JP6958233B2 - Thermoelectric converter and its manufacturing method - Google Patents

Thermoelectric converter and its manufacturing method Download PDF

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JP6958233B2
JP6958233B2 JP2017207275A JP2017207275A JP6958233B2 JP 6958233 B2 JP6958233 B2 JP 6958233B2 JP 2017207275 A JP2017207275 A JP 2017207275A JP 2017207275 A JP2017207275 A JP 2017207275A JP 6958233 B2 JP6958233 B2 JP 6958233B2
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JP2019079991A (en
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陽一 ▲高▼橋
坂井田　敦資
谷口　敏尚
倫央 郷古
岡本　圭司
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Denso Corp
Toyota Motor Corp
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    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
    • H02N11/00—Generators or motors not provided for elsewhere; Alleged perpetua mobilia obtained by electric or magnetic means
    • 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
    • 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
    • H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
    • H10N10/17—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects characterised by the structure or configuration of the cell or thermocouple forming the device
    • 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
    • H10N10/80—Constructional details
    • H10N10/81—Structural details of the junction
    • H10N10/817—Structural details of the junction the junction being non-separable, e.g. being cemented, sintered or soldered

Description

本発明は、熱電変換装置およびその製造方法に関するものである。 The present invention relates to a thermoelectric conversion device and a method for manufacturing the same.

特許文献１に、プリント基板およびその製造方法が記載されている。このプリント基板では、絶縁層を挟んで配置された導体パターン同士を接続する導電性組成物の側面が凹曲面形状となっている。これによれば、プリント基板に曲げ等の変形応力が加わった場合に、導電性組成物のうち導体パターンとの接続部付近に応力が集中することを抑制することができる。この結果、導体パターンと導電性組成物との接続の信頼性を高めることができる。 Patent Document 1 describes a printed circuit board and a method for manufacturing the printed circuit board. In this printed circuit board, the side surface of the conductive composition that connects the conductor patterns arranged so as to sandwich the insulating layer has a concave curved surface shape. According to this, when a deformation stress such as bending is applied to the printed circuit board, it is possible to suppress the concentration of stress in the vicinity of the connection portion of the conductive composition with the conductor pattern. As a result, the reliability of the connection between the conductor pattern and the conductive composition can be improved.

また、このプリント基板の製造方法では、絶縁層に形成されたビアホール内に層間接続材料を充填する。その後、層間接続材料を複数の導体パターンの層間で加圧しつつ加熱する。これにより、ビアホール内に一体化した導電性組成物を形成する。このとき、加熱前と比較して導電性組成物の体積が減少する。これにより、導電性組成物の側面を凹曲面形状にすることができる。 Further, in this method of manufacturing a printed circuit board, an interlayer connection material is filled in a via hole formed in an insulating layer. Then, the interlayer connection material is heated while being pressurized between the layers of the plurality of conductor patterns. As a result, a conductive composition integrated in the via hole is formed. At this time, the volume of the conductive composition is reduced as compared with that before heating. Thereby, the side surface of the conductive composition can be formed into a concave curved surface shape.

特開２００２−３５９４７０号公報JP-A-2002-359470.

ところで、絶縁基材と、熱電部材と、導体パターンとを備える熱電変換装置がある。この絶縁基材は、第１面とその反対側の第２面とを有するシート状である。この熱電部材は、絶縁基材を第１面から第２面まで貫くように絶縁基材に設けられる。この熱電部材は、熱および電気エネルギーを相互に変換する特性を持つ部材である。この導体パターンは、絶縁基材の第１面および第２面に設けられる。この導体パターンは、熱電部材と接続される。 By the way, there is a thermoelectric conversion device including an insulating base material, a thermoelectric member, and a conductor pattern. This insulating base material is in the form of a sheet having a first surface and a second surface on the opposite side thereof. This thermoelectric member is provided on the insulating base material so as to penetrate the insulating base material from the first surface to the second surface. This thermoelectric member is a member having a property of mutually converting heat and electric energy. This conductor pattern is provided on the first surface and the second surface of the insulating base material. This conductor pattern is connected to the thermoelectric member.

このような構成の熱電変換装置においても、上記のプリント基板のように、熱電部材の側面を凹曲面形状にすることができれば、導体パターンと熱電部材との接続の信頼性を高めることができる。 Even in a thermoelectric conversion device having such a configuration, if the side surface of the thermoelectric member can be formed into a concave curved surface shape as in the above-mentioned printed circuit board, the reliability of the connection between the conductor pattern and the thermoelectric member can be improved.

しかし、熱電変換装置では、熱電部材を形成するときの熱電部材の体積減少幅が、プリント基板の導電性組成物の体積減少幅よりも小さい。このため、熱電部材の側面を凹曲面形状にすることができない。または、熱電部材の側面が凹曲面形状になっても、凹み具合が小さい。凹み具合が小さいとは、凹みが緩やかであることを意味する。この結果、熱電変換装置に変形応力が加わった場合に、熱電部材のうち導体パターンとの接続部付近に応力が集中することを抑制することができない。よって、熱電変換装置では、導体パターンと熱電部材との接続の信頼性を高めることができないという課題が、発明者によって見出された。 However, in the thermoelectric conversion device, the volume reduction width of the thermoelectric member when forming the thermoelectric member is smaller than the volume reduction width of the conductive composition of the printed circuit board. Therefore, the side surface of the thermoelectric member cannot be formed into a concave curved surface shape. Alternatively, even if the side surface of the thermoelectric member has a concave curved surface shape, the degree of dent is small. A small dent means that the dent is gentle. As a result, when deformation stress is applied to the thermoelectric conversion device, it is not possible to suppress the concentration of stress in the vicinity of the connection portion of the thermoelectric member with the conductor pattern. Therefore, the inventor has found a problem that the thermoelectric converter cannot improve the reliability of the connection between the conductor pattern and the thermoelectric member.

本発明は、上記点に鑑みて、導体パターンと熱電部材との接続の信頼性を高めることができる熱電変換装置の製造方法を提供することを目的とする。また、本発明は、導体パターンと熱電部材との接続の信頼性が高い熱電変換装置を提供することを他の目的とする。 In view of the above points, it is an object of the present invention to provide a method for manufacturing a thermoelectric conversion device capable of increasing the reliability of the connection between the conductor pattern and the thermoelectric member. Another object of the present invention is to provide a thermoelectric conversion device having high reliability in connecting a conductor pattern and a thermoelectric member.

上記目的を達成するため、請求項１に記載の発明の熱電変換装置の製造方法は、
第１面（１２１）と第１面の反対側の第２面（１２２）とを有するシート状の絶縁基材（１２）と、絶縁基材を第１面から第２面まで貫くように絶縁基材に設けられた未焼結の熱電部材と、第１面に設けられ、熱電部材と接する第１導体パターン（２６）と、第２面に設けられ、熱電部材と接する第２導体パターン（２８）とを有する構造体（７０、８５）を形成すること（Ｓ２）と、
構造体を加熱しながら絶縁基材の厚さ方向（Ｄ１）に構造体を加圧すること（Ｓ３）とを含み、
構造体を形成することは、
第１層（３０）と、絶縁基材のうち第１層よりも第１面側に位置する第２層（３２）とを有し、第１層は、加圧するときに流動する樹脂材料で構成され、第２層は、第１層よりも薄いとともに、加圧するときに第１層を構成する樹脂材料よりも流動し難い絶縁材料で構成された絶縁基材を用いることと、
第１層および第２層に熱電部材の側面が接するように、熱電部材を絶縁基材に設けることとを含み、
加圧することにおいては、第１層を流動させながら熱電部材を焼結させることにより、焼結後の熱電部材の側面（１９、２１）のうち第１層に接する部分（１９１、２１１）を凹曲面形状とする熱電変換装置の製造方法。 In order to achieve the above object, the method for manufacturing the thermoelectric conversion device according to claim 1 is
A sheet-shaped insulating base material (12) having a first surface (121) and a second surface (122) opposite to the first surface, and an insulating base material so as to penetrate from the first surface to the second surface. a thermoelectric element unsintered provided in the substrate, is provided on the first surface, the first conductor pattern in contact with the thermoelectric element (26), provided on the second surface, the second conductor pattern in contact with the thermoelectric element ( To form a structure (70, 85) having 28) and (S2),
Including pressurizing the structure in the thickness direction (D1) of the insulating base material (S3) while heating the structure.
Forming a structure is
It has a first layer (30) and a second layer (32) of the insulating base material located on the first surface side of the first layer, and the first layer is a resin material that flows when pressed. The second layer is made of an insulating base material that is thinner than the first layer and that is less likely to flow than the resin material that constitutes the first layer when pressed.
Including providing the thermoelectric member on the insulating base material so that the side surfaces of the thermoelectric member are in contact with the first layer and the second layer.
In pressurizing, the thermoelectric member is sintered while the first layer is flowing, so that the portion (191, 211) of the side surface (19, 21) of the thermoelectric member after sintering that is in contact with the first layer is recessed. A method for manufacturing a thermoelectric converter having a curved surface shape.

これによれば、加熱しながら加圧しているときにおいて、第１層は流動するが、第２層は第１層よりも流動しない。このため、未焼結の熱電部材の側面のうち第１層に接する部分にかかる圧力は、未焼結の熱電部材の側面のうち第２層に接する部分の圧力よりも大きい。これにより、焼結後の熱電部材の側面のうち第１層に接する部分を、凹曲面形状とすることができる。絶縁基材が第２層を有していない場合の熱電部材の側面と比較して、第１層に接する部分を曲がりが急な凹曲面形状とすることができる。すなわち、第１層に接する部分の凹曲面形状の凹み具合を大きくできる。 According to this, when the pressure is applied while heating, the first layer flows, but the second layer does not flow as much as the first layer. Therefore, the pressure applied to the portion of the side surface of the unsintered thermoelectric member that is in contact with the first layer is larger than the pressure of the portion of the side surface of the unsintered thermoelectric member that is in contact with the second layer. As a result, the portion of the side surface of the sintered thermoelectric member that is in contact with the first layer can be formed into a concave curved surface shape. Compared with the side surface of the thermoelectric member when the insulating base material does not have the second layer, the portion in contact with the first layer can have a concave curved surface shape with a steep bend. That is, the degree of denting of the concave curved surface shape of the portion in contact with the first layer can be increased.

この結果、熱電変換装置に変形応力が加わった場合い、熱電部材のうち第１導体パターンとの接続部付近および第２導体パターンとの接続部付近に応力が集中することを抑制することができる。よって、第１導体パターンおよび第２導体パターンのそれぞれの導体パターンと熱電部材との接続の信頼性が高い熱電変換装置を製造することができる。 As a result, when deformation stress is applied to the thermoelectric converter, it is possible to prevent the stress from concentrating in the vicinity of the connection portion with the first conductor pattern and the vicinity of the connection portion with the second conductor pattern among the thermoelectric members. .. Therefore, it is possible to manufacture a thermoelectric conversion device having high reliability of connection between each conductor pattern of the first conductor pattern and the second conductor pattern and the thermoelectric member.

また、請求項５に記載の発明の熱電変換装置は、
第１面（１２１）と第１面の反対側の第２面（１２２）とを有するシート状の絶縁基材（１２）と、
絶縁基材に設けられた熱電部材（１８、２０）と、
第１面に設けられ、熱電部材と接続された第１導体パターン（２６）と、
第２面に設けられ、熱電部材と接続された第２導体パターン（２８）とを備え、
絶縁基材は、第１層（３０）と、絶縁基材において第１層よりも第１面側に位置し、第１層よりも薄い第２層（３２）とを有し、
第１層は、温度の上昇によって軟化する樹脂材料で構成され、
第２層は、第１層を構成する樹脂材料の軟化温度よりも軟化温度または耐熱温度が高い絶縁材料で構成されており、
熱電部材は、第１層および第２層に熱電部材の側面が接するように配置されており、
熱電部材の側面（１９、２１）のうち第１層に接する部分（１９１、２１１）は、凹曲面形状である熱電変換装置。 Further, the thermoelectric conversion device of the invention according to claim 5 is
A sheet-like insulating base material (12) having a first surface (121) and a second surface (122) opposite to the first surface, and
Thermoelectric members (18, 20) provided on the insulating base material and
A first conductor pattern (26) provided on the first surface and connected to a thermoelectric member,
A second conductor pattern (28) provided on the second surface and connected to the thermoelectric member is provided.
The insulating base material has a first layer (30) and a second layer (32) which is located on the first surface side of the insulating base material and is thinner than the first layer.
The first layer is composed of a resin material that softens as the temperature rises.
The second layer is composed of an insulating material having a softening temperature or a heat resistant temperature higher than the softening temperature of the resin material constituting the first layer.
The thermoelectric member is arranged so that the side surface of the thermoelectric member is in contact with the first layer and the second layer.
Of the side surfaces (19, 21) of the thermoelectric member, the portions (191, 211) in contact with the first layer are thermoelectric conversion devices having a concave curved surface shape.

