JPH0570221A - Nonreducing dielectric ceramic composition - Google Patents
Nonreducing dielectric ceramic compositionInfo
- Publication number
- JPH0570221A JPH0570221A JP3258318A JP25831891A JPH0570221A JP H0570221 A JPH0570221 A JP H0570221A JP 3258318 A JP3258318 A JP 3258318A JP 25831891 A JP25831891 A JP 25831891A JP H0570221 A JPH0570221 A JP H0570221A
- Authority
- JP
- Japan
- Prior art keywords
- mol
- composition
- dielectric constant
- dielectric
- dielectric ceramic
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 29
- 239000000919 ceramic Substances 0.000 title claims abstract description 7
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims abstract description 8
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims 1
- 238000009413 insulation Methods 0.000 abstract description 11
- 239000000075 oxide glass Substances 0.000 abstract description 4
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 abstract 2
- 229910002971 CaTiO3 Inorganic materials 0.000 abstract 1
- 229910002113 barium titanate Inorganic materials 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(III) oxide Inorganic materials O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 abstract 1
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 abstract 1
- JYTUFVYWTIKZGR-UHFFFAOYSA-N holmium oxide Inorganic materials [O][Ho]O[Ho][O] JYTUFVYWTIKZGR-UHFFFAOYSA-N 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910052573 porcelain Inorganic materials 0.000 description 11
- 239000003990 capacitor Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 239000010953 base metal Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910010293 ceramic material Inorganic materials 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000003989 dielectric material Substances 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Inorganic Insulating Materials (AREA)
- Control Of Motors That Do Not Use Commutators (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【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 in particular, a non-reducing dielectric porcelain used as a dielectric material such as a laminated capacitor having a base metal such as nickel as an internal electrode material. It relates to a 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 ceramic material has a property of being reduced to a semiconductor when it is fired under a neutral or reducing low oxygen partial pressure. Therefore, the internal electrode material is not melted at a temperature at which the dielectric ceramic material is sintered, and is not oxidized even if fired under a high oxygen partial pressure that does not turn the dielectric ceramic material into a semiconductor, for example, a noble metal such as Pd or Pt. Had to use. This has been a major obstacle to cost reduction of manufactured multilayer capacitors.
【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
Ｏ3 −ＭｎＯ−ＭｇＯ系の組成や、特公昭６１−１４６
１１号のＢａＴｉＯ3 −（Ｍｇ，Ｚｎ，Ｓｒ，Ｃａ）Ｏ
−Ｂ2 Ｏ3 −ＳｉＯ2 系の組成が提案されてきた。Therefore, 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 the internal electrodes. However, when such a base metal is used as a material for the internal electrode and fired under the 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 the internal electrodes, even if it is fired in a neutral or reducing atmosphere with a low oxygen partial pressure, it does not become a semiconductor and is sufficiently used as a dielectric material for a capacitor. There has been a need for a dielectric porcelain material having a specific resistance and excellent dielectric properties.
As a dielectric ceramic material satisfying these conditions, for example, BaTiO 3 —CaZr disclosed in JP-A-62-256422.
O 3 -MnO-MgO system composition or, JP 61-146
No. 11 BaTiO 3 — (Mg, Zn, Sr, Ca) O
Compositions based on the —B 2 O 3 —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 がＭｎなどとともに耐メ
ッキ性に劣った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。However, in the non-reducing dielectric ceramic composition disclosed in JP-A-62-256422, CaZrO 3 forms a secondary phase having poor plating resistance together with Mn and the like. Since it is easy to do so, there is a risk that reliability may be deteriorated at high temperatures.
【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 2000.
˜2800, which is the dielectric constant of a conventional porcelain composition using a noble metal such as Pd 3000 to 3500
It was inferior compared to. Therefore, replacing the composition with the conventional material as it is for cost reduction is disadvantageous in terms of miniaturization and large capacity of the capacitor, and a problem remains.
【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。Further, the temperature change rate (TCC) of the dielectric constant of this composition is -25 ° C with reference to the capacitance value of 20 ° C.
± 85% in the temperature range from + 85 ° C to + 85 ° C
At a high temperature exceeding ℃, it exceeds 10%, and E
There is a drawback that the X7R characteristic defined by IA is also largely deviated.
