JPH09110521A - Semiconductor ceramic composition and ptc thermistor - Google Patents
Semiconductor ceramic composition and ptc thermistorInfo
- Publication number
- JPH09110521A JPH09110521A JP7265189A JP26518995A JPH09110521A JP H09110521 A JPH09110521 A JP H09110521A JP 7265189 A JP7265189 A JP 7265189A JP 26518995 A JP26518995 A JP 26518995A JP H09110521 A JPH09110521 A JP H09110521A
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- ceramic composition
- semiconductor ceramic
- batio
- ptc thermistor
- Prior art date
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- Compositions Of Oxide Ceramics (AREA)
- Semiconductor Integrated Circuits (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、電子機器等の回路
部品や無接点式電流制御用として使用される半導体セラ
ミック組成物及びＰＴＣサーミスターに関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor ceramic composition and a PTC thermistor used for circuit parts such as electronic equipment and non-contact type current control.
【０００２】[0002]
【従来の技術】近年、音響機器、映像機器、情報通信機
器等の高集積化に伴い、回路保護用の***品として低
抵抗で破壊電圧が高いＰＴＣサーミスターが要求されて
いる。2. Description of the Related Art In recent years, with the high integration of audio equipment, video equipment, information communication equipment, etc., PTC thermistors with low resistance and high breakdown voltage have been required as safety parts for circuit protection.
【０００３】このＰＴＣ（Ｐｏｓｉｔｉｖｅ Ｔｅｍｐ
ｅｒａｔｕｒｅ Ｃｏｅｆｆｉｃｉｅｎｔ）サーミスタ
ーは正特性サーミスターあるいは単にサーミスターとも
略称されるが、温度の上昇と共に抵抗値が増大するもの
で、消費電力が増えて自身の温度上昇が高まると、抵抗
が高くなり電力消費を抑制させる作用をする。特に高温
（数百度以上）で動作する高温型ＰＴＣサーミスターに
使用される材料にはＢａＴｉＯ3系とＳｉ系等がある
が、製造が容易であることからＢａＴｉＯ3系の方が用
いられることが多い。ＢａＴｉＯ3の一般式で表される
チタン酸バリウムは、ＢａＣＯ3等のＢａ化合物やＴｉ
Ｏ2等のＴｉ化合物をほぼ１：１で混合して焼結したペ
ロブスカイト型の結晶構造を有する強誘電体磁器であ
る。ＢａＴｉＯ3系はこのＢａＴｉＯ3にその原子価を制
御する異種原子をドープして伝導性を持たせて半導体化
した半導体セラミック組成物であって、これを用いたＰ
ＴＣサーミスターはＢａＴｉＯ3に特有の、キューリ温
度における相転移によりその抵抗値が急激に増大し電気
伝導性が大幅に低下する現象を利用したものである。そ
こで従来からより使用しやすいＰＴＣサーミスターを得
るために、半導体セラミック組成物であるＢａＴｉＯ3
の抵抗値、キューリ温度や抵抗値の変化率及び破壊電圧
等が改善されてきている。This PTC (Positive Temp)
Erasure Coefficient) Thermistors are also abbreviated as positive temperature coefficient thermistors or simply thermistors, but the resistance value increases as the temperature rises. When the power consumption increases and the temperature rises, the resistance increases and the power consumption increases. Acts to suppress consumption. In particular, materials used for high temperature PTC thermistors that operate at high temperatures (several hundreds of degrees or more) include BaTiO 3 series and Si series, but BaTiO 3 series is preferably used because it is easy to manufacture. Many. Barium titanate represented by the general formula of BaTiO 3 is a Ba compound such as BaCO 3 or Ti.
This is a ferroelectric ceramic having a perovskite type crystal structure in which a Ti compound such as O 2 is mixed at a ratio of about 1: 1 and sintered. The BaTiO 3 system is a semiconductor ceramic composition in which this BaTiO 3 is doped with a heteroatom for controlling its valence to make it conductive and is made into a semiconductor.
The TC thermistor utilizes a phenomenon peculiar to BaTiO 3 in which the resistance value sharply increases due to the phase transition at the Curie temperature and the electric conductivity is significantly lowered. Therefore, in order to obtain a PTC thermistor that is easier to use than before, BaTiO 3 which is a semiconductor ceramic composition is used.
The resistance value, Curie temperature, rate of change of resistance value, breakdown voltage, etc. have been improved.
【０００４】そこで、このＢａＴｉＯ3を改善したもの
として、従来次のような技術（特開平３−６５５５９号
公報）が提案されている。この技術はＢａＴｉＯ3系を
主成分とし、添加剤としてＮｂ2Ｏ5を０．０４〜０．０
６モル％使用し、正の温度係数を有し、また室温におけ
る抵抗率が小さく、キュリー点以上の温度における抵抗
率の立ち上がり幅の大きいＢａＴｉＯ3半導体を得よう
とするものである。Therefore, the following technique (Japanese Patent Laid-Open No. 3-65559) has been conventionally proposed as an improvement of BaTiO 3 . This technique is mainly composed of BaTiO 3 system and contains Nb 2 O 5 as an additive in an amount of 0.04 to 0.04.
It is intended to obtain a BaTiO 3 semiconductor which uses 6 mol%, has a positive temperature coefficient, has a low resistivity at room temperature, and has a large rise width of the resistivity at a temperature above the Curie point.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、特開平
３−６５５５９号公報に記載されたＢａＴｉＯ3半導体
は、抵抗率の立ち上がり幅が改善され、室温抵抗率は
６．７７Ωｃｍ以上と小さいものの、直流破壊電圧が１
９．８Ｖ／ｍｍ以下程度で、高温型ＰＴＣサーミスター
をさらに小型化し、電子回路保護用の***品として使
用するには十分でないという問題点を有していた。However, the BaTiO 3 semiconductor described in Japanese Patent Laid-Open No. 3-65559 has an improved resistance rising width and a room temperature resistivity as small as 6.77 Ωcm or more, but has a DC breakdown. Voltage is 1
At a voltage of about 9.8 V / mm or less, there is a problem that the high temperature type PTC thermistor cannot be further miniaturized and used as a safety component for protecting electronic circuits.
【０００６】そこで本発明は前記従来の問題点を解決す
るもので、比抵抗が小さく、破壊電圧が高く、小型で回
路設計の容易な半導体セラミック組成物及びＰＴＣサー
ミスターを得ることを目的とするものである。Therefore, the present invention is intended to solve the above-mentioned conventional problems, and an object thereof is to obtain a semiconductor ceramic composition and a PTC thermistor having a small specific resistance, a high breakdown voltage, a small size, and easy circuit design. It is a thing.
