JP2544118B2 - Method for manufacturing thermoelectric element for electronic wrist watch - Google Patents
Method for manufacturing thermoelectric element for electronic wrist watchInfo
- Publication number
- JP2544118B2 JP2544118B2 JP61257678A JP25767886A JP2544118B2 JP 2544118 B2 JP2544118 B2 JP 2544118B2 JP 61257678 A JP61257678 A JP 61257678A JP 25767886 A JP25767886 A JP 25767886A JP 2544118 B2 JP2544118 B2 JP 2544118B2
- Authority
- JP
- Japan
- Prior art keywords
- grooves
- thermoelectric
- thermoelectric element
- wrist watch
- electronic wrist
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 210000000707 wrist Anatomy 0.000 title claims description 8
- 239000000463 material Substances 0.000 claims description 26
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 239000011521 glass Substances 0.000 description 7
- 238000005245 sintering Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229910002908 (Bi,Sb)2(Te,Se)3 Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000036760 body temperature Effects 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- -1 for example Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/01—Manufacture or treatment
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Electromechanical Clocks (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、体温と外気温の温度差を利用する電子腕時
計用熱電素子の製造方法に関するものである。TECHNICAL FIELD The present invention relates to a method for manufacturing a thermoelectric element for an electronic wristwatch, which utilizes a temperature difference between a body temperature and an outside air temperature.
本発明は、電子腕時計の２次電池または大容量コンデ
ンサの充電源として使用する熱電素子の製造において、
多数の溝が一定の間隔で形成されたガラスのような耐熱
断熱部材の溝に熱電材料を形成し、これを一定間隔で切
断して有機樹脂と積層し、その後電極を形成することに
より、微細で数千個の熱電材料を直列に結合する必要の
ある、電子腕時計用熱電素子を効率的に、しかもできる
だけ大きな温度差の生じるよう製造することを可能とす
るものである。The present invention relates to the manufacture of a thermoelectric element used as a charging source for a secondary battery or a large capacity capacitor of an electronic wrist watch,
By forming a thermoelectric material in the grooves of a heat-resistant and heat-insulating member such as glass in which a large number of grooves are formed at regular intervals, cutting this at regular intervals, laminating it with an organic resin, and then forming electrodes It is possible to efficiently manufacture a thermoelectric element for an electronic wristwatch, in which several thousand thermoelectric materials need to be connected in series, so as to produce a temperature difference as large as possible.
電子腕時計において、体温を利用した熱電素子と大容
量コンデンサまたは２次電池との組合せにより半永久電
源を得ることができる。In an electronic wrist watch, a semi-permanent power supply can be obtained by combining a thermoelectric element using body temperature with a large-capacity capacitor or a secondary battery.
この場合、常温付近で最も優れた性能指数をもつ熱電
材料として、(Bi,Sb)2(Te,Se)3系熱電材料があるが、こ
の材料でもＮ形及びＰ形ともゼーベック係数は200μV/k
程度であり、従って例えば温度差２℃で電圧2Vを得るに
は５千個もの素子が必要となる。In this case, as a thermoelectric material having the best figure of merit at around room temperature, there is a (Bi, Sb) 2 (Te, Se) 3 series thermoelectric material, and even in this material, the Seebeck coefficient is 200 μV / n for both N type and P type. k
Therefore, to obtain a voltage of 2V with a temperature difference of 2 ° C., for example, 5,000 elements are required.
腕時計の場合、利用できる面積は６cm2程度が限度で
あり、また熱電素子においては温度差方向の素子厚は大
きいほど温度差が生じやすくなるため、その素子構造は
例えば0.1mm×0.1mm×7mm程度素子片を数千個直列に結
合する必要があり、それを実現する方法としては例えば
昭和61年電気学会全国大会講演論文集No.1194にみられ
るごとく厚膜法の利用が考えられる。In the case of a wristwatch, the usable area is limited to about 6 cm 2 , and in the thermoelectric element, the greater the element thickness in the temperature difference direction, the easier the temperature difference becomes. Therefore, the element structure is, for example, 0.1 mm × 0.1 mm × 7 mm. It is necessary to connect several thousand element pieces in series, and as a method for realizing this, the thick film method can be used, for example, as shown in Proceedings of the Annual Meeting of the Institute of Electrical Engineers of Japan, 1986, No. 1194.
