、［１−ブチル−３−（２−ヒドロキシエチル）イミダゾリウムテトラフルオロボレイト］、１−エチル−３−メチルイミダゾリウムクロライド、１−エチル−３−メチルイミダゾリウムブロミド、１−ブチル−３−メチルイミダゾリウムクロライド、１−ヘキシル−３−メチルイミダゾリウムクロライド、１−オクチル−３−メチルイミダゾリウムクロライド、１−デシル−３−メチルイミダゾリウムクロライド、１−デシル−３−メチルイミダゾリウムブロミド、１−ドデシル−３−メチルイミダゾリウムクロライド、１−テトラデシル−３−メチルイミダゾリウムクロライド、１−エチル−３−メチルイミダゾリウムテトラフロオロボレート、１−ブチル−３−メチルイミダゾリウムテトラフロオロボレート、１−ヘキシル−３−メチルイミダゾリウムテトラフロオロボレート、１−エチル−３−メチルイミダゾリウムヘキサフルオロホスフェート、１−ブチル−３−メチルイミダゾリウムヘキサフルオロホスフェート、１−メチル−３−ブチルイミダゾリウムメチルスルフェート、１、３−ジブチルイミダゾリウムメチルスルフェート等が挙げられる。この中で、［１−ブチル−３−（２−ヒドロキシエチル）イミダゾリウムブロミド］、［１−ブチル−３−（２−ヒドロキシエチル）イミダゾリウムテトラフルオロボレイト］が好ましい。 Specific examples of the ionic liquid in which the cation component contains an imidazolium cation and a derivative thereof include [1-butyl-3- (2-hydroxyethyl) imidazolium bromide] and [1-butyl-3- (2 -Hydroxyethyl) imidazolium tetrafluoroborate], 1-ethyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium bromide, 1-butyl-3-methylimidazolium chloride, 1-hexyl-3 -Methylimidazolium chloride, 1-octyl-3-methylimidazolium chloride, 1-decyl-3-methylimidazolium chloride, 1-decyl-3-methylimidazolium bromide, 1-dodecyl-3-methylimidazolium chloride, 1-tetradecyl-3-methylimidazo Um chloride, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3 -Methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-methyl-3-butylimidazolium methylsulfate, 1,3-dibutylimidazolium methylsulfate and the like. Among them, [1-butyl-3- (2-hydroxyethyl) imidazolium bromide] and [1-butyl-3- (2-hydroxyethyl) imidazolium tetrafluoroborate] are preferable.
上記のイオン液体は、電気伝導率が１０−７Ｓ／ｃｍ以上であることが好ましく、１０−６Ｓ／ｃｍ以上であることがより好ましい。イオン伝導度が上記範囲であれば、導電補助剤として、熱電半導体微粒子間の電気伝導率の低減を効果的に抑制することができる。 The above ionic liquid preferably has an electric conductivity of 10 −7 S / cm or more, and more preferably 10 −6 S / cm or more. When the ionic conductivity is within the above range, a decrease in the electrical conductivity between the thermoelectric semiconductor particles can be effectively suppressed as a conductive auxiliary.
また、上記のイオン液体は、分解温度が３００℃以上であることが好ましい。分解温度が上記範囲であれば、後述するように、熱電半導体組成物からなる薄膜をアニール処理した場合でも、導電補助剤としての効果を維持することができる。 Further, the ionic liquid preferably has a decomposition temperature of 300 ° C. or higher. When the decomposition temperature is in the above range, the effect as a conductive auxiliary agent can be maintained even when a thin film made of a thermoelectric semiconductor composition is annealed, as described later.
また、上記のイオン液体は、熱重量測定（ＴＧ）による３００℃における質量減少率が１０％以下であることが好ましく、５％以下であることがより好ましく、１％以下であることがさらに好ましい。質量減少率が上記範囲であれば、後述するように、熱電半導体組成物からなる薄膜をアニール処理した場合でも、導電補助剤としての効果を維持することができる。 Further, the ionic liquid has a mass reduction rate at 300 ° C. by thermogravimetry (TG) of preferably 10% or less, more preferably 5% or less, and still more preferably 1% or less. . When the mass reduction rate is in the above range, as described later, even when the thin film made of the thermoelectric semiconductor composition is annealed, the effect as the conductive auxiliary agent can be maintained.
前記イオン液体の前記熱電半導体組成物中の配合量は、好ましくは０．０１〜５０質量％、より好ましくは０．５〜３０質量％、さらに好ましくは１．０〜２０質量％である。前記イオン液体の配合量が、上記範囲内であれば、電気伝導率の低下が効果的に抑制され、高い熱電性能を有する膜が得られる。 The compounding amount of the ionic liquid in the thermoelectric semiconductor composition is preferably 0.01 to 50% by mass, more preferably 0.5 to 30% by mass, and further preferably 1.0 to 20% by mass. When the amount of the ionic liquid is within the above range, a decrease in electric conductivity is effectively suppressed, and a film having high thermoelectric performance can be obtained.
（耐熱性樹脂）
本発明に用いる耐熱性樹脂は、熱電半導体微粒子間のバインダーとして働き、熱電変換材料の屈曲性を高めるためのものである。該耐熱性樹脂は、特に制限されるものではないが、熱電半導体組成物からなる薄膜をアニール処理等により熱電半導体微粒子を結晶成長させる際に、樹脂としての機械的強度及び熱伝導率等の諸物性が損なわれず維持される耐熱性樹脂を用いる。
前記耐熱性樹脂としては、例えば、ポリアミド樹脂、ポリアミドイミド樹脂、ポリイミド樹脂、ポリエーテルイミド樹脂、ポリベンゾオキサゾール樹脂、ポリベンゾイミダゾール樹脂、エポキシ樹脂、及びこれらの樹脂の化学構造を有する共重合体等が挙げられる。前記耐熱性樹脂は、単独でも又は２種以上組み合わせて用いてもよい。これらの中でも、耐熱性がより高く、且つ薄膜中の熱電半導体微粒子の結晶成長に悪影響を及ぼさないという点から、ポリアミド樹脂、ポリアミドイミド樹脂、ポリイミド樹脂、エポキシ樹脂が好ましく、屈曲性に優れるという点からポリアミド樹脂、ポリアミドイミド樹脂、ポリイミド樹脂がより好ましい。前述の支持体として、ポリイミドフィルムを用いた場合、該ポリイミドフィルムとの密着性などの点から、耐熱性樹脂としては、ポリイミド樹脂がより好ましい。なお、本発明においてポリイミド樹脂とは、ポリイミド及びその前駆体を総称する。
(Heat-resistant resin)
The heat-resistant resin used in the present invention functions as a binder between the thermoelectric semiconductor fine particles, and serves to enhance the flexibility of the thermoelectric conversion material. The heat-resistant resin is not particularly limited. However, when a thin film of the thermoelectric semiconductor composition is subjected to crystal growth of thermoelectric semiconductor particles by annealing or the like, various properties such as mechanical strength and thermal conductivity of the resin are used. Use a heat-resistant resin whose physical properties are maintained without being impaired.
Examples of the heat-resistant resin include polyamide resins, polyamide-imide resins, polyimide resins, polyetherimide resins, polybenzoxazole resins, polybenzimidazole resins, epoxy resins, and copolymers having a chemical structure of these resins. Is mentioned. The heat resistant resins may be used alone or in combination of two or more. Among these, polyamide resin, polyamide imide resin, polyimide resin, and epoxy resin are preferable in that they have higher heat resistance and do not adversely affect the crystal growth of the thermoelectric semiconductor fine particles in the thin film, and are excellent in flexibility. Thus, a polyamide resin, a polyamideimide resin, and a polyimide resin are more preferable. When a polyimide film is used as the above-described support, the heat-resistant resin is more preferably a polyimide resin from the viewpoint of adhesion to the polyimide film. In the present invention, the polyimide resin is a general term for polyimide and its precursor.
前記耐熱性樹脂は、分解温度が３００℃以上であることが好ましい。分解温度が上記範囲であれば、後述するように、熱電半導体組成物からなる薄膜をアニール処理した場合でも、バインダーとして機能が失われることなく、熱電変換材料の屈曲性を維持することができる。 The heat-resistant resin preferably has a decomposition temperature of 300 ° C. or higher. When the decomposition temperature is in the above range, the flexibility of the thermoelectric conversion material can be maintained without losing the function as a binder even when the thin film made of the thermoelectric semiconductor composition is annealed, as described later.
また、前記耐熱性樹脂は、熱重量測定（ＴＧ）による３００℃における質量減少率が１０％以下であることが好ましく、５％以下であることがより好ましく、１％以下であることがさらに好ましい。質量減少率が上記範囲であれば、後述するように、熱電半導体組成物からなる薄膜をアニール処理した場合でも、バインダーとして機能が失われることなく、熱電変換材料の屈曲性を維持することができる。 Further, the heat-resistant resin preferably has a mass reduction rate at 300 ° C. by thermogravimetry (TG) of 10% or less, more preferably 5% or less, and still more preferably 1% or less. . If the mass reduction rate is in the above range, as described later, even when the thin film made of the thermoelectric semiconductor composition is annealed, the flexibility of the thermoelectric conversion material can be maintained without losing the function as a binder. .
