JP2011124446A - Thermistor element - Google Patents

Thermistor element Download PDF

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JP2011124446A
JP2011124446A JP2009282042A JP2009282042A JP2011124446A JP 2011124446 A JP2011124446 A JP 2011124446A JP 2009282042 A JP2009282042 A JP 2009282042A JP 2009282042 A JP2009282042 A JP 2009282042A JP 2011124446 A JP2011124446 A JP 2011124446A
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thermistor
metal oxide
sintered body
oxide sintered
thermistor element
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Sho Shimizu
翔 清水
Toshiaki Fujita
利晃 藤田
Kazutaka Fujiwara
和崇 藤原
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Mitsubishi Materials Corp
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermistor element capable of improving responsiveness while preventing reduction deterioration, and improving an insertion property in case mounting. <P>SOLUTION: The thermistor element includes: a metal oxide sintered body 2 for a thermistor, formed with at least one pair of jointing holes 2a; at least one pair of lead wires 3 jointed to the metal oxide sintered body 2 for a thermistor in an inserted state into the jointing holes 2a; and insulating cover materials 4 partially covering a surface of the metal oxide sintered body 2 for a thermistor, wherein each insulating cover material 4 covers an exposed part 2c of an interfacial surface where the lead wire 3 is jointed to the metal oxide sintered body 2 for a thermistor. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

本発明は、例えば自動車関係等の温度計測に用いられるサーミスタ素子に関する。   The present invention relates to a thermistor element used for temperature measurement such as for automobiles.

通常、自動車エンジン周りの触媒温度や排気系温度等を測定センサには、１０００℃付近の非常に高温まで測定可能なサーミスタ素子が求められる。このサーミスタ素子は、一般的に、金属酸化物焼結体（例えば、ペロブスカイト型Ｙ（Ｃｒ，Ｍｎ）Ｏ３）とＰｔ線とからなるものが利用される。例えば、特許文献１には、室温と１０００℃との間のヒートサイクルに耐えられるために、金属酸化物焼結体中に２本のＰｔ線が挿入され、これらのＰｔ線が金属酸化物の焼結によって強固に固定されたサーミスタ素子が知られている。 Normally, a thermistor element that can measure a catalyst temperature around an automobile engine, an exhaust system temperature, and the like up to a very high temperature around 1000 ° C. is required. Generally, the thermistor element is made of a metal oxide sintered body (for example, perovskite type Y (Cr, Mn) O 3 ) and a Pt line. For example, in Patent Document 1, in order to withstand a heat cycle between room temperature and 1000 ° C., two Pt lines are inserted into a metal oxide sintered body, and these Pt lines are made of metal oxide. A thermistor element firmly fixed by sintering is known.

また、サーミスタ素子は、ステンレス（ＳＵＳ）等の金属ケースに実装されて使用されるが、高温での還元劣化があるため、素子全体を耐還元材料でコーティングする方法が知られている。すなわち、実装時にサーミスタ素子を収納するケースに使用されるステンレス鋼が高温で酸化され易く、ケースの内面が酸化されて気密に封止した内部の酸素濃度を低下させてしまうと共に、サーミスタ素子から酸素を奪って還元を引き起こし、サーミスタ特性に影響を与えてしまう。このため、従来では、素子全体を耐還元性の被膜でコーティングすることで、還元劣化を防いでいる。例えば、特許文献２には、サーミスタチップの部分を複数の金属酸化物の組み合わせとシリカを含む導電性増強作用をしない焼結促進材とから組成された被覆材によって被覆して焼成した高温耐熱型サーミスタが提案されている。   A thermistor element is mounted and used in a metal case such as stainless steel (SUS). However, since there is a reduction deterioration at a high temperature, a method of coating the entire element with a reduction resistant material is known. That is, the stainless steel used for the case that houses the thermistor element during mounting is easily oxidized at a high temperature, and the inner surface of the case is oxidized to reduce the oxygen concentration inside the airtight seal. It causes reduction and affects the thermistor characteristics. For this reason, conventionally, reduction degradation is prevented by coating the entire element with a reduction-resistant film. For example, in Patent Document 2, a thermistor chip portion is coated with a coating material composed of a combination of a plurality of metal oxides and a sintering accelerator that does not enhance conductivity, including silica, and is fired by heating. A thermistor has been proposed.

特開２００７−２２０９１２号公報JP 2007-220912 A 特許第４１８３６６６号公報Japanese Patent No. 4183666

上記従来の技術には、以下の課題が残されている。
従来技術では、金属ケース実装時に起きる還元劣化を防止するために、耐還元材料で素子全体をコーティングしているが、この場合、素子全体の熱容量が増加してしまい、サーミスタ素子の応答性が悪化してしまう不都合があった。また、素子全体を被覆するために素子全体の外形サイズが大きくなり、サーミスタ素子を金属ケースに実装する際の挿入性が悪くなってしまう。さらに、サーミスタ本体と金属ケースとの間隔が被膜の分だけ広がるため、金属ケースとサーミスタ本体との間隔を近づけることができず、この点からも応答性が低下してしまう問題があった。 The following problems remain in the conventional technology.
In the prior art, the entire element is coated with a reduction-resistant material in order to prevent the reduction deterioration that occurs when the metal case is mounted. In this case, however, the heat capacity of the entire element increases and the responsiveness of the thermistor element deteriorates. There was an inconvenience. In addition, since the entire outer size of the element is increased to cover the entire element, the insertion property when the thermistor element is mounted on the metal case is deteriorated. Furthermore, since the distance between the thermistor body and the metal case is increased by the amount of the coating, the distance between the metal case and the thermistor body cannot be reduced, and there is a problem that the responsiveness is lowered from this point.

本発明は、前述の課題に鑑みてなされたもので、還元劣化を防ぎつつ応答性を向上させると共にケース実装時の挿入性も向上させることができるサーミスタ素子を提供することを目的とする。   The present invention has been made in view of the above-described problems, and an object of the present invention is to provide a thermistor element capable of improving responsiveness while preventing reduction deterioration and improving insertability when mounting a case.