これによれば、第１層と第２層とを有する絶縁基材が用いられている。このため、熱電変換装置を次のように製造することができる。 According to this, an insulating base material having a first layer and a second layer is used. Therefore, the thermoelectric conversion device can be manufactured as follows.

シート状の絶縁基材と、未焼結の熱電部材と、第１導体パターンと、第２導体パターンとを有する構造体を形成する。このとき、絶縁基材は、第１層と第２層とを有する。熱電部材は、第１層および第２層に熱電部材の側面が接するように設けられている。第１導体パターンは、絶縁基材の第１面に設けられ、熱電部材に接している。第２導体パターンは、絶縁基材の第２面に設けられ、熱電部材に接している。 A structure having a sheet-shaped insulating base material, an unsintered thermoelectric member, a first conductor pattern, and a second conductor pattern is formed. At this time, the insulating base material has a first layer and a second layer. The thermoelectric member is provided so that the side surface of the thermoelectric member is in contact with the first layer and the second layer. The first conductor pattern is provided on the first surface of the insulating base material and is in contact with the thermoelectric member. The second conductor pattern is provided on the second surface of the insulating base material and is in contact with the thermoelectric member.

そして、構造体を加熱しながら加圧する。このとき、第１層は流動するが、第２層は第１層よりも流動しない温度で加熱する。このため、未焼結の熱電部材の側面のうち第１層に接する部分にかかる圧力は、未焼結の熱電部材の側面のうち第２層に接する部分の圧力よりも大きい。これにより、焼結後の熱電部材の側面のうち第１層に接する部分を、絶縁基材が第２層を有していない場合の熱電部材の側面と比較して、曲がりが急な凹曲面形状とすることができる。すなわち、第１層に接する部分の凹曲面形状の凹み具合を大きくできる。 Then, the structure is pressurized while being heated. At this time, the first layer flows, but the second layer is heated at a temperature that does not flow as much as the first layer. Therefore, the pressure applied to the portion of the side surface of the unsintered thermoelectric member that is in contact with the first layer is larger than the pressure of the portion of the side surface of the unsintered thermoelectric member that is in contact with the second layer. As a result, the portion of the side surface of the thermoelectric member after sintering that is in contact with the first layer is a concave curved surface that bends sharply as compared with the side surface of the thermoelectric member when the insulating base material does not have the second layer. It can be shaped. That is, the degree of denting of the concave curved surface shape of the portion in contact with the first layer can be increased.

よって、熱電部材のうち第１導体パターンとの接続部付近および第２導体パターンとの接続部付近に応力が集中することを抑制することができる。第１導体パターンおよび第２導体パターンのそれぞれの導体パターンと熱電部材との接続の信頼性が高い熱電変換装置を提供することができる。 Therefore, it is possible to suppress the concentration of stress in the vicinity of the connection portion with the first conductor pattern and the vicinity of the connection portion with the second conductor pattern among the thermoelectric members. It is possible to provide a thermoelectric conversion device having high reliability of connection between each conductor pattern of the first conductor pattern and the second conductor pattern and the thermoelectric member.

なお、この欄および特許請求の範囲で記載した各手段の括弧内の符号は、後述する実施形態に記載の具体的手段との対応関係を示す一例である。 In addition, the reference numerals in parentheses of each means described in this column and the scope of claims are an example showing the correspondence with the specific means described in the embodiment described later.

第１実施形態における熱電変換装置の平面図である。It is a top view of the thermoelectric conversion apparatus in 1st Embodiment. 図１中のII−II線断面図である。FIG. 2 is a cross-sectional view taken along the line II-II in FIG. 図２中のIII部の拡大図である。It is an enlarged view of the part III in FIG. 第１実施形態における熱電変換装置の製造工程を示すフローチャートである。It is a flowchart which shows the manufacturing process of the thermoelectric conversion apparatus in 1st Embodiment. 用意工程における絶縁基材、第１保護部材および第２保護部材の断面図である。It is sectional drawing of the insulating base material, the 1st protective member and the 2nd protective member in the preparation process. 図５中の絶縁基材の製造工程を示す図である。It is a figure which shows the manufacturing process of the insulating base material in FIG. 図６に続く絶縁基材の製造工程を示す図である。It is a figure which shows the manufacturing process of the insulating base material following FIG. 図７に続く絶縁基材の製造工程を示す図である。It is a figure which shows the manufacturing process of the insulating base material following FIG. 図８に続く絶縁基材の製造工程を示す図である。It is a figure which shows the manufacturing process of the insulating base material following FIG. 図９に続く絶縁基材の製造工程を示す図である。It is a figure which shows the manufacturing process of the insulating base material following FIG. 積層体の形成工程における積層体の断面図である。It is sectional drawing of the laminated body in the process of forming a laminated body. 加熱加圧工程中における比較例１の熱電変換装置の断面図である。It is sectional drawing of the thermoelectric conversion apparatus of Comparative Example 1 in the heating and pressurizing process. 加熱加圧工程後における比較例１の熱電変換装置の断面図である。It is sectional drawing of the thermoelectric conversion apparatus of Comparative Example 1 after a heating and pressurizing step. 加熱加圧工程中における第１実施形態の熱電変換装置の断面図である。It is sectional drawing of the thermoelectric conversion apparatus of 1st Embodiment in a heating and pressurizing process. 第２実施形態における熱電変換装置の製造工程のうち用意工程での第１基材部および第２基材部の断面図である。It is sectional drawing of the 1st base material part and the 2nd base material part in the preparation process in the manufacturing process of the thermoelectric conversion apparatus in 2nd Embodiment. 図１５の第１基材部および第２基材部の製造工程を示す断面図である。It is sectional drawing which shows the manufacturing process of the 1st base material part and the 2nd base material part of FIG. 図１６に続く第１基材部および第２基材部の製造工程を示す断面図である。It is sectional drawing which shows the manufacturing process of the 1st base material part and the 2nd base material part following FIG. 第２実施形態における積層工程および加熱加圧工程における積層体の断面図である。It is sectional drawing of the laminated body in the laminating step and the heating and pressurizing step in 2nd Embodiment. 第２実施形態における熱電変換装置の断面図である。It is sectional drawing of the thermoelectric conversion apparatus in 2nd Embodiment. 加熱加圧工程中における第３実施形態の熱電変換装置の断面図である。It is sectional drawing of the thermoelectric conversion apparatus of 3rd Embodiment in a heating and pressurizing process. 加熱加圧工程後における第３実施形態の熱電変換装置の断面図である。It is sectional drawing of the thermoelectric conversion apparatus of 3rd Embodiment after a heating and pressurizing step.

以下、本発明の実施形態について図に基づいて説明する。なお、以下の各実施形態相互において、互いに同一もしくは均等である部分には、同一符号を付して説明を行う。 Hereinafter, embodiments of the present invention will be described with reference to the drawings. In each of the following embodiments, parts that are the same or equal to each other will be described with the same reference numerals.

（第１実施形態）
図１、２に示すように、熱電変換装置１０は、シート状である。図１では、第１保護部材１４が省略されている。 (First Embodiment)
As shown in FIGS. 1 and 2, the thermoelectric conversion device 10 has a sheet shape. In FIG. 1, the first protective member 14 is omitted.

図２に示すように、熱電変換装置１０は、第１面１０１とその反対側の第２面１０２とを有する。熱電変換装置１０は、絶縁基材１２と、第１保護部材１４と、第２保護部材１６とを備える。絶縁基材１２と、第１保護部材１４と、第２保護部材１６とのそれぞれは、シート状であって、可撓性を有する。このため、熱電変換装置１０は、可撓性を有する。 As shown in FIG. 2, the thermoelectric conversion device 10 has a first surface 101 and a second surface 102 on the opposite side thereof. The thermoelectric conversion device 10 includes an insulating base material 12, a first protective member 14, and a second protective member 16. Each of the insulating base material 12, the first protective member 14, and the second protective member 16 is in the form of a sheet and has flexibility. Therefore, the thermoelectric conversion device 10 has flexibility.

絶縁基材１２には、複数の第１熱電部材１８と、複数の第２熱電部材２０とが設けられている。複数の第１熱電部材１８および複数の第２熱電部材２０のそれぞれが、熱電部材に相当する。熱電部材は、粉末状の熱電材料が焼結した状態のものである。熱電材料は、熱および電気エネルギーを相互に変換する特性を持つ固体材料である。熱電材料としては、半導体材料や金属材料が挙げられる。 The insulating base material 12 is provided with a plurality of first thermoelectric members 18 and a plurality of second thermoelectric members 20. Each of the plurality of first thermoelectric members 18 and the plurality of second thermoelectric members 20 corresponds to thermoelectric members. The thermoelectric member is a state in which a powdered thermoelectric material is sintered. Thermoelectric materials are solid materials that have the property of converting heat and electrical energy into each other. Examples of thermoelectric materials include semiconductor materials and metal materials.

具体的には、絶縁基材１２は、第１面１２１とその反対側の第２面１２２とを有する。絶縁基材１２には、その厚さ方向に貫通する複数の第１貫通孔２２と複数の第２貫通孔２４とが形成されている。複数の第１貫通孔２２のそれぞれには、第１熱電材料で構成された第１熱電部材１８が配置されている。複数の第２貫通孔２４のそれぞれには、第２熱電材料で構成された第２熱電部材２０が配置されている。第２熱電材料は、第１熱電材料とは異なる熱電材料である。本実施形態では、複数の第１熱電部材１８のそれぞれはＰ型半導体材料で構成されている。複数の第２熱電部材２０のそれぞれはＮ型半導体材料で構成されている。 Specifically, the insulating base material 12 has a first surface 121 and a second surface 122 on the opposite side thereof. The insulating base material 12 is formed with a plurality of first through holes 22 and a plurality of second through holes 24 penetrating in the thickness direction thereof. A first thermoelectric member 18 made of a first thermoelectric material is arranged in each of the plurality of first through holes 22. A second thermoelectric member 20 made of a second thermoelectric material is arranged in each of the plurality of second through holes 24. The second thermoelectric material is a thermoelectric material different from the first thermoelectric material. In the present embodiment, each of the plurality of first thermoelectric members 18 is made of a P-type semiconductor material. Each of the plurality of second thermoelectric members 20 is made of an N-type semiconductor material.

熱電変換装置１０は、複数の第１導体パターン２６と、複数の第２導体パターン２８とを備える。複数の第１導体パターン２６のそれぞれは、絶縁基材１２の第１面１２１に設けられている。複数の第１導体パターン２６のそれぞれは、所望のパターンとされた導体膜である。複数の第１導体パターン２６のそれぞれは、複数の第１熱電部材１８と複数の第２熱電部材２０とのうち隣り合う第１熱電部材１８と第２熱電部材２０とを接続している。 The thermoelectric conversion device 10 includes a plurality of first conductor patterns 26 and a plurality of second conductor patterns 28. Each of the plurality of first conductor patterns 26 is provided on the first surface 121 of the insulating base material 12. Each of the plurality of first conductor patterns 26 is a conductor film having a desired pattern. Each of the plurality of first conductor patterns 26 connects the first thermoelectric member 18 and the second thermoelectric member 20 which are adjacent to each other among the plurality of first thermoelectric members 18 and the plurality of second thermoelectric members 20.

複数の第２導体パターン２８のそれぞれは、絶縁基材１２の第２面１２２に設けられている。複数の第２導体パターン２８のそれぞれは、所望のパターンとされた導体膜である。複数の第２導体パターン２８のそれぞれは、複数の第１熱電部材１８と複数の第２熱電部材２０とのうち隣り合う第１熱電部材１８と第２熱電部材２０とを接続している。複数の第１導体パターン２６のそれぞれと複数の第２導体パターン２８のそれぞれとによって、複数の第１熱電部材１８のそれぞれと複数の第２熱電部材２０のそれぞれとが交互に直列に接続されている。 Each of the plurality of second conductor patterns 28 is provided on the second surface 122 of the insulating base material 12. Each of the plurality of second conductor patterns 28 is a conductor film having a desired pattern. Each of the plurality of second conductor patterns 28 connects the first thermoelectric member 18 and the second thermoelectric member 20 which are adjacent to each other among the plurality of first thermoelectric members 18 and the plurality of second thermoelectric members 20. Each of the plurality of first conductor patterns 26 and each of the plurality of second conductor patterns 28 alternately connect each of the plurality of first thermoelectric members 18 and each of the plurality of second thermoelectric members 20 in series. There is.