前記耐熱性樹脂の前記熱電半導体組成物中の配合量は、０．１〜４０質量％、好ましくは０．５〜２０質量％、より好ましくは、１〜２０質量％、さらに好ましくは２〜１５質量％である。前記耐熱性樹脂の配合量が、上記範囲内であれば、高い熱電性能と皮膜強度が両立した膜が得られる。 The compounding amount of the heat-resistant resin in the thermoelectric semiconductor composition is 0.1 to 40% by mass, preferably 0.5 to 20% by mass, more preferably 1 to 20% by mass, and further preferably 2 to 15% by mass. % By mass. When the amount of the heat-resistant resin is within the above range, a film having both high thermoelectric performance and high film strength can be obtained.
本発明で用いる熱電半導体組成物には、前記熱半導体微粒子、前記耐熱性樹脂及び前記イオン液体以外に、必要に応じて、さらに分散剤、造膜助剤、光安定剤、酸化防止剤、粘着付与剤、可塑剤、着色剤、樹脂安定剤、充てん剤、顔料、導電性フィラー、導電性高分子、硬化剤等の他の添加剤を含んでいてもよい。これらの添加剤は、１種単独で、あるいは２種以上を組み合わせて用いることができる。 In the thermoelectric semiconductor composition used in the present invention, in addition to the heat semiconductor fine particles, the heat-resistant resin and the ionic liquid, if necessary, further a dispersant, a film-forming aid, a light stabilizer, an antioxidant, an adhesive Other additives such as a imparting agent, a plasticizer, a colorant, a resin stabilizer, a filler, a pigment, a conductive filler, a conductive polymer, and a curing agent may be included. These additives can be used alone or in combination of two or more.
本発明で用いる熱電半導体組成物の調製方法は、特に制限はなく、超音波ホモジナイザー、スパイラルミキサー、プラネタリーミキサー、ディスパーサー、ハイブリッドミキサー等の公知の方法により、前記熱電半導体微粒子と前記イオン液体及び前記耐熱性樹脂、必要に応じて前記その他の添加剤、さらに溶媒を加えて、混合分散させ、当該熱電半導体組成物を調製すればよい。
前記溶媒としては、例えば、トルエン、酢酸エチル、メチルエチルケトン、アルコール、テトラヒドロフラン、メチルピロリドン、エチルセロソルブ等の溶媒などが挙げられる。これらの溶媒は、１種を単独で用いてもよく、２種以上を混合して用いてもよい。熱電半導体組成物の固形分濃度としては、該組成物が塗工に適した粘度であればよく、特に制限はない。
The method for preparing the thermoelectric semiconductor composition used in the present invention is not particularly limited, and the thermoelectric semiconductor particles and the ionic liquid may be prepared by a known method such as an ultrasonic homogenizer, a spiral mixer, a planetary mixer, a disperser, and a hybrid mixer. What is necessary is just to add the said heat-resistant resin, the said other additive as needed, and also a solvent, mix and disperse, and just prepare the said thermoelectric semiconductor composition.
Examples of the solvent include solvents such as toluene, ethyl acetate, methyl ethyl ketone, alcohol, tetrahydrofuran, methylpyrrolidone, and ethyl cellosolve. These solvents may be used alone or as a mixture of two or more. The solid content concentration of the thermoelectric semiconductor composition is not particularly limited as long as the composition has a viscosity suitable for coating.
前記熱電半導体組成物からなる薄膜は、後述するペルチェ冷却素子の製造方法で説明するように、支持体上に、前記熱電半導体組成物を塗布し、乾燥することで形成することができる。このように形成することで、簡便に低コストで大面積の熱電変換材料を得ることができる。 The thin film made of the thermoelectric semiconductor composition can be formed by applying the thermoelectric semiconductor composition on a support and drying it, as described in a method of manufacturing a Peltier cooling element described below. By forming in this manner, a large-area thermoelectric conversion material can be easily obtained at low cost.
前記熱電半導体組成物からなる薄膜の厚みは、特に制限はないが、熱電性能と皮膜強度の点から、好ましくは１００ｎｍ〜２００μｍ、より好ましくは３００ｎｍ〜１５０μｍ、さらに好ましくは５μｍ〜１５０μｍである。本発明のペルチェ冷却素子は熱伝導性フィルムの貼付により２００μｍ以下の薄膜であっても、従来の数ｍｍオーダーのモジュールと同等の温度差を付与することが可能である。 The thickness of the thin film made of the thermoelectric semiconductor composition is not particularly limited, but is preferably 100 nm to 200 μm, more preferably 300 nm to 150 μm, and still more preferably 5 μm to 150 μm from the viewpoint of thermoelectric performance and film strength. The Peltier cooling element of the present invention can provide a temperature difference equivalent to that of a conventional module of the order of several mm even if the Peltier cooling element is a thin film having a thickness of 200 μm or less by sticking a heat conductive film.
＜熱伝導性フィルム＞
Ｉｎ−ｐｌａｎｅ型熱電変換モジュールにおいては、電気的に直列に接続された、薄膜からなるｐ型及びｎ型熱電素子の接合部の温度が、接続方向に、例えば、交互に高温部及び低温部となる。本発明に用いる熱伝導性フィルムは、生じた高温部と低温部間の面内方向の温度勾配を、特定の方向に選択的に変換する、すなわち、熱伝導性フィルムの厚み方向の温度勾配に変換するために用いられる。具体的には、熱伝導性フィルムの構成、配置等を適宜調整し、熱伝導性フィルム外面間の温度差を効率良く得られるように制御することにより、Ｉｎ−ｐｌａｎｅ型ペルチェ冷却素子とした時に、冷却性能をより向上させることができる。また、前記熱電変換材料と組み合わせることで、さらに優れた冷却効果が得られる。
<Thermal conductive film>
In the In-plane type thermoelectric conversion module, the temperature of the junction of the thin-film p-type and n-type thermoelectric elements electrically connected in series, in the connection direction, for example, alternately with the high-temperature part and the low-temperature part Become. The heat conductive film used in the present invention selectively converts the generated temperature gradient in the in-plane direction between the high-temperature portion and the low-temperature portion into a specific direction, that is, a temperature gradient in the thickness direction of the heat conductive film. Used to convert. Specifically, by appropriately adjusting the configuration, arrangement, and the like of the heat conductive film, and controlling the temperature difference between the outer surfaces of the heat conductive film to be efficiently obtained, an In-plane type Peltier cooling element can be obtained. The cooling performance can be further improved. Further, by combining with the thermoelectric conversion material, a more excellent cooling effect can be obtained.
本発明に用いる熱伝導性フィルムは、高熱伝導部と低熱伝導部とから構成される。熱伝導性フィルムは、用途に応じて、例えば、薄膜との絶縁性、密着強度を向上させる等のために、接着剤層を積層することが好ましい。
例えば、図１（ｂ）における熱伝導性フィルム６Ａ又は６Ｂは、高熱伝導部７と低熱伝導部８とからなり、高熱伝導部７と低熱伝導部８とが交互に配置され、さらに接着剤層９が積層されたフィルム構成となっている。熱伝導性フィルムを構成する高熱伝導部と低熱伝導部の配置は、特に制限されず、適宜調整して用いられる。
The heat conductive film used in the present invention is composed of a high heat conductive part and a low heat conductive part. It is preferable that the heat conductive film is laminated with an adhesive layer, for example, in order to improve insulation properties and adhesion strength with a thin film, etc., depending on the use.
For example, the heat conductive film 6A or 6B in FIG. 1B includes a high heat conductive portion 7 and a low heat conductive portion 8, wherein the high heat conductive portions 7 and the low heat conductive portions 8 are alternately arranged, and further, an adhesive layer 9 is a laminated film configuration. The arrangement of the high heat conductive portion and the low heat conductive portion constituting the heat conductive film is not particularly limited, and is appropriately adjusted and used.
〈高熱伝導部〉
高熱伝導部は、樹脂組成物、金属等から形成されるが、柔軟性の優れるフィルムが得られることから、樹脂組成物から形成されることが好ましい。前記高熱伝導部の形状は、特に制限はなく、用いるペルチェ冷却素子の仕様に応じて、適宜変更することができる。ここで、本発明における高熱伝導部は、後述する低熱伝導部よりも熱伝導率が高いほうをいう。
<High heat conduction section>
The high heat conductive portion is formed from a resin composition, a metal, or the like, but is preferably formed from a resin composition because a film having excellent flexibility is obtained. The shape of the high heat conducting portion is not particularly limited, and can be appropriately changed according to the specification of the Peltier cooling element to be used. Here, the high heat conducting part in the present invention means one having a higher thermal conductivity than a low heat conducting part described later.
（樹脂）
高熱伝導部に用いる樹脂は、特に限定されないが、電子部品分野等で使用されているものの中から任意の樹脂を適宜選択することができる。
樹脂としては、熱硬化性樹脂、熱可塑性樹脂、光硬化性樹脂等が挙げられる。耐熱性に優れ、放熱性が低下しにくいという点からポリイミド、ポリアミドイミドが好ましい。
(resin)
The resin used for the high heat conductive portion is not particularly limited, but any resin can be appropriately selected from those used in the field of electronic components and the like.