本発明は、前記課題を解決するために以下の構成を採用した。すなわち、本発明のサーミスタ素子は、少なくとも一対の接合用孔が形成されたサーミスタ用金属酸化物焼結体と、前記接合用孔内に一部が配された状態で前記サーミスタ用金属酸化物焼結体に接合された少なくとも一対のリード線と、前記サーミスタ用金属酸化物焼結体の表面を部分的に覆う絶縁性被覆材と、を備え、該絶縁性被覆材が、前記リード線と前記サーミスタ用金属酸化物焼結体とが接合している界面の露出部分を覆っていることを特徴とする。   The present invention employs the following configuration in order to solve the above problems. That is, the thermistor element of the present invention includes a thermistor metal oxide sintered body in which at least a pair of bonding holes are formed and a metal oxide sintered body for the thermistor in a state in which a portion is disposed in the bonding holes. And at least a pair of lead wires joined to the bonded body, and an insulating coating material partially covering a surface of the metal oxide sintered body for the thermistor, the insulating coating material comprising the lead wire and the The exposed portion of the interface where the metal oxide sintered body for the thermistor is joined is covered.

このサーミスタ素子では、サーミスタ用金属酸化物焼結体の表面を部分的に覆う絶縁性被覆材が、還元の影響を直接受けるリード線とサーミスタ用金属酸化物焼結体とが接合している界面の露出部分を覆っているので、サーミスタ用金属酸化物焼結体中の還元劣化を効果的に防ぐと共に、被覆部分が限定されることで、素子全体の熱容量が抑えられ、素子全体を被覆した場合に比較して優れた応答性を得ることができる。また、素子サイズが、無被覆のものと大きく変わらないため、サーミスタ本体と実装するケース等との間隔を近づけることができ、この点からも応答性が向上する。さらに、同様の理由によりケースへの挿入性も向上すると共に、素子全体を覆う場合よりも絶縁性被覆材の使用量が少なくてすみ、製造コストの低減を図ることができる。   In this thermistor element, the insulating coating material that partially covers the surface of the metal oxide sintered body for the thermistor is the interface where the lead wire directly affected by the reduction and the metal oxide sintered body for the thermistor are joined. Since the exposed portion of the metal oxide sintered body is covered, the reduction deterioration in the metal oxide sintered body for the thermistor is effectively prevented, and the covering portion is limited, so that the heat capacity of the entire device is suppressed and the entire device is covered. Compared to the case, excellent responsiveness can be obtained. In addition, since the element size is not significantly different from that of the uncovered one, the distance between the thermistor body and the case to be mounted can be reduced, and the responsiveness is improved from this point. Further, for the same reason, the insertion property into the case is improved, and the amount of the insulating coating material used is smaller than that in the case of covering the entire element, and the manufacturing cost can be reduced.

また、本発明のサーミスタ素子は、前記絶縁性被覆材が、前記サーミスタ用金属酸化物焼結体の表面において対となる前記リード線の間も覆って設けられていることを特徴とする。
すなわち、このサーミスタ素子では、絶縁性被覆材が、サーミスタ用金属酸化物焼結体の表面において対となるリード線の間も覆って設けられているので、素子の電気特性に特に寄与する対となるリード線の間の表面における還元も絶縁性被覆材によって抑制することで、より還元劣化を防ぐことができる。 Further, the thermistor element of the present invention is characterized in that the insulating coating material is provided so as to cover between the pair of lead wires on the surface of the metal oxide sintered body for the thermistor.
That is, in this thermistor element, since the insulating coating material is provided so as to cover the pair of lead wires on the surface of the metal oxide sintered body for the thermistor, the pair that particularly contributes to the electrical characteristics of the element. Reduction on the surface between the lead wires is also suppressed by the insulating coating material, so that reduction degradation can be further prevented.

また、本発明のサーミスタ素子は、前記絶縁性被覆材が、耐還元性を有する金属酸化物を含有した無機接着剤であることを特徴とする。
すなわち、このサーミスタ素子では、絶縁性被覆材が、耐還元性を有する金属酸化物を含有した無機接着剤であるので、ディスペンサー等で所定部分に滴下して焼成させることで、容易に耐熱性及び耐還元性を有する膜を被覆可能である。 In the thermistor element of the present invention, the insulating coating material is an inorganic adhesive containing a metal oxide having reduction resistance.
That is, in this thermistor element, the insulating coating material is an inorganic adhesive containing a metal oxide having a reduction resistance. A film having reduction resistance can be coated.

また、本発明のサーミスタ素子は、前記サーミスタ用金属酸化物焼結体が、一般式：（１−ｚ）ＡＢＯ３＋ｚＹ２Ｏ３（ただし、ＡＢＯ３はペロブスカイト型酸化物、０＜ｚ≦０．８）で示される複合酸化物焼結体であって、表面にＹ２Ｏ３層が析出されていることを特徴とする。
すなわち、このサーミスタ素子では、サーミスタ用金属酸化物焼結体が、一般式：（１−ｚ）ＡＢＯ３＋ｚＹ２Ｏ３（ただし、ＡＢＯ３はペロブスカイト型酸化物、０＜ｚ≦０．８）で示される複合酸化物焼結体であって、表面にＹ２Ｏ３層が析出されているので、上記絶縁性被覆材に覆われていない表面に析出した絶縁膜のＹ２Ｏ３層により、該表面における還元劣化も抑制することができる。
さらに、Ｙ２Ｏ３を入れることで、ペロブスカイト酸化物とＹ２Ｏ３の混合焼結体材料との焼成が助長され、高密度、かつ酸素の出入りが少なくなるサーミスタ材料がもたらされ、抵抗値変化を抑制することができる。 In the thermistor element of the present invention, the metal oxide sintered body for the thermistor has a general formula: (1-z) ABO 3 + zY 2 O 3 (where ABO 3 is a perovskite oxide, 0 <z ≦ 0 .8), characterized in that a Y 2 O 3 layer is deposited on the surface.
That is, in this thermistor element, the metal oxide sintered body for the thermistor has a general formula: (1-z) ABO 3 + zY 2 O 3 (where ABO 3 is a perovskite oxide, 0 <z ≦ 0.8). Since the Y 2 O 3 layer is deposited on the surface, the Y 2 O 3 layer of the insulating film deposited on the surface not covered with the insulating coating material Further, reduction degradation on the surface can be suppressed.
Furthermore, by adding Y 2 O 3 , firing of the mixed sintered body material of perovskite oxide and Y 2 O 3 is promoted, resulting in a thermistor material having high density and less oxygen ingress and egress. Value change can be suppressed.