図１に示すように、複数の第１熱電部材１８のそれぞれにおける第１導体パターン２６との接続部の平面形状は、円形状である。複数の第２熱電部材２０のそれぞれにおける第１導体パターン２６との接続部の平面形状は、円形状である。図示しないが、複数の第１熱電部材１８のそれぞれにおける第２導体パターン２８との接続部の平面形状も、円形状である。複数の第２熱電部材２０のそれぞれにおける第２導体パターン２８との接続部の平面形状も、円形状である。 As shown in FIG. 1, the planar shape of the connection portion of each of the plurality of first thermoelectric members 18 with the first conductor pattern 26 is circular. The planar shape of the connection portion of each of the plurality of second thermoelectric members 20 with the first conductor pattern 26 is a circular shape. Although not shown, the planar shape of the connection portion of each of the plurality of first thermoelectric members 18 with the second conductor pattern 28 is also circular. The planar shape of the connection portion of each of the plurality of second thermoelectric members 20 with the second conductor pattern 28 is also circular.

図２に示すように、第１保護部材１４は、絶縁基材１２の第１面１２１側に積層されている。第１保護部材１４は、第１導体パターン２６および第１面１２１のうち第１導体パターン２６が設けられていない部分を覆っている。第１保護部材１４は、熱可塑性樹脂で構成されている。第１保護部材１４を構成する熱可塑性樹脂としては、熱可塑性ポリイミド樹脂が挙げられる。 As shown in FIG. 2, the first protective member 14 is laminated on the first surface 121 side of the insulating base material 12. The first protective member 14 covers the portion of the first conductor pattern 26 and the first surface 121 where the first conductor pattern 26 is not provided. The first protective member 14 is made of a thermoplastic resin. Examples of the thermoplastic resin constituting the first protective member 14 include a thermoplastic polyimide resin.

第２保護部材１６は、絶縁基材１２の第２面１２２側に積層されている。第２保護部材１６は、第２導体パターン２８を覆っている。第２保護部材１６は、熱可塑性樹脂で構成されている。第２保護部材１６を構成する熱可塑性樹脂としては、熱可塑性ポリイミド樹脂が挙げられる。本実施形態では、第２保護部材１６は、第１保護部材１４と同じ材料で構成されている。第２保護部材１６は、第１保護部材１４と異なる材料で構成されていてもよい。 The second protective member 16 is laminated on the second surface 122 side of the insulating base material 12. The second protective member 16 covers the second conductor pattern 28. The second protective member 16 is made of a thermoplastic resin. Examples of the thermoplastic resin constituting the second protective member 16 include a thermoplastic polyimide resin. In the present embodiment, the second protective member 16 is made of the same material as the first protective member 14. The second protective member 16 may be made of a material different from that of the first protective member 14.

図３に示すように、絶縁基材１２は、中間層３０と、第１外層３２と、第２外層３４とを有する。中間層３０が絶縁基材の第１層に相当する。第１外層３２が絶縁基材の第２層に相当する。第２外層３４が絶縁基材の第３層に相当する。 As shown in FIG. 3, the insulating base material 12 has an intermediate layer 30, a first outer layer 32, and a second outer layer 34. The intermediate layer 30 corresponds to the first layer of the insulating base material. The first outer layer 32 corresponds to the second layer of the insulating base material. The second outer layer 34 corresponds to the third layer of the insulating base material.

第１外層３２は、絶縁基材１２において中間層３０よりも第１面１２１側に位置する。すなわち、第１外層３２は、中間層３０に対して、中間層３０の厚さ方向Ｄ１の一方側に積層されている。第２外層３４は、絶縁基材１２において中間層３０よりも第２面１２２側に位置する。すなわち、第２外層３４は、中間層３０に対して、中間層３０の厚さ方向Ｄ１の他方側に積層されている。中間層３０は、絶縁基材１２において第１外層３２と第２外層３４との間に位置する。 The first outer layer 32 is located on the first surface 121 side of the insulating base material 12 with respect to the intermediate layer 30. That is, the first outer layer 32 is laminated on one side of the intermediate layer 30 in the thickness direction D1 with respect to the intermediate layer 30. The second outer layer 34 is located on the second surface 122 side of the intermediate layer 30 in the insulating base material 12. That is, the second outer layer 34 is laminated on the other side of the intermediate layer 30 in the thickness direction D1 with respect to the intermediate layer 30. The intermediate layer 30 is located between the first outer layer 32 and the second outer layer 34 in the insulating base material 12.

中間層３０は、熱可塑性樹脂で構成されている。熱可塑性樹脂は、温度の上昇によって軟化する樹脂材料である。第１外層３２と第２外層３４とのそれぞれは、中間層３０を構成する熱可塑性樹脂よりも軟化温度が高い熱可塑性樹脂で構成されている。 The intermediate layer 30 is made of a thermoplastic resin. Thermoplastic resin is a resin material that softens as the temperature rises. Each of the first outer layer 32 and the second outer layer 34 is made of a thermoplastic resin having a softening temperature higher than that of the thermoplastic resin constituting the intermediate layer 30.

図３に示すように、第１熱電部材１８の側面１９の一部は、凹曲面形状である。凹曲面形状とは、凹状に面が連続して曲がっている形状である。 As shown in FIG. 3, a part of the side surface 19 of the first thermoelectric member 18 has a concave curved surface shape. The concave curved surface shape is a shape in which the surfaces are continuously bent in a concave shape.

具体的には、第１熱電部材１８は、中間層３０、第１外層３２および第２外層３４に第１熱電部材１８の側面１９が接するように配置されている。すなわち、第１熱電部材１８の側面１９は、中間層３０と接する部分１９１と、第１外層３２と接する部分１９２と、第２外層３４と接する部分１９３とを有する。第１熱電部材１８の側面１９のうち中間層３０と接する部分１９１が、凹曲面形状となっている。このため、第１熱電部材１８のうち中間層３０と接する部分では、絶縁基材１２の厚さ方向Ｄ１の端部側から中央部側に向かうにつれて、第１熱電部材１８が徐々に細くなっている。第１熱電部材１８の側面１９のうち第１外層３２と接する部分１９２と第２外層３４と接する部分１９３とは、絶縁基材１２の厚さ方向Ｄ１に平行またはそれに近い形状となっている。このため、第１熱電部材１８のうち第１外層３２および第２外層３４と接する部分では、第１熱電部材１８の太さが均一またはそれに近い形状となっている。 Specifically, the first thermoelectric member 18 is arranged so that the side surface 19 of the first thermoelectric member 18 is in contact with the intermediate layer 30, the first outer layer 32, and the second outer layer 34. That is, the side surface 19 of the first thermoelectric member 18 has a portion 191 in contact with the intermediate layer 30, a portion 192 in contact with the first outer layer 32, and a portion 193 in contact with the second outer layer 34. The portion 191 of the side surface 19 of the first thermoelectric member 18 in contact with the intermediate layer 30 has a concave curved surface shape. Therefore, in the portion of the first thermoelectric member 18 in contact with the intermediate layer 30, the first thermoelectric member 18 gradually becomes thinner from the end side to the central portion side in the thickness direction D1 of the insulating base material 12. There is. Of the side surface 19 of the first thermoelectric member 18, the portion 192 in contact with the first outer layer 32 and the portion 193 in contact with the second outer layer 34 have a shape parallel to or close to the thickness direction D1 of the insulating base material 12. Therefore, in the portion of the first thermoelectric member 18 that is in contact with the first outer layer 32 and the second outer layer 34, the thickness of the first thermoelectric member 18 is uniform or close to that.

このように、第１熱電部材１８の側面１９において、中間層３０と接する部分１９１は、第１外層３２と接する部分１９２と第２外層３４と接する部分１９３との両方よりも、曲がりが急な凹曲面形状となっている。 As described above, on the side surface 19 of the first thermoelectric member 18, the portion 191 in contact with the intermediate layer 30 is sharper than both the portion 192 in contact with the first outer layer 32 and the portion 193 in contact with the second outer layer 34. It has a concave curved surface shape.

図２に示すように、第１熱電部材１８と同様に、第２熱電部材２０の側面２１の一部は、凹曲面形状である。具体的には、第２熱電部材２０は、中間層３０、第１外層３２および第２外層３４に第２熱電部材２０の側面２１が接するように配置されている。すなわち、第２熱電部材２０の側面２１は、中間層３０と接する部分２１１と、第１外層３２と接する部分２１２と、第２外層３４と接する部分２１３とを有する。第２熱電部材２０の側面２１のうち中間層３０と接する部分２１１が、凹曲面形状となっている。第２熱電部材２０の側面２１のうち第１外層３２と接する部分２１２と第２外層３４と接する部分２１３とは、絶縁基材１２の厚さ方向に平行またはそれに近い形状となっている。 As shown in FIG. 2, a part of the side surface 21 of the second thermoelectric member 20 has a concave curved surface shape, similarly to the first thermoelectric member 18. Specifically, the second thermoelectric member 20 is arranged so that the side surface 21 of the second thermoelectric member 20 is in contact with the intermediate layer 30, the first outer layer 32, and the second outer layer 34. That is, the side surface 21 of the second thermoelectric member 20 has a portion 211 in contact with the intermediate layer 30, a portion 212 in contact with the first outer layer 32, and a portion 213 in contact with the second outer layer 34. The portion 211 of the side surface 21 of the second thermoelectric member 20 in contact with the intermediate layer 30 has a concave curved surface shape. Of the side surface 21 of the second thermoelectric member 20, the portion 212 in contact with the first outer layer 32 and the portion 213 in contact with the second outer layer 34 have a shape parallel to or close to the thickness direction of the insulating base material 12.

このように、第２熱電部材２０の側面２１において、中間層３０と接する部分２１１は、第１外層３２と接する部分２１２と第２外層３４と接する部分２１３との両方よりも、曲がりが急な凹曲面形状となっている。 As described above, on the side surface 21 of the second thermoelectric member 20, the portion 211 in contact with the intermediate layer 30 is sharper than both the portion 212 in contact with the first outer layer 32 and the portion 213 in contact with the second outer layer 34. It has a concave curved surface shape.

このような構造の熱電変換装置１０は、例えば、熱流束センサとして用いられる。この場合、図２に示す第１面１２１から第２面１２２に向かう方向にて、熱が熱電変換装置１０を通過する。このとき、熱電変換装置１０の第１面１２１側と第２面１２２側に温度差が生じる。これにより、ゼーベック効果によって、複数の第１熱電部材１８と複数の第２熱電部材２０とに熱起電力が発生する。熱電変換装置１０は、この熱起電力、具体的には、電圧をセンサ信号として出力する。 The thermoelectric conversion device 10 having such a structure is used as, for example, a heat flux sensor. In this case, heat passes through the thermoelectric conversion device 10 in the direction from the first surface 121 to the second surface 122 shown in FIG. At this time, a temperature difference occurs between the first surface 121 side and the second surface 122 side of the thermoelectric conversion device 10. As a result, due to the Seebeck effect, thermoelectromotive forces are generated in the plurality of first thermoelectric members 18 and the plurality of second thermoelectric members 20. The thermoelectric conversion device 10 outputs this thermoelectromotive force, specifically, a voltage as a sensor signal.

次に、熱電変換装置１０の製造方法について説明する。図４に示すように、用意工程Ｓ１と、積層体の形成工程Ｓ２と、加熱加圧工程Ｓ３とが順に行われる。 Next, a method of manufacturing the thermoelectric conversion device 10 will be described. As shown in FIG. 4, the preparation step S1, the laminate forming step S2, and the heating and pressurizing step S3 are sequentially performed.

用意工程Ｓ１では、図５に示すように、絶縁基材１２と、第１保護部材１４と、第２保護部材１６とを用意する。図５では、絶縁基材１２と第１保護部材１４と第２保護部材１６とが並んで図示されている。 In the preparation step S1, as shown in FIG. 5, the insulating base material 12, the first protective member 14, and the second protective member 16 are prepared. In FIG. 5, the insulating base material 12, the first protective member 14, and the second protective member 16 are shown side by side.