【０００７】また、上記の組成物に対し直流電圧を印加
した場合、静電容量が大きく変化するという欠点もあっ
た。Further, when a direct current voltage is applied to the above composition, there is a drawback that the electrostatic capacity changes greatly.
【０００８】それゆえに、この発明の主たる目的は、誘
電率が３０００以上、絶縁抵抗がｌｏｇＩＲで１２．０
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し、直流バイア
ス電圧印加に対し、静電容量の変化率が小さい磁器を得
ることができ、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る、非還元性誘電体磁器組成物を提
供することである。Therefore, the main object of the present invention is to have a dielectric constant of 3000 or more and an insulation resistance of 12.0 in log IR.
It is satisfied that the temperature characteristic of the dielectric constant is within ± 15% over a wide range of −55 ° C. to 125 ° C. with reference to the capacitance value of 25 ° C. The present invention is to provide a non-reducing dielectric porcelain composition that can obtain a porcelain having a small rate of change in capacitance and that can be fired without the tissue becoming a semiconductor even under a low oxygen partial pressure. ..
【０００９】[0009]
【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 Ｏ3 ，Ｄｙ2 Ｏ3 ，Ｈ
ｏ2 Ｏ3 ，Ｅｒ2 Ｏ3 の中から選ばれる少なくとも１種
類の希土類酸化物（Ｒｅ2 Ｏ3 ）と、Ｃｏ2 Ｏ3 との配
合比が、ＢａＴｉＯ3 ９２．０〜９９．４モル％と、
Ｒｅ2 Ｏ3 ０．３〜４．０モル％と、Ｃｏ2 Ｏ3
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、ＭｇＯ
０．５〜５．０モル％と、ＣａＴｉＯ3 ０．５〜４．
０モル％とを含有し、さらに上記成分を１００重量部と
して、ＢａＯ−ＳｒＯ−Ｌｉ2 Ｏ−ＳｉＯ2 を主成分と
する酸化物ガラスを０．５〜２．５重量部含有する、非
還元性誘電体磁器組成物である。The present invention is directed to BaTiO 3 containing 0.04% by weight or less of an alkali metal oxide contained as an impurity, Tb 2 O 3 , Dy 2 O 3 and H.
The compounding ratio of at least one rare earth oxide (Re 2 O 3 ) selected from o 2 O 3 and Er 2 O 3 and Co 2 O 3 is BaTiO 3 92.0 to 99.4 mol%. When,
Re 2 O 3 and 0.3 to 4.0 wt mol%, Co 2 O 3
0.2 to 4.0 mol% of BaO and 0.2 to 3.0 mol% of MnO as secondary components with respect to 100 mol% of the main component within the range of 0.3 to 4.0 mol%. , MgO
And 0.5 to 5.0 mol%, CaTiO 3 0.5~4.
0 mol% and further contains 0.5 to 2.5 parts by weight of an oxide glass containing BaO—SrO—Li 2 O—SiO 2 as a main component, with 100 parts by weight of the above components being non-reduced. Dielectric porcelain composition.
【００１０】[0010]
【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
組成物によって得られる磁器は、ｌｏｇＩＲで１２．０
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特性を満足し、直流バイアス特性にも優れて
いる。The non-reducing dielectric ceramic composition according to the present invention is 1260 to 1260 in a neutral or reducing atmosphere.
Even if it is fired at a temperature of 1300 ° C., the structure is not reduced to become a semiconductor. Furthermore, the porcelain obtained by this non-reducing dielectric porcelain composition has a log IR of 12.0.
It exhibits a high insulation resistance value as described above, a high dielectric constant of 3,000 or more, and the capacitance temperature change rate also satisfies the X7R characteristic defined by the EIA and is excellent in DC bias characteristic.
【００１１】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, when the non-reducing dielectric ceramic composition according to the present invention is used as a dielectric material of a laminated ceramic capacitor, a base metal material represented by Ni or the like can be used as an internal electrode material. Therefore, compared with the conventional one using a noble metal such as Pd, it is possible to significantly reduce the cost without deteriorating the characteristics.