本発明によれば、以下の効果を奏する。
すなわち、本発明に係るサーミスタ素子によれば、サーミスタ用金属酸化物焼結体の表面を部分的に覆う絶縁性被覆材が、還元の影響を直接受けるリード線とサーミスタ用金属酸化物焼結体とが接合している界面の露出部分を覆っているので、還元劣化を効果的に防ぐと共に、優れた応答性を得ることができる。したがって、本発明のサーミスタ素子は、抵抗値ばらつきが少なく特性の均一性が高いと共に応答性に優れ、特に、自動車エンジン周りの触媒温度や排気系温度を検出する高温測定用センサとして好適である。 The present invention has the following effects.
That is, according to the thermistor element according to the present invention, the insulating coating material partially covering the surface of the thermistor metal oxide sintered body is directly affected by the reduction of the lead wire and the thermistor metal oxide sintered body. Covers the exposed part of the interface where the two are joined, so that reduction degradation can be effectively prevented and excellent responsiveness can be obtained. Therefore, the thermistor element of the present invention has little variation in resistance value, high uniformity of characteristics and excellent responsiveness, and is particularly suitable as a high-temperature measurement sensor for detecting the catalyst temperature and exhaust system temperature around the automobile engine.

本発明に係るサーミスタ素子の第１実施形態を示す断面図である。It is sectional drawing which shows 1st Embodiment of the thermistor element which concerns on this invention. 第１実施形態において、サーミスタ素子を示す下面図である。In 1st Embodiment, it is a bottom view which shows a thermistor element. 第１実施形態において、サーミスタ温度センサを示す断面図である。In 1st Embodiment, it is sectional drawing which shows a thermistor temperature sensor. 本発明に係るサーミスタ素子の第２実施形態を示す断面図である。It is sectional drawing which shows 2nd Embodiment of the thermistor element which concerns on this invention. 本発明に係るサーミスタ素子の２つの比較例を示す断面図である。It is sectional drawing which shows two comparative examples of the thermistor element which concerns on this invention. 本発明に係るサーミスタ素子の第１実施形態の他の例を示す断面図である。It is sectional drawing which shows the other example of 1st Embodiment of the thermistor element which concerns on this invention.

以下、本発明に係るサーミスタ素子の第１実施形態を、図１から図３を参照しながら説明する。なお、以下の説明に用いる各図面では、各部材を認識可能又は認識容易な大きさとするために縮尺を適宜変更している。   Hereinafter, a first embodiment of a thermistor element according to the present invention will be described with reference to FIGS. In each drawing used for the following description, the scale is appropriately changed in order to make each member recognizable or easily recognizable.

本実施形態のサーミスタ素子１は、図１及び図２に示すように、一対の接合用孔２ａが形成されたサーミスタ用金属酸化物焼結体２と、接合用孔２ａ内に一部が配された状態でサーミスタ用金属酸化物焼結体２に接合された一対のリード線３と、サーミスタ用金属酸化物焼結体２の表面を部分的に覆う絶縁性被覆材４と、を備えている。   As shown in FIGS. 1 and 2, the thermistor element 1 of the present embodiment has a metal oxide sintered body 2 for a thermistor in which a pair of bonding holes 2a are formed, and a part thereof is disposed in the bonding hole 2a. A pair of lead wires 3 joined to the thermistor metal oxide sintered body 2 in an applied state, and an insulating coating material 4 partially covering the surface of the thermistor metal oxide sintered body 2. Yes.

上記サーミスタ用金属酸化物焼結体２は、一般式：（１−ｚ）ＡＢＯ３＋ｚＹ２Ｏ３（ただし、ＡＢＯ３はペロブスカイト型酸化物、０＜ｚ≦０．８）で示される複合酸化物焼結体であって、表面にＹ２Ｏ３層２ｂが析出されている。
例えば、このサーミスタ用金属酸化物焼結体２は、一般式：（１−ｚ）Ｙ（Ｃｒ１−ｘＭｎｘ）Ｏ３＋ｚＹ２Ｏ３（ただし、０．０≦ｘ≦１．０、０＜ｚ≦０．８）で示されるものであり、特に、一般式：（１−ｚ）（Ｙ１−ｙＬａｙ）（Ｃｒ１−ｘＭｎｘ）Ｏ３＋ｚＹ２Ｏ３（ただし、０．０≦ｘ≦１．０、０．０≦ｙ≦１．０、０＜ｚ≦０．８）で示される複合酸化物を含む焼結体で構成されていることが好ましい。 The metal oxide sintered body 2 for the thermistor is a composite oxide represented by the general formula: (1-z) ABO 3 + zY 2 O 3 (where ABO 3 is a perovskite oxide, 0 <z ≦ 0.8). This is a sintered product, and the Y 2 O 3 layer 2b is deposited on the surface.
For example, the metal oxide sintered body 2 for the thermistor has a general formula: (1-z) Y (Cr 1-x Mn x ) O 3 + zY 2 O 3 (where 0.0 ≦ x ≦ 1.0, 0 <z ≦ 0.8). In particular, the general formula: (1-z) (Y 1-y La y ) (Cr 1-x Mn x ) O 3 + zY 2 O 3 (provided that It is preferably made of a sintered body containing a composite oxide represented by 0.0 ≦ x ≦ 1.0, 0.0 ≦ y ≦ 1.0, and 0 <z ≦ 0.8.

なお、サーミスタ素子１の電気特性を示すパラメータであるＢ定数は、（Ｙ１−ｚＬａｚ）１−ｙＡｙ（Ｃｒ１−ｘＭｎｘ）Ｏ３のｘ，ｙ，ｚ量を変えることによって調整する。ただし、例えば、Ｂ定数が小さくなると、抵抗値も小さくなるので、形状を変えて抵抗調節できない場合は、絶縁体材料を混合焼結し、抵抗値を上げる必要がある。なお、絶縁体材料をＹ２Ｏ３とすることが好ましいが、これを他の絶縁体材料、例えば、ＺｒＯ２，ＭｇＯ，Ａｌ２Ｏ３，ＣｅＯ２に変更しても構わない。 Note that the B constant, which is a parameter indicating the electrical characteristics of the thermistor element 1, changes the x, y, z amount of (Y 1−z La z ) 1−y A y (Cr 1−x Mn x ) O 3. Adjust by. However, for example, as the B constant decreases, the resistance value also decreases. Therefore, if the resistance cannot be adjusted by changing the shape, it is necessary to mix and sinter the insulator material to increase the resistance value. Although the insulator material is preferably Y 2 O 3 , it may be changed to another insulator material such as ZrO 2 , MgO, Al 2 O 3 , or CeO 2 .

