KR970003343B1 - Dielectric magnetic composite material - Google Patents

Dielectric magnetic composite material Download PDF

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KR970003343B1
KR970003343B1 KR1019880015705A KR880015705A KR970003343B1 KR 970003343 B1 KR970003343 B1 KR 970003343B1 KR 1019880015705 A KR1019880015705 A KR 1019880015705A KR 880015705 A KR880015705 A KR 880015705A KR 970003343 B1 KR970003343 B1 KR 970003343B1
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composition
dielectric
temperature
dielectric magnetic
dielectric constant
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송인엽
안기성
신문철
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삼성전기 주식회사
서주인
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/08—Inorganic dielectrics
    • H01G4/12—Ceramic dielectrics

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Abstract

The dielectric magnetic compound is widely used as a circuit element in communication equipments, color TVs and so on and can be sintered at a low temperature of 1100deg. C or less. The dielectric magnetic compound is formed by adding SiO2, ZnO, B2O3, and Al2O3 to a main component comprised of BaTiO3, TiO2, Nd2O3, Bi2O3, and PbO.

Description

유전체 자기조성물Dielectric Self Composition

제1도는 본 발명의 실시예 3, 8, 12, 14, 17 조성물의 온도에 대한 유전율의 변화율을 나타낸 그래프이다.1 is a graph showing the rate of change of permittivity with respect to the temperature of the composition of Examples 3, 8, 12, 14, 17 of the present invention.

본 발명은 유전율이 크며, 유전손실이 작고 또한 유전율의 온도계수가 작으며, 넓은 온도범위에서 일정한 값을 지니는 온도보상용 유전체 자기조성물에 관한 것으로, 이 온도보상용 자기 유전체 조성물은 통신기기, 칼라 TV 등의 회로소자로서 많이 이용될수 있으며, 1100℃ 미만의 저온에서 소결이 가능하여 적층콘덴서 제조시 내부전극으로서 은-팔라듐 합금을 사용할 수가 있어 원가절감에도 기여할수 있는 세라믹 유전체 조성물이다.The present invention relates to a temperature compensation dielectric magnetic composition having a high dielectric constant, a low dielectric loss, a low temperature coefficient of dielectric constant, and having a constant value over a wide temperature range. It can be widely used as a circuit element, etc., it is possible to sinter at a low temperature of less than 1100 ℃ to use a silver-palladium alloy as an internal electrode when manufacturing a multilayer capacitor is a ceramic dielectric composition that can contribute to cost reduction.

종래의 온도보상용 유전체 자기재료의 조성물은 소성이 1270∼1400℃의 고온에서 행해 졌으며, 적층 세라믹 콘덴서 제조시 세라믹 그린시트 사이에 내부전극을 삽입하여 적층한 후 소성하는 공정이 있는데 세라믹 재료의 소성과 내부전극의 소부가 동시에 행하여지기 때문에 내부전극으로서는 1270∼1400℃의 고온에서 견딜 수 있는 백금(Pt), 금(Au), 팔라듐(Pd) 등의 귀금속을 사용해야만 했다. 따라서 적층 세라믹 콘덴서의 가격은 높아지게 되었다. 또한 최근에는 1150℃ 미만의 저온에서 소성이 가능한 온도보상용 유전체 자기조성물이 보고되었는데 (미국특허, 4,628,404), 이는 기계적 강도가 고온소결 제품의 경우 보다 훨씬 약하기 때문에 장착시 제품이 파손되는 경우가 있게 되고, 또한 이러한 저온 소결된 제품은 고주파 특성중 Q값

Figure kpo00001
이 주파수가 증가함에 따라 급격히 감소하는 경향을 보이고 있는 등의 많은 실용상의 문제점이 있었다.The conventional composition of the temperature compensating dielectric ceramic material was fired at a high temperature of 1270 to 1400 ° C. In the manufacture of a multilayer ceramic capacitor, there is a process of laminating and inserting an internal electrode between ceramic green sheets and firing the ceramic material. Since the baking and the internal electrode were simultaneously performed, precious metals such as platinum (Pt), gold (Au), and palladium (Pd) that could withstand high temperatures of 1270 to 1400 ° C had to be used as the internal electrodes. Therefore, the price of the multilayer ceramic capacitor has increased. In addition, recently, a temperature compensation dielectric magnetic composition capable of firing at a low temperature of less than 1150 ° C. has been reported (US Pat. No. 4,628,404), which has a weaker mechanical strength than that of a high temperature sintered product. In addition, these low-temperature sintered products have a Q value of high frequency characteristics
Figure kpo00001
There have been many practical problems such as a tendency to decrease rapidly as the frequency increases.

