JP2958818B2 - Non-reducing dielectric porcelain composition - Google Patents

Non-reducing dielectric porcelain composition

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Publication number
JP2958818B2
JP2958818B2 JP3183578A JP18357891A JP2958818B2 JP 2958818 B2 JP2958818 B2 JP 2958818B2 JP 3183578 A JP3183578 A JP 3183578A JP 18357891 A JP18357891 A JP 18357891A JP 2958818 B2 JP2958818 B2 JP 2958818B2
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JP
Japan
Prior art keywords
mol
composition
dielectric
batio
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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JP3183578A
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Japanese (ja)
Other versions
JPH059067A (en
Inventor
山 俊 樹 西
地 幸 生 浜
部 行 雄 坂
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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Application filed by Murata Manufacturing Co Ltd filed Critical Murata Manufacturing Co Ltd
Priority to JP3183578A priority Critical patent/JP2958818B2/en
Priority to DE4220681A priority patent/DE4220681C2/en
Priority to US07/904,398 priority patent/US5268342A/en
Priority to FR9207823A priority patent/FR2679227B1/en
Publication of JPH059067A publication Critical patent/JPH059067A/en
Application granted granted Critical
Publication of JP2958818B2 publication Critical patent/JP2958818B2/en
Anticipated expiration legal-status Critical
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Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【産業上の利用分野】この発明は非還元性誘電体磁器組
成物に関し、特にたとえば、ニッケルなどの卑金属を内
部電極材料とする積層コンデンサなどの誘電体材料とし
て用いられる、非還元性誘電体磁器組成物に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-reducing dielectric porcelain composition, and more particularly to a non-reducing dielectric porcelain used as a dielectric material for a multilayer capacitor using a base metal such as nickel as an internal electrode material. Composition.

【0002】[0002]

【従来の技術】従来の誘電体磁器材料は、中性または還
元性の低酸素分圧下で焼成すると、還元され、半導体化
を起こすという性質を有していた。そのため、内部電極
材料としては、誘電体磁器材料の焼結する温度で溶融せ
ず、かつ誘電体磁器材料を半導体化させない高い酸素分
圧下で焼成しても酸化されない、たとえばPd,Ptな
どの貴金属を用いなければならなかった。これは、製造
される積層コンデンサの低コスト化の大きな妨げとなっ
ていた。
2. Description of the Related Art A conventional dielectric porcelain material has the property that when fired under a neutral or reducing low oxygen partial pressure, the material is reduced to become a semiconductor. Therefore, as the internal electrode material, a noble metal such as Pd or Pt which does not melt at the temperature at which the dielectric ceramic material sinters and is not oxidized even when fired under a high oxygen partial pressure which does not turn the dielectric ceramic material into a semiconductor. Had to be used. This has greatly hindered the cost reduction of the manufactured multilayer capacitor.

【0003】そこで、上述の問題点を解決するために、
たとえばNiなどの卑金属を内部電極の材料として使用
することが望まれていた。しかし、このような卑金属を
内部電極の材料として使用して、従来の条件で焼成する
と、電極材料が酸化してしまい、電極としての機能を果
たさない。そのため、このような卑金属を内部電極の材
料として使用するためには、酸素分圧の低い中性または
還元性の雰囲気において焼成しても半導体化せず、コン
デンサ用の誘電体材料として、十分な比抵抗と優れた誘
電特性とを有する誘電体磁器材料が必要とされていた。
これらの条件をみたす誘電体磁器材料として、たとえば
特開昭62−256422号のBaTiO3 −CaZr
3 −MnO−MgO系の組成や、特公昭61−146
11号のBaTiO3 −(Mg,Zn,Sr,Ca)O
−B2 3 −SiO2 系の組成が提案されてきた。
[0003] In order to solve the above problems,
For example, it has been desired to use a base metal such as Ni as a material for an internal electrode. However, if such a base metal is used as a material for an internal electrode and fired under conventional conditions, the electrode material is oxidized and does not function as an electrode. Therefore, in order to use such a base metal as a material for an internal electrode, it does not turn into a semiconductor even when baked in a neutral or reducing atmosphere having a low oxygen partial pressure, and is sufficient as a dielectric material for a capacitor. There has been a need for dielectric porcelain materials having specific resistance and excellent dielectric properties.
As dielectric ceramic materials satisfying these conditions, for example, BaTiO 3 of JP 62-256422 -CaZr
The composition of the O 3 —MnO—MgO system and Japanese Patent Publication No. 61-146
No. 11 BaTiO 3- (Mg, Zn, Sr, Ca) O
-B 2 O 3 composition -SiO 2 system have been proposed.