このサーミスタ用金属酸化物焼結体２は、例えば円柱状に形成され、軸線に沿った貫通孔である接合用孔２ａが一対形成されている。
これら接合用孔２ａに貫通して挿入されたリード線３は、電極線であって基端部がステンレス線５に接続されている。このリード線３は、１４００℃以上の高融点を有する金属線が好ましく、Ｐｔ線又はＰｔにＲｈが含有されている線、ＰｔにＩｒが含有されている線等が採用される。 The metal oxide sintered body 2 for the thermistor is formed, for example, in a columnar shape, and a pair of bonding holes 2a that are through holes along the axis is formed.
The lead wires 3 inserted through the bonding holes 2a are electrode wires, and the base ends are connected to the stainless steel wires 5. The lead wire 3 is preferably a metal wire having a high melting point of 1400 ° C. or higher, such as a Pt wire, a wire containing Rh in Pt, a wire containing Ir in Pt, or the like.

上記絶縁性被覆材４は、リード線３とサーミスタ用金属酸化物焼結体２とが接合している界面の露出部分２ｃを覆っている。すなわち、絶縁性被覆材４が、接合用孔２ａの開口端からリード線３が出ている基端部分の周囲のみを被覆している。
この絶縁性被覆材４は、耐還元性を有する金属酸化物（セラミックス）を含有した無機接着剤であり、例えば、Ａｌ２Ｏ３、ＳｉＯ２等セラミックスを主成分とした１０００℃〜１２００℃の耐熱性を有する一液性加熱硬化型の無機接着剤が採用される。なお、絶縁性被覆材４としては、耐還元性を有し絶縁性を有するなら、ＭｇＯやＺｒＯ２、Ｙ２Ｏ3などの他の酸化物を含む耐熱性接着剤でも構わない。 The insulating covering material 4 covers the exposed portion 2c of the interface where the lead wire 3 and the metal oxide sintered body 2 for the thermistor are joined. That is, the insulating covering material 4 covers only the periphery of the base end portion where the lead wire 3 protrudes from the opening end of the bonding hole 2a.
This insulating coating material 4 is an inorganic adhesive containing a metal oxide (ceramics) having resistance to reduction. For example, the insulating coating material 4 has a temperature of 1000 ° C. to 1200 ° C. mainly composed of ceramics such as Al 2 O 3 and SiO 2 . A one-component heat-curable inorganic adhesive having heat resistance is employed. The insulating coating material 4 may be a heat-resistant adhesive containing other oxides such as MgO, ZrO 2 , and Y 2 O 3 as long as it has reduction resistance and insulation.

本実施形態のサーミスタ素子１の製造方法は、まず、焼成により一般式：（１−ｚ）ＡＢＯ３＋ｚＹ２Ｏ３（ただし、ＡＢＯ３はペロブスカイト型酸化物、０＜ｚ≦０．８）で示される複合酸化物焼結体となるサーミスタ材料であるセラミックス粉末を秤量後にボールミルに入れ、Ｚｒボールとエタノールとを適量入れて混合を行う。 The method for producing the thermistor element 1 of the present embodiment is as follows. First, the general formula: (1-z) ABO 3 + zY 2 O 3 (where ABO 3 is a perovskite oxide, 0 <z ≦ 0.8) by firing. The ceramic powder, which is the thermistor material to be the composite oxide sintered body shown, is weighed and placed in a ball mill, and Zr balls and ethanol are mixed in an appropriate amount.

上記複合酸化物焼結体としては、例えば、一般式：（１−ｚ）（Ｙ１−ｙＬａｙ）（Ｃｒ１−ｘＭｎｘ）Ｏ３＋ｚＹ２Ｏ３（ただし、０．０≦ｘ≦１．０、０．０≦ｙ≦１．０、０＜ｚ≦０．８）で示されるものが採用される。上記混合したものを取り出して乾燥させた後、１１００℃、５時間にて焼成し、例えば、（Ｌａ０．５Ｙ０．５）（Ｃｒ０．６Ｍｎ０．４）Ｏ３の仮焼粉を得る。この仮焼粉と新たにＹ２Ｏ３の粉末とを秤量し、Ｚｒボールとエタノールとを用いてボールミルで粉砕、混合した後、乾燥させる。 Examples of the composite oxide sintered body include, for example, a general formula: (1-z) (Y 1-y La y ) (Cr 1-x Mn x ) O 3 + zY 2 O 3 (where 0.0 ≦ x ≦ 1.0, 0.0 ≦ y ≦ 1.0, 0 <z ≦ 0.8) are employed. After drying removed those listed above mixture, 1100 ° C., and calcined at 5 hours, for example, (La 0. 5 Y 0 . 5) (Cr 0. 6 Mn 0. 4) calcined powder of O 3 Get. The calcined powder and a new Y 2 O 3 powder are weighed, pulverized and mixed in a ball mill using Zr balls and ethanol, and then dried.

次に、上記金属酸化物からなるサーミスタ原料粉末を押出成型し、豚鼻状に一対の接合用孔２ａが形成された円柱状の成型体を得る。
まず、上記金属酸化物からなるサーミスタ原料粉末と水溶性有機バインダー粉と溶剤（純水）とを混合して混練することで、押出成型用坏土とする。なお、上記有機バインダー粉には、添加剤として可塑剤、潤滑剤、湿潤材等を加えてもよい。 Next, the thermistor raw material powder made of the above metal oxide is extrusion molded to obtain a cylindrical molded body in which a pair of bonding holes 2a are formed in a pig nose shape.
First, the thermistor powder made of the metal oxide, the water-soluble organic binder powder, and the solvent (pure water) are mixed and kneaded to obtain a clay for extrusion molding. In addition, a plasticizer, a lubricant, a wetting material, or the like may be added to the organic binder powder as an additive.

次に、押出成型機に坏土を投入し、坏土を真空引きしながら混合混練し、成型体用金型を通過させて押出成型し、一対の貫通孔を有したロッド状グリーン成型体を形成する。本実施形態では、例えば、２．０ｍｍ径、貫通孔の径（豚鼻径）０．３４ｍｍのロッド状グリーン成型体が形成される。   Next, the clay is put into an extrusion molding machine, mixed and kneaded while evacuating the clay, extruded through a molding die, and a rod-shaped green molded body having a pair of through holes is obtained. Form. In the present embodiment, for example, a rod-shaped green molded body having a diameter of 2.0 mm and a diameter of the through hole (pig nose diameter) of 0.34 mm is formed.