따라서, 본 발명은 전술한 문제점을 해결할 목적으로, BaTiO3, 10∼15wt%, TiO237∼45wt%, Nd2O328∼40wt%, Bi2O38.5∼13wt% 및 PbO 2∼5wt%로 구성된 주성분에 SiO2, ZnO, B2O3, Al2O3를 미량첨가 시켰다.Therefore, the present invention, for the purpose of solving the above problems, BaTiO 3 , 10-15wt%, TiO 2 37-45wt%, Nd 2 O 3 28-40wt%, Bi 2 O 3 8.5-13wt% and PbO 2-5wt A small amount of SiO 2 , ZnO, B 2 O 3 , and Al 2 O 3 was added to the main component consisting of%.

좀더 상세한 본 발명의 온도 보상용 유전체 자기조성물은 상기 주성분에 대해 SiO21.5∼2.5wt%, ZnO 1.5∼2.5wt%, B2O30.08∼1.3wt%, Al2O30.05∼3.0wt%가 첨가되는 것으로, 특히 Al2O3를 미량첨가 함으로써, 소결성을 향상시켜 상기 미국특허 4,628,404의 문제점을 획기적으로 개선시켰다.The more detailed temperature compensation dielectric ceramic composition of the present invention is SiO 2 1.5 to 2.5wt%, ZnO 1.5 to 2.5wt%, B 2 O 3 0.08 to 1.3wt%, Al 2 O 3 0.05 to 3.0wt% Is added, in particular by adding a small amount of Al 2 O 3 to improve the sintering properties and significantly improved the problem of the US Patent 4,628,404.

상기 조성물 성분에서 Bi2O3, PbO는 저온소결을 위해 첨가된 것이며, SiO2, ZnO 등을 유리질을 형성시켜 소결밀도를 높여주는 역할을 하게되며, B2O3는 내열충격성을 강하게 해주며 Al2O3는 소결성을 양호하게 하고, 절연저항을 높여주는 역할을 하게 된다.In the composition components, Bi 2 O 3 , PbO is added for low temperature sintering, and serves to increase the sintered density by forming glass such as SiO 2 , ZnO, B 2 O 3 to strengthen the thermal shock resistance Al 2 O 3 is to improve the sinterability and to increase the insulation resistance.

상기 본 발명의 조성물을 주성분에서, 티탄산 바륨을 10∼15wt%로 한정한 것은 10wt% 미만으로 되면 소결성이 현저하게 나빠지고 15wt% 이상이 되면 소결성이 나빠짐과 동시에 유전율의 온도특성이 좋지 않다.When the composition of the present invention is the main component, the barium titanate is limited to 10 to 15 wt%, and the sinterability is remarkably deteriorated when it is less than 10 wt%, and the sinterability is poor and the temperature characteristic of the dielectric constant is not good.

산화 네오디움을 37∼45wt%로 한정한 것은 37wt% 이하에서는 유전율이 낮고 45wt% 이상에서는 유전율의 온도특성을 만족시키지 못한다.The limit of neodymium oxide to 37 to 45 wt% is low in dielectric constant below 37 wt% and does not satisfy the temperature characteristic of dielectric constant above 45 wt%.