用意される絶縁基材１２には、未焼結の複数の第１熱電部材４０と、未焼結の複数の第２熱電部材４２とが設けられている。用意される第１保護部材１４には、絶縁基材１２側となる表面に複数の第１導体パターン２６が設けられている。用意される第２保護部材１６には、絶縁基材１２側となる表面に複数の第２導体パターン２８が設けられている。 The prepared insulating base material 12 is provided with a plurality of unsintered first thermoelectric members 40 and a plurality of unsintered second thermoelectric members 42. The prepared first protective member 14 is provided with a plurality of first conductor patterns 26 on the surface on the insulating base material 12 side. The prepared second protective member 16 is provided with a plurality of second conductor patterns 28 on the surface on the insulating base material 12 side.

ここで、図５に示す状態の絶縁基材１２は、次のようにして製造される。 Here, the insulating base material 12 in the state shown in FIG. 5 is manufactured as follows.

図６に示すように、中間層３０を構成する第１シート５０と、第１外層３２を構成する第２シート５２と、第２外層３４を構成する第３シート５４とを用意する。図６では、第１シート５０と第２シート５２と第３シート５４とが、並んで図示されている。第１シート５０は、加熱加圧工程Ｓ３で流動する樹脂材料で構成される。具体的には、第１シート５０は、加熱加圧工程Ｓ３の加熱温度である３２０℃よりも軟化温度が低い熱可塑性樹脂で構成される。このような熱可塑性樹脂として、ポリエーテルイミド樹脂が挙げられる。ポリエーテルイミド樹脂の軟化温度は、約２２０℃である。 As shown in FIG. 6, a first sheet 50 constituting the intermediate layer 30, a second sheet 52 forming the first outer layer 32, and a third sheet 54 forming the second outer layer 34 are prepared. In FIG. 6, the first sheet 50, the second sheet 52, and the third sheet 54 are shown side by side. The first sheet 50 is made of a resin material that flows in the heating and pressurizing step S3. Specifically, the first sheet 50 is made of a thermoplastic resin having a softening temperature lower than the heating temperature of 320 ° C. in the heating and pressurizing step S3. Examples of such a thermoplastic resin include polyetherimide resin. The softening temperature of the polyetherimide resin is about 220 ° C.

第２シート５２および第３シート５４は、加熱加圧工程Ｓ３で流動しない樹脂材料で構成される。具体的には、第２シート５２および第３シート５４は、３２０℃よりも軟化温度が高い熱可塑性樹脂で構成される。このような熱可塑性樹脂としては、熱可塑性ポリイミド樹脂、I型の液晶ポリマー、１．５型の液晶ポリマー、II型の液晶ポリマー等が挙げられる。 The second sheet 52 and the third sheet 54 are made of a resin material that does not flow in the heating and pressurizing step S3. Specifically, the second sheet 52 and the third sheet 54 are made of a thermoplastic resin having a softening temperature higher than 320 ° C. Examples of such a thermoplastic resin include a thermoplastic polyimide resin, an I-type liquid crystal polymer, a 1.5-type liquid crystal polymer, and a II-type liquid crystal polymer.

続いて、図７に示すように、第１シート５０と第２シート５２と第３シート５４とを積層して３枚のシートの積層体５６を形成する。このとき、第１シート５０の両側に第２シート５２と第３シート５４とを配置する。この積層体５６を加熱しながら加圧して、３枚のシートを一体化させる。このときの加熱加圧条件は、３枚のシートが融着する条件であればよく、加熱加圧工程Ｓ３での加熱加圧条件と同じでなくてもよい。加熱加圧条件は、例えば、真空中で、２９０−３２０℃、２．５−３．５ＭＰａを３０−５０分間である。 Subsequently, as shown in FIG. 7, the first sheet 50, the second sheet 52, and the third sheet 54 are laminated to form a laminated body 56 of three sheets. At this time, the second sheet 52 and the third sheet 54 are arranged on both sides of the first sheet 50. The laminated body 56 is pressurized while being heated to integrate the three sheets. The heating and pressurizing conditions at this time may be any conditions as long as the three sheets are fused, and may not be the same as the heating and pressurizing conditions in the heating and pressurizing step S3. The heating and pressurizing conditions are, for example, 290-320 ° C. and 2.5-3.5 MPa for 30-50 minutes in a vacuum.

これにより、中間層３０と、第１外層３２と、第２外層３４とを有する絶縁基材１２が形成される。中間層３０は、加熱加圧工程Ｓ３で流動する流動部である。第１外層３２および第２外層３４は加熱加圧工程Ｓ３で流動しない非流動部である。 As a result, the insulating base material 12 having the intermediate layer 30, the first outer layer 32, and the second outer layer 34 is formed. The intermediate layer 30 is a flowing portion that flows in the heating and pressurizing step S3. The first outer layer 32 and the second outer layer 34 are non-flowing portions that do not flow in the heating and pressurizing step S3.

このとき、第１外層３２と第２外層３４とのそれぞれの厚さは、中間層３０の厚さよりも薄くなっている。第１外層３２と第２外層３４とのそれぞれの厚さが、中間層３０の厚さよりも厚い場合、後述する加熱加圧工程Ｓ３において、絶縁基材１２の流動部が少なくなる。この場合、第１熱電部材１８の側面１９と第２熱電部材２０の側面２１とのそれぞれを所望の凹曲面形状とすることができない。 At this time, the thickness of each of the first outer layer 32 and the second outer layer 34 is thinner than the thickness of the intermediate layer 30. When the thickness of each of the first outer layer 32 and the second outer layer 34 is thicker than the thickness of the intermediate layer 30, the flow portion of the insulating base material 12 is reduced in the heating and pressurizing step S3 described later. In this case, the side surface 19 of the first thermoelectric member 18 and the side surface 21 of the second thermoelectric member 20 cannot each have a desired concave curved surface shape.

続いて、図８に示すように、ドリルまたはレーザーなどによって、複数の第１貫通孔２２および複数の第２貫通孔２４を絶縁基材１２に形成する。複数の第１貫通孔２２および複数の第２貫通孔２４のそれぞれは、絶縁基材１２を第１面１２１から第２面１２２まで貫通している。 Subsequently, as shown in FIG. 8, a plurality of first through holes 22 and a plurality of second through holes 24 are formed in the insulating base material 12 by a drill, a laser, or the like. Each of the plurality of first through holes 22 and the plurality of second through holes 24 penetrates the insulating base material 12 from the first surface 121 to the second surface 122.

続いて、図９に示すように、複数の第１貫通孔２２のそれぞれに、Ｐ型熱電ペースト５８を充填する。Ｐ型熱電ペースト５８は、粉末状のＰ型熱電材料を溶媒に分散させたものである。このとき、絶縁基材１２の第１面１２１に第１メタルマスク６０を設ける。第１メタルマスク６０は、複数の第１貫通孔２２を露出し、複数の第２貫通孔２４を覆った状態とする。この状態で、スキージ６２を用いて、Ｐ型熱電ペースト５８を充填する。Ｐ型熱電ペースト５８の充填後、第１メタルマスク６０を除去する。 Subsequently, as shown in FIG. 9, each of the plurality of first through holes 22 is filled with the P-type thermoelectric paste 58. The P-type thermoelectric paste 58 is a powdery P-type thermoelectric material dispersed in a solvent. At this time, the first metal mask 60 is provided on the first surface 121 of the insulating base material 12. The first metal mask 60 exposes a plurality of first through holes 22 and covers the plurality of second through holes 24. In this state, the P-type thermoelectric paste 58 is filled with the squeegee 62. After filling the P-type thermoelectric paste 58, the first metal mask 60 is removed.

続いて、図１０に示すように、複数の第２貫通孔２４のそれぞれに、Ｎ型熱電ペースト６４を充填する。Ｎ型熱電ペースト６４は、粉末状のＮ型熱電材料を溶媒に分散させたものである。このとき、絶縁基材１２の第１面１２１に第２メタルマスク６６を設ける。第２メタルマスク６６は、複数の第１貫通孔２２を覆い、複数の第２貫通孔２４を露出した状態とする。この状態で、スキージ６８を用いて、Ｎ型熱電ペースト６４を充填する。Ｎ型熱電ペースト６４の充填後、第２メタルマスク６６を除去する。 Subsequently, as shown in FIG. 10, each of the plurality of second through holes 24 is filled with the N-type thermoelectric paste 64. The N-type thermoelectric paste 64 is a powdery N-type thermoelectric material dispersed in a solvent. At this time, the second metal mask 66 is provided on the first surface 121 of the insulating base material 12. The second metal mask 66 covers the plurality of first through holes 22 and exposes the plurality of second through holes 24. In this state, the N-type thermoelectric paste 64 is filled with the squeegee 68. After filling the N-type thermoelectric paste 64, the second metal mask 66 is removed.

その後、Ｐ型熱電ペースト５８およびＮ型熱電ペースト６４を乾燥させる。Ｐ型熱電ペースト５８が乾燥することで、未焼結の第１熱電部材４０が形成される。Ｎ型熱電ペースト６４が乾燥することで、未焼結の第２熱電部材４２が形成される。このようにして、図５に示す状態の絶縁基材１２が形成される。 Then, the P-type thermoelectric paste 58 and the N-type thermoelectric paste 64 are dried. By drying the P-type thermoelectric paste 58, an unsintered first thermoelectric member 40 is formed. By drying the N-type thermoelectric paste 64, an unsintered second thermoelectric member 42 is formed. In this way, the insulating base material 12 in the state shown in FIG. 5 is formed.

積層体の形成工程Ｓ２では、図１１に示すように、絶縁基材１２と、第１保護部材１４と、第２保護部材１６とが積層された積層体７０を形成する。このとき、絶縁基材１２の第１面１２１側に第１保護部材１４を配置する。複数の第１導体パターン２６のそれぞれは、隣り合う未焼結の第１熱電部材４０と未焼結の第２熱電部材４２とに接触した状態とされる。絶縁基材１２の第２面１２２側に第２保護部材１６を配置する。複数の第２導体パターン２８のそれぞれは、隣り合う未焼結の第１熱電部材４０と未焼結の第２熱電部材４２とに接触した状態とされる。本実施形態では、積層体７０が、絶縁基材と熱電部材と第１導体パターンと第２導体パターンとを有する構造体に相当する。 In the layered body forming step S2, as shown in FIG. 11, the laminated body 70 in which the insulating base material 12, the first protective member 14, and the second protective member 16 are laminated is formed. At this time, the first protective member 14 is arranged on the first surface 121 side of the insulating base material 12. Each of the plurality of first conductor patterns 26 is in contact with the adjacent unsintered first thermoelectric member 40 and the unsintered second thermoelectric member 42. The second protective member 16 is arranged on the second surface 122 side of the insulating base material 12. Each of the plurality of second conductor patterns 28 is in contact with the adjacent unsintered first thermoelectric member 40 and the unsintered second thermoelectric member 42. In the present embodiment, the laminated body 70 corresponds to a structure having an insulating base material, a thermoelectric member, a first conductor pattern, and a second conductor pattern.

加熱加圧工程Ｓ３では、図１１に示すように、積層体７０の積層方向Ｄ１で、積層体７０を加熱しながら加圧する。積層体７０の積層方向Ｄ１は、絶縁基材１２の厚さ方向Ｄ１と同じである。このときの加熱加圧条件は、例えば、真空中で、２３０℃、１０ＭＰａを１０分間と、３２０℃、４ＭＰａを１０分間である。 In the heating and pressurizing step S3, as shown in FIG. 11, the laminated body 70 is pressurized while being heated in the stacking direction D1 of the laminated body 70. The stacking direction D1 of the laminated body 70 is the same as the thickness direction D1 of the insulating base material 12. The heating and pressurizing conditions at this time are, for example, 230 ° C. and 10 MPa for 10 minutes and 320 ° C. and 4 MPa for 10 minutes in a vacuum.

これにより、図２に示すように、絶縁基材１２と、第１保護部材１４と、第２保護部材１６とが一体化する。未焼結の複数の第１熱電部材４０のそれぞれが焼結して、焼結後の複数の第１熱電部材１８となる。未焼結の複数の第２熱電部材４２のそれぞれが焼結して、焼結後の複数の第２熱電部材２０となる。 As a result, as shown in FIG. 2, the insulating base material 12, the first protective member 14, and the second protective member 16 are integrated. Each of the plurality of unsintered first thermoelectric members 40 is sintered to become a plurality of first thermoelectric members 18 after sintering. Each of the plurality of unsintered second thermoelectric members 42 is sintered to become the plurality of sintered second thermoelectric members 20.