次に、押出成型後、ロッド状グリーン成型体を乾燥し、所定長さに切断して豚鼻状に貫通孔を有する切断成型体とする。本実施形態では、例えば、ロッド状乾燥成型体を１．００ｍｍ毎に切断した。
次に、丸棒状のＰｔ線である一対のリード線３を各接合用孔２ａにそれぞれ挿通させて取り付ける。なお、ロッド状グリーン成型体の貫通孔の径は、挿入性を考慮してリード線の径よりも大きくなるように設定される。また、ロッド状乾燥成型体及び切断成型体の貫通孔の径は、焼結時の収縮による接合性を考慮してリード線の径よりも焼成後に小さくなるように設定される。本実施形態では、貫通孔の径０．３４ｍｍに対し、０．３０ｍｍのリード線を挿入し、焼成後の貫通孔の径は０．３０ｍｍよりも小さくなるので、リード線を接合できる。 Next, after extrusion molding, the rod-shaped green molded body is dried and cut into a predetermined length to obtain a cut molded body having a through hole in a pig nose shape. In this embodiment, for example, the rod-shaped dry molded body was cut every 1.00 mm.
Next, a pair of lead wires 3, which are round bar-shaped Pt wires, are inserted through the respective joining holes 2 a and attached. The diameter of the through hole of the rod-shaped green molded body is set so as to be larger than the diameter of the lead wire in consideration of insertability. In addition, the diameters of the through holes of the rod-shaped dry molded body and the cut molded body are set so as to be smaller after firing than the diameter of the lead wire in consideration of the bondability due to shrinkage during sintering. In this embodiment, a lead wire of 0.30 mm is inserted with respect to the diameter of the through hole of 0.34 mm, and the diameter of the through hole after firing is smaller than 0.30 mm, so that the lead wire can be joined.

次に、貫通孔にリード線３を挿入した状態の切断成型体を、脱バインダー処理した後、約１５５０℃で５時間の焼成を行って、成型体をサーミスタ用金属酸化物焼結体２とすると共に接合用孔２ａに挿通したリード線３を接合、固定し、サーミスタ用金属酸化物焼結体とすることで、サーミスタ素子が得られる。   Next, the cut molded body in which the lead wire 3 is inserted into the through hole is subjected to binder removal treatment, and then fired at about 1550 ° C. for 5 hours, so that the molded body is sintered with the metal oxide sintered body 2 for the thermistor. At the same time, the thermistor element is obtained by joining and fixing the lead wire 3 inserted into the joining hole 2a to obtain a metal oxide sintered body for the thermistor.

このセラミックス粉体は、すでにペロブスカイトとなっているサーミスタ粉（これに絶縁体材料、例えばＹ２Ｏ３を混ぜた粉も含む）であり、仮焼後若しくは焼成後に砕いた粉、つまり焼成後にサーミスタになる焼成前のセラミックス粉や焼成後にサーミスタになっているセラミックスを砕いた粉でもよい。特に、セラミックス粉体は上記仮焼粉であることが好ましい。 This ceramic powder is a thermistor powder that has already become a perovskite (including a powder in which an insulator material, for example, Y 2 O 3 is mixed), and is crushed powder after calcining or calcining, that is, the thermistor after calcining. It may be a ceramic powder before firing, or a powder obtained by pulverizing ceramic that has become a thermistor after firing. In particular, the ceramic powder is preferably the calcined powder.

また、本実施形態のサーミスタ素子１は、成型過程で、押出成型法を採用しているが、豚鼻状に一対の接合用孔２ａが形成された円柱状の成型体を得るために、シート成型法、粉末プレス法を採用しても構わない。
また、本実施形態のサーミスタ素子１は、予め豚鼻状に一対の接合用孔２ａが形成された円柱状の素子を得て、リード線３を挿通させて、焼成によりリード線３を接合する手法を採用しているが、例えば、粉末プレス法を用いて、リード線３とサーミスタ原料粉末とを一体成型し、円柱状の成型体にリード線３が貫通、固定された成型体を得て、焼成、接合する手法を採用しても構わない。どちらの手法を用いても、焼成後円柱状のサーミスタ用金属酸化物焼結体２にリード線３が貫通、固定されたサーミスタ素子１が得られる。 Further, the thermistor element 1 of the present embodiment employs an extrusion molding method in the molding process, but in order to obtain a cylindrical molded body in which a pair of joining holes 2a are formed in a pig nose shape, A molding method or a powder pressing method may be adopted.
Further, the thermistor element 1 of the present embodiment obtains a columnar element in which a pair of bonding holes 2a are formed in a pig-nose shape in advance, inserts the lead wire 3, and joins the lead wire 3 by firing. Although the method is adopted, for example, the lead wire 3 and the thermistor raw powder are integrally molded by using a powder press method, and a molded body in which the lead wire 3 penetrates and is fixed to a cylindrical molded body is obtained. Alternatively, a method of firing and joining may be employed. Whichever method is used, the thermistor element 1 in which the lead wire 3 penetrates and is fixed to the cylindrical metal oxide sintered body 2 for thermistor after firing is obtained.

このサーミスタ用金属酸化物焼結体２は、一般式：（１−ｚ）ＡＢＯ３＋ｚＹ２Ｏ３（ただし、ＡＢＯ３はペロブスカイト型酸化物、０＜ｚ≦０．８）で示される複合酸化物焼結体であって、Ｙ２Ｏ３を入れることで、ペロブスカイト酸化物とＹ２Ｏ３の混合焼結体材料との焼成が助長され、高密度、かつ酸素の出入りが少なくなるサーミスタ材料がもたらされ、抵抗値変化を抑制することができる。 This metal oxide sintered body 2 for the thermistor has a composite oxidation represented by the general formula: (1-z) ABO 3 + zY 2 O 3 (where ABO 3 is a perovskite oxide, 0 <z ≦ 0.8). a thing sintered body, by inserting the Y 2 O 3, firing the mixed sintered material of the perovskite oxide and Y 2 O 3 is promoted, a high density, and out of the oxygen is reduced thermistor material Thus, a change in resistance value can be suppressed.

また、サーミスタ用金属酸化物焼結体２の表面には、焼成時に絶縁膜であるＹ２Ｏ３層２ｂが１〜１０μｍ程度析出される。この表面に析出した絶縁膜のＹ２Ｏ３層２ｂにより、該表面における還元劣化も抑制することができる。 On the surface of the metal oxide sintered body 2 for the thermistor, a Y 2 O 3 layer 2b, which is an insulating film, is deposited at about 1 to 10 μm during firing. Due to the Y 2 O 3 layer 2b of the insulating film deposited on the surface, reduction degradation on the surface can also be suppressed.