【０００７】[0007]
【課題を解決するための手段】上記目的を達成するため
に本発明の半導体セラミック組成物は、ＢａＴｉＯ3の
一般式で表されるチタン酸バリウム１モルに、副成分と
してＹをＹ2Ｏ3に換算して０．００１８〜０．００２７
モル、ＭｎがＭｎＣＯ3に換算して０．０００５〜０．
０００９モル、ＳｉがＳｉＯ2に換算して０．００５〜
０．０３モル含有されていることを特徴とする。In order to achieve the above object, the semiconductor ceramic composition of the present invention comprises 1 mol of barium titanate represented by the general formula of BaTiO 3 and Y as a subcomponent Y 2 O 3. Converted to 0.0018-0.0027
Mol, and Mn is in terms of MnCO 3 0.0005~0.
0009 mol, Si converted to SiO 2 is 0.005
It is characterized by containing 0.03 mol.
【０００８】これにより、比抵抗が小さく、破壊電圧が
高い半導体セラミック組成物が得られる。As a result, a semiconductor ceramic composition having a low specific resistance and a high breakdown voltage can be obtained.
【０００９】また、本発明のＰＴＣサーミスターは半導
体セラミック組成物からなる基板の対向した面にそれぞ
れ設けられた電極を備えていることが望ましい。Further, it is desirable that the PTC thermistor of the present invention is provided with electrodes provided on opposite surfaces of a substrate made of a semiconductor ceramic composition.
【００１０】これにより、比抵抗が小さく、小型で回路
設計の容易なＰＴＣサーミスターが得られる。As a result, a PTC thermistor having a small specific resistance, a small size, and an easy circuit design can be obtained.
【００１１】[0011]
【発明の実施の形態】本発明の請求項１に記載の発明
は、ＢａＴｉＯ3の一般式で表されるチタン酸バリウム
１モルに、副成分としてＹをＹ2Ｏ3に換算して０．００
１８〜０．００２７モル、ＭｎがＭｎＣＯ3に換算して
０．０００５〜０．０００９モル、ＳｉがＳｉＯ2に換
算して０．００５〜０．０３モル含有した半導体セラミ
ック組成物であり、焼結性がよく、比抵抗が小さく、抵
抗変化率が大きく、さらに破壊電圧が高くなるなるとい
う作用特性を有する。BEST MODE FOR CARRYING OUT THE INVENTION According to the first aspect of the present invention, 1 mol of barium titanate represented by the general formula of BaTiO 3 is added to Y 2 O 3 when Y is converted to Y 2 O 3 as an accessory component. 00
It is a semiconductor ceramic composition containing 18 to 0.0027 mol, Mn 0.0005 to 0.0009 mol in terms of MnCO 3 , and Si 0.005 to 0.03 mol in terms of SiO 2. It has good working properties, a small specific resistance, a large resistance change rate, and a higher breakdown voltage.
【００１２】また、請求項２に記載の発明は、半導体セ
ラミック組成物からなる基板の対向した面にそれぞれ設
けられた電極を備えたＰＴＣサーミスターであり、半導
体セラミック組成物と電極はオーム性接触を形成し、温
度上昇とともに急激に比抵抗が大きくなるという作用を
有する。The invention according to claim 2 is a PTC thermistor equipped with electrodes provided on opposite surfaces of a substrate made of a semiconductor ceramic composition, wherein the semiconductor ceramic composition and the electrode are in ohmic contact. Has the effect of rapidly increasing the specific resistance as the temperature rises.
【００１３】また、請求項３に記載の発明は、基板の厚
みが０．０４〜２．５ｍｍとしたＰＴＣサーミスターで
あり、基板強度が大きく、比抵抗が小さいという作用を
有する。Further, the invention according to claim 3 is a PTC thermistor in which the thickness of the substrate is 0.04 to 2.5 mm, and has the action of high substrate strength and low specific resistance.
【００１４】以下、本発明の実施の形態について、（表
１）、（表２）及び図１、図２、図３を用いて説明す
る。Embodiments of the present invention will be described below with reference to (Table 1) and (Table 2) and FIGS. 1, 2 and 3.
【００１５】（実施の形態１）まず、本発明の半導体セ
ラミック組成物の主成分であるＢａＴｉＯ3の製造法に
ついて述べる。重量比で純度９９％以上のシュウ酸バリ
ウムチタニル（ＢａＴｉＯ（Ｃ2Ｏ4）2・４Ｈ2Ｏ）を６
００℃の温度で空気中にて約１０時間加熱する。このよ
うに加熱分解して、粉末状で重量比で純度が９９％以上
のＢａＴｉＯ3が得られる。この得られた主成分のＢａ
ＴｉＯ3の１モルに重量比で純度９９．８％以上のＹ2Ｏ
3、ＭｎＣＯ3及びＳｉＯ2をそれぞれ副成分として添加
し、（表１）に示した組成比になるように２６種類の一
次混合物を作成した。（表１）は主成分のＢａＴｉＯ3
を１モルとして副成分の含有量を変えたものである。(Embodiment 1) First, a method for producing BaTiO 3 which is the main component of the semiconductor ceramic composition of the present invention will be described. 6% barium titanyl oxalate (BaTiO (C 2 O 4 ) 2 .4H 2 O) having a purity of 99% or more by weight is used.
Heat in air at a temperature of 00 ° C. for about 10 hours. By thermal decomposition in this manner, powdery BaTiO 3 having a purity of 99% or more by weight is obtained. Ba of the obtained main component
Y 2 O having a purity of 99.8% or more in a weight ratio to 1 mol of TiO 3.
3 , MnCO 3 and SiO 2 were added as sub-components, respectively, and 26 kinds of primary mixtures were prepared so as to have the composition ratios shown in (Table 1). Table 1 shows the main component BaTiO 3.
Is 1 mol and the contents of the subcomponents are changed.