さらに、加熱加圧工程Ｓ３では、加熱と加圧によって中間層３０が流動する。第１外層３２および第２外層３４は流動しない。これにより、図２に示すように、複数の第１熱電部材１８と複数の第２熱電部材２０のそれぞれの熱電部材１８、２０の側面１９、２１のうち中間層３０に接する部分１９１、２１１が凹曲面形状になる。このようにして、上記した構造の熱電変換装置１０が製造される。 Further, in the heating and pressurizing step S3, the intermediate layer 30 flows by heating and pressurizing. The first outer layer 32 and the second outer layer 34 do not flow. As a result, as shown in FIG. 2, the portions 191, 211 of the side surfaces 19, 21 of the plurality of first thermoelectric members 18 and the plurality of second thermoelectric members 20, respectively, which are in contact with the intermediate layer 30, are formed. It has a concave curved shape. In this way, the thermoelectric conversion device 10 having the above-mentioned structure is manufactured.

ここで、それぞれの熱電部材１８、２０の側面１９、２１のうち中間層３０に接する部分１９１、２１１が凹曲面形状になる理由について、比較例１を用いて説明する。 Here, the reason why the portions 191 and 211 in contact with the intermediate layer 30 of the side surfaces 19 and 21 of the thermoelectric members 18 and 20 have a concave curved surface shape will be described with reference to Comparative Example 1.

比較例１は、図１２に示すように、絶縁基材１２が１層で構成されている点が、本実施形態と異なる。この絶縁基材１２は、本実施形態の中間層３０と同じ材料のみで構成されている。 Comparative Example 1 is different from the present embodiment in that the insulating base material 12 is composed of one layer as shown in FIG. The insulating base material 12 is made of only the same material as the intermediate layer 30 of the present embodiment.

比較例１では、加熱加圧工程Ｓ３において、絶縁基材１２の全体が流動する。このため、図１２中の矢印Ａ１で示すように、未焼結の熱電部材７２の側面７３に対してほぼ均等に圧力がかかる。図１２中の矢印Ａ１の長さが圧力の大きさを示している。 In Comparative Example 1, in the heating and pressurizing step S3, the entire insulating base material 12 flows. Therefore, as shown by the arrow A1 in FIG. 12, the pressure is applied substantially evenly to the side surface 73 of the unsintered thermoelectric member 72. The length of the arrow A1 in FIG. 12 indicates the magnitude of the pressure.

この結果、図１３に示すように、加熱加圧工程Ｓ３の後において、焼結後の熱電部材７４の側面７５は、ゆるやかに湾曲している。すなわち、熱電変換装置Ｊ１０の断面において、焼結後の熱電部材７４の側面７５は、絶縁基材１２の厚さ方向Ｄ１にほぼ平行となる。さらに換言すると、焼成後の熱電部材７４は、太さがほぼ同じ円柱状となる。 As a result, as shown in FIG. 13, after the heating and pressurizing step S3, the side surface 75 of the sintered thermoelectric member 74 is gently curved. That is, in the cross section of the thermoelectric conversion device J10, the side surface 75 of the thermoelectric member 74 after sintering is substantially parallel to the thickness direction D1 of the insulating base material 12. In other words, the thermoelectric member 74 after firing has a columnar shape having substantially the same thickness.

これに対して、本実施形態では、加熱加圧工程Ｓ３において、中間層３０は流動するが、第１外層３２および第２外層３４は流動しない。 On the other hand, in the present embodiment, in the heating and pressurizing step S3, the intermediate layer 30 flows, but the first outer layer 32 and the second outer layer 34 do not flow.

このため、図１４中の矢印Ａ２で示すように、未焼結の第１熱電部材４０のうち第１外層３２に接する部分は、圧力がかからない、または、かかる圧力が小さい。未焼結の第１熱電部材４０のうち中間層３０に接する部分は、中間層３０の流動によって大きな圧力がかかる。図１４中の矢印Ａ２の長さが応力の大きさを示している。 Therefore, as shown by the arrow A2 in FIG. 14, no pressure is applied to the portion of the unsintered first thermoelectric member 40 in contact with the first outer layer 32, or the pressure applied is small. A large pressure is applied to the portion of the unsintered first thermoelectric member 40 in contact with the intermediate layer 30 due to the flow of the intermediate layer 30. The length of arrow A2 in FIG. 14 indicates the magnitude of stress.

本実施形態の絶縁基材１２の厚さが比較例１の絶縁基材１２の厚さと同じ場合、未焼結の第１熱電部材４０が加熱加圧工程Ｓ３で流動する樹脂と接する面積は、比較例１の熱電部材７２が加熱加圧工程Ｓ３で流動する樹脂と接する面積よりも小さい。このため、未焼結の第１熱電部材４０が流動する樹脂から受ける力が比較例１の場合と同じであれば、未焼結の第１熱電部材４０が中間層３０から受ける圧力が大きくなる。 When the thickness of the insulating base material 12 of the present embodiment is the same as the thickness of the insulating base material 12 of Comparative Example 1, the area where the unsintered first thermoelectric member 40 comes into contact with the resin flowing in the heating and pressurizing step S3 is determined. The area where the thermoelectric member 72 of Comparative Example 1 is in contact with the flowing resin in the heating and pressurizing step S3 is smaller. Therefore, if the force received by the unsintered first thermoelectric member 40 from the flowing resin is the same as in the case of Comparative Example 1, the pressure received by the unsintered first thermoelectric member 40 from the intermediate layer 30 increases. ..

さらに、中間層３０が流動するときでは、図１４に示すように、中間層３０のうち第１外層３２および第２外層３４に近い部分３０１、３０２は、第１外層３２および第２外層３４との摩擦によって流動し難い。一方、中間層３０のうち第１外層３２および第２外層３４から遠い部分３０３は、流動しやすい。このため、流動する樹脂に、厚さ方向の端部から中央部に向かうにつれて流速が高いという流速分布が生じる。この結果、未焼結の第１熱電部材４０の側面４１にかかる圧力は、絶縁基材１２の厚さ方向での側面４１の端部から中央部に向かうにつれて大きくなる。 Further, when the intermediate layer 30 flows, as shown in FIG. 14, the portions 301 and 302 of the intermediate layer 30 close to the first outer layer 32 and the second outer layer 34 are combined with the first outer layer 32 and the second outer layer 34. It is difficult to flow due to friction. On the other hand, of the intermediate layer 30, the portion 303 far from the first outer layer 32 and the second outer layer 34 tends to flow. For this reason, the flowing resin has a flow velocity distribution in which the flow velocity increases from the end portion in the thickness direction toward the center portion. As a result, the pressure applied to the side surface 41 of the unsintered first thermoelectric member 40 increases from the end portion to the central portion of the side surface 41 in the thickness direction of the insulating base material 12.

これにより、図３に示すように、焼成後の第１熱電部材１８の側面１９のうち中間層３０に接する部分１９１を、第１外層３２に接する部分１９２と第２外層３４に接する部分１９３との両方よりも曲がりが急な凹曲面形状にすることができる。この結果、比較例１の熱電部材７４の側面７５と比較して、中間層３０に接する部分１９１を、曲がりが急な凹曲面形状とすることができる。すなわち、中間層３０に接する部分１９１の凹曲面形状の凹み具合を大きくできる。凹み具合が大きいとは、曲率半径で比較すると、曲率半径が小さいことを意味する。 As a result, as shown in FIG. 3, of the side surface 19 of the first thermoelectric member 18 after firing, the portion 191 in contact with the intermediate layer 30 becomes the portion 192 in contact with the first outer layer 32 and the portion 193 in contact with the second outer layer 34. It is possible to make a concave curved surface shape with a steeper bend than both of. As a result, the portion 191 in contact with the intermediate layer 30 can be formed into a concave curved surface shape with a steep bend as compared with the side surface 75 of the thermoelectric member 74 of Comparative Example 1. That is, the degree of denting of the concave curved surface shape of the portion 191 in contact with the intermediate layer 30 can be increased. A large degree of dent means that the radius of curvature is small when compared in terms of radius of curvature.

同様の理由により、焼成後の第２熱電部材２０の側面２１のうち中間層３０に接する部分２１１を、第１外層３２に接する部分２１２と第２外層３４に接する部分２１３との両方よりも曲がりが急な凹曲面形状にすることができる。 For the same reason, the portion 211 of the side surface 21 of the second thermoelectric member 20 after firing, which is in contact with the intermediate layer 30, is bent more than both the portion 212 in contact with the first outer layer 32 and the portion 213 in contact with the second outer layer 34. Can be made into a steep concave curved surface shape.

図１３に示すように、比較例１の熱電変換装置Ｊ１０では、焼成後の熱電部材７４の側面７５が、ゆるやかに湾曲している。このため、比較例１の熱電変換装置Ｊ１０に曲げ等の変形応力が加わった場合、熱電部材７４のうち第１導体パターン２６と第２導体パターン２８のそれぞれの導体パターン２６、２８との接続部付近７４１、７４２に応力が集中する。このため、比較例１の熱電変換装置Ｊ１０では、導体パターン２６、２８と熱電部材７４との接続の信頼性が低い。 As shown in FIG. 13, in the thermoelectric converter J10 of Comparative Example 1, the side surface 75 of the thermoelectric member 74 after firing is gently curved. Therefore, when a deformation stress such as bending is applied to the thermoelectric conversion device J10 of Comparative Example 1, the connection portion between the first conductor pattern 26 and the second conductor pattern 28 of the thermoelectric member 74 and the conductor patterns 26 and 28, respectively. Stress is concentrated in the vicinity 741 and 742. Therefore, in the thermoelectric conversion device J10 of Comparative Example 1, the reliability of the connection between the conductor patterns 26 and 28 and the thermoelectric member 74 is low.

これに対して、上記の通り、本実施形態の熱電変換装置１０では、図２に示すように、それぞれの熱電部材１８、２０の側面１９、２１のうち中間層３０に接する部分１９１、２１１が凹曲面形状となっている。この凹曲面形状は、比較例１の熱電部材７４の側面７５と比較して、曲がり具合が急である。すなわち、この凹曲面形状は、比較例１の熱電部材７４の側面７５と比較して、凹み具合が大きい。 On the other hand, as described above, in the thermoelectric conversion device 10 of the present embodiment, as shown in FIG. 2, the portions 191 and 211 of the side surfaces 19 and 21 of the thermoelectric members 18 and 20 in contact with the intermediate layer 30 are formed. It has a concave curved surface shape. This concave curved surface shape has a steeper bend than the side surface 75 of the thermoelectric member 74 of Comparative Example 1. That is, this concave curved surface shape has a large degree of depression as compared with the side surface 75 of the thermoelectric member 74 of Comparative Example 1.

このため、本実施形態の熱電変換装置１０に曲げ等の変形応力が加わった場合、図３に示すように、第１熱電部材１８のうち側面１９が凹曲面形状である部分１９１の周辺部１８１に応力を分散させることができる。この結果、第１熱電部材１８のうちそれぞれの導体パターン２６、２８との接続部付近１８２、１８３に生じる応力集中を抑制することができる。第２熱電部材２０においても同様である。よって、本実施形態によれば、それぞれの導体パターン２６、２８とそれぞれの熱電部材１８、２０との接続の信頼性を高めることができる。 Therefore, when a deformation stress such as bending is applied to the thermoelectric conversion device 10 of the present embodiment, as shown in FIG. 3, the peripheral portion 181 of the portion 191 of the first thermoelectric member 18 whose side surface 19 has a concave curved surface shape is formed. The stress can be dispersed. As a result, it is possible to suppress the stress concentration that occurs in the vicinity of the connection portions 182 and 183 with the conductor patterns 26 and 28 of the first thermoelectric member 18. The same applies to the second thermoelectric member 20. Therefore, according to the present embodiment, the reliability of the connection between the respective conductor patterns 26 and 28 and the respective thermoelectric members 18 and 20 can be improved.