산화티탄을 28∼40wt%로 한 것은 28wt% 미만에서는 소결이 어려우며, 40wt%를 초과하면 유전율의 온도특성이 마이너스 측으로 큰 값을 지니게 된다. 산화비스무스를 8.5∼13wt%로 한 것은 8.5wt% 미만에서는 소결성이 좋지 않고 13wt% 이상에서는 고주파에 있어서 Q 값이 작아지기 때문이다. 산화납을 2∼5wt%로 한 것은 이 범위 외에서는 소결성이 좋지 않기 때문이다. 미량첨가 성분으로 B2O2, ZnO, SiO2를 상기 %로 각기 한정한 것은 그 wt% 미만에서는 유전율의 온도특성을 만족시키지 못하며, 그 wt% 이상에서는 유전율이 저하하기 때문이다.It is difficult to sinter titanium oxide at 28 to 40 wt%, but less than 28 wt%, and if it exceeds 40 wt%, the temperature characteristic of dielectric constant has a large value toward the negative side. The reason why bismuth oxide is 8.5 to 13 wt% is that the sinterability is poor at less than 8.5 wt% and the Q value is decreased at high frequency at 13 wt% or more. The reason for setting the lead oxide to 2 to 5 wt% is that the sinterability is not good outside this range. B 2 O 2 , ZnO, and SiO 2 are limited to the above percentages as the minor additives because the temperature characteristic of the dielectric constant is less than the wt%, and the dielectric constant decreases at the wt% or more.

산화알루미늄을 0.05∼3wt%로 한정한 것은 0.05wt% 이하에서는 소결성이 좋지 못하여, 3wt% 이상에서는 유전율이 낮아지기 때문이다.The aluminum oxide is limited to 0.05 to 3 wt% because the sinterability is not good at 0.05 wt% or less, and the dielectric constant is lowered at 3 wt% or more.

상술한 바와 같은 본 발명의 온도보상용 유전체 자기조성물에 의한 효과는 소결온도가 1100℃ 미만이므로 적층세라믹 콘덴서 제조시 상대적으로 은함유량이 많은 은-팔라듐 합금 전극을 사용할 수 있으므로 제조단가를 낮출 수 있으며, 또한, 종래의 NPO(Negative Positive Zero) 조성물보다 높은 유전 값을 지니고 있어 내부 전극의 층수를 적게 할수 있고 소형화가 가능하여 제조단가의 절감 및 가전제품의 경박 소형화를 유도할수 있다.As described above, the effect of the temperature-compensated dielectric magnetic composition of the present invention is that the sintering temperature is less than 1100 ° C., so that the silver-palladium alloy electrode having a relatively high silver content can be used in the manufacture of the multilayer ceramic capacitor, thereby lowering the manufacturing cost. In addition, since it has a higher dielectric value than the conventional NPO (Negative Positive Zero) composition, it is possible to reduce the number of layers of the internal electrode and to miniaturize, leading to a reduction in manufacturing cost and a lighter and smaller size of home appliances.

다음의 실시예에서 본 발명의 조성물의 제조방법 및 그 효과에 대하여 구체적으로 설명한다. 그러나, 다음의 실시예가 본 발명의 범위를 한정하는 것은 아니다.In the following examples, the preparation method of the composition of the present invention and the effects thereof will be described in detail. However, the following examples do not limit the scope of the present invention.

[실시예]EXAMPLE

99% 이상의 순도를 갖는 BaTiO3, TiO2, Nd2O3, Bi2O3, PbO, SiO2, ZnO, B2O3, Al2O3를 하기 표 1의 조성비율을 이루도록 평량을 한 뒤, 비닐 자(Jar)와 지르코니아(ZrO2) 볼을 이용하여 플레니터리 밀(Planetary Mill)에서 3시간동안 습식혼합하였다.BaTiO 3 , TiO 2 , Nd 2 O 3 , Bi 2 O 3 , PbO, SiO 2 , ZnO, B 2 O 3 and Al 2 O 3 having a purity of 99% or more were weighed to achieve the composition ratio of Table 1 below. Thereafter, wet mixing was performed for 3 hours in a planetary mill using vinyl jar and zirconia (ZrO 2 ) balls.

잘 혼합된 슬러리를 건조한후 920℃에서 4시간 하소하였다. 이 하소물을 볼밀로 분쇄한 뒤 유기결합체(PVA)를 첨가하여 직경12㎜, 두께1㎜로 1500㎏/㎠의 압력으로 성형하였다. 성형된 시편을 1100℃ 미만에서 2시간 소성하였다The well mixed slurry was dried and calcined at 920 ° C. for 4 hours. The calcined product was pulverized with a ball mill and then organic binder (PVA) was added to form a 12 mm diameter and 1 mm thickness at a pressure of 1500 kg / cm 2. The molded specimens were calcined at less than 1100 ° C. for 2 hours.