【００１６】[0016]
【表１】 [Table 1]
【００１７】（表１）において１〜２６の試料はＹ2Ｏ3
を０．００１５〜０．００３１モルの間で変化させ、Ｍ
ｎＣＯ3を０．０００３〜０．００１１モルの間で変化
させ、ＳｉＯ2を０．００３〜０．０３５モルの間で変
化させたものである。ただし表中に・印を付与したもの
は本発明の範囲外の比較例である。また（表２）は（表
１）に示した一次混合物の試験番号１〜２６の比抵抗
（Ωｃｍ）と破壊電圧（Ｖ／ｍｍ）に関する特性を示す
ものである。In Table 1, samples 1 to 26 are Y 2 O 3
Of 0.0015 to 0.0031 mol, and M
nCO 3 was changed between 0.0003 and 0.0011 mol, and SiO 2 was changed between 0.003 and 0.035 mol. However, those marked with-in the table are comparative examples outside the scope of the present invention. Further, (Table 2) shows the characteristics of the primary mixtures shown in (Table 1) regarding the specific resistance (Ωcm) and the breakdown voltage (V / mm) of Test Nos. 1-26.
【００１８】[0018]
【表２】 [Table 2]
【００１９】ここでは、副成分のＹ、Ｍｎ、およびＳｉ
成分をそれぞれＹ2Ｏ3、ＭｎＣＯ3及びＳｉＯ2等の化合
物で添加しているが、これ以外の化合物で添加すること
もできる。その場合にも添加する化合物量のモル量を添
加すればよい。Here, Y, Mn, and Si which are subcomponents are used.
The components are added as compounds such as Y 2 O 3 , MnCO 3 and SiO 2, but other compounds may be added. Also in that case, the molar amount of the compound to be added may be added.
【００２０】この一次混合物をポットミルに入れジルコ
ニヤボールとともに約２４時間湿式混合し、Ｙ2Ｏ3、Ｍ
ｎＣＯ3及びＳｉＯ2が均一に分散して含有する二次混合
物を得た。次にこの二次混合物を約１０００℃４時間空
気中で焼成し、仮焼物を得た。この仮焼物を約１ミクロ
ン以下の粒子にまで解砕し、有機結合材として約５％濃
度のＰＶＡ（ポリビニルアルコール）溶液を１０重量％
加え、成形しやすいように４０〜５０ミクロンの顆粒状
に造粒した。この造粒した粉末を約１０００Ｋｇ／ｃｍ
2の圧力で加圧し、直径が約１３ｍｍで厚みが約１．２
ｍｍの円板状に成形した。この成形体を約２５０℃／時
間の速度昇温し、空気中約１３００℃で１時間焼結さ
せ、１００℃／時間の速度で降温しＹ2Ｏ3、ＭｎＯおよ
びＳｉＯ2を含有したＢａＴｉＯ3からなるペロブスカイ
ト型の焼結体を得た。このようにして（表１）に示した
試料番号１〜２６の試料を各１０個づつ作成した。This primary mixture was placed in a pot mill and wet mixed with zirconia balls for about 24 hours to obtain Y 2 O 3 and M.
A secondary mixture containing nCO 3 and SiO 2 uniformly dispersed therein was obtained. Next, this secondary mixture was calcined in air at about 1000 ° C. for 4 hours to obtain a calcined product. This calcined product is crushed to particles of about 1 micron or less, and 10% by weight of a PVA (polyvinyl alcohol) solution having a concentration of about 5% is used as an organic binder.
In addition, it was granulated into granules of 40 to 50 microns to facilitate molding. About 1000 kg / cm of this granulated powder
Pressed with a pressure of 2 , the diameter is about 13 mm and the thickness is about 1.2
It was formed into a disk shape of mm. The compact was heated at a rate of about 250 ° C./hour, sintered in air at about 1300 ° C. for 1 hour, and cooled at a rate of 100 ° C./hour to produce BaTiO 3 containing Y 2 O 3 , MnO and SiO 2. A perovskite type sintered body was obtained. In this manner, 10 samples of sample numbers 1 to 26 shown in (Table 1) were prepared.
【００２１】次に、比抵抗と破壊電圧を測定するために
上記試料にオーム性電極を形成した。そこでオーム性電
極の形成方法について述べる。ここでオーム性電極とは
接触部の電圧−電流特性がオームの法則に従うもので、
半導体部とリード線との接触部は電圧と電流が比例する
ことが必要である。円板状のＢａＴｉＯ3焼結体の対向
する両面を溶剤で洗浄して脱脂する。その後水洗し、２
〜３％濃度のフッ酸溶液で１０分程度エッチングする。
このエッチングはメッキ層の剥離強度を強くするためで
ある。このエッチングしたＢａＴｉＯ3焼結体を塩化第
１錫の塩酸溶液に数分間浸漬し、その表面に錫イオンを
吸着させる。この錫イオンはＢａＴｉＯ 3焼結体の電極
面の活性化を促進する。つぎにこの錫イオンを吸着した
面を０．０３重量％のパラジウム溶液に浸漬し、パラジ
ウムを吸着させる。この吸着したパラジウムは次の無電
解メッキの触媒作用を引き起こす。無電解メッキは硫酸
ニッケル溶液をＰＨ＝８〜９．５に調整し、４０〜５０
℃の温度に加温し約２０分間浸漬して行う。こうして２
〜５ミクロンの厚さのニッケル層がメッキされる。この
無電解メッキされたＢａＴｉＯ3焼結体を約５００℃の
温度で２０分程度熱処理することで、ＢａＴｉＯ3焼結
体とニッケル電極はオーム性接触しオーム性電極が形成
される。Next, in order to measure the specific resistance and the breakdown voltage,
An ohmic electrode was formed on the sample. So oh
A method of forming the pole will be described. Here is the ohmic electrode
The voltage-current characteristic of the contact part follows Ohm's law,
Voltage and current are proportional to the contact area between the semiconductor and the lead wire
It is necessary. Disc-shaped BaTiOThreeOpposite of sintered body
Clean both sides with a solvent to degrease. Then wash with water, 2
Etching is performed with a hydrofluoric acid solution having a concentration of 3% for about 10 minutes.
This etching is to increase the peel strength of the plating layer.
is there. This etched BaTiOThreeChloride the sintered body
Immerse 1 tin in hydrochloric acid solution for a few minutes, and tin ion on the surface
Adsorb. This tin ion is BaTiO 3. ThreeSintered electrode
Promotes surface activation. Next, this tin ion was adsorbed
Immerse the surface in 0.03% by weight palladium solution and
Adsorb um. This adsorbed palladium is
Causes catalysis of deplating. Electroless plating is sulfuric acid
Adjust the nickel solution to PH = 8-9.5, 40-50
It is heated at a temperature of ℃ and immersed for about 20 minutes. Thus 2
A ~ 5 micron thick nickel layer is plated. this
Electroless plated BaTiOThreeSintered at about 500 ℃
By heat treating at a temperature of about 20 minutes, BaTiO 3ThreeSintering
The body and the nickel electrode are in ohmic contact to form an ohmic electrode.