【0004】[0004]

【発明が解決しようとする課題】しかしながら、特開昭
62−256422号に開示されている非還元性誘電体
磁器組成物では、CaZrO3 や焼成過程で生成するC
aTiO3 が、Mnなどとともに二次相を生成しやすい
ため、高温における信頼性の低下につながる危険性があ
った。また、この組成物は、容量の経時変化(エージン
グ率,%/dec)が、大きく実用的でないという問題
点もあった。
However, in the non-reducing dielectric ceramic composition disclosed in Japanese Patent Application Laid-Open No. 62-256422, CaZrO 3 and C
Since aTiO 3 easily forms a secondary phase together with Mn and the like, there is a danger that reliability at a high temperature is reduced. In addition, this composition has a problem that the change with time of the capacity (aging rate,% / dec) is large and not practical.

【0005】また、特公昭61−14611号に開示さ
れている組成物は、得られる誘電体の誘電率が2000
〜2800であり、Pdなどの貴金属を使用している従
来からの磁器組成物の誘電率である3000〜3500
と比較すると劣っていた。したがって、この組成物をコ
ストダウンのために、そのまま従来の材料と置き換える
のは、コンデンサの小型大容量化という点で不利であ
り、問題が残されていた。
The composition disclosed in JP-B-61-14611 has a dielectric constant of 2,000.
22800, which is the dielectric constant of a conventional porcelain composition using a noble metal such as Pd.
It was inferior compared to. Therefore, replacing this composition with a conventional material as it is for cost reduction is disadvantageous in terms of increasing the size and the capacity of a capacitor, and there remains a problem.

【0006】さらに、この組成物の誘電率の温度変化率
(TCC)は、20℃の容量値を基準として、−25℃
から+85℃の温度範囲では±10%であるが、+85
℃を超える高温では、10%を大きく超えてしまい、E
IAに規定されているX7R特性をも大きくはずれてし
まうという欠点があった。
[0006] Further, the temperature change rate (TCC) of the dielectric constant of this composition is -25 ° C based on the capacitance value of 20 ° C.
± 10% in the temperature range from
At high temperatures exceeding ℃, it greatly exceeds 10%, and E
There is a disadvantage that the X7R characteristics specified in the IA are greatly deviated.

【0007】それゆえに、この発明の主たる目的は、低
酸素分圧下であっても、組織が半導体化せず焼成可能で
あり、かつ誘電率が3000以上、絶縁抵抗がlogI
Rで11.0以上であり、さらに誘電率の温度特性が、
25℃の容量値を基準として、−55℃〜125℃の広
い範囲にわたって±15%の範囲内にあることを満足す
る、非還元性誘電体磁器組成物を提供することである。
Therefore, a main object of the present invention is that even under a low oxygen partial pressure, the structure can be sintered without forming a semiconductor, the dielectric constant is 3000 or more, and the insulation resistance is logI.
R is 11.0 or more, and the temperature characteristic of the dielectric constant is
An object of the present invention is to provide a non-reducing dielectric ceramic composition that satisfies a range of ± 15% over a wide range from −55 ° C. to 125 ° C. based on a capacitance value of 25 ° C.

【0008】[0008]