また、図１３に示すように、比較例１の熱電変換装置Ｊ１０では、熱電部材７４と絶縁基材１２との境界が熱電変換装置Ｊ１０の面方向に対してほぼ垂直である。熱電部材７４の側面７５が熱電部材７４と絶縁基材１２との境界である。このため、熱電部材７４の存在割合と、絶縁基材１２の存在割合とが、熱電変換装置Ｊ１０の面方向において急激に変化している。この結果、比較例１の熱電変換装置Ｊ１０が冷熱サイクルにさらされると、絶縁基材１２と熱電部材７４との熱膨張係数の違いによって熱応力が発生する。この熱応力が熱電部材７４のうちそれぞれの導体パターン２６、２８との接続部付近７４１、７４２に集中する。このため、比較例１の熱電変換装置Ｊ１０では、導体パターン２６、２８と熱電部材７４との接続の信頼性が低い。 Further, as shown in FIG. 13, in the thermoelectric conversion device J10 of Comparative Example 1, the boundary between the thermoelectric member 74 and the insulating base material 12 is substantially perpendicular to the plane direction of the thermoelectric conversion device J10. The side surface 75 of the thermoelectric member 74 is the boundary between the thermoelectric member 74 and the insulating base material 12. Therefore, the abundance ratio of the thermoelectric member 74 and the abundance ratio of the insulating base material 12 change rapidly in the plane direction of the thermoelectric conversion device J10. As a result, when the thermoelectric converter J10 of Comparative Example 1 is exposed to the thermal cycle, thermal stress is generated due to the difference in the coefficient of thermal expansion between the insulating base material 12 and the thermoelectric member 74. This thermal stress is concentrated in 741 and 742 in the vicinity of the connection portions with the respective conductor patterns 26 and 28 in the thermoelectric member 74. Therefore, in the thermoelectric conversion device J10 of Comparative Example 1, the reliability of the connection between the conductor patterns 26 and 28 and the thermoelectric member 74 is low.

これに対して、本実施形態の熱電変換装置１０では、図３に示すように、第１熱電部材１８の側面１９のうち中間層３０に接する部分１９１は、凹曲面形状である。したがって、第１熱電部材１８と絶縁基材１２との境界は、熱電変換装置１０の面方向に対して垂直ではない。このため、熱電部材７４の存在割合と、絶縁基材１２の存在割合とが、熱電変換装置１０の面方向で段階的に変化している。 On the other hand, in the thermoelectric conversion device 10 of the present embodiment, as shown in FIG. 3, the portion 191 of the side surface 19 of the first thermoelectric member 18 in contact with the intermediate layer 30 has a concave curved surface shape. Therefore, the boundary between the first thermoelectric member 18 and the insulating base material 12 is not perpendicular to the plane direction of the thermoelectric converter 10. Therefore, the abundance ratio of the thermoelectric member 74 and the abundance ratio of the insulating base material 12 change stepwise in the plane direction of the thermoelectric conversion device 10.

これにより、本実施形態の熱電変換装置１０が冷熱サイクルにさらされたときに、絶縁基材１２と第１熱電部材１８との熱膨張係数の違いによって生じる熱応力を小さく抑えることできる。この結果、第１熱電部材１８のうちそれぞれの導体パターン２６、２８との接続部付近１８２、１８３にかかる応力を低減できる。第２熱電部材２０においても同様である。よって、本実施形態によれば、それぞれの導体パターン２６、２８とそれぞれの熱電部材１８、２０との接続の信頼性を高めることができる。 As a result, when the thermoelectric conversion device 10 of the present embodiment is exposed to a thermal cycle, the thermal stress caused by the difference in the coefficient of thermal expansion between the insulating base material 12 and the first thermoelectric member 18 can be suppressed to a small value. As a result, it is possible to reduce the stress applied to 182 and 183 near the connection portions of the first thermoelectric members 18 with the conductor patterns 26 and 28, respectively. The same applies to the second thermoelectric member 20. Therefore, according to the present embodiment, the reliability of the connection between the respective conductor patterns 26 and 28 and the respective thermoelectric members 18 and 20 can be improved.

（第２実施形態）
図１５−図１８を用いて、本実施形態の熱電変換装置１０の製造方法について説明する。本実施形態においても、図４に示すように、用意工程Ｓ１と、積層体の形成工程Ｓ２と、加熱加圧工程Ｓ３とが順に行われる。 (Second Embodiment)
A method of manufacturing the thermoelectric conversion device 10 of the present embodiment will be described with reference to FIGS. 15-18. Also in this embodiment, as shown in FIG. 4, the preparation step S1, the laminate forming step S2, and the heating and pressurizing step S3 are sequentially performed.

用意工程Ｓ１では、図１５に示すように、第１基材部８１と、第２基材部８２とを用意する。図１５では、積層前の第１基材部８１と第２基材部８２とが並んで図示されている。 In the preparation step S1, as shown in FIG. 15, the first base material portion 81 and the second base material portion 82 are prepared. In FIG. 15, the first base material portion 81 and the second base material portion 82 before laminating are shown side by side.

このとき、第１基材部８１には、未焼結の複数の第１熱電部材８３１と、未焼結の複数の第２熱電部材８４１とが設けられている。第１基材部８１には、複数の第１導体パターン２６が設けられている。第２基材部８２には、未焼結の複数の第１熱電部材８３２と、未焼結の複数の第２熱電部材８４２とが設けられている。第２基材部８２には、複数の第２導体パターン２８が設けられている。 At this time, the first base material portion 81 is provided with a plurality of unsintered first thermoelectric members 831 and a plurality of unsintered second thermoelectric members 841. A plurality of first conductor patterns 26 are provided on the first base material portion 81. The second base material portion 82 is provided with a plurality of unsintered first thermoelectric members 832 and a plurality of unsintered second thermoelectric members 842. A plurality of second conductor patterns 28 are provided on the second base material portion 82.

ここで、図１５に示す状態の第１基材部８１と第２基材部８２とは、次のようにして製造される。まず、図１６に示すように、第１シート８１１と第２シート８１２とを一体化して、シート状の第１基材部８１を形成する。第１シート８１１は、中間層３０の一部を構成する。第２シート８１２は、第１外層３２を構成する。第１シート８１１は、第１実施形態の第１シート５０と同様に、加熱加圧工程Ｓ３で流動する材料で構成される。第２シート８１２は、第２実施形態の第２シート５２と同様に、加熱加圧工程Ｓ３で流動しない材料で構成される。続いて、第２シート８１２の表面に複数の第１導体パターン２６を形成する。 Here, the first base material portion 81 and the second base material portion 82 in the state shown in FIG. 15 are manufactured as follows. First, as shown in FIG. 16, the first sheet 811 and the second sheet 812 are integrated to form a sheet-shaped first base material portion 81. The first sheet 811 constitutes a part of the intermediate layer 30. The second sheet 812 constitutes the first outer layer 32. The first sheet 811 is made of a material that flows in the heating and pressurizing step S3, similarly to the first sheet 50 of the first embodiment. The second sheet 812 is made of a material that does not flow in the heating and pressurizing step S3, like the second sheet 52 of the second embodiment. Subsequently, a plurality of first conductor patterns 26 are formed on the surface of the second sheet 812.

同様に、第３シート８２１と第４シート８２２とを一体化して、シート状の第２基材部８２を形成する。第３シート８２１は、中間層３０の他の一部を構成する。第４シート８２２は、第２外層３４を構成する。第３シート８２１は、第１実施形態の第１シート５０と同様に、加熱加圧工程Ｓ３で流動する材料で構成される。第４シート８２２は、第２実施形態の第３シート５４と同様に、加熱加圧工程Ｓ３で流動しない材料で構成される。続いて、第４シート８２２の表面に複数の第２導体パターン２８を形成する。 Similarly, the third sheet 821 and the fourth sheet 822 are integrated to form a sheet-shaped second base material portion 82. The third sheet 821 constitutes another part of the intermediate layer 30. The fourth sheet 822 constitutes the second outer layer 34. The third sheet 821 is made of a material that flows in the heating and pressurizing step S3, similarly to the first sheet 50 of the first embodiment. The fourth sheet 822 is made of a material that does not flow in the heating and pressurizing step S3, like the third sheet 54 of the second embodiment. Subsequently, a plurality of second conductor patterns 28 are formed on the surface of the fourth sheet 822.

続いて、図１７に示すように、第１基材部８１に複数の第１貫通孔８１３および複数の第２貫通孔８１４を形成する。複数の第１貫通孔８１３および複数の第２貫通孔８１４は、第１基材部８１の厚さ方向に第１基材部８１を貫通する。複数の第１貫通孔８１３のそれぞれと複数の第２貫通孔８１４それぞれとは交互に配置される。複数の第１導体パターン２６のそれぞれは、複数の第１貫通孔８１３および複数の第２貫通孔８１４の底を構成している。 Subsequently, as shown in FIG. 17, a plurality of first through holes 813 and a plurality of second through holes 814 are formed in the first base material portion 81. The plurality of first through holes 813 and the plurality of second through holes 814 penetrate the first base material portion 81 in the thickness direction of the first base material portion 81. Each of the plurality of first through holes 813 and each of the plurality of second through holes 814 are arranged alternately. Each of the plurality of first conductor patterns 26 constitutes the bottom of the plurality of first through holes 813 and the plurality of second through holes 814.

同様に、第２基材部８２に複数の第１貫通孔８２３および複数の第２貫通孔８２４を形成する。複数の第１貫通孔８２３および複数の第２貫通孔８２４は、第２基材部８２の厚さ方向に第２基材部８２を貫通する。複数の第１貫通孔８２３それぞれと複数の第２貫通孔８２４のそれぞれとは交互に配置される。複数の第２導体パターン２８のそれぞれは、複数の第１貫通孔８２３および複数の第２貫通孔８２４の底を構成している。 Similarly, a plurality of first through holes 823 and a plurality of second through holes 824 are formed in the second base material portion 82. The plurality of first through holes 823 and the plurality of second through holes 824 penetrate the second base material portion 82 in the thickness direction of the second base material portion 82. Each of the plurality of first through holes 823 and each of the plurality of second through holes 824 are arranged alternately. Each of the plurality of second conductor patterns 28 constitutes the bottom of the plurality of first through holes 823 and the plurality of second through holes 824.

続いて、図１５に示すように、第１基材部８１において、複数の第１貫通孔８１３のそれぞれに未焼結の第１熱電部材８３１を形成する。複数の第２貫通孔８１４のそれぞれに未焼結の第２熱電部材８４１を形成する。 Subsequently, as shown in FIG. 15, in the first base material portion 81, an unsintered first thermoelectric member 831 is formed in each of the plurality of first through holes 813. An unsintered second thermoelectric member 841 is formed in each of the plurality of second through holes 814.

同様に、第２基材部８２において、複数の第１貫通孔８２３のそれぞれに粉末状の第１熱電部材８３２を形成する。複数の第２貫通孔８２４のそれぞれに粉末状の第２熱電部材８４２を形成する。未焼結の第１熱電部材８３１、８３２の形成方法は、第１実施形態の未焼結の第１熱電部材４０の形成方法と同じである。未焼結の第２熱電部材８４１、８４２の形成方法は、第１実施形態の未焼結の第２熱電部材４２の形成方法と同じである。このようにして、図１５に示す状態の第１基材部８１と第２基材部８２とが形成される。 Similarly, in the second base material portion 82, a powdery first thermoelectric member 832 is formed in each of the plurality of first through holes 823. A powdery second thermoelectric member 842 is formed in each of the plurality of second through holes 824. The method for forming the unsintered first thermoelectric members 831 and 832 is the same as the method for forming the unsintered first thermoelectric member 40 of the first embodiment. The method for forming the unsintered second thermoelectric members 841 and 842 is the same as the method for forming the unsintered second thermoelectric member 42 of the first embodiment. In this way, the first base material portion 81 and the second base material portion 82 in the state shown in FIG. 15 are formed.

積層体の形成工程Ｓ２では、図１８に示すように、第１基材部８１と第２基材部８２とが積層された積層体８５を形成する。このとき、第１基材部８１の第１シート８１１と第２基材部８２の第３シート８２１とが接触する。これにより、第１実施形態と同様に、絶縁基材１２が形成される。また、第１基材部８１の複数の第１熱電部材８３１のそれぞれと第２基材部８２の複数の第１熱電部材８３２のそれぞれとが接触する。これにより、第１実施形態と同様に、未焼結の複数の第１熱電部材４０が形成される。また、第１基材部８１の複数の第２熱電部材８４１のそれぞれと第２基材部８２の複数の第２熱電部材８４２のそれぞれとが接触する。これにより、第１実施形態と同様に、未焼結の複数の第２熱電部材４２が形成される。 In the layered body forming step S2, as shown in FIG. 18, a laminated body 85 in which the first base material portion 81 and the second base material portion 82 are laminated is formed. At this time, the first sheet 811 of the first base material portion 81 and the third sheet 821 of the second base material portion 82 come into contact with each other. As a result, the insulating base material 12 is formed as in the first embodiment. Further, each of the plurality of first thermoelectric members 831 of the first base material portion 81 and each of the plurality of first thermoelectric members 832 of the second base material portion 82 come into contact with each other. As a result, a plurality of unsintered first thermoelectric members 40 are formed as in the first embodiment. Further, each of the plurality of second thermoelectric members 841 of the first base material portion 81 and each of the plurality of second thermoelectric members 842 of the second base material portion 82 come into contact with each other. As a result, a plurality of unsintered second thermoelectric members 42 are formed as in the first embodiment.