Is done.
【００２２】このようにして得られた本発明の半導体セ
ラミック組成物の特性が（表２）の比抵抗（Ωｃｍ）と
破壊電圧であるに示す。比抵抗と破壊電圧は、直径が約
１３ｍｍφで厚みが約１．２ｍｍの円板状のＢａＴｉＯ
3半導体磁器組成物にオーム性のニッケル電極を形成し
たもので測定した。比抵抗は２０℃の温度でＢａＴｉＯ
3 半導体磁器組成物の厚み１ｍｍ当たり２５Ｖの直流電
圧を３０秒間印加しその３０秒後に測定し、次式より求
めた。The characteristics of the semiconductor ceramic composition of the present invention thus obtained are shown in Table 2 below, which is specific resistance (Ωcm) and breakdown voltage. The specific resistance and the breakdown voltage are about 13 mmφ in diameter and about 1.2 mm in thickness, which is a disk-shaped BaTiO 3.
3 A semiconductor ceramic composition was measured with an ohmic nickel electrode formed. The specific resistance is BaTiO3 at a temperature of 20 ° C.
3 A DC voltage of 25 V per 1 mm of the thickness of the semiconductor porcelain composition was applied for 30 seconds, the measurement was performed 30 seconds after that, and the value was calculated from the following formula.
【００２３】ρ＝Ｒ・Ｓ／Ｔ ただし、 ρ：比抵抗（Ωｃｍ） Ｒ：抵抗の実測値（Ω） Ｓ：電極の面積（ｃｍ2） Ｔ：ＢａＴｉＯ3半導体磁器組成物の厚み 一方、直流破壊電圧はＢａＴｉＯ3半導体磁器組成物の
上記電極に直流電圧を印加し、次第に上昇させてＢａＴ
ｉＯ3半導体磁器組成物が破壊した時点の電圧を求め
た。これらの特性値は１０個の試料の単純平均値であ
る。Ρ = R · S / T where ρ: specific resistance (Ωcm) R: measured value of resistance (Ω) S: electrode area (cm 2 ) T: thickness of BaTiO 3 semiconductor porcelain composition The breakdown voltage is applied by applying a DC voltage to the above electrode of the BaTiO 3 semiconductor porcelain composition and gradually increasing the BaT 3
The voltage at the time when the iO 3 semiconductor ceramic composition was broken was determined. These characteristic values are simple average values of 10 samples.
【００２４】試料番号１６〜２６は本発明の範囲外のも
のであって、主成分のＢａＴｉＯ3１モルに副成分とし
てＹ2Ｏ3を０．００１７〜０．００３１モル、ＭｎＣＯ
3を０．０００３〜０．００１１モルおよびＳｉＯ2を
０．０００３〜０．０３５モル添加したものであるが、
破壊電圧は３０〜４５Ｖ／ｍｍと高く、比抵抗は３０．
５〜９０．８Ωｃｍと著しく高くなっている。比抵抗が
３０Ωｃｍ程度以上に高くなると、ＰＴＣサーミスター
として電子回路の保護回路に接続したとき回路抵抗が高
くなって、回路電圧を高くしなければならない等回路設
計が容易でなくなる。また主成分のＢａＴｉＯ3１モル
に副成分のＹ2Ｏ3が０．００１８モル未満では、ＢａＴ
ｉＯ3半導体磁器組成物の焼結性がよくなく比抵抗が高
くなり、０．００２７モルを超えると比抵抗は再び高く
なり実用的でなくなる。また、副成分のＭｎＣＯ3が
０．０００５モル未満では、比抵抗が高くＰＴＣサーミ
スターの立ち上がり特性が悪くなり、０．０００９モル
を超えると比抵抗は再び高くなって、回路設計が容易で
なくなる。さらに、副成分のＳｉＯ2が０．００５モル
未満では、ＢａＴｉＯ3半導体磁器組成物の焼結性がよ
くなく比抵抗が顕著に高くなり、０．０３モルを超える
と比抵抗は再び高くなり実用的でなくなる。Sample Nos. 16 to 26 are out of the range of the present invention, and 0.0017 to 0.0031 mol of Y 2 O 3 as a minor component to 1 mol of BaTiO 3 as a main component and MnCO 3.
0.003 to 0.0011 mol of 3 and 0.0003 to 0.035 mol of SiO 2 are added,
The breakdown voltage is as high as 30 to 45 V / mm, and the specific resistance is 30.
It is remarkably high at 5 to 90.8 Ωcm. When the specific resistance becomes higher than about 30 Ωcm, the circuit resistance becomes high when it is connected to the protection circuit of the electronic circuit as the PTC thermistor, so that the circuit design becomes difficult such as the necessity of increasing the circuit voltage. If the amount of the auxiliary component Y 2 O 3 is less than 0.0018 mol per 1 mol of the main component BaTiO 3 , the BaT
The sinterability of the io 3 semiconductor porcelain composition is not good and the specific resistance becomes high. When it exceeds 0.0027 mol, the specific resistance becomes high again and it becomes impractical. Further, when MnCO 3 as the accessory component is less than 0.0005 mol, the specific resistance is high and the rising characteristics of the PTC thermistor are poor, and when it exceeds 0.0009 mol, the specific resistance becomes high again and the circuit design becomes difficult. . Further, when the auxiliary component SiO 2 is less than 0.005 mol, the BaTiO 3 semiconductor porcelain composition does not have good sinterability, and the specific resistance is remarkably increased. It becomes untargetable.
【００２５】したがって本発明のように、副成分Ｙ2Ｏ3
を０．００１８〜０．００２７モル、ＭｎＣＯ3を０．
０００５〜０．０００９モル、ＳｉＯ2を０．００５〜
０．０３モルの範囲で添加すると、比抵抗が１５．９Ω
ｃｍ以下と低くて破壊電圧は２７Ｖ／ｍｍ以上と高いＰ
ＴＣサーミスター用に適したＢａＴｉＯ3半導体磁器が
得られることが分かる。Therefore, as in the present invention, the accessory component Y 2 O 3
Of 0.0018 to 0.0027 mol and MnCO 3 of 0.
0005 to 0.0009 mol, the SiO 2 0.005~
When added in the range of 0.03 mol, the specific resistance is 15.9Ω.
cm and below, breakdown voltage is 27V / mm and above, high P
It can be seen that a BaTiO 3 semiconductor ceramic suitable for a TC thermistor can be obtained.
【００２６】その理由を説明すると、本発明による副成
分のＹ2Ｏ3は、ＢａＴｉＯ3半導体磁器組成物に固溶
し、ＢａＴｉＯ3結晶のＢａの位置にＹ3+が入って伝導
電子を供給するドナーとなるため比抵抗が低くなって半
導体化するからである。また、副成分のＭｎＣＯ3はＢ
ａＴｉＯ3半導体磁器組成物の結晶粒界近傍に局在し、
高抵抗で正の抵抗温度係数を大きくする。さらに、副成
分のＳｉＯ2はＢａＴｉＯ3半導体磁器組成物の結晶の粒
界に析出し、液相焼結を起こして異常結晶粒成長を抑制
し、結晶粒径を均一にするので、破壊電圧を高くするこ
とができるからである。[0026] The reason will be described, Y 2 O 3 minor components according to the invention, BaTiO 3 solid solution in the semiconductor ceramic composition, supplying conduction electrons Y 3+ is entered at the position of Ba of BaTiO 3 crystals This is because it becomes a donor, which reduces the specific resistance and becomes a semiconductor. In addition, MnCO 3 as an accessory component is B
localized near the crystal grain boundaries of the aTiO 3 semiconductor porcelain composition,
High resistance and large positive temperature coefficient of resistance. Further, SiO 2 which is a sub-component is deposited on the grain boundaries of the crystals of the BaTiO 3 semiconductor porcelain composition, causes liquid phase sintering, suppresses abnormal grain growth, and makes the grain size uniform. This is because it can be raised.
【００２７】（実施の形態２）つぎに、ＰＴＣサーミス
ターの構造について図１について説明する。(Embodiment 2) Next, the structure of the PTC thermistor will be described with reference to FIG.
【００２８】図１は本発明の一実施の形態による表面実
装型のＰＴＣサーミスターの断面図で、１は大きさが２
ｍｍ角で厚みが約０．５ｍｍの角板状のＢａＴｉＯ3半
導体磁器組成物からなる基板、２、３は基板１の対向し
た面にそれぞれ設けたオーム性のニッケル電極で厚みが
約５ミクロンである。この形状のＰＴＣサーミスターは
電子回路基板上の電子回路に半田付け等によって直接接
続され電子回路を保護する保護回路を形成する。この保
護回路は電子回路の消費電力が増えてＰＴＣサーミスタ
ーの温度上昇が高まると、抵抗が高くなり電力消費を抑
制させ電子回路を保護する作用をする。必要に応じて電
極２、３にリード線を接続し、そのリード線を電子回路
基板上の電子回路に接続することもできる。このＰＴＣ
サーミスターは放熱性がよく、電流制御の応答性に優れ
ている。FIG. 1 is a sectional view of a surface mount type PTC thermistor according to an embodiment of the present invention, in which 1 is a size of 2.
Substrates 2, 3 made of BaTiO 3 semiconductor porcelain composition in the form of a square plate with a square of 0.5 mm and a thickness of about 0.5 mm are ohmic nickel electrodes provided on the opposite surfaces of the substrate 1, respectively, and have a thickness of about 5 μm. is there. The PTC thermistor of this shape is directly connected to an electronic circuit on an electronic circuit board by soldering or the like to form a protection circuit for protecting the electronic circuit. When the power consumption of the electronic circuit increases and the temperature rise of the PTC thermistor increases, this protection circuit increases resistance and suppresses power consumption to protect the electronic circuit. If necessary, lead wires may be connected to the electrodes 2 and 3, and the lead wires may be connected to an electronic circuit on the electronic circuit board. This PTC
The thermistor has good heat dissipation and excellent current control response.
【００２９】ここで基板１の厚みは０．０４ｍｍ〜２．
５ｍｍの範囲にあるのがよい。０．０４ｍｍ未満では基
板強度が低く取り扱いが困難であるし、２．５ｍｍ以上
ではＰＴＣサーミスターとして抵抗値が大きくなって実
用的でない。The substrate 1 has a thickness of 0.04 mm to 2.
It should be in the range of 5 mm. If it is less than 0.04 mm, the substrate strength is low and handling is difficult, and if it is 2.5 mm or more, the PTC thermistor has a large resistance value and is not practical.
【００３０】（実施の形態３）図２は本発明のもう一つ
の実施の形態による樹脂による部分被覆型のＰＴＣサー
ミスターの断面図である。図１と同じ符号については基
本的に同じ働きをするのでここでは説明を省略する。１
０は被覆材で、熱硬化性のプラスチックでシリコン系や
エポキシ系等からなる。この形状のＰＴＣサーミスター
は電子回路との接続部を除いて被覆材１０で被覆されて
おり、被覆厚みは０．５ｍｍ程度以下が適当である。こ
の接続部は被覆材１０で被覆されないで露出しており、
基板の放熱をよくしている。この形状のＰＴＣサーミス
ターは電子回路基板上の電子回路に半田付け等によって
直接接続され電子回路を保護する保護回路を形成する。
また、必要に応じてニッケル電極２、３にリード線を接
続し、そのリード線を電子回路基板上の電子回路に接続
することもできる。このＰＴＣサーミスターは絶縁性
や、耐湿性等の耐候性にも優れ、放熱性もよい。(Embodiment 3) FIG. 2 is a sectional view of a PTC thermistor partially covered with a resin according to another embodiment of the present invention. Since the same reference numerals as those in FIG. 1 basically have the same functions, the description thereof will be omitted here. 1
Reference numeral 0 denotes a coating material, which is a thermosetting plastic and is made of a silicone type or an epoxy type. The PTC thermistor of this shape is covered with the coating material 10 except for the connection portion with the electronic circuit, and the coating thickness is suitably about 0.5 mm or less. This connecting portion is exposed without being covered with the covering material 10,
Good heat dissipation from the board. The PTC thermistor of this shape is directly connected to an electronic circuit on an electronic circuit board by soldering or the like to form a protection circuit for protecting the electronic circuit.
If necessary, lead wires may be connected to the nickel electrodes 2 and 3, and the lead wires may be connected to an electronic circuit on the electronic circuit board. This PTC thermistor has excellent insulating properties, weather resistance such as moisture resistance, and good heat dissipation.
【００３１】（実施の形態４）図３は本発明のさらに他
の実施の形態による樹脂による全面被覆型のＰＴＣサー
ミスターの断面図である。図１、図２と同じ符号につい
ては基本的に同じ働きをするのでここでは説明を省略す
る。(Embodiment 4) FIG. 3 is a sectional view of a resin-coated PTC thermistor according to still another embodiment of the present invention. Since the same reference numerals as those in FIGS. 1 and 2 basically have the same functions, the description thereof will be omitted here.