【課題を解決するための手段】この発明は、不純物とし
て含まれるアルカリ金属酸化物の含有量が0.04重量
%以下のBaTiO3 と、Tb2 3 ,Dy2 3 ,H
2 3 ,Er2 3 の中から選ばれる少なくとも1種
類の希土類酸化物(Re2 3 )と、Co2 3 との配
合比が、BaTiO3 92.0〜99.4モル%と、
Re2 3 0.3〜4.0モル%と、Co2 3
0.3〜4.0モル%との範囲内にある主成分100モ
ル%に対し、副成分として、BaO 0.2〜4.0モ
ル%と、MnO 0.2〜3.0モル%と、SiO
2 0.2〜3.0モル%と、MgO 0.5〜5.0モ
ル%とを含有する、非還元性誘電体磁器組成物である。
According to the present invention, BaTiO 3 containing 0.04% by weight or less of alkali metal oxides contained as impurities, Tb 2 O 3 , Dy 2 O 3 , H
The mixing ratio of at least one rare earth oxide (Re 2 O 3 ) selected from o 2 O 3 and Er 2 O 3 to Co 2 O 3 is 92.0 to 99.4 mol% of BaTiO 3. When,
0.3 to 4.0 mol% of Re 2 O 3 and Co 2 O 3
With respect to 100 mol% of the main component in the range of 0.3 to 4.0 mol%, as subcomponents, 0.2 to 4.0 mol% of BaO and 0.2 to 3.0 mol% of MnO. , SiO
2 A non-reducing dielectric ceramic composition containing 0.2 to 3.0 mol% and MgO 0.5 to 5.0 mol%.

【0009】[0009]

【発明の効果】この発明にかかる非還元性誘電体磁器組
成物は、中性または還元性の雰囲気において1260〜
1300℃の温度で焼成しても、組織が還元されて半導
体化することがない。さらに、この非還元性誘電体磁器
組成物は、logIRで11.0以上の高い絶縁抵抗値
を示すとともに、3000以上の高誘電率を示し、容量
温度変化率もEIAに規定されているX7R特性を満足
する。
The non-reducing dielectric porcelain composition according to the present invention can be used in a neutral or reducing atmosphere in the range of 1260 to 1600.
Even if it is fired at a temperature of 1300 ° C., the structure is not reduced to be a semiconductor. Further, this non-reducing dielectric ceramic composition shows a high insulation resistance value of 11.0 or more in logIR, a high dielectric constant of 3000 or more, and a rate of change in capacitance with temperature defined by the EIA. To be satisfied.

【0010】したがって、この発明にかかる非還元性誘
電体磁器組成物を積層セラミックコンデンサの誘電体材
料として用いれば、内部電極材料としてNiなどで代表
される卑金属材料を用いることができる。そのため、従
来のPdなどの貴金属を用いたものに比べて、特性を落
とすことなく、大幅なコストダウンを行うことが可能と
なる。
Therefore, if the non-reducing dielectric ceramic composition according to the present invention is used as a dielectric material of a multilayer ceramic capacitor, a base metal material represented by Ni or the like can be used as an internal electrode material. Therefore, it is possible to significantly reduce the cost without deteriorating the characteristics as compared with the conventional one using a noble metal such as Pd.

【0011】この発明の上述の目的,その他の目的,特
徴および利点は、図面を参照して行う以下の実施例の詳
細な説明から一層明らかとなろう。
The above and other objects, features and advantages of the present invention will become more apparent from the following detailed description of embodiments with reference to the drawings.

【0012】[0012]

【実施例】出発原料として、不純物として含まれるアル
カリ金属酸化物の含有量が異なるBaTiO3 ,Ba/
Tiモル比補正のためのBaCO3 ,希土類酸化物,C
2 3 ,MnO,SiO2 ,MgOを準備した。これ
らの原料を表1に示す組成割合となるように秤量して、
秤量物を得た。なお、試料番号1〜29については、ア
ルカリ金属酸化物の含有量が0.03重量%のBaTi
3 を使用し、試料番号30については、アルカリ金属
酸化物の含有量が0.05重量%のBaTiO3 を使用
し、試料番号31については、アルカリ金属酸化物の含
有量が0.07重量%のBaTiO3 を使用した。
EXAMPLES As starting materials, BaTiO 3 , Ba / with different contents of alkali metal oxides contained as impurities.
BaCO 3 , rare earth oxide, C for Ti molar ratio correction
o 2 O 3 , MnO, SiO 2 and MgO were prepared. These raw materials were weighed so as to have the composition ratios shown in Table 1, and
A weighed product was obtained. For sample numbers 1 to 29, the content of the alkali metal oxide was 0.03% by weight of BaTi.
O 3 was used. For sample No. 30, BaTiO 3 having an alkali metal oxide content of 0.05% by weight was used. For sample No. 31, the alkali metal oxide content was 0.07 wt. % BaTiO 3 was used.