積層体８５は、第１実施形態の積層体７０に対して第１保護部材１４および第２保護部材１６を除いた構造である。本実施形態では、積層体８５が絶縁基材と熱電部材と第１導体パターンと第２導体パターンとを有する構造体に相当する。本実施形態においても、未焼結の複数の第１熱電部材４０および未焼結の複数の第２熱電部材４２のそれぞれの側面は、中間層３０、第１外層３２および第２外層３４に接している。 The laminated body 85 has a structure in which the first protective member 14 and the second protective member 16 are removed from the laminated body 70 of the first embodiment. In the present embodiment, the laminated body 85 corresponds to a structure having an insulating base material, a thermoelectric member, a first conductor pattern, and a second conductor pattern. Also in this embodiment, the side surfaces of the plurality of unsintered first thermoelectric members 40 and the plurality of unsintered second thermoelectric members 42 are in contact with the intermediate layer 30, the first outer layer 32, and the second outer layer 34. ing.

加熱加圧工程Ｓ３では、図１８に示すように、積層体８５の積層方向Ｄ１で、積層体８５を加熱しながら加圧する。この加熱加圧工程Ｓ３の条件は、第１実施形態の加熱加圧工程Ｓ３と同じである。これにより、第１基材部８１と、第２基材部８２とが一体化する。未焼結の複数の第１熱電部材４０のそれぞれが焼結して、焼結後の複数の第１熱電部材１８となる。未焼結の複数の第２熱電部材４２のそれぞれが焼結して、焼結後の複数の第２熱電部材２０となる。 In the heating and pressurizing step S3, as shown in FIG. 18, the laminated body 85 is pressurized while being heated in the laminating direction D1 of the laminated body 85. The conditions of the heating / pressurizing step S3 are the same as those of the heating / pressurizing step S3 of the first embodiment. As a result, the first base material portion 81 and the second base material portion 82 are integrated. Each of the plurality of unsintered first thermoelectric members 40 is sintered to become a plurality of first thermoelectric members 18 after sintering. Each of the plurality of unsintered second thermoelectric members 42 is sintered to become the plurality of sintered second thermoelectric members 20.

これにより、図１９に示す構造の熱電変換装置１０Ａが製造される。本実施形態においても、第１実施形態での説明の通り、それぞれの熱電部材１８、２０の側面１９、２１のうち中間層３０に接する部分１９１、２１１が凹曲面形状になる。よって、本実施形態においても、第１実施形態と同様の効果が得られる。 As a result, the thermoelectric conversion device 10A having the structure shown in FIG. 19 is manufactured. Also in the present embodiment, as described in the first embodiment, the portions 191 and 211 of the side surfaces 19 and 21 of the thermoelectric members 18 and 20 in contact with the intermediate layer 30 have a concave curved surface shape. Therefore, the same effect as that of the first embodiment can be obtained in this embodiment as well.

（第３実施形態）
第１実施形態の熱電変換装置１０の製造方法では、中間層３０と第１外層３２と第２外層３４との３層で構成された絶縁基材１２を用いていた。これに対して、本実施形態の熱電変換装置１０の製造方法では、図２０に示すように、主層３０と外層３２との２層で構成された絶縁基材１２を用いる。主層３０は、第１実施形態の中間層３０に相当する。外層３２は、第１実施形態の第１外層３２に相当する。本実施形態では、主層３０が絶縁基材の第１層に相当する。外層３２が絶縁基材の第２層に相当する。 (Third Embodiment)
In the method for manufacturing the thermoelectric conversion device 10 of the first embodiment, an insulating base material 12 composed of three layers of an intermediate layer 30, a first outer layer 32, and a second outer layer 34 was used. On the other hand, in the method for manufacturing the thermoelectric conversion device 10 of the present embodiment, as shown in FIG. 20, an insulating base material 12 composed of two layers, a main layer 30 and an outer layer 32, is used. The main layer 30 corresponds to the intermediate layer 30 of the first embodiment. The outer layer 32 corresponds to the first outer layer 32 of the first embodiment. In this embodiment, the main layer 30 corresponds to the first layer of the insulating base material. The outer layer 32 corresponds to the second layer of the insulating base material.

具体的には、本実施形態では、第１実施形態に対して、用意工程Ｓ１で用意する絶縁基材１２を、２層で構成された絶縁基材１２に変更する。積層体の形成工程Ｓ２および加熱加圧工程Ｓ３は、第１実施形態と同じである。 Specifically, in the present embodiment, the insulating base material 12 prepared in the preparation step S1 is changed to the insulating base material 12 composed of two layers with respect to the first embodiment. The laminate forming step S2 and the heating and pressurizing step S3 are the same as those in the first embodiment.

本実施形態の積層体の形成工程Ｓ２において、形成される積層体７０中の絶縁基材１２は、主層３０と外層３２との２層で構成されている。 In the laminate forming step S2 of the present embodiment, the insulating base material 12 in the laminate 70 to be formed is composed of two layers, a main layer 30 and an outer layer 32.

本実施形態の加熱加圧工程Ｓ３において、第１実施形態と同様に、主層３０は流動するが、外層３２は流動しない。このため、図２０中の矢印Ａ２で示すように、未焼結の第１熱電部材４０のうち外層３２に接する部分は、圧力がかからない、または、かかる圧力が小さい。未焼結の第１熱電部材４０のうち主層３０に接する部分は、主層３０の流動によって大きな圧力がかかる。 In the heating and pressurizing step S3 of the present embodiment, the main layer 30 flows, but the outer layer 32 does not flow, as in the first embodiment. Therefore, as shown by the arrow A2 in FIG. 20, no pressure is applied to the portion of the unsintered first thermoelectric member 40 in contact with the outer layer 32, or the pressure applied is small. A large pressure is applied to the portion of the unsintered first thermoelectric member 40 in contact with the main layer 30 due to the flow of the main layer 30.

本実施形態の絶縁基材１２の厚さが比較例１の絶縁基材１２の厚さと同じ場合、未焼結の第１熱電部材４０が加熱加圧工程Ｓ３で流動する樹脂と接する面積は、比較例１の熱電部材７２が加熱加圧工程Ｓ３で流動する樹脂と接する面積よりも小さい。このため、第１実施形態と同じ理由によって、図２１に示すように、焼成後の第１熱電部材１８の側面１９のうち主層３０に接する部分１９１を、外層３２に接する部分１９２よりも曲がりが急な凹曲面形状にすることができる。第２熱電部材２０の側面２１についても同様である。よって、第１実施形態と同様の効果が得られる。 When the thickness of the insulating base material 12 of the present embodiment is the same as the thickness of the insulating base material 12 of Comparative Example 1, the area where the unsintered first thermoelectric member 40 comes into contact with the resin flowing in the heating and pressurizing step S3 is determined. The area where the thermoelectric member 72 of Comparative Example 1 is in contact with the flowing resin in the heating and pressurizing step S3 is smaller. Therefore, for the same reason as in the first embodiment, as shown in FIG. 21, the portion 191 of the side surface 19 of the first thermoelectric member 18 after firing, which is in contact with the main layer 30, is bent more than the portion 192 in contact with the outer layer 32. Can be made into a steep concave curved surface shape. The same applies to the side surface 21 of the second thermoelectric member 20. Therefore, the same effect as that of the first embodiment can be obtained.

なお、本実施形態では、絶縁基材１２において、外層３２が主層３０の第１導体パターン２６側に配置されていた。しかしながら、絶縁基材１２において、外層３２が主層３０の第２導体パターン２８側に配置されていてもよい。 In the present embodiment, in the insulating base material 12, the outer layer 32 is arranged on the first conductor pattern 26 side of the main layer 30. However, in the insulating base material 12, the outer layer 32 may be arranged on the second conductor pattern 28 side of the main layer 30.

（他の実施形態）
（１）上記各実施形態では、第１外層３２、第２外層３４、外層３２は、熱可塑性樹脂で構成されていた。しかしながら、第１外層３２、第２外層３４、外層３２は、加熱加圧工程Ｓ３で流動しない他の絶縁材料で構成されていてもよい。他の絶縁材料は、中間層３０、主層３０を構成する樹脂材料の軟化温度よりも、他の絶縁材料の軟化温度または耐熱温度が高い材料である。他の絶縁材料としては、加熱加圧工程Ｓ３の温度よりも耐熱温度が高い熱硬化性樹脂が挙げられる。熱硬化性樹脂としては、エポキシ樹脂が挙げられる。また、他の絶縁材料としては、セラミックスが挙げられる。セラミックスの耐熱温度とは、セラミックスの溶融温度のことである。 (Other embodiments)
(1) In each of the above embodiments, the first outer layer 32, the second outer layer 34, and the outer layer 32 are made of a thermoplastic resin. However, the first outer layer 32, the second outer layer 34, and the outer layer 32 may be made of another insulating material that does not flow in the heating and pressurizing step S3. The other insulating material is a material having a softening temperature or a heat resistant temperature of the other insulating material higher than the softening temperature of the resin material constituting the intermediate layer 30 and the main layer 30. Examples of other insulating materials include thermosetting resins having a heat resistant temperature higher than the temperature of the heating and pressurizing step S3. Examples of the thermosetting resin include epoxy resins. Further, as another insulating material, ceramics can be mentioned. The heat-resistant temperature of ceramics is the melting temperature of ceramics.

（２）上記各実施形態では、第１外層３２、第２外層３４、外層３２は、加熱加圧工程Ｓ３で流動しない材料で構成されていた。しかしながら、第１外層３２、第２外層３４、外層３２は、中間層３０、主層３０を構成する樹脂材料よりも加熱加圧工程Ｓ３で流動し難い樹脂材料で構成されていてもよい。「流動し難い」とは、加熱加圧工程Ｓ３の条件のときに流動する樹脂材料の移動速度が遅いことを意味する。「移動速度が遅い」とは、単位時間当たりの移動距離が短いことを意味する。加熱加圧工程Ｓ３で流動し難い樹脂材料には、加熱加圧工程Ｓ３の温度よりも軟化点が低い熱可塑性材料が含まれる。ただし、この流動し難い樹脂材料は、加熱加圧工程Ｓ３後に、中間層３０、主層３０と区別できる材料であることが好ましい。流動し難い樹脂材料としては、クラボウ社製の商品名「ミドフィル」に代表される熱可塑性ポリイミド樹脂材料が挙げられる。この場合の中間層３０、主層３０を構成する樹脂材料としては、ポリエーテルイミド樹脂が挙げられる。 (2) In each of the above embodiments, the first outer layer 32, the second outer layer 34, and the outer layer 32 are made of a material that does not flow in the heating and pressurizing step S3. However, the first outer layer 32, the second outer layer 34, and the outer layer 32 may be made of a resin material that is less likely to flow in the heating and pressurizing step S3 than the resin material constituting the intermediate layer 30 and the main layer 30. “Difficult to flow” means that the moving speed of the resin material that flows under the conditions of the heating and pressurizing step S3 is slow. "Slow movement speed" means that the movement distance per unit time is short. The resin material that is difficult to flow in the heating and pressurizing step S3 includes a thermoplastic material having a softening point lower than the temperature in the heating and pressurizing step S3. However, it is preferable that the resin material that is difficult to flow is a material that can be distinguished from the intermediate layer 30 and the main layer 30 after the heating and pressurizing step S3. Examples of the resin material that does not easily flow include a thermoplastic polyimide resin material represented by the trade name "Midfill" manufactured by Kurabo Industries Ltd. Examples of the resin material constituting the intermediate layer 30 and the main layer 30 in this case include a polyetherimide resin.