厚膜法を利用する場合、形成できる厚みには限度があ
り、基板上に0.1mm×0.1mmの断面積で7mmもの厚みの熱
電材料を形成することは不可能であり、0.1mm×7mmの断
面積で0.1mmの厚みの熱電材料を基板に形成するという
ような方法をとらざる得ず、従って基板上に熱電材料を
形成し、それを数十層も積層するという複雑な工程を経
る必要がある。When using the thick film method, there is a limit to the thickness that can be formed, and it is impossible to form a thermoelectric material as thick as 7 mm with a cross-sectional area of 0.1 mm × 0.1 mm on the substrate, There is no choice but to use a method such as forming a thermoelectric material with a cross-sectional area of 0.1 mm thickness on the substrate, so it is necessary to go through the complicated process of forming the thermoelectric material on the substrate and laminating dozens of layers. There is.
また(Bi,Sb)2(Te,Se)3系熱電材料は非酸化性雰囲気で
500℃付近で焼結するため良好な結合剤が得られず、厚
膜法により微細な形状を精度及び形状制御性よく形成す
ることは難しい。また500℃付近の焼結のため基板とし
て熱伝導率の大きなガラスなどのような無機物質を使用
する必要があり、熱伝導率が小さく温度差の生じやすい
有機樹脂が使用できない。In addition, (Bi, Sb) 2 (Te, Se) 3 based thermoelectric materials are used in a non-oxidizing atmosphere.
Since it sinters at around 500 ° C, a good binder cannot be obtained, and it is difficult to form a fine shape with high precision and shape controllability by the thick film method. Further, since the sintering is performed at around 500 ° C., it is necessary to use an inorganic material such as glass having a large thermal conductivity as the substrate, and an organic resin having a small thermal conductivity and easily causing a temperature difference cannot be used.
本発明では、電子腕時計用熱電素子の製造において、
ガラスのような熱電材料の焼結に耐えるような耐熱断熱
部材に一定間隔で溝を形成し、この溝に熱電材料を形成
する。次にこの熱電材料の列に垂直に一定間隔に第２の
溝を形成し、第２の溝に有機樹脂を充填する。そして、
第２の溝の深さ方向に対し垂直に第２の溝の底部を切断
し、さらにその切断面と切断面の反対の面に電極を形成
することにより、簡易に精度よく、温度差の生じやすい
熱電素子を得ることができる。In the present invention, in the manufacture of thermoelectric elements for electronic wrist watches,
Grooves are formed at regular intervals in a heat resistant heat insulating member that can withstand the sintering of a thermoelectric material such as glass, and the thermoelectric material is formed in the grooves. Next, second grooves are formed at regular intervals in a row of the thermoelectric material, and the second grooves are filled with an organic resin. And
By cutting the bottom of the second groove perpendicularly to the depth direction of the second groove and further forming an electrode on the cut surface and the surface opposite to the cut surface, it is possible to easily and accurately generate a temperature difference. An easy thermoelectric element can be obtained.
以下図面により詳細に説明する。 The details will be described below with reference to the drawings.