소성된 시편 양면에 은 전극을 발라 780℃에서 10분간 소부시켰다. 각 시편에 대해서, 측정조건을 25℃, 1MHz로 하여 유전율(εr), Q

Figure kpo00002
및 유전율의 온도계수(TCC)를 측정한 결과를 표1에 나타냈다. 유전율의 온도계수(TCC)는 25℃∼＋125℃의 온도 범위에서 측정한 값이며, 절연저항은 250DCV에서 1분동안 인가한 후 측정한 값이다. 제1도에서는 상기 실시예중 3, 8, 12, 14, 17 조성물의 온도에 대한 유전율의 변화율을 도시하였다.Silver electrodes were applied to both sides of the fired specimens and baked for 10 minutes at 780 ° C. For each specimen, the dielectric constant (εr) and Q were measured at 25 ° C and 1 MHz.
Figure kpo00002
And the result of measuring the temperature constant (TCC) of dielectric constant is shown in Table 1. The dielectric constant (TCC) of the dielectric constant is measured in the temperature range of 25 ° C to + 125 ° C, and the insulation resistance is measured after application at 250 DCV for 1 minute. Figure 1 shows the rate of change of permittivity with respect to the temperature of the composition 3, 8, 12, 14, 17 in the above examples.

[비교실시예]Comparative Example

본 발명의 범주에 벗어나는 조성을 가진 조성물을 본 발명에 따른 조성물과 대비할 목적으로 하기 표1의 * 로 표시한 조성대로 상기 실시예와 동일한 방법으로 제조하여 동일한 측정방법으로 그 물성을 측정하여 표1에 기재하였는바, 하기 표1에서 보는 바와 같이 소성온도가 높고 유전율이 낮으며, Q값 또한 주파수가 증가함에 따라 급격히 감소함을 알수 있었다.In order to prepare a composition having a composition outside the scope of the present invention and a composition according to the present invention in the same manner as in the above-described composition according to the composition indicated by * in Table 1 to measure the physical properties by the same measuring method in Table 1 As described in Table 1, the firing temperature is high, the dielectric constant is low, and the Q value was also found to decrease rapidly with increasing frequency.

Figure kpo00003
Figure kpo00003

Figure kpo00004
Figure kpo00004

Figure kpo00005
Figure kpo00005

Claims (3)

BaTiO3, TiO2, Nd2O3, Bi2O3및 PbO로 구성된 주성분에 SiO2, ZnO, B2O3및 Al2O3를 첨가하는 것을 특징으로 하는 유전체 자기조성물.A dielectric magnetic composition comprising SiO 2 , ZnO, B 2 O 3 and Al 2 O 3 added to a main component composed of BaTiO 3 , TiO 2 , Nd 2 O 3 , Bi 2 O 3, and PbO. 제1항에 있어서, BaTiO310∼15wt%, TiO237∼4wt%, Nd2O328∼40wt%, Bi2O38.5∼13wt% 및 PbO 2∼5wt%인 것을 특징으로 하는 유전체 자기 조성물.The dielectric ceramic according to claim 1, wherein BaTiO 3 10-15 wt%, TiO 2 37-4 wt%, Nd 2 O 3 28-40 wt%, Bi 2 O 3 8.5-13 wt%, and PbO 2-5 wt%. Composition. 제1항에 있어서, 주성분에 대해 SiO21.5∼2.5wt%, ZnO 1.5∼2.5wt%, B2O30.08∼1.3wt%, Al2O30.05∼3.0wt% 첨가되는 것을 특징으로 하는 유전체 자기조성물.The dielectric material according to claim 1, wherein 1.5 to 2.5 wt% of SiO 2, 1.5 to 2.5 wt% of ZnO, 0.08 to 1.3 wt% of B 2 O 3 , and 0.05 to 3.0 wt% of Al 2 O 3 are added to the main component. Self composition.
KR1019880015705A 1988-11-28 1988-11-28 Dielectric magnetic composite material KR970003343B1 (en)

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