【0013】[0013]

【表1】 [Table 1]

【0014】得られた秤量物に酢酸ビニル系バインダを
5重量%添加した後、PSZボールを用いたボールミル
で十分に湿式混合した。次に、この混合物中の分散媒を
蒸発、乾燥した後、整粒の工程を経て粉末を得た。得ら
れた粉末を2ton/cm2 の圧力で、直径10mm、
厚さ1mmの円板状にプレス成形して、成形体を得た。
After 5% by weight of a vinyl acetate binder was added to the obtained weighed material, the mixture was thoroughly wet-mixed with a ball mill using PSZ balls. Next, after the dispersion medium in this mixture was evaporated and dried, a powder was obtained through a sizing process. The obtained powder was subjected to a pressure of 2 ton / cm 2 and a diameter of 10 mm,
It was press-molded into a disk having a thickness of 1 mm to obtain a molded body.

【0015】次いで、このようにして得られた成形体
を、空気中において400℃で3時間保持の条件で脱バ
インダを行った後、H2 /N2 の体積比率が3/100
の還元雰囲気ガス気流中において、表2に示す温度で2
時間焼成し、磁器を得た。
Next, the compact obtained in this manner is subjected to binder removal under the condition of being kept at 400 ° C. for 3 hours in the air, and then the volume ratio of H 2 / N 2 is 3/100.
At a temperature shown in Table 2 in a reducing atmosphere gas stream.
Firing for a time resulted in porcelain.

【0016】[0016]

【表2】 [Table 2]

【0017】得られた磁器の両面に、銀ペーストを塗布
して、焼き付けることにより、銀電極を形成してコンデ
ンサとした。そして、このコンデンサの室温における誘
電率ε,誘電損失tanδ,絶縁抵抗値(logIR)
および容量の温度変化率(TCC)を測定した。その結
果を表2に示す。
A silver paste was applied to both sides of the obtained porcelain and baked to form silver electrodes to form capacitors. Then, the dielectric constant ε, dielectric loss tan δ, insulation resistance value (logIR) of the capacitor at room temperature.
And the rate of temperature change of the capacity (TCC) was measured. Table 2 shows the results.

【0018】なお、誘電率ε,誘電損失tanδについ
ては、温度25℃、周波数1kHz、交流電圧1Vの条
件で測定した。また、絶縁抵抗値については、温度25
℃において直流電圧500Vを2分間印加して測定し、
その結果を対数値(logIR)で示す。さらに、温度
変化率(TCC)については、25℃の容量値を基準と
した時の−55℃,125℃における変化率(ΔC-55
/C25,ΔC+125/C25)および−55℃〜+125℃
の間において、容量温度変化率が最大である値の絶対
値、いわゆる最大変化率(|ΔC/C25max )につい
て示す。
The dielectric constant ε and the dielectric loss tan δ were measured under the conditions of a temperature of 25 ° C., a frequency of 1 kHz, and an AC voltage of 1 V. In addition, the insulation resistance value was measured at a temperature of 25.
Measured by applying a DC voltage of 500 V for 2 minutes at ℃
The results are shown as logarithmic values (logIR). Further, as for the temperature change rate (TCC), the change rates at −55 ° C. and 125 ° C. based on the capacitance value at 25 ° C. (ΔC −55
/ C 25 , ΔC +125 / C 25 ) and -55 ° C to + 125 ° C
The absolute value of the value at which the capacitance temperature change rate is the maximum, that is, the so-called maximum change rate (| ΔC / C 25 | max ) is shown.

【0019】表2から明らかなように、この発明にかか
る非還元性誘電体磁器組成物は、優れた特性を示す。
As is clear from Table 2, the non-reducing dielectric ceramic composition according to the present invention exhibits excellent characteristics.

【0020】この発明において主成分および副成分の範
囲を上述のように限定する理由は次の通りである。
The reason for limiting the ranges of the main component and the subcomponent in the present invention as described above is as follows.

【0021】まず、主成分の範囲の限定理由について説
明する。
First, the reason for limiting the range of the main component will be described.