次に、耐熱性及び耐還元性を持つ無機接着剤を、リード線３とサーミスタ用金属酸化物焼結体２とが接合している界面の露出部分であり還元の影響を直接受ける２ｃを含んだ部分にディスペンサーで滴下して被覆した。なお、無機接着剤には、ケイ酸塩溶液に絶縁性セラミックスを加えたものを用いた。被覆後、以下のような工程を行い、絶縁性被覆材４を部分的に形成する。
（１）無機接着剤の塗布後、室温、大気中で２４ｈ乾燥。
（２）９０℃、２ｈで加熱脱水。
（３）１５０℃、１ｈ以上加熱。
（４）１０００℃、１０ｈ以上加熱。 Next, the inorganic adhesive having heat resistance and reduction resistance includes 2c that is an exposed portion of the interface where the lead wire 3 and the metal oxide sintered body 2 for the thermistor are joined and is directly affected by reduction. The portion was covered with a dispenser. In addition, what added insulating ceramics to the silicate solution was used for the inorganic adhesive agent. After coating, the following steps are performed to partially form the insulating coating material 4.
(1) After applying the inorganic adhesive, it is dried in the air at room temperature for 24 hours.
(2) Heat dehydration at 90 ° C. for 2 hours.
(3) Heat at 150 ° C. for 1 hour or longer.
(4) Heat at 1000 ° C. for 10 hours or more.

すなわち、接合用孔２ａの開口端からリード線３が出ている基端部分の周囲のみを被覆するように、絶縁性被覆材４が形成されることで、サーミスタ素子１が作製される。なお、被覆後の素子サイズは、耐還元性を上げるには大きい方が好ましいが、あまりに大きすぎと熱容量が増加し応答性が下がってしまう恐れがある。耐還元性と応答性とを考慮し、本実施形態では被覆材の厚みを１００μｍ程度に設定した。
なお、本サーミスタ素子１には、絶縁膜であるＹ２Ｏ３層２ｂが形成されているが、厚さが１〜１０μｍ程度と薄いため、リード線３とサーミスタ用金属酸化物焼結体２とが接合している界面の露出部分であり還元の影響を直接受ける２ｃを含んだ部分を覆うのには、Ｙ２Ｏ３層の厚さが不十分であり、Ｙ２Ｏ３層だけでは還元による抵抗値上昇を十分に抑えることが難しい。 That is, the thermistor element 1 is manufactured by forming the insulating covering material 4 so as to cover only the periphery of the base end portion where the lead wire 3 protrudes from the opening end of the bonding hole 2a. Note that the element size after coating is preferably large in order to increase the reduction resistance, but if it is too large, the heat capacity may increase and the responsiveness may decrease. In consideration of reduction resistance and responsiveness, the thickness of the coating material is set to about 100 μm in this embodiment.
In addition, although the Y 2 O 3 layer 2b which is an insulating film is formed in this thermistor element 1, since the thickness is as thin as about 1 to 10 μm, the lead wire 3 and the metal oxide sintered body 2 for the thermistor are used. to cover the bets the portion containing 2c directly affected in a exposed portion of the interface are joined reduction is insufficient thickness of the Y 2 O 3 layer, only Y 2 O 3 layer It is difficult to sufficiently suppress the increase in resistance value due to reduction.

次に、図３に示すように、サーミスタ用金属酸化物焼結体２の周囲を包み込むように絶縁セラミックス製のチューブ７を嵌め込む。さらに、アルミナ製の２孔式絶縁管８の各孔８ａに２本のリード線３をそれぞれ挿通し、リード線３を根本まで２孔式絶縁管８で保護する。その後、この状態のサーミスタ素子１を先端部が閉塞された円筒状ステンレス製のケース９に入れ、密閉性を確保することにより、サーミスタ温度センサ１０が得られる。   Next, as shown in FIG. 3, a tube 7 made of insulating ceramics is fitted so as to wrap around the metal oxide sintered body 2 for the thermistor. Further, the two lead wires 3 are inserted into the respective holes 8a of the two-hole insulating tube 8 made of alumina, and the lead wires 3 are protected to the root by the two-hole insulating tube 8. Then, the thermistor temperature sensor 10 is obtained by putting the thermistor element 1 in this state into a cylindrical stainless steel case 9 whose tip is closed to ensure hermeticity.

このように本実施形態のサーミスタ素子１では、サーミスタ用金属酸化物焼結体２の表面を部分的に覆う絶縁性被覆材４が、還元の影響を直接受けるリード線３とサーミスタ用金属酸化物焼結体２とが接合している界面の露出部分２ｃを覆っているので、サーミスタ用金属酸化物焼結体２中の還元劣化を効果的に防ぐと共に、被覆部分が限定されることで、素子全体の熱容量が抑えられ、素子全体を被覆した場合に比較して優れた応答性を得ることができる。   As described above, in the thermistor element 1 of the present embodiment, the insulating coating 4 that partially covers the surface of the thermistor metal oxide sintered body 2 is directly affected by the reduction of the lead wire 3 and the thermistor metal oxide. Since the exposed portion 2c of the interface where the sintered body 2 is joined is covered, reduction degradation in the metal oxide sintered body 2 for the thermistor is effectively prevented, and the covering portion is limited, The heat capacity of the entire element is suppressed, and excellent responsiveness can be obtained as compared with the case where the entire element is covered.

また、素子サイズが、無被覆のものと大きく変わらないため、サーミスタ本体と実装するケース９との間隔を近づけることができ、この点からも応答性が向上する。さらに、同様の理由によりケース９への挿入性も向上すると共に、素子全体を覆う場合よりも絶縁性被覆材４の使用量が少なくてすみ、製造コストの低減を図ることができる。
また、絶縁性被覆材４が、耐還元性を有する金属酸化物を含有した無機接着剤であるので、ディスペンサー等で所定部分に滴下して焼成させることで、容易に耐熱性及び耐還元性を有する膜を被覆可能である。 In addition, since the element size is not significantly different from that of the uncovered one, the distance between the thermistor body and the mounting case 9 can be reduced, and the responsiveness is also improved in this respect. Furthermore, for the same reason, the insertability into the case 9 is improved, and the amount of the insulating coating material 4 used is smaller than that in the case of covering the entire element, and the manufacturing cost can be reduced.
Moreover, since the insulating coating material 4 is an inorganic adhesive containing a metal oxide having reduction resistance, it can be easily added with heat resistance and reduction resistance by being dropped onto a predetermined portion with a dispenser and firing. It is possible to coat a film having the same.