（３）第１、第３実施形態では、中間層３０が１層で構成されていた。しかしながら、中間層３０は複数層で構成されていてもよい。同様に、第２実施形態では、中間層３０が第１シート８１１と第３シート８２１との２層で構成されていた。しかしながら、中間層３０は３層以上で構成されていてもよい。中間層３０が複数の層で構成される場合、複数の層のそれぞれは、同じ材料に限らず、異なる材料であってもよい。 (3) In the first and third embodiments, the intermediate layer 30 is composed of one layer. However, the intermediate layer 30 may be composed of a plurality of layers. Similarly, in the second embodiment, the intermediate layer 30 is composed of two layers, the first sheet 811 and the third sheet 821. However, the intermediate layer 30 may be composed of three or more layers. When the intermediate layer 30 is composed of a plurality of layers, each of the plurality of layers is not limited to the same material, but may be a different material.

（４）本発明は上記した実施形態に限定されるものではなく、特許請求の範囲に記載した範囲内において適宜変更が可能であり、様々な変形例や均等範囲内の変形をも包含する。また、上記各実施形態は、互いに無関係なものではなく、組み合わせが明らかに不可な場合を除き、適宜組み合わせが可能である。また、上記各実施形態において、実施形態を構成する要素は、特に必須であると明示した場合および原理的に明らかに必須であると考えられる場合等を除き、必ずしも必須のものではないことは言うまでもない。また、上記各実施形態において、実施形態の構成要素の個数、数値、量、範囲等の数値が言及されている場合、特に必須であると明示した場合および原理的に明らかに特定の数に限定される場合等を除き、その特定の数に限定されるものではない。また、上記各実施形態において、構成要素等の材質、形状、位置関係等に言及するときは、特に明示した場合および原理的に特定の材質、形状、位置関係等に限定される場合等を除き、その材質、形状、位置関係等に限定されるものではない。 (4) The present invention is not limited to the above-described embodiment, and can be appropriately modified within the scope of claims, and includes various modifications and modifications within an equal range. Further, the above-described embodiments are not unrelated to each other, and can be appropriately combined unless the combination is clearly impossible. Further, in each of the above embodiments, it goes without saying that the elements constituting the embodiment are not necessarily essential except when it is clearly stated that they are essential and when they are clearly considered to be essential in principle. stomach. Further, in each of the above embodiments, when numerical values such as the number, numerical values, quantities, and ranges of the constituent elements of the embodiment are mentioned, when it is clearly stated that they are particularly essential, and in principle, the number is clearly limited to a specific number. It is not limited to the specific number except when it is done. Further, in each of the above embodiments, when referring to the material, shape, positional relationship, etc. of the constituent elements, etc., except when specifically specified or when the material, shape, positional relationship, etc. are limited to a specific material, shape, positional relationship, etc. in principle. , The material, shape, positional relationship, etc. are not limited.

１０ 熱電変換装置
１２ 絶縁基材
１８ 第１熱電部材
１９ 第１熱電部材の側面
２０ 第２熱電部材
２１ 第２熱電部材の側面
３０ 中間層、主層
３２ 第１外層、外層
３４ 第２外層 10 Thermoelectric converter 12 Insulated base material 18 1st thermoelectric member 19 Side surface of 1st thermoelectric member 20 2nd thermoelectric member 21 Side surface of 2nd thermoelectric member 30 Intermediate layer, main layer 32 1st outer layer, outer layer 34 2nd outer layer

Claims (8)

熱電変換装置の製造方法であって、
第１面（１２１）と第１面の反対側の第２面（１２２）とを有するシート状の絶縁基材（１２）と、前記絶縁基材を前記第１面から前記第２面まで貫くように前記絶縁基材に設けられた未焼結の熱電部材と、前記第１面に設けられ、前記熱電部材と接する第１導体パターン（２６）と、前記第２面に設けられ、前記熱電部材と接する第２導体パターン（２８）とを有する構造体（７０、８５）を形成すること（Ｓ２）と、
前記構造体を加熱しながら前記絶縁基材の厚さ方向（Ｄ１）に前記構造体を加圧すること（Ｓ３）とを含み、
前記構造体を形成することは、
第１層（３０）と、前記絶縁基材のうち前記第１層よりも前記第１面側に位置する第２層（３２）とを有し、前記第１層は、前記加圧するときに流動する樹脂材料で構成され、前記第２層は、前記第１層よりも薄いとともに、前記加圧するときに前記第１層を構成する樹脂材料よりも流動し難い絶縁材料で構成された前記絶縁基材を用いることと、
前記第１層および前記第２層に前記熱電部材の側面が接するように、前記熱電部材を前記絶縁基材に設けることとを含み、
前記加圧することにおいては、前記第１層を流動させながら前記熱電部材を焼結させることにより、焼結後の前記熱電部材の側面（１９、２１）のうち前記第１層に接する部分（１９１、２１１）を凹曲面形状とする熱電変換装置の製造方法。 It is a manufacturing method of thermoelectric conversion equipment.
A sheet-shaped insulating base material (12) having a first surface (121) and a second surface (122) opposite to the first surface, and the insulating base material penetrates from the first surface to the second surface. the thermoelectric element of green provided in the insulating substrate, provided on the first surface, the first conductor pattern in contact with the thermoelectric element (26), provided on the second surface, the thermoelectric as Forming a structure (70, 85) having a second conductor pattern (28) in contact with a member (S2),
This includes pressurizing the structure in the thickness direction (D1) of the insulating base material while heating the structure (S3).
Forming the structure
It has a first layer (30) and a second layer (32) of the insulating base material located on the first surface side of the first layer, and the first layer is formed when the pressure is applied. The insulation is made of a fluid resin material, and the second layer is thinner than the first layer and is made of an insulating material that is less likely to flow than the resin material constituting the first layer when pressed. Using a base material and
This includes providing the thermoelectric member on the insulating base material so that the side surfaces of the thermoelectric member are in contact with the first layer and the second layer.
In the pressurization, the thermoelectric member is sintered while the first layer is flowing, so that the portion (191) of the side surfaces (19, 21) of the thermoelectric member after sintering that is in contact with the first layer. , 211) is a method for manufacturing a thermoelectric converter having a concave curved surface shape. 前記絶縁基材を用いることにおいては、前記第１層を構成する樹脂材料として、前記加圧するときの加熱温度よりも軟化温度が低い熱可塑性樹脂を用いるとともに、前記第２層を構成する絶縁材料として、前記加熱温度よりも軟化温度が高い熱可塑性樹脂、または、前記加熱温度よりも耐熱温度が高い熱硬化性樹脂を用いる請求項１に記載の熱電変換装置の製造方法。 In using the insulating base material, as the resin material constituting the first layer, a thermoplastic resin having a softening temperature lower than the heating temperature at the time of pressurization is used, and the insulating material constituting the second layer is used. The method for manufacturing a thermoelectric conversion device according to claim 1, wherein a thermoplastic resin having a softening temperature higher than the heating temperature or a thermosetting resin having a heat resistant temperature higher than the heating temperature is used. 前記絶縁基材を用いることにおいては、前記絶縁基材のうち前記第１層よりも前記第２面側に位置する第３層（３４）を有し、前記第３層は、前記第１層よりも薄いとともに、前記加圧するときに前記第１層を構成する樹脂材料よりも流動し難い絶縁材料で構成された前記絶縁基材を用い、
前記熱電部材を前記絶縁基材に設けることにおいては、前記第３層に前記熱電部材の側面が接するように、前記熱電部材を前記絶縁基材に設ける請求項１または２に記載の熱電変換装置の製造方法。 In using the insulating base material, the insulating base material has a third layer (34) located on the second surface side of the first layer, and the third layer is the first layer. Using the insulating base material made of an insulating material which is thinner than the resin material and which is less likely to flow than the resin material constituting the first layer when pressurized.
The thermoelectric conversion device according to claim 1 or 2, wherein when the thermoelectric member is provided on the insulating base material, the thermoelectric member is provided on the insulating base material so that the side surface of the thermoelectric member is in contact with the third layer. Manufacturing method. 前記絶縁基材を用いることにおいては、前記第３層を構成する絶縁材料として、前記加圧するときの加熱温度よりも軟化温度が高い熱可塑性樹脂、または、前記加熱温度よりも耐熱温度が高い熱硬化性樹脂を用いる請求項３に記載の熱電変換装置の製造方法。 In using the insulating base material, as the insulating material constituting the third layer, a thermoplastic resin having a softening temperature higher than the heating temperature at the time of pressurization, or heat having a heat resistant temperature higher than the heating temperature. The method for manufacturing a thermoelectric conversion device according to claim 3, wherein a curable resin is used. 熱電変換装置であって、
第１面（１２１）と前記第１面の反対側の第２面（１２２）とを有するシート状の絶縁基材（１２）と、
前記絶縁基材に設けられた熱電部材（１８、２０）と、
前記第１面に設けられ、前記熱電部材と接続された第１導体パターン（２６）と、
前記第２面に設けられ、前記熱電部材と接続された第２導体パターン（２８）とを備え、
前記絶縁基材は、第１層（３０）と、前記絶縁基材において前記第１層よりも前記第１面側に位置し、前記第１層よりも薄い第２層（３２）とを有し、
前記第１層は、温度の上昇によって軟化する樹脂材料で構成され、
前記第２層は、前記第１層を構成する樹脂材料の軟化温度よりも軟化温度または耐熱温度が高い絶縁材料で構成されており、
前記熱電部材は、前記第１層および前記第２層に前記熱電部材の側面が接するように配置されており、
前記熱電部材の側面（１９、２１）のうち前記第１層に接する部分（１９１、２１１）は、凹曲面形状である熱電変換装置。 It is a thermoelectric converter
A sheet-shaped insulating base material (12) having a first surface (121) and a second surface (122) opposite to the first surface, and
The thermoelectric members (18, 20) provided on the insulating base material and
A first conductor pattern (26) provided on the first surface and connected to the thermoelectric member, and
A second conductor pattern (28) provided on the second surface and connected to the thermoelectric member is provided.
The insulating base material has a first layer (30) and a second layer (32) which is located on the first surface side of the insulating base material and is thinner than the first layer. death,
The first layer is composed of a resin material that softens as the temperature rises.
The second layer is made of an insulating material having a softening temperature or a heat resistant temperature higher than the softening temperature of the resin material constituting the first layer.
The thermoelectric member is arranged so that the side surface of the thermoelectric member is in contact with the first layer and the second layer.
Of the side surfaces (19, 21) of the thermoelectric member, the portions (191, 211) in contact with the first layer are thermoelectric conversion devices having a concave curved surface shape. 前記第１層は、熱可塑性樹脂で構成され、
前記第２層は、前記第１層を構成する熱可塑性樹脂の軟化温度よりも軟化温度が高い熱可塑性樹脂、または、前記第１層を構成する熱可塑性樹脂の軟化温度よりも耐熱温度が高い熱硬化性樹脂で構成されている請求項５に記載の熱電変換装置。 The first layer is made of a thermoplastic resin and is made of a thermoplastic resin.
The second layer has a heat resistant temperature higher than the softening temperature of the thermoplastic resin constituting the first layer or the softening temperature of the thermoplastic resin constituting the first layer. The thermoelectric conversion device according to claim 5, which is made of a thermosetting resin. 前記絶縁基材は、さらに、前記絶縁基材において前記第１層よりも前記第２面側に位置し、前記第１層よりも薄い第３層（３４）を有し、
前記第３層は、前記第１層を構成する樹脂材料の軟化温度よりも軟化温度または耐熱温度が高い絶縁材料で構成されており、
前記熱電部材は、前記第３層に前記熱電部材の側面が接するように配置されている請求項５または６に記載の熱電変換装置。 The insulating base material further has a third layer (34) located on the second surface side of the insulating base material with respect to the first layer and thinner than the first layer.
The third layer is made of an insulating material having a softening temperature or a heat resistant temperature higher than the softening temperature of the resin material constituting the first layer.
The thermoelectric conversion device according to claim 5 or 6, wherein the thermoelectric member is arranged so that the side surface of the thermoelectric member is in contact with the third layer. 前記第３層は、前記第１層を構成する熱可塑性樹脂の軟化温度よりも軟化温度が高い熱可塑性樹脂、または、前記第１層を構成する熱可塑性樹脂の軟化温度よりも耐熱温度が高い熱硬化性樹脂で構成されている請求項７に記載の熱電変換装置。 The third layer has a heat resistant temperature higher than the softening temperature of the thermoplastic resin constituting the first layer or the softening temperature of the thermoplastic resin constituting the first layer. The thermoelectric conversion device according to claim 7, which is made of a thermosetting resin.
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