【0022】主成分であるBaTiO3 の構成比率を9
2.0〜99.4モル%とするのは、構成比率が92.
0モル%未満の場合には、希土類元素およびCo2 3
の構成比率が多くなるため、試料番号4に示すように、
絶縁抵抗値および誘電率の低下が生じ好ましくない。ま
た、BaTiO3 の構成比率が99.4モル%を超える
場合には、希土類元素およびCo2 3 の添加の効果が
なく、試料番号3に示すように、高温部(キュリー点付
近)の容量温度変化率が大きく(+)側にはずれ好まし
くない。さらに、BaTiO3 中のアルカリ金属酸化物
含有量を0.04%以下とするのは、0.04%を超え
ると、試料番号30および31に示すように、誘電率の
低下が生じ、実用的でなくなり好ましくない。
The composition ratio of BaTiO 3 as the main component is 9
The content of 2.0 to 99.4 mol% is determined when the composition ratio is 92.0 mol%.
If less than 0 mol%, rare earth elements and Co 2 O 3
Is increased, as shown in sample number 4,
Undesirably, the insulation resistance value and the dielectric constant decrease. When the composition ratio of BaTiO 3 exceeds 99.4 mol%, the effect of the addition of the rare earth element and Co 2 O 3 has no effect, and as shown in Sample No. 3, the capacity of the high-temperature portion (near the Curie point) The rate of temperature change is large and shifts to the (+) side, which is not preferable. Further, the reason why the content of the alkali metal oxide in BaTiO 3 is set to 0.04% or less is that if the content exceeds 0.04%, as shown in Sample Nos. 30 and 31, the dielectric constant decreases, and Is not preferred.

【0023】次に、副成分の範囲の限定理由について説
明する。
Next, the reasons for limiting the range of the subcomponent will be described.

【0024】BaO添加量を0.2〜4.0モル%とす
るのは、添加量が0.2モル%未満の場合には、試料番
号9に示すように、雰囲気焼成中に組織が半導体化し、
絶縁抵抗値の著しい低下をまねくので好ましくない。ま
た、添加量が4.0モル%を超える場合には、試料番号
12に示すように、焼結性が低下するので好ましくな
い。
The reason why the amount of BaO is set to 0.2 to 4.0 mol% is that when the addition amount is less than 0.2 mol%, as shown in sample No. 9, the structure of the semiconductor during the firing in the atmosphere is changed to the semiconductor. And
It is not preferable because the insulation resistance value is remarkably reduced. On the other hand, if the addition amount exceeds 4.0 mol%, as shown in Sample No. 12, the sinterability decreases, which is not preferable.

【0025】また、MnO添加量を0.2〜3.0モル
%とするのは、添加量が0.2モル%未満の場合には、
試料番号17に示すように、組織の耐還元性向上に効果
がなくなり、絶縁抵抗値の著しい低下をまねくので好ま
しくない。また、添加量が3.0モル%を超える場合に
は、試料番号15に示すように、絶縁抵抗値の低下が生
じるので好ましくない。
The reason why the addition amount of MnO is 0.2 to 3.0 mol% is that when the addition amount is less than 0.2 mol%,
As shown in Sample No. 17, the effect of improving the reduction resistance of the structure is lost and the insulation resistance value is remarkably reduced, which is not preferable. On the other hand, if the addition amount exceeds 3.0 mol%, as shown in Sample No. 15, the insulation resistance value decreases, which is not preferable.

【0026】SiO2 添加量を0.2〜5.0モル%と
するのは、添加量が0.2モル%未満の場合には、試料
番号23に示すように、焼結温度の低下に効果がなく好
ましくない。また、添加量が5.0モル%を超える場合
には、試料番号20に示すように、誘電率εの低下が生
じるので好ましくない。
The reason why the addition amount of SiO 2 is 0.2 to 5.0 mol% is that if the addition amount is less than 0.2 mol%, as shown in sample No. 23, the sintering temperature decreases. Ineffective and not preferred. On the other hand, if the addition amount exceeds 5.0 mol%, as shown in Sample No. 20, the dielectric constant ε decreases, which is not preferable.

【0027】最後に、MgO添加量を0.5〜5.0モ
ル%とするのは、添加量が0.5モル%未満の場合に
は、試料番号24に示すように、容量温度変化率をフラ
ットにする効果がなく、特に低温側で(−)側にはずれ
る傾向があるとともに、絶縁抵抗値向上の効果もなくな
るので好ましくない。また、添加量が5.0モル%を超
える場合には、試料番号29に示すように、誘電率εお
よび絶縁抵抗値の低下が生じるので好ましくない。
Finally, the reason why the addition amount of MgO is 0.5 to 5.0 mol% is that when the addition amount is less than 0.5 mol%, as shown in Sample No. 24, Has no effect of flattening, and tends to deviate to the (-) side particularly at a low temperature side, and the effect of improving the insulation resistance value is also lost. On the other hand, if the addition amount exceeds 5.0 mol%, as shown in Sample No. 29, the dielectric constant ε and the insulation resistance value decrease, which is not preferable.

【0028】なお、表2に示す特性データは、単板コン
デンサにおいて得られたデータであるが、同じ組成物を
シート成形し、チップ加工を行った積層コンデンサにお
いても、今回のデータとほぼ同等の結果が得られる。
Note that the characteristic data shown in Table 2 is data obtained for a single-plate capacitor. However, a multilayer capacitor obtained by forming a sheet of the same composition and processing a chip has almost the same data as the present data. The result is obtained.

Claims (1)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】 不純物として含まれるアルカリ金属酸化
物の含有量が0.04重量%以下のBaTiO3 と、T
2 3 ,Dy2 3 ,Ho2 3 ,Er2 3 の中か
ら選ばれる少なくとも1種類の希土類酸化物(Re2
3 )と、Co2 3 との配合比が、 BaTiO3 92.0〜99.4モル%、 Re2 3 0.3〜4.0モル%、および Co2 3 0.3〜4.0モル% の範囲内にある主成分100モル%に対し、 副成分として、 BaO 0.2〜4.0モル%、 MnO 0.2〜3.0モル%、 SiO2 0.2〜3.0モル%、および MgO 0.5〜5.0モル% を含有する、非還元性誘電体磁器組成物。
1. BaTiO 3 having an alkali metal oxide content of 0.04% by weight or less as an impurity,
b 2 O 3 , Dy 2 O 3 , Ho 2 O 3 , Er 2 O 3 at least one rare earth oxide (Re 2 O 3)
3 ) and Co 2 O 3 in a proportion of 92.0 to 99.4 mol% of BaTiO 3, 0.3 to 4.0 mol% of Re 2 O 3 , and 0.3 to 4 of Co 2 O 3 relative to 100 mol of the main ingredient% which is within the range of 2.0 mol%, as an auxiliary component, BaO 0.2 to 4.0 mol%, MnO 0.2 to 3.0 mol%, SiO 2 0.2 to 3 A non-reducing dielectric porcelain composition containing 0.0 mol%, and 0.5 to 5.0 mol% of MgO.
JP3183578A 1991-06-27 1991-06-27 Non-reducing dielectric porcelain composition Expired - Lifetime JP2958818B2 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP3183578A JP2958818B2 (en) 1991-06-27 1991-06-27 Non-reducing dielectric porcelain composition
DE4220681A DE4220681C2 (en) 1991-06-27 1992-06-24 Non-reducing, dielectric, ceramic composition
US07/904,398 US5268342A (en) 1991-06-27 1992-06-25 Nonreducing dielectric ceramic composition
FR9207823A FR2679227B1 (en) 1991-06-27 1992-06-25 NON-REDUCING DIELECTRIC CERAMIC COMPOSITION.

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JP3183578A JP2958818B2 (en) 1991-06-27 1991-06-27 Non-reducing dielectric porcelain composition

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JP4392821B2 (en) 2000-10-24 2010-01-06 株式会社村田製作所 Dielectric ceramic, manufacturing method thereof, and multilayer ceramic capacitor
JP2002164247A (en) 2000-11-24 2002-06-07 Murata Mfg Co Ltd Dielectric ceramic composition and layered ceramic capacitor
JP3705141B2 (en) 2001-03-19 2005-10-12 株式会社村田製作所 Dielectric ceramic, manufacturing method and evaluation method thereof, and multilayer ceramic electronic component
US6829136B2 (en) 2002-11-29 2004-12-07 Murata Manufacturing Co., Ltd. Dielectric ceramic, method for making the same, and monolithic ceramic capacitor
JP4100173B2 (en) 2003-01-08 2008-06-11 株式会社村田製作所 Dielectric ceramic and multilayer ceramic capacitors
JP3882054B2 (en) 2003-07-07 2007-02-14 株式会社村田製作所 Multilayer ceramic capacitor
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