次に、本発明に係るサーミスタ素子の第２実施形態について、図４を参照して以下に説明する。なお、以下の実施形態の説明において、上記実施形態において説明した同一の構成要素には同一の符号を付し、その説明は省略する。   Next, a second embodiment of the thermistor element according to the present invention will be described below with reference to FIG. Note that, in the following description of the embodiment, the same components described in the above embodiment are denoted by the same reference numerals, and the description thereof is omitted.

第２実施形態と第１実施形態との異なる点は、第１実施形態では、絶縁性被覆材４が、リード線３とサーミスタ用金属酸化物焼結体２とが接合している界面の露出部分２ｃのみを局所的に覆っているのに対し、第２実施形態のサーミスタ素子２１では、図４に示すように、絶縁性被覆材２４が、サーミスタ用金属酸化物焼結体２の表面において対となるリード線３の間も覆って設けられている点である。   The difference between the second embodiment and the first embodiment is that, in the first embodiment, the insulating coating 4 is exposed at the interface where the lead wire 3 and the metal oxide sintered body 2 for the thermistor are joined. Whereas only the portion 2c is locally covered, in the thermistor element 21 of the second embodiment, as shown in FIG. 4, the insulating coating material 24 is formed on the surface of the metal oxide sintered body 2 for the thermistor. It is a point provided so as to cover between the pair of lead wires 3.

すなわち、第２実施形態では、絶縁性被覆材２４が、円柱状のサーミスタ用金属酸化物焼結体２の外周面を除き、両方の端面のほぼ全体に設けられており、上記露出部分２ｃだけでなく一対のリード線３の間にも耐熱性の無機接着剤を滴下して再焼成させることで被覆を行っている。
このように第２実施形態のサーミスタ素子２１では、絶縁性被覆材２４が、サーミスタ用金属酸化物焼結体２の表面において対となるリード線３の間も覆って設けられているので、素子の電気特性に特に寄与する対となるリード線３の間の表面における還元も絶縁性被覆材２４によって抑制することで、より還元劣化を防ぐことができる。 That is, in the second embodiment, the insulating coating material 24 is provided on almost the entire end surfaces except for the outer peripheral surface of the cylindrical metal oxide sintered body 2 for thermistor, and only the exposed portion 2c. In addition, the coating is performed by dropping a heat-resistant inorganic adhesive between the pair of lead wires 3 and refiring.
Thus, in the thermistor element 21 of the second embodiment, the insulating coating material 24 is provided so as to cover between the pair of lead wires 3 on the surface of the metal oxide sintered body 2 for the thermistor. By reducing the reduction on the surface between the pair of lead wires 3 that particularly contribute to the electrical characteristics, the insulating coating material 24 can also suppress the reduction deterioration.

上記第１及び第２実施形態のサーミスタ素子１，２１を実際に製造した実施例１及び２について、耐還元性及び応答性を評価した結果を、図５及び図６を参照して説明する。
上記耐還元性の評価は、作製したサーミスタ素子を短時間で還元処理した場合について検証した。この際の還元処理条件は、１０−１１ａｔｍの酸素雰囲気で、１０００℃、１時間とし、還元処理前後の２５℃での抵抗値を測定した。一方で応答性の指標となる熱時定数は周囲温度を２５℃にして素子に電流を流し、自己発熱によって５０℃まで温度を上昇させた後、電流を止めて素子温度が５０℃から２５℃の温度差の６３．２％すなわち３４．２℃になるまでの時間を測定した。 The results of evaluating reduction resistance and responsiveness for Examples 1 and 2 in which the thermistor elements 1 and 21 of the first and second embodiments are actually manufactured will be described with reference to FIGS. 5 and 6.
The evaluation of the reduction resistance was verified for the case where the produced thermistor element was reduced in a short time. The reduction treatment conditions at this time were 1000 ° C. for 1 hour in an oxygen atmosphere of 10 −11 atm, and the resistance values at 25 ° C. before and after the reduction treatment were measured. On the other hand, the thermal time constant as an index of responsiveness is that the ambient temperature is 25 ° C., a current is passed through the device, the temperature is raised to 50 ° C. by self-heating, the current is stopped, and the device temperature is 50 ° C. to 25 ° C. The time until the temperature difference reached 63.2%, that is, 34.2 ° C., was measured.

また、比較のため、図５の（ａ）に示すように、絶縁性被覆材４でサーミスタ用金属酸化物焼結体２を全く覆わない状態とした比較例１のサーミスタ素子１１１と、図５の（ｂ）に示すように、絶縁性被覆材１０４でサーミスタ用金属酸化物焼結体２を全体的に覆った状態とした比較例２のサーミスタ素子１２１と、を作製して、上記と同様に耐還元性及び応答性の評価を行った。これら実施例１及び２と比較例１及び２との評価結果を、以下の表１に示す。   For comparison, as shown in FIG. 5A, the thermistor element 111 of Comparative Example 1 in which the insulating coating material 4 does not cover the thermistor metal oxide sintered body 2 at all, and FIG. As shown in (b), the thermistor element 121 of Comparative Example 2 in which the thermistor metal oxide sintered body 2 was entirely covered with the insulating coating material 104 was produced, and the same as described above. In addition, reduction resistance and responsiveness were evaluated. The evaluation results of Examples 1 and 2 and Comparative Examples 1 and 2 are shown in Table 1 below.

Figure 2011124446
Figure 2011124446

これらの評価結果からわかるように、絶縁性被覆材４で覆われておらずサーミスタ用金属酸化物焼結体２全体が露出している比較例１では、還元状態に置いた後の抵抗変化率が大きいのに対し、本発明の実施例１及び２では、絶縁性被覆材１０４でサーミスタ用金属酸化物焼結体２全体を覆った比較例２とほぼ同様の低い値が得られている。つまり、リード線とサーミスタ用金属酸化物焼結体とが接合している界面の露出部分が還元の影響を直接受けており、その部分を重点的に絶縁性被覆材で覆うことで還元による抵抗値上昇を効果的に抑制することができる。   As can be seen from these evaluation results, in Comparative Example 1 where the entire metal oxide sintered body 2 for the thermistor is not covered with the insulating coating material 4 and exposed, the rate of change in resistance after being placed in the reduced state On the other hand, in Examples 1 and 2 of the present invention, the same low value is obtained as in Comparative Example 2 in which the entire metal oxide sintered body 2 for the thermistor is covered with the insulating coating material 104. In other words, the exposed part of the interface where the lead wire and the metal oxide sintered body for the thermistor are joined is directly affected by the reduction. An increase in value can be effectively suppressed.