熱電材料の焼結が可能な無機物質、例えばガラスなど
により第１図（ａ）に示すような一定間隔で溝を形成し
た部材を用意し、これに第１図（ｂ）に示すようにガラ
ス１の溝に熱電材料２を形成する。これは例えば(Bi,S
b)2(Se,Te)3系の熱電材料の粉体をプロピレングリコー
ルなどを混合して適度な粘度をもったペーストとしてこ
れを充填し、非酸化性雰囲気で470℃前後で焼結するこ
とにより得られる。A member having grooves formed at regular intervals as shown in FIG. 1 (a) is prepared from an inorganic substance capable of sintering a thermoelectric material, for example, glass, and glass is provided as shown in FIG. 1 (b). The thermoelectric material 2 is formed in the groove 1. This is for example (Bi, S
b) Mixing powder of 2 (Se, Te) 3 type thermoelectric material with propylene glycol, etc. as a paste with an appropriate viscosity, filling this, and sintering at around 470 ° C in a non-oxidizing atmosphere. Is obtained by
このようにして得られた、一定間隔で熱電材料を埋め
込んだ耐熱断熱部材を、第１図（ｃ）に示すように、熱
電材料列に垂直に、温度差を与え方向に平行に一定間隔
で熱電材料２を分離する。As shown in FIG. 1 (c), the heat-resistant and heat-insulating members obtained by embedding the thermoelectric material at regular intervals are obtained at regular intervals in a direction perpendicular to the thermoelectric material row and parallel to the direction in which the temperature difference is given. The thermoelectric material 2 is separated.
次に第１図（ｄ）に示すように分離した熱電材料２の
間にエポキシ系などの有機樹脂３を充填する。Next, as shown in FIG. 1D, an organic resin 3 such as an epoxy resin is filled between the separated thermoelectric materials 2.
次に第１図（ｅ）に示すように、ガラス１の下部の連
結部を除去し、第１図（ｆ）に示すように直列になるよ
うにＮ形とＰ形熱電材料間を電極４で結ぶ。Next, as shown in FIG. 1 (e), the lower connecting portion of the glass 1 is removed, and as shown in FIG. 1 (f), an electrode 4 is provided between the N-type and P-type thermoelectric materials so as to be in series. Tie in.
素子の周囲は有機樹脂３により保護断熱する。 The periphery of the element is protected and insulated by the organic resin 3.
電極はスパッタなどで金属層を形成し、フォトリソグ
ラフィで所定のパターンにするなどにより形成できる。The electrodes can be formed by forming a metal layer by sputtering or the like and forming a predetermined pattern by photolithography.
本発明では微細な熱電素子を固定補強し、断熱する耐
熱断熱部材がまた成形用の型及び焼結容器の役目をも果
たすものであり、極めて効率的である。In the present invention, the heat-resistant and heat-insulating member that fixes and reinforces the fine thermoelectric element and insulates it also serves as a molding die and a sintering container, and is extremely efficient.
(Bi,Sb)2(Se,Te)3系熱電材料は500℃付近での非酸化
性雰囲気での焼結を行なうため通常の酸化物の厚膜に使
用する結合剤が使用できず、従って熱電材料をペースト
状にして利用した場合、形状及び精度の制御性が劣る欠
点があるが、本発明によれば、予め焼結収縮を見込んで
おけばそのような問題は生じない。Since (Bi, Sb) 2 (Se, Te) 3 -based thermoelectric materials are sintered in a non-oxidizing atmosphere at around 500 ° C, the binder used for thick oxide films cannot be used, and therefore When the thermoelectric material is used in the form of a paste, the controllability of the shape and accuracy is inferior, but according to the present invention, such a problem does not occur if sintering shrinkage is expected in advance.
このようにして得られた熱電素子は最終的には第２図
に断面で示すように、電極４の上に絶縁層５を形成し、
更にその上に伝熱板６を形成する。The thermoelectric element thus obtained finally has an insulating layer 5 formed on the electrode 4 as shown in cross section in FIG.
Further, the heat transfer plate 6 is formed thereon.
第３図には上記のようにして得た熱電素子を利用した
電子腕時計の斜視図を示す。熱電素子よりなる発電部７
と電子回路及び大容量コンデンサなどの充電装置を内部
にもつ表示部８よりなる。FIG. 3 shows a perspective view of an electronic wrist watch using the thermoelectric element obtained as described above. Power generator 7 consisting of thermoelectric elements
And a display unit 8 having therein an electronic circuit and a charging device such as a large-capacity capacitor.