Examples of the resin include a thermosetting resin, a thermoplastic resin, and a photocurable resin. Polyimide and polyamide imide are preferred because they are excellent in heat resistance and hardly deteriorate heat radiation.
高熱伝導部は、所望の熱伝導率に調整するために、上記樹脂と熱伝導性フィラー及び／又は導電性炭素化合物とを含む樹脂組成物から形成されることが好ましい。
以下、熱伝導性フィラー及び導電性炭素化合物を「熱伝導率調整用物質」ということがある。
熱伝導性フィラーとしては、特に制限はないが、シリカ、アルミナ、酸化マグネシウム等の金属酸化物、窒化ケイ素、窒化アルミニウム、窒化マグネシウム、窒化ホウ素等の金属窒化物、銅、アルミニウム等の金属から選ばれる少なくとも１種類、また、導電性炭素化合物としては、カーボンブラック、カーボンナノチューブ（ＣＮＴ）、グラフェン、カーボンナノファイバー等から選ばれる少なくとも１種類が好ましい。
The high heat conducting portion is preferably formed from a resin composition containing the above resin and a heat conductive filler and / or a conductive carbon compound in order to adjust the heat conductivity to a desired value.
Hereinafter, the thermally conductive filler and the conductive carbon compound may be referred to as a “thermal conductivity adjusting substance”.
The heat conductive filler is not particularly limited, but is selected from metal oxides such as silica, alumina and magnesium oxide, metal nitrides such as silicon nitride, aluminum nitride, magnesium nitride and boron nitride, and metals such as copper and aluminum. The conductive carbon compound is preferably at least one selected from carbon black, carbon nanotube (CNT), graphene, carbon nanofiber, and the like.
〈低熱伝導部〉
低熱伝導部は、前記高熱伝導部よりも熱伝導率が低い材料であれば特に限定されず、樹脂組成物、金属等から形成される。なかでも、柔軟性の優れる基材が得られることから、樹脂組成物から形成されることが好ましい。樹脂としては、特に制限されないが、前述した高熱伝導部に用いた樹脂と同一種類の樹脂が挙げられる。通常、機械的特性、接着性等の観点から高熱伝導部に用いる樹脂と同一樹脂を用いる。
なお、前記高熱伝導部の熱伝導率より十分低ければ、該樹脂組成物中に熱伝導率調整用物質を含んでいてもよく、例えば、硬化収縮率の低減効果を有する中空フィラー等が挙げられる。
中空フィラーとしては、特に制限されず、公知のものを用いることができ、例えば、ガラスバルーン、シリカバルーン、シラスバルーン、フライアッシュバルーン、金属ケイ酸塩等のバルーン（中空体）である無機物系中空フィラー、また、アクリロニトリル、塩化ビニリデン、フェノール樹脂、エポキシ樹脂、尿素樹脂等のバルーン（中空体）である有機樹脂物系中空フィラーが挙げられる。中空フィラーは１種単独で、又は２種以上を組み合わせて用いることができる。このなかで、物質自身の熱伝導率が金属酸化物の中で比較的低く、さらに体積抵抗率、コストの観点から、無機物系中空フィラーであるガラス中空フィラー、又はシリカ中空フィラーが好ましい。具体的には、ガラス中空フィラーとしては、例えば、住友スリーエム社製のグラスバブルズ（ソーダ石灰硼珪酸ガラス）等が、シリカ中空フィラーとしては、例えば、日鉄鉱業株式会社製のシリナックス（登録商標）等が挙げられる。
なお、本発明における、「中空フィラー」とは、フィラーを構成材料とする外殻を有し、内部が中空構造（内部は空気以外に、不活性気体等の気体で満たされていてもよく、真空であってもよい）となっているフィラーをいい、該中空構造としては、特に制限されず、例えば、中空構造が球体であっても楕円体等であってもよく、中空構造が複数あってもよい。
中空フィラーの形状は、特に制限されるものではないが、本発明のペルチェ冷却素子に貼付した際に、それらの接触又は機械的損傷により、冷却特性又は電気特性等が損なわれない形状であればよく、例えば、板状（鱗片状を含む）、球状、針状、棒状、繊維状のいずれでもよい。均一分散、熱伝導率性を低下させる観点からは、球状であることが好ましい。
<Low thermal conductivity>
The low heat conductive portion is not particularly limited as long as it has a lower thermal conductivity than the high heat conductive portion, and is formed of a resin composition, a metal, or the like. Above all, it is preferable to be formed from a resin composition, since a substrate having excellent flexibility can be obtained. The resin is not particularly limited, but may be the same type of resin as the resin used for the above-described high heat conducting portion. Usually, the same resin as the resin used for the high heat conducting portion is used from the viewpoint of mechanical properties, adhesiveness and the like.
In addition, if it is sufficiently lower than the thermal conductivity of the high thermal conductive portion, the resin composition may include a thermal conductivity adjusting substance, and examples thereof include a hollow filler having an effect of reducing the curing shrinkage. .
The hollow filler is not particularly limited, and a known filler can be used. For example, an inorganic hollow such as a balloon (hollow body) such as a glass balloon, a silica balloon, a shirasu balloon, a fly ash balloon, and a metal silicate is used. Fillers, and organic resin-based hollow fillers that are balloons (hollow bodies) such as acrylonitrile, vinylidene chloride, phenolic resins, epoxy resins, and urea resins are also included. The hollow filler can be used alone or in combination of two or more. Among these, a glass hollow filler or a silica hollow filler, which is an inorganic hollow filler, is preferable from the viewpoint of volume resistivity and cost, since the substance itself has a relatively low thermal conductivity among metal oxides. Specifically, as the glass hollow filler, for example, Glass Bubbles (soda lime borosilicate glass) manufactured by Sumitomo 3M Limited, and as the silica hollow filler, for example, Silex (registered trademark) manufactured by Nittetsu Mining Co., Ltd. Trademark) and the like.
In the present invention, the "hollow filler" has an outer shell having a filler as a constituent material, and the inside has a hollow structure (the inside may be filled with a gas such as an inert gas other than air, The hollow structure may be a sphere, an ellipsoid, or the like, and may have a plurality of hollow structures. You may.
The shape of the hollow filler is not particularly limited, but when affixed to the Peltier cooling element of the present invention, as long as the shape does not impair cooling characteristics or electrical characteristics due to their contact or mechanical damage. For example, the shape may be any of a plate shape (including a scale shape), a spherical shape, a needle shape, a rod shape, and a fiber shape. From the viewpoint of reducing the uniform dispersion and the thermal conductivity, the particles are preferably spherical.
高熱伝導部及び低熱伝導部のそれぞれの層の厚さは、１〜２００μｍが好ましく、３〜１００μｍがさらに好ましい。この範囲であれば、熱を特定の方向に選択的に放熱することができる。また、高熱伝導部及び低熱伝導部のそれぞれの層の厚さは、同じであっても異なっていてもよい。
高熱伝導部及び低熱伝導部のそれぞれの層の幅は、適用するペルチェ冷却素子の仕様により適宜調整して用いるが、通常、０．０１〜３ｍｍ、好ましくは０．１〜２ｍｍ、さらに好ましくは０．５〜１．５ｍｍである。この範囲であれば、熱を特定の方向に選択的に放熱することができる。また、高熱伝導部及び低熱伝導部のそれぞれの層の幅は、同じであっても異なっていてもよい。
The thickness of each layer of the high heat conduction part and the low heat conduction part is preferably from 1 to 200 μm, more preferably from 3 to 100 μm. Within this range, heat can be selectively radiated in a specific direction. The thickness of each layer of the high heat conduction part and the low heat conduction part may be the same or different.
The width of each layer of the high heat conduction part and the low heat conduction part is appropriately adjusted and used depending on the specification of the Peltier cooling element to be applied, and is usually 0.01 to 3 mm, preferably 0.1 to 2 mm, more preferably 0 to 2 mm. 0.5 to 1.5 mm. Within this range, heat can be selectively radiated in a specific direction. Further, the width of each layer of the high heat conduction part and the low heat conduction part may be the same or different.
高熱伝導部の熱伝導率は、低熱伝導部の熱伝導率に比べて十分に高ければよく、熱伝導率が０．５（Ｗ／ｍ・Ｋ）以上が好ましく、１．０（Ｗ／ｍ・Ｋ）以上がより好ましく、１．３（Ｗ／ｍ・Ｋ）以上がさらに好ましい。高熱伝導部の熱伝導率の上限は、特に制限はないが、通常２０００（Ｗ／ｍ・Ｋ）以下が好ましく、５００（Ｗ／ｍ・Ｋ）以下がより好ましい。 The thermal conductivity of the high thermal conductivity portion may be sufficiently higher than the thermal conductivity of the low thermal conductivity portion, and the thermal conductivity is preferably 0.5 (W / m · K) or more, and 1.0 (W / m · K) or more, more preferably 1.3 (W / m · K) or more. The upper limit of the thermal conductivity of the high thermal conductivity portion is not particularly limited, but is usually preferably 2000 (W / m · K) or less, more preferably 500 (W / m · K) or less.
低熱伝導部の熱伝導率は、０．５（Ｗ／ｍ・Ｋ）未満が好ましく、０．３（Ｗ／ｍ・Ｋ）以下がより好ましく、０．２５（Ｗ／ｍ・Ｋ）以下がさらに好ましい。高熱伝導部及び低熱伝導部のそれぞれの熱伝導率が上記のような範囲にあれば、熱を特定の方向に選択的に放熱することができる。 The thermal conductivity of the low thermal conductive portion is preferably less than 0.5 (W / m · K), more preferably 0.3 (W / m · K) or less, and 0.25 (W / m · K) or less. More preferred. If the heat conductivity of each of the high heat conduction part and the low heat conduction part is in the above range, heat can be selectively radiated in a specific direction.
［ペルチェ冷却素子の製造方法］
本発明のペルチェ冷却素子の製造方法は、支持体上に、熱電半導体微粒子、耐熱性樹脂及びイオン液体を含む熱電半導体組成物からなる薄膜を有する熱電変換材料を用いたペルチェ冷却素子の製造方法であって、支持体上に、熱電半導体微粒子、耐熱性樹脂及びイオン液体を含む熱電半導体組成物を塗布し、乾燥し、薄膜を形成する工程、該薄膜をアニール処理する工程、さらに高熱伝導部と低熱伝導部とを備えた熱伝導性フィルムを片面又は両面に貼付する工程を含む、ペルチェ冷却素子の製造方法である。
以下、本発明に含まれる工程について、順次説明する。
[Method of manufacturing Peltier cooling element]
The method of manufacturing a Peltier cooling element of the present invention is a method of manufacturing a Peltier cooling element using a thermoelectric conversion material having a thin film made of a thermoelectric semiconductor composition containing thermoelectric semiconductor fine particles, a heat-resistant resin and an ionic liquid on a support. A thermoelectric semiconductor fine particle, a thermoelectric semiconductor composition containing a heat-resistant resin and an ionic liquid, coated on a support, dried, a step of forming a thin film, a step of annealing the thin film, and a high heat conductive portion. A method for manufacturing a Peltier cooling element, including a step of attaching a heat conductive film having a low heat conductive portion to one or both surfaces.
Hereinafter, the steps included in the present invention will be sequentially described.
（薄膜形成工程）
本発明に用いた熱電半導体組成物を、支持体上に塗布する方法としては、スクリーン印刷、フレキソ印刷、グラビア印刷、スピンコート、ディップコート、ダイコート、スプレーコート、バーコート、ドクターブレード等の公知の方法が挙げられ、特に制限されない。塗膜をパターン状に形成する場合は、所望のパターンを有するスクリーン版を用いて簡便にパターン形成が可能なスクリーン印刷、スロットダイコート等が好ましく用いられる。
次いで、得られた塗膜を乾燥することにより、薄膜が形成されるが、乾燥方法としては、熱風乾燥、熱ロール乾燥、赤外線照射等、従来公知の乾燥方法が採用できる。加熱温度は、通常、８０〜１５０℃であり、加熱時間は、加熱方法により異なるが、通常、数秒〜数十分である。
また、熱電半導体組成物の調製において溶媒を使用した場合、加熱温度は、使用した溶媒を乾燥できる温度範囲であれば、特に制限はない。
(Thin film formation process)
As a method of applying the thermoelectric semiconductor composition used in the present invention on a support, screen printing, flexographic printing, gravure printing, spin coating, dip coating, die coating, spray coating, bar coating, known as a doctor blade and the like There is no particular limitation. When the coating film is formed in a pattern, screen printing, slot die coating, and the like, which can easily form a pattern using a screen plate having a desired pattern, are preferably used.
Subsequently, the obtained coating film is dried to form a thin film. As the drying method, conventionally known drying methods such as hot air drying, hot roll drying, and infrared irradiation can be employed. The heating temperature is usually 80 to 150 ° C., and the heating time varies depending on the heating method, but is usually several seconds to several tens of minutes.
When a solvent is used in the preparation of the thermoelectric semiconductor composition, the heating temperature is not particularly limited as long as the used solvent can be dried.
（アニール処理工程）
得られた熱電変換材料は、薄膜形成後、さらにアニール処理（以下、「アニール処理Ｂ」ということがある。）を行う。該アニール処理Ｂを行うことで、熱電性能を安定化させるとともに、薄膜中の熱電半導体微粒子を結晶成長させることができ、熱電性能をさらに向上させることができる。アニール処理Ｂは、特に限定されないが、通常、ガス流量が制御された、窒素、アルゴン等の不活性ガス雰囲気下、同じく水素等の還元ガス雰囲気下、または真空条件下で行われ、用いる樹脂及びイオン性流体の耐熱温度等に依存するが、１００〜５００℃で、数分〜数十時間行われ、不活性ガス及び還元ガスの混合ガス雰囲気下で行うことがより好ましい。
(Annealing process)
After forming the thin film, the obtained thermoelectric conversion material is further subjected to an annealing treatment (hereinafter, sometimes referred to as “annealing treatment B”). By performing the annealing treatment B, the thermoelectric performance can be stabilized, and the thermoelectric semiconductor particles in the thin film can be crystal-grown, so that the thermoelectric performance can be further improved. Although the annealing treatment B is not particularly limited, it is usually performed under an inert gas atmosphere such as nitrogen or argon, in which the gas flow rate is controlled, under a reducing gas atmosphere such as hydrogen, or under vacuum conditions. Although it depends on the heat resistance temperature of the ionic fluid, it is carried out at 100 to 500 ° C. for several minutes to several tens of hours, and more preferably in an atmosphere of a mixed gas of an inert gas and a reducing gas.
（熱伝導性フィルム貼付工程）
熱伝導性フィルム貼付工程は、前記アニール処理工程で得られた薄膜の片面又は両面に、高熱伝導部及び低熱伝導部を有する熱伝導性フィルムを貼付し、Ｉｎ−ｐｌａｎｅ型のペルチェ冷却素子を作製する工程である。通常、冷却性能の観点から、両面に貼付する。
熱伝導性フィルムの貼付は、ｐ型熱電素子とｎ型熱電素子とが交互に電気的に直列に接続された薄膜上になされ、熱伝導性フィルムを貼付後、ｐｎ接合部の温度が、接続方向に交互に高温部及び低温部となるように、薄膜と熱伝導性フィルム間（両面に貼付する場合は、熱伝導性フィルム／薄膜／熱伝導性フィルムの３者間）のアライメントを精度よくとり、貼付する。
例えば、熱伝導性フィルムの貼付は、図１においては、以下のように行われる。
（１）作製した前記アニール処理工程で得られた薄膜の一方の面側に対し、電極５ｂ、５ｄに共通の電極間中心線５ｂｄ上に、接着剤層９を介し熱伝導性フィルム６Ａの高熱伝導部と低熱伝導部の界面が重なるように配置し、ロールラミネーター（日本オフィスラミネーター株式会社製、ＲＳＬ−３８２Ｓ）等を用いて熱伝導性フィルム６Ａを貼付する。
（２）前記薄膜の他方の面側に、支持体２及び接着剤層９を介し、熱伝導性フィルム６Ｂを、高熱伝導部と低熱伝導部とが、前記熱伝導性フィルム６Ａの高熱伝導部と低熱伝導部に対し互いに異種の熱伝導部同士が対向するように、ロールラミネーター等を用いて貼付する。
なお、（１）と（２）の貼付順序は、特に制限されない。
(Heat conductive film sticking process)
In the heat conductive film sticking step, a heat conductive film having a high heat conductive part and a low heat conductive part is stuck on one or both surfaces of the thin film obtained in the annealing treatment step to produce an In-plane type Peltier cooling element. This is the step of performing Usually, it is stuck on both sides from the viewpoint of cooling performance.
The heat conductive film is attached on a thin film in which the p-type thermoelectric element and the n-type thermoelectric element are alternately electrically connected in series, and after the heat conductive film is attached, the temperature of the pn junction becomes lower. The alignment between the thin film and the heat conductive film (or the heat conductive film / thin film / heat conductive film, when sticking on both sides) is precisely performed so that the hot and cold parts alternately in the direction. Take and attach.
For example, the attachment of the heat conductive film is performed as follows in FIG.
(1) With respect to one surface side of the thin film obtained in the annealing process, the high heat of the heat conductive film 6A is disposed on the center line 5bd between the electrodes common to the electrodes 5b and 5d with the adhesive layer 9 interposed therebetween. The heat conductive film 6A is attached using a roll laminator (RSL-382S, manufactured by Japan Office Laminator Co., Ltd.) or the like so that the interface between the conductive portion and the low heat conductive portion overlaps.
(2) On the other surface side of the thin film, the heat conductive film 6B, the high heat conductive portion and the low heat conductive portion are interposed via the support 2 and the adhesive layer 9, and the high heat conductive portion of the heat conductive film 6A. It is attached using a roll laminator or the like such that different types of heat conductive portions face each other with respect to the low heat conductive portion.
The order of pasting (1) and (2) is not particularly limited.
本発明の製造方法によれば、簡便な方法で熱電性能が高く、低コストの熱電変換材料を用いたペルチェ冷却素子を得ることができる。 According to the manufacturing method of the present invention, it is possible to obtain a Peltier cooling element using a low-cost thermoelectric conversion material having high thermoelectric performance by a simple method.
次に、本発明を実施例によりさらに詳細に説明するが、本発明は、これらの例によってなんら限定されるものではない。 Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
実施例及び比較例で作製した熱電変換材料の熱電性能評価、屈曲性評価及びペルチェ冷却素子の冷却特性評価は、以下の方法で行った。 The thermoelectric performance evaluation, the flexibility evaluation, and the cooling characteristic evaluation of the Peltier cooling element of the thermoelectric conversion materials produced in the examples and the comparative examples were performed by the following methods.
＜熱電性能評価＞
（ａ）電気伝導率
実施例及び比較例で作製した熱電変換材料を、表面抵抗測定装置（三菱化学社製、商品名：ロレスタＧＰ ＭＣＰ−Ｔ６００）により、四端子法で試料の表面抵抗値を測定し、電気伝導率（σ）を算出した。
（ｂ）ゼーベック係数
ＪＩＳ Ｃ ２５２７:１９９４に準拠して実施例及び比較例で作製した熱電変換材料の熱起電力を測定し、ゼーベック係数（Ｓ）を算出した。作製した熱変換材料の一端を加熱して、熱変換材料の両端に生じる温度差をクロメル−アルメル熱電対を使用し測定し、熱電対設置位置に隣接した電極から熱起電力を測定した。
具体的には、温度差と起電力を測定する試料の両端間距離を２５ｍｍとし、一端を２０℃に保ち、他端を２５℃から５０℃まで１℃刻みで加熱し、その際の熱起電力を測定して、傾きからゼーベック係数（Ｓ）を算出した。なお、熱電対及び電極の設置位置は、薄膜の中心線に対し、互いに対称の位置にあり、熱電対と電極の距離は１ｍｍである。
（ｃ）熱伝導率
作製した熱電変換材料の熱伝導率測定は３ω法を用いて熱伝導率（λ）を算出した。
得られた、電気伝導率、ゼーベック係数及び熱伝導率から、熱電性能指数Ｚ（Ｚ＝σＳ２／λ）を求め、無次元熱電性能指数ＺＴ（Ｔ＝３００Ｋ）を算出した。
また、熱伝導性放熱フィルムの高熱伝導部、低熱伝導部の熱伝導率は、熱伝導率測定装置（ＥＫＯ社製、ＨＣ−１１０）を用いて、測定した。
<Thermoelectric performance evaluation>
(A) Electric Conductivity The thermoelectric conversion materials prepared in Examples and Comparative Examples were subjected to a surface resistance measurement device (manufactured by Mitsubishi Chemical Corporation, trade name: Loresta GP MCP-T600) to determine the surface resistance value of the sample by a four-terminal method. It measured and calculated the electric conductivity ((sigma)).
(B) Seebeck coefficient The thermoelectric power of the thermoelectric conversion materials produced in Examples and Comparative Examples was measured according to JIS C 2527: 1994, and the Seebeck coefficient (S) was calculated. One end of the produced heat conversion material was heated, a temperature difference generated at both ends of the heat conversion material was measured using a chromel-alumel thermocouple, and a thermoelectromotive force was measured from an electrode adjacent to the thermocouple installation position.
Specifically, the distance between both ends of the sample for measuring the temperature difference and the electromotive force was set to 25 mm, one end was kept at 20 ° C., and the other end was heated from 25 ° C. to 50 ° C. in 1 ° C. steps. The power was measured, and the Seebeck coefficient (S) was calculated from the slope. The thermocouple and the electrode were installed at positions symmetrical to each other with respect to the center line of the thin film, and the distance between the thermocouple and the electrode was 1 mm.
(C) Thermal conductivity In the measurement of the thermal conductivity of the produced thermoelectric conversion material, the thermal conductivity (λ) was calculated using the 3ω method.
From the obtained electric conductivity, Seebeck coefficient and thermal conductivity, a thermoelectric figure of merit Z (Z = σS 2 / λ) was obtained, and a dimensionless thermoelectric figure of merit ZT (T = 300K) was calculated.
Moreover, the thermal conductivity of the high thermal conductive part and the low thermal conductive part of the thermal conductive heat dissipation film was measured using a thermal conductivity measuring device (HC-110, manufactured by EKO).
＜冷却特性評価＞
実施例及び比較例で作製したｐ型及びｎ型熱電素子、及び熱伝導性フィルムを用いて構成したＩｎ−ｐｌａｎｅ型ペルチェ冷却素子を、図２に示す冷却特性評価ユニット１１の所定の位置に配置し、冷却特性評価を行った。
具体的には、被着体である加熱ユニット１３に、Ｉｎ−ｐｌａｎｅ型ペルチェ冷却素子１２を構成するＩｎ−ｐｌａｎｅ型熱電変換モジュール１２ａの一方の熱伝導性フィルム１２ｂの冷却面側（吸熱側）を貼付し、他方の熱伝導性フィルム１２ｃの排熱面側（放熱側）には、ヒートシンク１４を介してチラーユニット１５（冷却水；温度設定０℃）を配置した。加熱ユニット１３から３Ｗの熱量を供給し、Ｉｎ−ｐｌａｎｅ型ペルチェ冷却素子１２の熱電素子の両端の電極に、直流電源より０．５Ｖ印加した時のＩｎ−ｐｌａｎｅ型ペルチェ冷却素子１２の冷却面側と、Ｉｎ−ｐｌａｎｅ型ペルチェ冷却素子１２の排熱面側との温度差を測定した。
なお、加熱ユニット１３とＩｎ−ｐｌａｎｅ型ペルチェ冷却素子１２間に熱伝導グリス１６を、Ｉｎ−ｐｌａｎｅ型ペルチェ冷却素子１２とヒートシンク１４間に熱伝導グリス１７を、ヒートシンク１４とチラーユニット１５間に熱伝導グリス１８を設け、それぞれの界面において、空気を巻き込みにくくし、熱抵抗を低く抑えた。
<Cooling characteristic evaluation>
The p-type and n-type thermoelectric elements manufactured in the example and the comparative example, and the In-plane type Peltier cooling element configured using the heat conductive film are arranged at predetermined positions of the cooling characteristic evaluation unit 11 illustrated in FIG. Then, the cooling characteristics were evaluated.
Specifically, the heating unit 13 as the adherend is provided with a cooling surface side (heat absorbing side) of one of the heat conductive films 12b of the In-plane type thermoelectric conversion module 12a constituting the In-plane type Peltier cooling element 12. Was attached, and a chiller unit 15 (cooling water; temperature setting: 0 ° C.) was disposed via a heat sink 14 on the heat-dissipating surface side (radiation side) of the other heat conductive film 12 c. The heating unit 13 supplies 3 W of heat and the cooling surface side of the In-plane type Peltier cooling element 12 when 0.5 V is applied from a DC power source to both electrodes of the thermoelectric element of the In-plane type Peltier cooling element 12. , And the temperature difference between the heat-dissipating surface side of the In-plane type Peltier cooling element 12 was measured.
The heat conduction grease 16 is provided between the heating unit 13 and the In-plane Peltier cooling element 12, the heat conduction grease 17 is provided between the In-plane Peltier cooling element 12 and the heat sink 14, and the heat conduction grease 17 is provided between the heat sink 14 and the chiller unit 15. The conductive grease 18 was provided to make it difficult for air to be entrained at each interface and to reduce the thermal resistance.
＜屈曲性評価＞
実施例及び比較例で作製した熱電変換材料について、円筒形マンドレル法によりマンドレル径φ１０ｍｍの時の薄膜の屈曲性を評価した。円筒形マンドレル試験前後で、熱電変換材料の外観評価及び熱電性能評価を行い、以下の基準で屈曲性を評価した。
試験前後で熱電変換材料の外観に異常が見られず無次元熱電性能指数ＺＴが変化しない場合：◎
試験前後で熱電変換材料の外観に異常が見られずＺＴの減少が３０％未満であった場合：○
試験後に熱電変換材料にクラック等の割れが発生したり、ＺＴが３０％以上減少した場合：×
<Flexibility evaluation>
With respect to the thermoelectric conversion materials produced in the examples and comparative examples, the flexibility of the thin film when the mandrel diameter was 10 mm was evaluated by the cylindrical mandrel method. Before and after the cylindrical mandrel test, the appearance evaluation and thermoelectric performance evaluation of the thermoelectric conversion material were performed, and the flexibility was evaluated based on the following criteria.
When no abnormality is observed in the appearance of the thermoelectric conversion material before and after the test, and the dimensionless thermoelectric performance index ZT does not change: ◎
When no abnormality was observed in the appearance of the thermoelectric conversion material before and after the test and the decrease in ZT was less than 30%: ○
When cracks such as cracks occur in the thermoelectric conversion material after the test, or when ZT is reduced by 30% or more: ×
（熱電半導体微粒子の作製方法）
ビスマス−テルル系熱電半導体材料であるｐ型ビスマステルライドＢｉ０．４Ｔｅ３Ｓｂ１．６（高純度化学研究所製、粒径：１８０μｍ）を、遊星型ボールミル（フリッチュジャパン社製、Ｐｒｅｍｉｕｍ ｌｉｎｅ Ｐ−７）を使用し、窒素ガス雰囲気下で粉砕することで、平均粒径１．２μｍの熱電半導体微粒子Ｔ１を作製した。粉砕して得られた熱電半導体微粒子に関して、レーザー回折式粒度分析装置（ＣＩＬＡＳ社製、１０６４型）により粒度分布測定を行った。
また、ビスマス−テルル系熱電半導体材料であるｎ型ビスマステルライドＢｉ２Ｔｅ３（高純度化学研究所製、粒径：１８０μｍ）を上記と同様に粉砕し、平均粒径１．４μｍの熱電半導体微粒子Ｔ２を作製した。
(Method for producing thermoelectric semiconductor particles)
A bismuth-tellurium-based thermoelectric semiconductor material, p-type bismuth telluride Bi 0.4 Te 3 Sb 1.6 (manufactured by Kojundo Chemical Laboratory, particle size: 180 μm) was mixed with a planetary ball mill (Premium line P, manufactured by Fritsch Japan). Using -7), the particles were pulverized in a nitrogen gas atmosphere to produce thermoelectric semiconductor particles T1 having an average particle diameter of 1.2 μm. The particle size distribution of the thermoelectric semiconductor fine particles obtained by the pulverization was measured by a laser diffraction type particle size analyzer (manufactured by CILAS, Model 1064).
In addition, n-type bismuth telluride Bi 2 Te 3 (manufactured by Kojundo Chemical Laboratory, particle size: 180 μm), which is a bismuth-tellurium-based thermoelectric semiconductor material, is pulverized in the same manner as described above, and thermoelectric semiconductor fine particles having an average particle size of 1.4 μm. T2 was produced.
（実施例１）
（１）熱電半導体組成物の作製
表１に示す実施例１に記載した配合量になるように、得られたビスマス−テルル系熱電半導体材料の微粒子Ｔ１と、耐熱性樹脂としてポリイミド前駆体であるポリアミック酸（シグマアルドリッチ社製、ポリ(ピロメリト酸二無水物−ｃｏ−４,４’−オキシジアニリン、固形分濃度：１５質量%)溶液、溶媒：メチルピロリドン、３００℃における質量減少率：０．９％）、及びイオン液体１として［１−ブチル−３−（２−ヒドロキシエチル）イミダゾリウムブロミド、電気伝導率：３．５×１０−５Ｓ／ｃｍ］とを加え、それらを混合分散し、ｐ型ビスマステルライドの微粒子Ｔ１を含む熱電半導体組成物からなる塗工液Ｐを調製した。同様に、微粒子Ｔ１を微粒子Ｔ２に変更し、ｎ型ビスマステルライドの微粒子Ｔ２を含む熱電半導体組成物からなる塗工液Ｎを調製した。
（２）熱電性能評価用サンプルの作製
（１）で調製した塗工液Ｐを、スクリーン印刷により支持体であるポリイミドフィルム（東レデュポン社製、商品名「カプトン」、厚さ５０μｍ）上に塗布し、温度１５０℃で、１０分間アルゴン雰囲気下で乾燥し、厚さが１０μｍの薄膜を形成した。次いで、得られた薄膜に対し、水素とアルゴンの混合ガス（水素：アルゴン＝５体積％：９５体積％）雰囲気下で、加温速度５Ｋ／ｍｉｎで昇温し、４１５℃で１時間保持し、薄膜形成後のアニール処理Ｂを行うことにより、熱電半導体材料の微粒子を結晶成長させ、ｐ型熱電変換材料を作製した。同様の方法で、（１）で調製した塗工液Ｎを用い、ｎ型熱電変換材料を作製した。
（３）熱伝導性シートの作製
シリコーン樹脂Ａ（旭化成ワッカー社製、「ＳｉｌＧｅｌ６１２−Ａ」）１９．８質量部、シリコーン樹脂Ｂ（旭化成ワッカー社製、「ＳｉｌＧｅｌ６１２−Ｂ」）１９．８質量部、硬化遅延剤（旭化成ワッカー社製、「ＰＴ８８」）０．４質量部、熱伝導性フィラーとして、アルミナ（昭和電工社製、「アルナビーズＣＢ−Ａ２０Ｓ」、平均粒子径２０μｍ）４０質量部、と窒化ホウ素（昭和電工社製、「ショウビーエヌ ＵＨＰ−２」、平均粒子径１２μｍ）２０質量部を添加し、自転・公転ミキサー（ＴＨＩＮＫＹ社製、「ＡＲＥ−２５０」）を用いて混合分散し、高熱伝導部形成用の樹脂組成物を調製した。
一方、シリコーン樹脂Ａ（旭化成ワッカー社製、「ＳｉｌＧｅｌ６１２−Ａ」）３1．７質量部、シリコーン樹脂Ｂ（旭化成ワッカー社製、「ＳｉｌＧｅｌ６１２−Ｂ」）３1．７質量部、硬化遅延剤（旭化成ワッカー社製、「ＰＴ８８」）０．６質量部、中空フィラーとして、ガラス中空フィラー（住友スリーエム社製、「グラスバブルズＳ３８」、平均粒子径４０μｍ、真密度０．３８ｇ／ｃｍ３）３６質量部を添加（低熱伝導部全体積中、中空フィラーが６０体積％含有）し、自転・公転ミキサー（ＴＨＩＮＫＹ社製、「ＡＲＥ−２５０」）を用いて混合分散し、低熱伝導部形成用の樹脂組成物を調製した。
次に、剥離可能な支持基材（リンテック社製、「ＰＥＴ５０ＦＤ」）の剥離処理された面に、前記高熱伝導部形成用の樹脂組成物を、ディスペンサー（武蔵エンジニアリング社製、「ＭＬ−８０８ＦＸｃｏｍ−ＣＥ」）を用いて塗布し、ストライプ状パターン（幅１ｍｍ×長さ１００ｍｍ、厚み５０μｍ、パターン中心間距離２ｍｍ）からなる高熱伝導部を形成した。さらに、その上からアプリケータを用いて、低熱伝導部形成用の樹脂組成物を塗布し、１５０℃で３０分間硬化させることで、該高熱伝導部のストライプ状パターン間に、高熱伝導部と同じ厚さの低熱伝導部が形成された熱伝導性シートを得た。なお、高熱伝導部上には、低熱伝導部が形成されていないことを確認した。
一方、剥離シート（リンテック社製、ＰＥＴ５０ＦＤ）の剥離処理された面に、シリコーン系接着剤を塗布し、９０℃で１分間乾燥させ、厚さ１０μｍの接着剤層を形成した。接着剤層と基材を貼り合わせ、剥離シートおよび剥離可能な支持基材で挟持された構成の熱伝導性（接着）シートを作製した。前記基材の接着剤層と接する面とは反対側の面において、高熱伝導部と低熱伝導部との段差は実質的に存在しなかった。
（４）Ｉｎ−ｐｌａｎｅ型ペルチェ冷却素子の作製
図１（ａ）に示すように、スクリーン印刷法によりあらかじめ形成した電極５ａ〜５ｅ（銅電極パターン、厚み：１０μｍ）を有する、支持体２であるポリイミドフィルム（東レデュポン社製、商品名「カプトン」、厚み：５０μｍ）上に、（１）で調製した塗工液Ｐ及び塗工液Ｎを用い、スクリーン印刷法により、ｐ型熱電素子３及びｎ型熱電素子４の薄膜が上記電極を介し電気的に直列になるように塗布し、その後、温度１５０℃で１０分間アルゴンガス雰囲気下で乾燥し、それぞれの厚みが１００μｍの薄膜を形成した。得られた薄膜に対し、アルゴンガス雰囲気下で、加温速度５Ｋ／ｍｉｎで昇温し、４１５℃で１時間、アニール処理Ｂを行うことにより、熱電半導体材料の微粒子を結晶成長させ、電極を備えたｐ型及びｎ型熱電素子の薄膜を作製した（Ｉｎ−ｐｌａｎｅ型熱電変換モジュール）。
次いで、得られたＩｎ−ｐｌａｎｅ型熱電変換モジュールの薄膜の両面に、（３）で得られた熱伝導性フィルム（接着剤層付）を、図１（ｂ）のように、高熱伝導部７と低熱伝導部８とが同一面上では交互に、対向面上同士では互いに向き合うように配置するよう貼付し、Ｉｎ−ｐｌａｎｅ型ペルチェ冷却素子を作製した。
(Example 1)
(1) Preparation of thermoelectric semiconductor composition Fine particles T1 of the obtained bismuth-tellurium-based thermoelectric semiconductor material and a polyimide precursor as a heat-resistant resin so as to have the compounding amount described in Example 1 shown in Table 1. Polyamic acid (manufactured by Sigma-Aldrich, poly (pyromellitic dianhydride-co-4,4'-oxydianiline, solids concentration: 15% by mass) solution, solvent: methylpyrrolidone, mass loss at 300 ° C .: 0) 9.9%), and [1-butyl-3- (2-hydroxyethyl) imidazolium bromide, electric conductivity: 3.5 × 10 −5 S / cm] as the ionic liquid 1, and they were mixed and dispersed. Then, a coating liquid P composed of a thermoelectric semiconductor composition containing fine particles T1 of p-type bismuth telluride was prepared. Similarly, the fine particles T1 were changed to fine particles T2, and a coating liquid N composed of a thermoelectric semiconductor composition containing the fine particles T2 of n-type bismuth telluride was prepared.
(2) Preparation of Thermoelectric Performance Evaluation Sample The coating liquid P prepared in (1) was applied by screen printing onto a polyimide film (Kapton, trade name, manufactured by Toray DuPont, thickness: 50 μm) as a support. Then, the film was dried at a temperature of 150 ° C. for 10 minutes in an argon atmosphere to form a thin film having a thickness of 10 μm. Next, the obtained thin film is heated at a heating rate of 5 K / min under a mixed gas of hydrogen and argon (hydrogen: argon = 5 vol%: 95 vol%) atmosphere and kept at 415 ° C. for 1 hour. By performing the annealing B after the formation of the thin film, the fine particles of the thermoelectric semiconductor material were crystal-grown to produce a p-type thermoelectric conversion material. In the same manner, an n-type thermoelectric conversion material was produced using the coating liquid N prepared in (1).
(3) Preparation of Thermal Conductive Sheet 19.8 parts by mass of silicone resin A (manufactured by Asahi Kasei Wacker Inc., “SilGel612-A”) and 19.8 parts by mass of silicone resin B (manufactured by Asahi Kasei Wacker Inc., “SilGel612-B”) 0.4 parts by mass of a curing retarder ("PT88", manufactured by Asahi Kasei Wacker Co., Ltd.), and 40 parts by mass of alumina (manufactured by Showa Denko KK, "Alnabeads CB-A20S", average particle diameter 20 μm) as a heat conductive filler. 20 parts by mass of boron nitride (manufactured by Showa Denko K.K., “SHOWN UHP-2”, average particle size: 12 μm) is added, and mixed and dispersed using a rotation / revolution mixer (THINKY “ARE-250”). , A resin composition for forming a high heat conductive portion was prepared.
On the other hand, 31.7 parts by mass of silicone resin A (manufactured by Asahi Kasei Wacker Co., Ltd., “SilGel612-A”), 31.7 parts by mass of silicone resin B (manufactured by Asahi Kasei Wacker Co., Ltd., “SilGel612-B”), curing retarder (Asahi Kasei Wacker Co., Ltd.) (PT88), 0.6 parts by mass; glass hollow filler (Glass Bubbles S38, Sumitomo 3M, average particle diameter 40 μm, true density 0.38 g / cm 3 ) 36 parts by mass as a hollow filler (The volume of the hollow filler is 60% by volume in the total volume of the low heat conducting part), and mixed and dispersed using a rotation / revolution mixer (“ARE-250” manufactured by THINKY) to obtain a resin composition for forming the low heat conducting part. Was prepared.
Next, the resin composition for forming a high thermal conductive portion was coated on a surface of a peelable support base material ("PET50FD" manufactured by Lintec) with a dispenser ("ML-808FXcom-" manufactured by Musashi Engineering Co., Ltd.). CE ") to form a high thermal conductive portion composed of a stripe pattern (width 1 mm × length 100 mm, thickness 50 μm, distance between pattern centers 2 mm). Further, by using an applicator from above, a resin composition for forming a low thermal conductive portion is applied, and cured at 150 ° C. for 30 minutes, thereby forming the same as the high thermal conductive portion between the stripe patterns of the high thermal conductive portion. A heat conductive sheet on which a low heat conductive portion having a thickness was formed was obtained. In addition, it confirmed that the low heat conduction part was not formed on the high heat conduction part.
On the other hand, a silicone-based adhesive was applied to the release-treated surface of a release sheet (PIN50FD, manufactured by Lintec Corporation) and dried at 90 ° C. for 1 minute to form an adhesive layer having a thickness of 10 μm. The adhesive layer and the base material were attached to each other to produce a thermally conductive (adhesive) sheet having a configuration sandwiched between a release sheet and a peelable support base material. On the surface of the substrate opposite to the surface in contact with the adhesive layer, there was substantially no step between the high heat conduction portion and the low heat conduction portion.
(4) Production of In-plane type Peltier cooling element As shown in FIG. 1A, a support 2 having electrodes 5a to 5e (copper electrode pattern, thickness: 10 μm) formed in advance by a screen printing method. Using a coating liquid P and a coating liquid N prepared in (1) on a polyimide film (manufactured by Toray Dupont, trade name "Kapton", thickness: 50 μm), p-type thermoelectric elements 3 and The thin film of the n-type thermoelectric element 4 was applied so as to be electrically connected in series via the electrode, and then dried at 150 ° C. for 10 minutes in an argon gas atmosphere to form a thin film having a thickness of 100 μm. The obtained thin film is heated at a heating rate of 5 K / min under an argon gas atmosphere, and annealed at 415 ° C. for 1 hour to grow fine particles of thermoelectric semiconductor material, thereby forming an electrode. Thin films of the provided p-type and n-type thermoelectric elements were produced (In-plane type thermoelectric conversion module).
Next, on both surfaces of the thin film of the obtained In-plane type thermoelectric conversion module, the heat conductive film (with an adhesive layer) obtained in (3) was applied as shown in FIG. And the low-heat-conducting portion 8 were attached so as to be arranged alternately on the same surface, and to face each other on the opposing surfaces, to produce an In-plane type Peltier cooling element.
（実施例２）
イオン液体（イオン液体１）を、１−ブチル−３−（２−ヒドロキシエチル）イミダゾリウムブロミドから１−ブチル−４−メチルピリジニウムヨージド（シグマアルドリッチジャパン社製、イオン液体２、電気伝導率：１．８×１０−５Ｓ／ｃｍ）に変更した以外は、実施例１と同様にして、ｐ型熱電変換材料、ｎ型熱電変換材料及びＩｎ−ｐｌａｎｅ型ペルチェ冷却素子を作製した。
(Example 2)
An ionic liquid (ionic liquid 1) was converted from 1-butyl-3- (2-hydroxyethyl) imidazolium bromide to 1-butyl-4-methylpyridinium iodide (Sigma Aldrich Japan, ionic liquid 2, electric conductivity: A p-type thermoelectric conversion material, an n-type thermoelectric conversion material, and an In-plane Peltier cooling element were produced in the same manner as in Example 1 except that the temperature was changed to 1.8 × 10 −5 S / cm).
（実施例３）
イオン液体１の添加量を１０質量％に変更した以外は、実施例１と同様にして、ｐ型熱電変換材料、ｎ型熱電変換材料及びＩｎ−ｐｌａｎｅ型ペルチェ冷却素子を作製した。
(Example 3)
A p-type thermoelectric conversion material, an n-type thermoelectric conversion material, and an In-plane Peltier cooling element were produced in the same manner as in Example 1 except that the amount of the ionic liquid 1 was changed to 10% by mass.
（実施例４）
イオン液体１の添加量を４０質量％に変更した以外は、実施例１と同様にして、ｐ型熱電変換材料、ｎ型熱電変換材料及びＩｎ−ｐｌａｎｅ型ペルチェ冷却素子を作製した。
(Example 4)
Except that the addition amount of the ionic liquid 1 was changed to 40% by mass, a p-type thermoelectric conversion material, an n-type thermoelectric conversion material, and an In-plane type Peltier cooling element were produced in the same manner as in Example 1.
（実施例５）
中空フィラーとしてシリカ中空フィラーである中空ナノシリカ（日鉄鉱業株式会社製、「シリナックス（登録商標）」、平均粒子径１０５ｎｍ、真密度０．５７ｇ/ｃｍ３）を用いた以外は実施例１と同様にＩｎ−ｐｌａｎｅ型ペルチェ冷却素子を作製した。
(Example 5)
Example 1 was the same as Example 1 except that hollow nano-silica (“Silinax (registered trademark)”, an average particle diameter of 105 nm, true density of 0.57 g / cm 3 , manufactured by Nittetsu Mining Co., Ltd.) was used as the hollow filler. Similarly, an In-plane type Peltier cooling element was manufactured.
（比較例１）
イオン液体を加えず、ポリイミド樹脂の配合量を５質量％から１０質量％にした以外は、実施例１と同様にして、ｐ型熱電変換材料、ｎ型熱電変換材料及びＩｎ−ｐｌａｎｅ型ペルチェ冷却素子を作製した。
(Comparative Example 1)
P-type thermoelectric conversion material, n-type thermoelectric conversion material, and In-plane Peltier cooling were performed in the same manner as in Example 1 except that the amount of the polyimide resin was changed from 5% by mass to 10% by mass without adding the ionic liquid. An element was manufactured.
（比較例２）
耐熱性樹脂を加えず、導電性高分子であるポリ（３，４−エチレンジオキシチオフェン）とポリスチレンスルホン酸イオンの混合物ＰＥＤＯＴ：ＰＳＳとイオン液体１と熱電半導体微粒子を表１に記載の配合で混合分散した熱電半導体組成物からなる塗工液を調製し、ｐ型熱電変換材料、ｎ型熱電変換材料及びＩｎ−ｐｌａｎｅ型ペルチェ冷却素子を作製した。
(Comparative Example 2)
A mixture of poly (3,4-ethylenedioxythiophene), which is a conductive polymer, and polystyrenesulfonate ion, PEDOT: PSS, ionic liquid 1, and thermoelectric semiconductor fine particles were added in the form shown in Table 1 without adding a heat-resistant resin. A coating liquid composed of the mixed and dispersed thermoelectric semiconductor composition was prepared, and a p-type thermoelectric conversion material, an n-type thermoelectric conversion material, and an In-plane Peltier cooling element were produced.
（比較例３）
耐熱性樹脂をポリスチレン（３００℃における質量減少率：１００％）に変更した以外は、実施例１と同様にして、ｐ型熱電変換材料、ｎ型熱電変換材料及びＩｎ−ｐｌａｎｅ型ペルチェ冷却素子を作製した。
(Comparative Example 3)
A p-type thermoelectric conversion material, an n-type thermoelectric conversion material, and an In-plane Peltier cooling element were prepared in the same manner as in Example 1 except that the heat-resistant resin was changed to polystyrene (mass reduction at 300 ° C .: 100%). Produced.
（比較例４）
熱伝導性フィルムを高熱伝導部、低熱伝導部のパターンを有さないポリイミドフィルム（東レデュポン社製、商品名「カプトン」、厚み：５０μｍ）に変更した以外は、実施例１と同様にして、Ｉｎ−ｐｌａｎｅ型ペルチェ冷却素子を作製した。
(Comparative Example 4)
Except that the heat conductive film was changed to a polyimide film having no pattern of a high heat conductive part and a low heat conductive part (manufactured by Toray DuPont, trade name “Kapton”, thickness: 50 μm), in the same manner as in Example 1, An In-plane type Peltier cooling element was manufactured.
実施例１〜５及び比較例１〜４で得られたｐ型熱電変換材料、ｎ型熱電変換材料の熱電性能評価、屈曲性評価、及びＩｎ−ｐｌａｎｅ型ペルチェ冷却素子の冷却特性評価に係る結果を表２に示す。 Results related to thermoelectric performance evaluation, bending property evaluation, and cooling property evaluation of In-plane type Peltier cooling elements of p-type thermoelectric conversion materials and n-type thermoelectric conversion materials obtained in Examples 1 to 5 and Comparative Examples 1 to 4. Are shown in Table 2.
実施例１〜５の熱電変換材料は、イオン液体を加えない比較例１に比べて、無次元熱電性能指数ＺＴが１オーダー又はそれ以上高く、また、円筒形マンドレル試験前後で、熱電変換材料にクラック等の割れが発生することもなく、無次元熱電性能指数ＺＴがほとんど低下せず、屈曲性が優れていることが分かった。さらに、耐熱性樹脂を使用しない比較例２（耐熱性の低い導電性高分子のみ使用）に比べ、無次元熱電性能指数ＺＴ及び屈曲性がはるかに優れていることが分かった。
実施例１〜５の熱伝導性フィルムを備えたＩｎ−ｐｌａｎｅ型ペルチェ冷却素子は、イオン液体を加えない比較例１に比べて、冷却面（吸熱側）と排熱面（発熱側）との温度差が小さいことから、電圧印加による冷却効果と熱交換可能な排熱量に収まっており高性能なペルチェ能を有していることが分かった。
実施例１の高熱伝導部と低熱伝導部を交互に備え、熱を特定の方向に選択的に放熱可能な熱伝導性フィルムを用いたＩｎ−ｐｌａｎｅ型ペルチェ冷却素子は、低熱伝導部のみを備える熱制御性を有しない熱伝導性フィルムを用いた比較例４に比べて、冷却面（吸熱側）の温度が−１０℃〜０℃と低く、熱伝導性フィルムによりスムーズに熱交換が行われているため、排熱面の温度がチラーによる冷却で十分冷却されていることから、より冷却効果が優れていることが分かった。
The thermoelectric conversion materials of Examples 1 to 5 had a dimensionless thermoelectric figure of merit ZT higher by one order or more than that of Comparative Example 1 to which no ionic liquid was added, and had a thermoelectric conversion material before and after the cylindrical mandrel test. It was found that cracks and the like did not occur, the dimensionless thermoelectric figure of merit ZT hardly decreased, and the flexibility was excellent. Furthermore, it was found that the dimensionless thermoelectric figure of merit ZT and the flexibility were far superior to Comparative Example 2 in which no heat-resistant resin was used (using only a conductive polymer having low heat resistance).
The In-plane type Peltier cooling device provided with the heat conductive films of Examples 1 to 5 has a cooling surface (heat absorbing side) and a heat discharging surface (heat generating side) in comparison with Comparative Example 1 in which no ionic liquid is added. Since the temperature difference was small, it was found that the temperature was within the cooling effect by applying voltage and the amount of heat that could be exchanged, and that it had a high-performance Peltier function.
The In-plane type Peltier cooling element using the heat conductive film which is provided with the high heat conductive portions and the low heat conductive portions alternately and can selectively radiate heat in a specific direction according to the first embodiment includes only the low heat conductive portion. As compared with Comparative Example 4 using a heat conductive film having no heat controllability, the temperature of the cooling surface (heat absorbing side) is as low as −10 ° C. to 0 ° C., and heat exchange is performed smoothly by the heat conductive film. Therefore, since the temperature of the exhaust heat surface was sufficiently cooled by cooling by the chiller, it was found that the cooling effect was more excellent.
本発明のペルチェ冷却素子は、簡便に低コストで製造可能であり、熱電性能に優れる薄膜の熱電変換材料と、熱を特定の方向に選択的に放熱可能な熱伝導性フィルムとで構成されていることから、エレクトロニクス機器の小型化、コンパクト化にともなう機器内部の蓄熱を抑制する用途に用いることができる。例えば、半導体素子である、ＣＭＯＳ（Ｃｏｍｐｌｅｍｅｎｔａｒｙ Ｍｅｔａｌ Ｏｘｉｄｅ Ｓｅｍｉｃｏｎｄｕｃｔｏｒ Ｉｍａｇｅ Ｓｅｎｓｏｒ）、ＣＣＤ（Ｃｈａｒｇｅ Ｃｏｕｐｌｅｄ Ｄｅｖｉｃｅ）、ＭＥＭＳ（Ｍｉｃｒｏ Ｅｌｅｃｔｒｏ Ｍｅｃｈａｎｉｃａｌ Ｓｙｓｔｅｍｓ）、受光素子等の各種センサーの温度制御、光通信用レーザーや産業用高出力レーザーの温度制御、半導体分野におけるシリコンウェハーや薬液の温度制御等に用いられる。 The Peltier cooling element of the present invention can be easily manufactured at low cost, is composed of a thin-film thermoelectric conversion material having excellent thermoelectric performance, and a heat conductive film capable of selectively releasing heat in a specific direction. Therefore, it can be used for the purpose of suppressing heat storage inside the electronic equipment due to the miniaturization and downsizing of the electronic equipment. For example, as a semiconductor element, a CMOS (Complementary Metal Oxide Semiconductor Image Sensor), a CCD (Charge Coupled Device), a MEMS (Micro Electro-Mechanical system for various kinds of lasers such as a Micro Electro-Mechanical System, a light sensor for industrial use, a high-temperature sensor for various types of lasers, and a light receiving sensor for industrial systems). It is used for temperature control of output lasers, temperature control of silicon wafers and chemicals in the semiconductor field, and the like.
１：Ｉｎ−ｐｌａｎｅ型熱電変換モジュール
２：支持体
３：ｐ型熱電素子
４：ｎ型熱電素子
５ａ，５ｂ，５ｃ，５ｄ，５ｅ：電極
５ｂｄ：電極間中心線
６Ａ，６Ｂ：熱伝導性フィルム
７：高熱伝導部
８：低熱伝導部
９：接着剤層
１０：Ｉｎ−ｐｌａｎｅ型ペルチェ冷却素子
１１：冷却特性評価ユニット
１２：Ｉｎ−ｐｌａｎｅ型ペルチェ冷却素子
１２ａ：Ｉｎ−ｐｌａｎｅ型熱電変換モジュール
１２ｂ，１２ｃ：熱伝導性フィルム
１３：加熱ユニット
１４：ヒートシンク
１５：チラーユニット
１６，１７，１８：熱伝導グリス
４１：Ｐ型熱電素子
４２：Ｎ型熱電素子
４３：電極（銅）
４４：フィルム状基板
４５：フィルム状基板
４６：熱電変換モジュール
４７，４８：熱伝導率の低い材料（ポリイミド）
４９，５０：熱伝導率の高い材料（銅）
1: In-plane thermoelectric conversion module 2: support 3: p-type thermoelectric element 4: n-type thermoelectric elements 5a, 5b, 5c, 5d, 5e: electrode 5bd: center line 6A, 6B between electrodes: heat conductive film 7: High heat conduction part 8: Low heat conduction part 9: Adhesive layer 10: In-plane type Peltier cooling element 11: Cooling characteristic evaluation unit 12: In-plane type Peltier cooling element 12a: In-plane type thermoelectric conversion module 12b, 12c: thermal conductive film 13: heating unit 14: heat sink 15: chiller units 16, 17, 18: thermal conductive grease 41: P-type thermoelectric element 42: N-type thermoelectric element 43: electrode (copper)
44: film-like substrate 45: film-like substrate 46: thermoelectric conversion modules 47, 48: material with low thermal conductivity (polyimide)
49, 50: High thermal conductivity material (copper)
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