また、応答性を示す熱時定数は、絶縁性被覆材１０４でサーミスタ用金属酸化物焼結体２全体を覆った比較例２が最も大きく応答性が劣っているのに対し、本発明の実施例１及び２では、比較例２よりも小さい熱時定数が得られており、特に実施例１では、絶縁性被覆材４で覆われておらずサーミスタ用金属酸化物焼結体２全体が露出している比較例１に近い熱時定数が得られ、優れた応答性を示すことがわかる。焼結体２全体が露出している比較例１に近い熱時定数が得られ、優れた応答性を示すことがわかる。つまり、本実施形態では、応答性を維持しながら耐還元性を向上させることができる。   In addition, the thermal time constant indicating responsiveness is the largest in Comparative Example 2 in which the entire metal oxide sintered body 2 for the thermistor is covered with the insulating coating material 104, whereas the responsiveness is inferior. In Examples 1 and 2, a thermal time constant smaller than that in Comparative Example 2 was obtained. In particular, in Example 1, the entire metal oxide sintered body 2 for the thermistor that was not covered with the insulating coating material 4 was exposed. It can be seen that a thermal time constant close to that of Comparative Example 1 is obtained, and excellent responsiveness is exhibited. It can be seen that a thermal time constant close to that of Comparative Example 1 in which the entire sintered body 2 is exposed is obtained, and excellent responsiveness is exhibited. That is, in this embodiment, reduction resistance can be improved while maintaining responsiveness.

なお、本発明の技術範囲は上記各実施形態及び上記各実施例に限定されるものではなく、本発明の趣旨を逸脱しない範囲において種々の変更を加えることが可能である。   The technical scope of the present invention is not limited to the above embodiments and examples, and various changes can be made without departing from the spirit of the present invention.

例えば、本実施形態では電極線であるリード線がサーミスタ用金属酸化物焼結体を貫通しているが、他の例として、図６のような形状のサーミスタ素子１３１であっても構わない。すなわち、第１実施形態のサーミスタ素子１では、４箇所の露出部分２ｃを絶縁性被覆材４で覆っているが、このサーミスタ１３１の場合、リード線３の先端が有底の接合用孔２ａに埋め込まれてサーミスタ用金属酸化物焼結体２を貫通しておらず、２箇所の露出部分２ｃを絶縁性被覆材４で覆っている。このように接合用孔２ａは、第１実施形態のように貫通孔であっても、第２実施形態のように有底の非貫通穴であっても構わない。したがって、リード線３が途中まで挿入されて埋め込まれているタイプでも、絶縁性被覆材４が界面の露出部分２ｃを覆っているので、還元劣化を効果的に防ぐことができる。   For example, in this embodiment, the lead wire which is an electrode wire penetrates the metal oxide sintered body for the thermistor, but as another example, the thermistor element 131 having a shape as shown in FIG. That is, in the thermistor element 1 of the first embodiment, the four exposed portions 2c are covered with the insulating coating material 4, but in the case of this thermistor 131, the tip of the lead wire 3 is formed into the bottomed bonding hole 2a. It is embedded and does not penetrate the metal oxide sintered body 2 for the thermistor, and the two exposed portions 2 c are covered with the insulating coating material 4. Thus, the bonding hole 2a may be a through hole as in the first embodiment or a bottomed non-through hole as in the second embodiment. Therefore, even in the type in which the lead wire 3 is inserted and embedded partway, since the insulating coating material 4 covers the exposed portion 2c of the interface, reduction degradation can be effectively prevented.

１，２１，１１１，１２１，１３１…サーミスタ素子、２…サーミスタ用金属酸化物焼結体、２ａ…接合用孔、２ｂ…Ｙ２Ｏ３層、２ｃ…リード線とサーミスタ用金属酸化物焼結体とが接合している界面の露出部分、３…リード線、４，２４，１０４…絶縁性被覆材 1,21,111,121,131 ... thermistor element, 2 ... metal oxide sintered body for thermistor, 2a ... joining holes, 2b ... Y 2 O 3 layer, 2c ... lead wire and a thermistor metal oxide sintered Exposed portion of the interface where the body is joined, 3 ... lead wire, 4, 24, 104 ... insulating coating

Claims (4)

少なくとも一対の接合用孔が形成されたサーミスタ用金属酸化物焼結体と、
前記接合用孔内に一部が配された状態で前記サーミスタ用金属酸化物焼結体に接合された少なくとも一対のリード線と、
前記サーミスタ用金属酸化物焼結体の表面を部分的に覆う絶縁性被覆材と、を備え、
該絶縁性被覆材が、前記リード線と前記サーミスタ用金属酸化物焼結体とが接合している界面の露出部分を覆っていることを特徴とするサーミスタ素子。 A metal oxide sintered body for a thermistor in which at least a pair of bonding holes are formed;
At least a pair of lead wires joined to the metal oxide sintered body for the thermistor in a state where a part thereof is disposed in the joining hole;
An insulating coating material partially covering the surface of the metal oxide sintered body for the thermistor,
The thermistor element, wherein the insulating covering material covers an exposed portion of an interface where the lead wire and the metal oxide sintered body for the thermistor are joined. 請求項１に記載のサーミスタ素子において、
前記絶縁性被覆材が、前記サーミスタ用金属酸化物焼結体の表面において対となる前記リード線の間も覆って設けられていることを特徴とするサーミスタ素子。 The thermistor element according to claim 1,
The thermistor element, wherein the insulating covering material is provided so as to cover between the pair of lead wires on the surface of the metal oxide sintered body for the thermistor. 請求項１又は２に記載のサーミスタ素子において、
前記絶縁性被覆材が、耐還元性を有する金属酸化物を含有した無機接着剤であることを特徴とするサーミスタ素子。 The thermistor element according to claim 1 or 2,
The thermistor element, wherein the insulating coating material is an inorganic adhesive containing a metal oxide having reduction resistance. 請求項１から３のいずれか一項に記載のサーミスタ素子において、
前記サーミスタ用金属酸化物焼結体が、一般式：（１−ｚ）ＡＢＯ３＋ｚＹ２Ｏ３（ただし、ＡＢＯ３はペロブスカイト型酸化物、０＜ｚ≦０．８）で示される複合酸化物焼結体であって、表面にＹ２Ｏ３層が析出されていることを特徴とするサーミスタ素子。 In the thermistor element according to any one of claims 1 to 3,
The metal oxide sintered body for the thermistor is a composite oxide represented by the general formula: (1-z) ABO 3 + zY 2 O 3 (where ABO 3 is a perovskite oxide, 0 <z ≦ 0.8). A thermistor element which is a sintered body and has a Y 2 O 3 layer deposited on the surface thereof.
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