以上述べたように本発明によれば、多数の溝を形成し
た耐熱断熱部材の溝に熱電材料を形成し、この熱電材料
を一定間隔で切断分離し、その間に有機樹脂を形成する
という工程で熱電素子を製造することにより高性能な電
子腕時計用熱電素子を簡易に得ることができる。As described above, according to the present invention, a thermoelectric material is formed in the grooves of the heat-resistant and heat-insulating member having a large number of grooves, the thermoelectric material is cut and separated at regular intervals, and an organic resin is formed therebetween. By manufacturing the thermoelectric element, a high-performance thermoelectric element for an electronic wristwatch can be easily obtained.
第１図（ａ）から第１図（ｆ）は、熱電素子の製造工程
を示す斜視図であり、第２図は、完成した熱電素子の断
面図であり、第３図は、熱電素子をもつ電子腕時計の斜
視図である。 １……ガラス ２……熱電材料 ３……有機樹脂 ４……電極 ５……絶縁層 ６……伝熱板 ７……発電部 ８……表示部1 (a) to 1 (f) are perspective views showing a manufacturing process of the thermoelectric element, FIG. 2 is a sectional view of the completed thermoelectric element, and FIG. 3 shows the thermoelectric element. It is a perspective view of an electronic wrist watch. 1 …… Glass 2 …… Thermoelectric material 3 …… Organic resin 4 …… Electrode 5 …… Insulating layer 6 …… Heat transfer plate 7 …… Power generation section 8 …… Display section
Claims (1)
熱電素子の製造方法において、 耐熱断熱部材に一定間隔で第１の複数の溝を形成し、 前記溝に熱電材料を形成し、 前記熱電材料の列に垂直に一定間隔に第２の複数の溝を
形成し、 前記第２の複数の溝に有機樹脂を充填し、 前記第２の複数の溝の深さ方向に対し垂直に前記第２の
複数の溝の底部を切断し、 前記切断面と前記切断面の反対の面に電極を形成するこ
とを特徴とする電子腕時計用熱電素子の製造方法。1. A method for manufacturing a thermoelectric element used as an energy source for an electronic wrist watch, wherein a plurality of first grooves are formed in a heat resistant heat insulating member at regular intervals, and a thermoelectric material is formed in the grooves. A second plurality of grooves are formed perpendicularly to the row at regular intervals, the second plurality of grooves are filled with an organic resin, and the second plurality of grooves are perpendicular to the depth direction of the second plurality of grooves. A method for manufacturing a thermoelectric element for an electronic wrist watch, wherein bottoms of a plurality of grooves are cut, and electrodes are formed on the cut surface and a surface opposite to the cut surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61257678A JP2544118B2 (en) | 1986-10-29 | 1986-10-29 | Method for manufacturing thermoelectric element for electronic wrist watch |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61257678A JP2544118B2 (en) | 1986-10-29 | 1986-10-29 | Method for manufacturing thermoelectric element for electronic wrist watch |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63110779A JPS63110779A (en) | 1988-05-16 |
| JP2544118B2 true JP2544118B2 (en) | 1996-10-16 |
Family
ID=17309583
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61257678A Expired - Fee Related JP2544118B2 (en) | 1986-10-29 | 1986-10-29 | Method for manufacturing thermoelectric element for electronic wrist watch |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2544118B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10321921A (en) * | 1997-05-22 | 1998-12-04 | Ngk Insulators Ltd | Thermoelectric conversion module and its manufacture |
| US6310383B1 (en) | 1997-08-01 | 2001-10-30 | Citizen Watch Co., Ltd. | Thermoelectric element and method for manufacturing the same |
-
1986
- 1986-10-29 JP JP61257678A patent/JP2544118B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63110779A (en) | 1988-05-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |