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KR900005267B1 - Process for the production of ptc thermistors - Google Patents

Process for the production of ptc thermistors Download PDF

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KR900005267B1
KR900005267B1 KR1019840002770A KR840002770A KR900005267B1 KR 900005267 B1 KR900005267 B1 KR 900005267B1 KR 1019840002770 A KR1019840002770 A KR 1019840002770A KR 840002770 A KR840002770 A KR 840002770A KR 900005267 B1 KR900005267 B1 KR 900005267B1
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KR850000811A (en
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게이이찌 미네기시
도꾸지 아끼바
다다오 가또오
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지찌부 세멘트 가부시끼가이샤
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01CRESISTORS
    • H01C7/00Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/02Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01CRESISTORS
    • H01C17/00Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/02Apparatus or processes specially adapted for manufacturing resistors adapted for manufacturing resistors with envelope or housing
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01CRESISTORS
    • H01C1/00Details
    • H01C1/02Housing; Enclosing; Embedding; Filling the housing or enclosure
    • H01C1/024Housing; Enclosing; Embedding; Filling the housing or enclosure the housing or enclosure being hermetically sealed
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01CRESISTORS
    • H01C7/00Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/02Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient
    • H01C7/022Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient mainly consisting of non-metallic substances
    • H01C7/023Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient mainly consisting of non-metallic substances containing oxides or oxidic compounds, e.g. ferrites
    • H01C7/025Perovskites, e.g. titanates

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Abstract

내용 없음.No content.

Description

PTC 더어미스터의 제조법Recipe of PTC Thermistor

제1도는 본 발명에 따른 제조 공정의 단계중 한 실시예를 보여주는 사시도.1 is a perspective view showing one embodiment of the steps of the manufacturing process according to the invention.

제2도 내지 제4도는 다른 조건하에서 준비된 제품의 온도 비저항 특성을 보여주는 특성도.2 to 4 are characteristic diagrams showing the temperature resistivity characteristics of a product prepared under different conditions.

본 발명은 PTC 더어미스터의 제조법에 관한 것이다. 종래 기술에 공지된 바와같이, 온도만을 감지하는데 목적이 있는 더어미스터는 습도나 기체같은 다른 요소에 의하여 영향을 미치는 것을 방지하기 위하여 유리나 수지로 봉입된다.The present invention relates to a method for producing a PTC thermistor. As is known in the art, the demisters, which are intended only for sensing temperature, are encapsulated in glass or resin to prevent them from being affected by other factors such as humidity or gas.

특히 NTC(negative temperature coefficient) 더어미스터에서는, 수지 봉입형의 디스크형 더어미스터 이외에도 값싸고 양상선이 풍부한 특성이 안정된 유리-봉입형 더어미스트가 실용화되어 있다.In particular, in the negative temperature coefficient (NTC) thermistor, in addition to the resin-enclosed disk type thermistor, a glass-encapsulated type thermist having a stable and inexpensive line-rich characteristic has been put to practical use.

그러나, PTC 더어미스터에서는, 수지 봉입형의 디스크형 PTC 더어미스터 또는 금속이 전극에 기계적으로 압압한 PTC 더어미스터 등이 이용될 뿐이다. 이 이유는 더어미스터 소자가 유리로 봉입될 때 온도 및 분위기에 의하여 크게 영향을 받는 PTC 더어미스터의 특성 때문이다.However, in the PTC thermistor, only a resin encapsulated disk-type PTC thermistor or a PTC thermistor in which a metal is mechanically pressed against an electrode is used. This is because of the properties of the PTC thermistor which is greatly affected by temperature and atmosphere when the thermistor element is encapsulated in glass.

종래 NTC 더어미스터는 진공이나 N2, 또 Ar 가스 분위기에서 유리 봉입하여 듀메트 선 또는 히터가 산화되는 것을 방지한다.Conventional NTC thermistors are glass encapsulated in a vacuum, N 2 , or Ar gas atmosphere to prevent oxidation of the dumet wire or heater.

본 발명자들에 의하여 이루어진 연구 결과로, PTC 더어미스터에 환원 분위기내에서 봉입하는 이러한 유리의 응용은 그 성질을 상당한 정도까지 저하시키게 되는 것이 드러난다. 이러한 조건하에서, 유리 봉입온도는 650℃ 만큼 높이 도달하여, 이러한 온도에서 PTC 더어미스터의 특성은 상당히 저하된다는 것을 알게 되었다.As a result of the research made by the inventors, the application of such glass encapsulated in a PTC thermistor in a reducing atmosphere is found to degrade its properties to a considerable extent. Under these conditions, it has been found that the glass encapsulation temperature reaches as high as 650 ° C., at which temperature the properties of the PTC demister are significantly degraded.

미합중국 특허 제3,377,561호는 공기중에서 유리를 사용하여 정의 온도 계수 반도체 자기물질을 봉입하는 단계로 구성되는 PTC 더어미스터의 제조법이 기술되어 있다. 상기 식견에 따라서, 본 발명의 주목적은 저항 변화가 충분히 크고, 특히 스위칭 온도에서 있어서 현저한 저항 변화를 하여 안정된 특성을 가진 값싼 유리 봉입형 PTC 더어미스터를 제공하는 것이다.U.S. Patent No. 3,377,561 describes a method for manufacturing a PTC demister which consists of encapsulating a positive temperature coefficient semiconductor magnetic material using glass in air. According to the above findings, the main object of the present invention is to provide an inexpensive glass encapsulated PTC thermistor which has a sufficiently large resistance change and particularly a significant resistance change at the switching temperature to have stable characteristics.

본 발명에 따라, 공기, 산소 또는 공기가 0% 이상 내지 100% 이하의 용량을 포함하는 공기/산소 혼합 분위기중에서 560℃ 이하의 연화점을 가지는 저융점 유리를 사용하여 정의 온도계수 반도체 자기물질을 봉입하여 PTC 더어미스터의 제조법이 제공된다.According to the present invention, a positive temperature coefficient semiconductor magnetic material is encapsulated using low melting glass having a softening point of 560 ° C. or lower in an air / oxygen mixed atmosphere containing air, oxygen or air containing a capacity of 0% to 100%. There is provided a method of manufacturing a PTC thermistor.

본 발명에서 이용된 정의 온도 계수를 가지는 반도체 자기물질에 따라서, 바륨 티탄 기본 성분에 3가 안티몬, 3가 비스무트, 5가 탄탈륨, 5가 니오브 또는 희토류 금속중 어느 하나를 첨가함으로써 얻어진 것이 언급되어 있다.According to the semiconductor magnetic material having a positive temperature coefficient used in the present invention, it is mentioned that it is obtained by adding any one of trivalent antimony, trivalent bismuth, pentavalent tantalum, pentavalent niobium or rare earth metal to the barium titanium base component. .

이용된 유리는 450℃ 내지 560℃까지의 포괄적인 연화점을 가지며, B2O3-PbO-ZnO, B2O3-PbO-SiO2, B2O3-PbO-TiO2, B2O3-PbO-SiO2-Al2O3-ZnO, B2O3-PbO-V2O5, SiO2-PbO-K2O, SiO2-PbO-Na2O 및 SiO2-PbO-K2O-Na2O로 구성된 유리를 포함한다.The glass used has a comprehensive softening point from 450 ° C. to 560 ° C., B 2 O 3 -PbO-ZnO, B 2 O 3 -PbO-SiO 2 , B 2 O 3 -PbO-TiO 2 , B 2 O 3 -PbO-SiO 2 -Al 2 O 3 -ZnO, B 2 O 3 -PbO-V 2 O 5 , SiO 2 -PbO-K 2 O, SiO 2 -PbO-Na 2 O and SiO 2 -PbO-K 2 And glass composed of O-Na 2 O.

SiO2-PbO-K2O 베이스 유리가 우선하여 주어지는데, 이 유리는 리드선(듀메트선, 즉 Cu로 도금된 Fe-Ni 합금선)에 대하여 바람직한 열 팽창 및 신축성을 보이기 때문이다. 450℃이하의 연화점을 가지는 유리가 이용될 때, 결정 유리-봉입형 PTC 더어미스터가 사용되는 온도에 어떠한 제한이 부과된다.The SiO 2 -PbO-K 2 O base glass is given preferentially because it exhibits desirable thermal expansion and stretchability with respect to lead wire (dumet wire, ie, Fe-Ni alloy wire plated with Cu). When glass having a softening point of 450 ° C. or less is used, certain limitations are imposed on the temperature at which the crystalline glass-encapsulated PTC thermistor is used.

제1도에 따라서, 반도체 바륨 티탄늄 자기 물질(1)은 최종 더어미스터 소자가 봉입되어야 하는 유리관(4)의 길이를 고려하여 적절한 두께로 슬라이스된다. 은 전극(2 및 2)은 얻은 소자의 양쪽에 인가되어, 600%에서 20분동안 놓여 있게 된다.According to FIG. 1, the semiconductor barium titanium titanium magnetic material 1 is sliced to an appropriate thickness in consideration of the length of the glass tube 4 in which the final demister element should be enclosed. Silver electrodes 2 and 2 are applied to both sides of the obtained device, and are placed at 600% for 20 minutes.

제1a도는 구비된 전극 소자의 단면을 보여준다. 제1(b)도에서 보는 바와같이, 소자는 유리관(4)의 직경에 대응하는 임의의 길이로 절단된다. 소자는 560℃이하의 연화점을 가지는 유리의 관(4)내에 위치되어 듀메트선(3 및 3)이 삽입되는 양끝 속으로 봉입된다.Figure 1a shows a cross section of the electrode element provided. As shown in Fig. 1 (b), the element is cut into an arbitrary length corresponding to the diameter of the glass tube 4. The device is placed in a tube 4 of glass with a softening point below 560 ° C. and enclosed into both ends into which the dumet lines 3 and 3 are inserted.

마지막으로, 유리관(4)은 탄소 히터 지그(heater jig)의 수단으로 봉입된다. 봉입온도는 이용된 유리의 연화점에 따라서 결정되며, 50℃이상에서 이용된 유리의 연화점보다 일반적으로 높다. 종래 기술 NTC 유리 봉입 더어미스터에 있어서, 560℃를 초과하는 연화점을 가지는 유리가 이용되어 봉입은 610℃을 초과하는 온도에서 실행된다.Finally, the glass tube 4 is sealed by means of a carbon heater jig. The encapsulation temperature depends on the softening point of the glass used and is generally higher than the softening point of the glass used above 50 ° C. In the prior art NTC glass encapsulated thermistors, glass having a softening point above 560 ° C. is used so that the encapsulation is carried out at a temperature above 610 ° C.

PTC 더어미스터의 봉입이 이러한 조건아래서 실행된다면, 결과 PTC 더어미스터의 특성의 현저한 저하가 생긴다. 그러나 그 특성이 560℃이하의 연화점을 가지는 저융점 유리로 더어미스터 소자를 봉입함으로써 열화가 적고 안정한 PTC 더어미스터를 얻는 것이 가능하다.If the sealing of the PTC thermistor is carried out under these conditions, a significant deterioration of the properties of the resulting PTC thermistor occurs. However, it is possible to obtain stable PTC thermistor with little deterioration by encapsulating the thermistor element with low melting glass having a softening point of 560 ° C. or less.

제2도는 120℃의 큐리 온도를 가지는 PTC 더어미스터 소자가 기술적으로 유리로 봉입되는 실험 동작의 결과를 보여준다. 결과 특성이 초기 특성보다 약간 저하될지라도, 536℃ 또는 560℃의 연화점을 가지는 유리로 봉입된 PTC 더어미스터 소자는 우수한 특성을 나타내는 것을 알 수 있다. 또한 다른 큐리 점(Curie point)을 가지는 PTC 더어미스터 소자로 유사한 결과를 얻는 것을 발견하였다. 제2도의 결과는 표 1에 수치적으로 주어진다.2 shows the results of an experimental operation in which PTC thermistor elements with a Curie temperature of 120 ° C. are technically encapsulated in glass. Although the resulting characteristic is slightly lower than the initial characteristic, it can be seen that the PTC demister element encapsulated with glass having a softening point of 536 ° C or 560 ° C exhibits excellent properties. It was also found that similar results were obtained with PTC thermistor devices with different Curie points. The results of FIG. 2 are given numerically in Table 1.

제3도는 다양한 분위기에서 유리로 봉입된 PTC 더어미스터의 특성도이다. 이용된 PTC 더어미스터는 120℃의 큐리점을 가졌으며, 봉입은 610℃에서 실행되었다. 공기 또는 산소 기체 중에서 봉입하면 진공 또는 불활성 또는 환원 가스 분위기에서 취급된 것과 비교하면 더 좋은 PTC 더어미스터를 양산할 수 있다.3 is a characteristic diagram of PTC thermistors encapsulated in glass in various atmospheres. The PTC thermistors used had a Curie point of 120 ° C. and encapsulation was carried out at 610 ° C. Encapsulation in air or oxygen gas yields better PTC thermistors compared to those handled in a vacuum or inert or reducing gas atmosphere.

제3도의 결과는 표 2에 수치적으로 주어진다. 공기/산소 혼합 분위기 중에서 혹은 다른 큐리점을 가지는 PTC 더어미스터 소자를 가지고 유사한 결과를 얻을 수 있음을 알 수 있다.The results of FIG. 3 are given numerically in Table 2. It can be seen that similar results can be obtained in an air / oxygen mixed atmosphere or with a PTC demister device having a different Curie point.

제4도는 공기 또는 산소 기체중에서 유리로 120℃의 큐리 온도를 가지는 PTC 더어미스터의 소자를 봉입함으로써 얻는 PTC 더어미스터의 비저항과 온도 사이의 관계를 보여주는 도표이다. 제4도의 결과는 표 3에 수치적으로 주어진다.4 is a chart showing the relationship between the specific resistance and temperature of a PTC thermistor obtained by encapsulating the element of a PTC thermistor having a Curie temperature of 120 ° C. with glass in air or oxygen gas. The results of FIG. 4 are given numerically in Table 3.

이러한 결과로부터, 본 발명에 따른 제조법에 의하여 저항의 큰 변화를 보이며, 봉입 전의 특성에 상당하는 PTC 더어미스터가 얻어진다. 공기/산소 혼합 분위기에서 혹은 다른 큐리 점을 가지는 PTC 더어미스터 소자를 가지고 유사한 결과를 얻을 수 있음을 알 수 있다.From these results, a PTC changer showing a large change in resistance by the manufacturing method according to the present invention and corresponding to the characteristics before sealing is obtained. It can be seen that similar results can be obtained with an air / oxygen mixed atmosphere or with a PTC dermistor device with different Curie points.

탄소 히터 지그 위치에서, 다른 히터 지그, 예를 들면, 금속 히팅 지그는 유리관(4)을 봉입하는 데 이용된다.In the carbon heater jig position, another heater jig, for example a metal heating jig, is used to enclose the glass tube 4.

[표 1]TABLE 1

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[표 2]TABLE 2

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[표 3]TABLE 3

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상기에서 설명한 바와 같이, 본 발명은 우수한 특성을 가지는 PTC 더어미스터를 저렴하게 제조할 수 있으며, 그 산업적 가치도 또한 높은 것이다.As described above, the present invention can inexpensively manufacture a PTC thermistor having excellent characteristics, and its industrial value is also high.

Claims (13)

저융점 유리(4)를 사용하여 공기, 산소 또는 공기가 용량 백분율로 0% 이상 100%이하를 포함하는 공기/산소 혼합 분위기하에서 560℃이하의 연화점을 가지는 정의 온도 계수 반도체 자기물질(1)을 봉입하는 단계로 구성되는 것을 특징으로 하는 PTC 더어미스터의 제조법.A low temperature melting glass 4 is used to define a positive temperature coefficient semiconductor magnetic material 1 having a softening point of 560 ° C. or less in an air / oxygen mixed atmosphere in which air, oxygen or air contains 0% to 100% by volume percentage. The method of manufacturing a PTC thermistor, characterized in that consisting of a step of sealing. 제1항에 있어서, 유리(4)는 450℃ 내지 560℃까지의 포괄적인 연화점을 가지는 것을 특징으로 하는 제조법.2. Process according to claim 1, characterized in that the glass (4) has a comprehensive softening point from 450 ° C to 560 ° C. 제1항 또는 제2항에 있어서, 유리(4)는 양끝에서 봉입된 관 형태인 것을 특징으로 하는 제조법.Method according to claim 1 or 2, characterized in that the glass (4) is in the form of a tube enclosed at both ends. 제3항에 있어서, 리드선(3)은 그 봉입된 관 형태인 것을 특징으로 하는 제조법.4. Process according to claim 3, characterized in that the lead wire (3) is in the form of a sealed tube. 제3항에 있어서, 전극(2)은 유리관(4)에 삽입에 앞서 반도체 물질(1)의 반대편에 인가되는 것을 특징으로 하는 제조법.4. Process according to claim 3, characterized in that the electrode (2) is applied opposite the semiconductor material (1) prior to insertion into the glass tube (4). 제4항에 있어서, 전극(2)은 유리관(4)에 삽입에 앞서 반도체 물질(1)의 반대편에 인가되는 것을 특징으로 하는 제조법.5. Process according to claim 4, characterized in that the electrode (2) is applied opposite the semiconductor material (1) prior to insertion into the glass tube (4). 제1항 또는 제2항 또는 제4항 또는 제5항 또는 제6항에 있어서, 이용된 유리는 B2O3-PbO-ZnO, B2O3-PbO-SiO2, B2O3-PbO-TiO2, B2O3-PbO-SiO2-Al2O3-ZnO, B2O3-PbO-V2O5, SiO2-PbO-K2O, SiO2-PbO-Na2O 또는 SiO2-PbO-K2O-Na2O로 구성되는 것을 특징으로 하는 제조법.The glass used according to claim 1 or 2 or 4 or 5 or 6, B 2 O 3 -PbO-ZnO, B 2 O 3 -PbO-SiO 2 , B 2 O 3- PbO-TiO 2, B 2 O 3 -PbO-SiO 2 -Al 2 O 3 -ZnO, B 2 O 3 -PbO-V 2 O 5, SiO 2 -PbO-K 2 O, SiO 2 -PbO-Na 2 A process characterized by consisting of O or SiO 2 -PbO-K 2 O-Na 2 O. 제3항에 있어서, 이용된 유리는 B2O3-PbO-ZnO, B2O3-PbO-SiO2, B2O3-PbO-TiO2, B2O3-PbO-SiO2-Al2O3-ZnO, B2O3-PbO-V2O5, SiO2-PbO-K2O, SiO2-PbO-Na2O 또는 SiO2-PbO-K2O-Na2O로 구성되는 것을 특징으로 하는 제조법.The glass according to claim 3, wherein the glass used is B 2 O 3 -PbO-ZnO, B 2 O 3 -PbO-SiO 2 , B 2 O 3 -PbO-TiO 2 , B 2 O 3 -PbO-SiO 2 -Al It consists of a 2 O 3 -ZnO, B 2 O 3 -PbO-V 2 O 5, SiO 2 -PbO-K 2 O, SiO 2 -PbO-Na 2 O or SiO 2 -PbO-K 2 O- Na 2 O The manufacturing method characterized by the above-mentioned. 제1항 또는 제2항 또는 제4항 또는 제5항 또는 제6항 또는 제8항에 있어서, 반도체 물질(1)은 바륨 티탄 자기물질인 것을 특징으로 하는 제조법.9. A method according to claim 1 or 2 or 4 or 5 or 6 or 8, characterized in that the semiconductor material (1) is a barium titanium magnetic material. 제3항에 있어서, 반도체 물질(1)은 바륨 티탄 자기물질인 것을 특징으로 하는 제조법.4. A method according to claim 3, wherein the semiconductor material (1) is a barium titanium magnetic material. 제7항에 있어서, 반도체 물질(1)은 바륨 티탄 자기물질인 것을 특징으로 하는 제조법.8. A method according to claim 7, wherein the semiconductor material (1) is a barium titanium magnetic material. 제7항에 있어서, 바륨 티탄 자기물질은 3가 안티몬, 5가 니오브 또는 희토류 금속중 어느 하나가 첨가되는 것을 특징으로 하는 제조법.8. The method of claim 7, wherein the barium titanium magnetic material is added with any one of trivalent antimony, pentavalent niobium, and rare earth metals. 제10항 또는 제11항에 있어서, 바륨 티탄 자기물질은 3가 안티몬, 5가 니오브 또는 희토류 금속중 어느 하나가 첨가되는 것을 특징으로 하는 제조법.The method according to claim 10 or 11, wherein the barium titanium magnetic material is added with any one of trivalent antimony, pentavalent niobium or rare earth metal.
KR1019840002770A 1983-06-11 1984-05-21 Process for the production of ptc thermistors Expired KR900005267B1 (en)

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EP0129997B1 (en) 1988-08-31
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