【００３２】ここでは基板１は直径が約８ｍｍφで厚み
が約０．３ｍｍの円板状である。４、５は銀電極でオー
ム性のニッケル電極２、３に接合されている。８、９は
リード線６、７を銀電極４、５に接合する半田である。
この銀電極４、５はオーム性のニッケル電極２、３の表
面に直径約６．０ｍｍφのＡｇペーストを塗布し、８０
０〜８５０゜Ｃの温度範囲内で熱処理して形成したもの
である。銀電極４、５はリード線６、７のニッケル電極
２、３への接合強度を高くするもので、使用時にリード
線６、７が外れ、電流制御ができなくなるのを防いで、
信頼性の高いＰＴＣサーミスターを提供することができ
る。リード線６、７は電子回路基板上の電子回路に接続
され電子回路を保護する保護回路を形成する。このＰＴ
Ｃサーミスターは絶縁性や、耐湿性等の耐候性にさらに
優れ、信頼性も高い。Here, the substrate 1 is a disk having a diameter of about 8 mmφ and a thickness of about 0.3 mm. Silver electrodes 4 and 5 are bonded to the ohmic nickel electrodes 2 and 3. Reference numerals 8 and 9 are solders for joining the lead wires 6 and 7 to the silver electrodes 4 and 5.
The silver electrodes 4 and 5 are obtained by applying an Ag paste having a diameter of about 6.0 mmφ to the surfaces of the ohmic nickel electrodes 2 and 3, and
It is formed by heat treatment within a temperature range of 0 to 850 ° C. The silver electrodes 4 and 5 increase the bonding strength of the lead wires 6 and 7 to the nickel electrodes 2 and 3, and prevent the lead wires 6 and 7 from coming off during use and being unable to control the current.
It is possible to provide a highly reliable PTC thermistor. The lead wires 6 and 7 are connected to an electronic circuit on the electronic circuit board to form a protection circuit for protecting the electronic circuit. This PT
The C thermistor has further excellent insulation and weather resistance such as moisture resistance, and high reliability.
【００３３】[0033]
【実施例】次に、本発明の具体例を説明する。Next, specific examples of the present invention will be described.
【００３４】（実施例１）試料番号１の半導体セラミッ
ク組成物は、主成分のＢａＴｉＯ3１モルに副成分とし
てＹ2Ｏ3を０．００２２モル、ＭｎＣＯ3を０．０００
７モルおよびＳｉＯ2を０．０２モル添加したもので、
比抵抗は１５．４Ωｃｍと低いが、破壊電圧は３１Ｖ／
ｍｍと高い。The semiconductor ceramic composition of (Example 1) Sample No. 1, 0.0022 mole Y 2 O 3 as a subcomponent to BaTiO 3 1 mol of the main component, the MnCO 3 0.000
7 mol and 0.02 mol of SiO 2 are added,
The specific resistance is as low as 15.4 Ωcm, but the breakdown voltage is 31 V /
mm and high.
【００３５】（実施例２）試料番号２の半導体セラミッ
ク組成物は、試料番号１と主成分の量と副成分のＭｎＣ
Ｏ3およびＳｉＯ2の添加量を同じにして、Ｙ2Ｏ3のみを
０．００２０モルと少なくしたもので、比抵抗は８．７
Ωｃｍとさらに低くなっているが破壊電圧は２８Ｖ／ｍ
ｍと高い。(Example 2) The semiconductor ceramic composition of Sample No. 2 was the same as Sample No. 1 except for the amount of the main component and MnC as the accessory component.
O 3 and the amount of SiO 2 in the same, which was only Y 2 O 3 reduced 0.0020 mol, the specific resistance 8.7
Ωcm is lower, but the breakdown voltage is 28V / m
m and high.
【００３６】（実施例３）試料番号３の半導体セラミッ
ク組成物は、試料番号１と主成分の量と副成分のＭｎＣ
Ｏ3およびＳｉＯ2の添加量を同じにして、Ｙ2Ｏ3のみを
０．００１８モルとさらに少なくしたもので、比抵抗は
１１．２Ωｃｍとやや高くなって、破壊電圧は３０Ｖ／
ｍｍとさらに高くなる。(Example 3) The semiconductor ceramic composition of Sample No. 3 had the same composition as Sample No. 1, the amount of the main component, and MnC as the sub-component.
O 3 and the amount of SiO 2 in the same, which was further reduced with 0.0018 mole only Y 2 O 3, specific resistance is slightly high as 11.2Omucm, breakdown voltage 30 V /
It will be as high as mm.
【００３７】（実施例４）試料番号４の半導体セラミッ
ク組成物は、試料番号１と主成分の量と副成分のＭｎＣ
Ｏ3およびＳｉＯ2の添加量を同じにして、Ｙ2Ｏ3のみを
０．００２４モルと多くしたもので、比抵抗は１５．９
Ωｃｍとさらに高くなって、破壊電圧も３５Ｖ／ｍｍと
いっそう高くなる。(Example 4) The semiconductor ceramic composition of Sample No. 4 had the same composition as Sample No. 1, the amount of the main component and MnC as the accessory component.
O 3 and the amount of SiO 2 in the same, which was only Y 2 O 3 was large as 0.0024 moles, the specific resistance 15.9
It becomes even higher at Ωcm, and the breakdown voltage becomes even higher at 35 V / mm.
【００３８】（実施例５）試料番号５の半導体セラミッ
ク組成物は、試料番号１と主成分の量と副成分のＭｎＣ
Ｏ3およびＳｉＯ2の添加量を同じにして、Ｙ2Ｏ3のみを
０．００２７モルとさらに多くしたもので、比抵抗は
９．６Ωｃｍと低くなって、破壊電圧は２７Ｖ／ｍｍと
やや低くなるが、充分実用化の範囲である。(Example 5) The semiconductor ceramic composition of Sample No. 5 was the same as Sample No. 1 except that the amount of the main component and MnC as the minor component were small.
By adding the same amount of O 3 and SiO 2 and further increasing only Y 2 O 3 to 0.0027 mol, the specific resistance was lowered to 9.6 Ωcm and the breakdown voltage was slightly low to 27 V / mm. However, it is within the range of practical application.
【００３９】（実施例６）試料番号６の半導体セラミッ
ク組成物は、主成分のＢａＴｉＯ3１モルに副成分とし
てＹ2Ｏ3を０．２２モル、ＭｎＣＯ3を０．０００５モ
ルおよびＳｉＯ2を０．０１モル添加したもので、比抵
抗は１２．６Ωｃｍであるが、破壊電圧は３５Ｖ／ｍｍ
と充分高い。[0039] (Example 6) semiconductor ceramic compositions of Sample No. 6, Y 2 O 3 and 0.22 mol as a secondary component in BaTiO 3 1 mol of the main component, the MnCO 3 0.0005 mol and SiO 2 With 0.01 mol added, the specific resistance is 12.6 Ωcm, but the breakdown voltage is 35 V / mm.
And high enough.
【００４０】（実施例７）試料番号７の半導体セラミッ
ク組成物は、試料番号６と主成分の量と副成分のＹ2Ｏ3
およびＳｉＯ2の添加量を同じにして、ＭｎＣＯ3のみを
０．０００６モルとしたもので、比抵抗は１０．４Ωｃ
ｍと低くなるが、破壊電圧は３１Ｖ／ｍｍと高くなる。(Example 7) The semiconductor ceramic composition of Sample No. 7 was the same as Sample No. 6, the amount of the main component and Y 2 O 3 as the accessory component.
And the addition amount of SiO 2 is the same, only MnCO 3 is 0.0006 mol, and the specific resistance is 10.4 Ωc.
Although it is as low as m, the breakdown voltage is as high as 31 V / mm.
【００４１】（実施例８）試料番号８の半導体セラミッ
ク組成物は、試料番号６と主成分の量と副成分のＹ2Ｏ3
およびＳｉＯ2の添加量を同じにして、ＭｎＣＯ3のみを
０．０００８モルとしたもので、比抵抗は７．９Ωｃｍ
とかなり低くなるが、破壊電圧は２９Ｖ／ｍｍと充分高
い。(Example 8) The semiconductor ceramic composition of Sample No. 8 was the same as Sample No. 6, the amount of the main component and Y 2 O 3 as the accessory component.
And the amount of SiO 2 added was the same, and MnCO 3 alone was 0.0008 mol, and the specific resistance was 7.9 Ωcm.
However, the breakdown voltage is sufficiently high at 29 V / mm.
【００４２】（実施例９）試料番号９の半導体セラミッ
ク組成物は、試料番号６と主成分の量と副成分のＹ2Ｏ3
およびＳｉＯ2の添加量を同じにして、ＭｎＣＯ3のみを
０．０００９モルとしたもので、比抵抗は６．３Ωｃｍ
とさらに低くなるが、破壊電圧は３３Ｖ／ｍｍと充分高
い。(Example 9) The semiconductor ceramic composition of Sample No. 9 was the same as Sample No. 6, the amount of the main component and Y 2 O 3 as the accessory component.
And the addition amount of SiO 2 is the same, only MnCO 3 is 0.0009 mol, and the specific resistance is 6.3 Ωcm.
However, the breakdown voltage is sufficiently high at 33 V / mm.
【００４３】（実施例１０）試料番号１０の半導体セラ
ミック組成物は、主成分のＢａＴｉＯ3１モルに副成分
としてＹ2Ｏ3を０．００２２モル、ＭｎＣＯ3 を０．０
００７モルおよびＳｉＯ2を０．００５モル添加したも
ので、比抵抗は５．５Ωｃｍと低いが、破壊電圧は３０
Ｖ／ｍｍと充分高い。Example 10 In the semiconductor ceramic composition of Sample No. 10, 1 mol of BaTiO 3 as a main component, 0.0022 mol of Y 2 O 3 as a minor component, and 0.02 MnCO 3 as secondary components.
007 mol and 0.005 mol of SiO 2 were added, the specific resistance was as low as 5.5 Ωcm, but the breakdown voltage was 30.
V / mm is high enough.
【００４４】（実施例１１）試料番号１１の半導体セラ
ミック組成物は、試料番号１０と主成分の量と副成分の
Ｙ2Ｏ3およびＭｎＣＯ3の添加量を同じにして、ＳｉＯ2
のみを０．０１モルとしたもので、比抵抗は６．６Ωｃ
ｍと低くなるが、破壊電圧は３２Ｖ／ｍｍかなり高い。The semiconductor ceramic composition of (Example 11) Sample No. 11, in the same amount of Y 2 O 3 and MnCO 3 amounts subcomponent of the sample No. 10 and the main component, SiO 2
With only 0.01 mol, the specific resistance is 6.6 Ωc
Although it is as low as m, the breakdown voltage is considerably higher than 32 V / mm.
【００４５】（実施例１２）試料番号１２の半導体セラ
ミック組成物は、試料番号１０と主成分の量と副成分の
Ｙ2Ｏ3およびＭｎＣＯ3の添加量を同じにして、ＳｉＯ2
のみを０．０１５モルとしたもので、比抵抗は８．２Ω
ｃｍと低く、破壊電圧は３８Ｖ／ｍｍとさらに高くな
る。The semiconductor ceramic composition of (Example 12) Sample No. 12, in the same amount of Y 2 O 3 and MnCO 3 amounts subcomponent of the sample No. 10 and the main component, SiO 2
Only 0.015 mol, the specific resistance is 8.2Ω
cm, and the breakdown voltage is as high as 38 V / mm.
【００４６】（実施例１３）試料番号１３の半導体セラ
ミック組成物は、試料番号１０と主成分の量と副成分の
Ｙ2Ｏ3およびＭｎＣＯ3の添加量を同じにして、ＳｉＯ2
のみを０．０２モルとしたもので、比抵抗は７．５Ωｃ
ｍと低く、破壊電圧は３７Ｖ／ｍｍと充分に高くなる。The semiconductor ceramic composition of (Example 13) Sample No. 13, in the same amount of Y 2 O 3 and MnCO 3 amounts subcomponent of the sample No. 10 and the main component, SiO 2
Only 0.02 mol, the specific resistance is 7.5 Ωc
m, which is low, and the breakdown voltage is sufficiently high, 37 V / mm.
【００４７】（実施例１４）試料番号１４の半導体セラ
ミック組成物は、試料番号１０と主成分の量と副成分の
Ｙ2Ｏ3およびＭｎＣＯ3の添加量を同じにして、ＳｉＯ2
のみを０．０２５モルとしたもので、比抵抗は１２．７
Ωｃｍとやや高くなり、破壊電圧は３６Ｖ／ｍｍと充分
に高くなる。[0047] (Example 14) semiconductor ceramic compositions of Sample No. 14, in the same amount of Y 2 O 3 and MnCO 3 amounts subcomponent of the sample No. 10 and the main component, SiO 2
With only 0.025 mol, the specific resistance is 12.7.
Ωcm, which is slightly high, and the breakdown voltage, which is 36V / mm, is sufficiently high.
【００４８】（実施例１５）試料番号１５の半導体セラ
ミック組成物は、試料番号１０と主成分の量と副成分の
Ｙ2Ｏ3およびＭｎＣＯ3の添加量を同じにして、ＳｉＯ2
のみを０．０３モルとしたもので、比抵抗は１５．８Ω
ｃｍと高くなるが、破壊電圧も３５Ｖ／ｍｍと充分に高
い。The semiconductor ceramic composition of (Example 15) Sample No. 15, in the same amount of Y 2 O 3 and MnCO 3 amounts subcomponent of the sample No. 10 and the main component, SiO 2
Only 0.03 mol, the specific resistance is 15.8Ω
However, the breakdown voltage is sufficiently high at 35 V / mm.
【００４９】[0049]
【発明の効果】以上から明らかなように本発明によれ
ば、ＢａＴｉＯ3の一般式で表されるチタン酸バリウム
１モルに、副成分としてＹをＹ2Ｏ3に換算して０．００
１８〜０．００２７モル、ＭｎがＭｎＣＯ3に換算して
０．０００５〜０．０００９モル、ＳｉがＳｉＯ2に換
算して０．００５〜０．０３モル含有されているから、
比抵抗が小さく、破壊電圧が高く、ＰＴＣサーミスター
に最適の半導体セラミック組成物を通常のセラミックの
製法によって容易に得ることができるという効果を有す
る。As is apparent from the above, according to the present invention, 1 mol of barium titanate represented by the general formula of BaTiO 3 is added to Y 2 O 3 when Y is converted to Y 2 O 3 as an auxiliary component, and the amount is 0.002.
18 to 0.0027 mol, Mn is 0.0005 to 0.0009 mol in terms of MnCO 3 , and Si is 0.005 to 0.03 mol in terms of SiO 2 .
It has an effect that the specific resistance is small, the breakdown voltage is high, and the semiconductor ceramic composition most suitable for the PTC thermistor can be easily obtained by a usual ceramic manufacturing method.
【００５０】また、半導体セラミック組成物からなる基
板の対向した面にそれぞれ設けられた電極を備えたＰＴ
Ｃサーミスターであるから、小型で面実装に適し、放熱
性がよく、電流制御の応答性に優れ、回路設計が容易に
なるという効果を有する。PTs provided with electrodes provided on opposite surfaces of a substrate made of a semiconductor ceramic composition, respectively.
Since it is a C thermistor, it is small and suitable for surface mounting, has good heat dissipation, has excellent current control responsiveness, and has the effect of facilitating circuit design.
【００５１】さらに、基板の厚みが０．０４〜２．５ｍ
ｍからなるＰＴＣサーミスターであるから、比抵抗が小
さく、基板強度の強く、絶縁性や耐湿性等の耐候性に優
れ、信頼性も高いという効果を有する。Further, the thickness of the substrate is 0.04 to 2.5 m.
Since it is a PTC thermistor made of m, it has effects of low specific resistance, strong substrate strength, excellent weather resistance such as insulation and moisture resistance, and high reliability.
【図１】本発明の一実施の形態による表面実装型のＰＴ
Ｃサーミスターの断面図FIG. 1 is a surface mount type PT according to an embodiment of the present invention.
Cross section of C thermistor
【図２】本発明のもう一つの実施の形態による樹脂によ
る部分被覆型のＰＴＣサーミスターの断面図FIG. 2 is a sectional view of a PTC thermistor partially coated with resin according to another embodiment of the present invention.
【図３】本発明のさらに他の実施の形態による樹脂によ
る全面被覆型のＰＴＣサーミスターの断面図FIG. 3 is a sectional view of a resin-coated PTC thermistor according to still another embodiment of the present invention.
１ 基板 ２、３ ニッケル電極 ４、５ 銀電極 ６、７ リード線 ８、９ 半田 １０ 被覆材 1 substrate 2, 3 nickel electrode 4, 5 silver electrode 6, 7 lead wire 8, 9 solder 10 coating material
Claims (3)
バリウム１モルに、副成分としてＹをＹ2Ｏ3に換算して
０．００１８〜０．００２７モル、ＭｎがＭｎＣＯ3に
換算して０．０００５〜０．０００９モル、ＳｉがＳｉ
Ｏ2に換算して０．００５〜０．０３モル含有されてい
ることを特徴とする半導体セラミック組成物。1. To 1 mol of barium titanate represented by the general formula of BaTiO 3 , 0.0018 to 0.0027 mol of Y as Y 2 O 3 as a subcomponent and Mn converted to MnCO 3. 0.0005 to 0.0009 mol, Si is Si
A semiconductor ceramic composition containing 0.005 to 0.03 mol in terms of O 2 .
の対向した面にそれぞれ設けられた電極を備えているこ
とを特徴とするＰＴＣサーミスター。2. A PTC thermistor, comprising electrodes provided on opposite surfaces of a substrate made of the semiconductor ceramic composition.
あることを特徴とする請求項２記載のＰＴＣサーミスタ
ー。3. The PTC thermistor according to claim 2, wherein the substrate has a thickness of 0.04 to 2.5 mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7265189A JPH09110521A (en) | 1995-10-13 | 1995-10-13 | Semiconductor ceramic composition and ptc thermistor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7265189A JPH09110521A (en) | 1995-10-13 | 1995-10-13 | Semiconductor ceramic composition and ptc thermistor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09110521A true JPH09110521A (en) | 1997-04-28 |
Family
ID=17413801
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7265189A Pending JPH09110521A (en) | 1995-10-13 | 1995-10-13 | Semiconductor ceramic composition and ptc thermistor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09110521A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100431442B1 (en) * | 2002-01-17 | 2004-05-14 | 주식회사 광원 | Water proof thermister for automobile applications |
| JP2020024663A (en) * | 2018-08-06 | 2020-02-13 | 深セン明創自控技術有限公司 | New type housing environment measurement device |
-
1995
- 1995-10-13 JP JP7265189A patent/JPH09110521A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100431442B1 (en) * | 2002-01-17 | 2004-05-14 | 주식회사 광원 | Water proof thermister for automobile applications |
| JP2020024663A (en) * | 2018-08-06 | 2020-02-13 | 深セン明創自控技術有限公司 | New type housing environment measurement device |
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