【００１２】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-mentioned objects, other objects, features and advantages of the present invention will become more apparent from the following detailed description of the embodiments with reference to the drawings.
【００１３】[0013]
【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
ｏ2 Ｏ3 ，ＭｎＯ，ＭｇＯ，ＣａＴｉＯ3 ，酸化物ガラ
スを準備した。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〜
３２については、アルカリ金属酸化物の含有量が０．０
３重量％のＢａＴｉＯ3 を使用し、試料番号３３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３４については、アル
カリ金属酸化物の含有量が０．０７重量％のＢａＴｉＯ
3 を使用した。Example As starting materials, BaTiO 3 , Ba / Ba / having different contents of alkali metal oxides contained as impurities
BaCO 3 , rare earth oxide, C for correcting Ti molar ratio
o 2 O 3 , MnO, MgO, CaTiO 3 , and oxide glass were prepared. These raw materials were weighed so that the composition ratios shown in Table 1 were obtained to obtain a weighed product. Sample numbers 1 to
32, the content of alkali metal oxide was 0.0
3 using the% by weight of BaTiO 3, for sample No. 33, the content of alkali metal oxides using BaTiO 3 of 0.05 wt%, the sample No. 34, the content of alkali metal oxide 0.07 wt% BaTiO
3 was used.
【００１４】[0014]
【表１】 [Table 1]
【００１５】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 adding 5% by weight of a vinyl acetate binder to the obtained weighed product, it was sufficiently wet-mixed by a ball mill using PSZ balls. Next, the dispersion medium in this mixture was evaporated and dried, and then a powder was obtained through a step of sizing. The obtained powder was treated at a pressure of 2 ton / cm 2 with a diameter of 10 mm,
A 1 mm thick disc was press-molded to obtain a molded body.
【００１６】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 thus obtained molded body is debindered in air at 400 ° C. for 3 hours, and then the H 2 / N 2 volume ratio is 3/100.
2 in the reducing atmosphere gas stream at the temperature shown in Table 2.
It was fired for an hour to obtain porcelain.
【００１７】[0017]
【表２】 [Table 2]
【００１８】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（ｌｏｇＩ
Ｒ），容量の温度変化率（ＴＣＣ）および直流バイアス
特性を測定した。その結果を表２に示す。Silver paste was applied to both surfaces of the obtained porcelain and baked to form silver electrodes, thereby obtaining a capacitor. The dielectric constant ε, the dielectric loss tan δ, the insulation resistance value (logI
R), the temperature change rate of capacity (TCC), and the DC bias characteristic were measured. The results are shown in Table 2.
【００１９】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／Ｃ25｜max ）につい
て示す。また、直流バイアス特性については、２．０
（ｋＶ／ｍｍ）の電界強度になるように、直流電圧をか
けた際の静電容量値の、電圧を印加しない場合の静電容
量値に対する変化率で示す。The dielectric constant ε and the dielectric loss tan δ were measured under the conditions of temperature of 25 ° C., frequency of 1 kHz and AC voltage of 1V. Also, regarding the insulation resistance value, the temperature is 25
Apply a DC voltage of 500V for 2 minutes at
The results are shown by logarithmic value (logIR). Further, regarding the temperature change rate (TCC), the change rate (ΔC −55 at −55 ° C. and 125 ° C. when the capacitance value at 25 ° C. is used as a reference.
/ C 25 , ΔC +125 / C 25 ) and -55 ° C to + 125 ° C
In between, the absolute value of the value at which the capacity temperature change rate is maximum, that is, the so-called maximum change rate (| ΔC / C 25 | max ) is shown. For the DC bias characteristic, 2.0
The rate of change of the capacitance value when a DC voltage is applied so that the electric field strength is (kV / mm) is shown with respect to the capacitance value when no voltage is applied.
【００２０】また、図１は実施例および比較例につい
て、直流印加電界強度を変化させたときの容量変化率を
示すグラフである。FIG. 1 is a graph showing the rate of change in capacitance when the DC applied electric field strength was changed for the examples and comparative examples.
【００２１】表２および図１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 and FIG. 1, the non-reducing dielectric ceramic composition according to the present invention exhibits excellent characteristics.
【００２２】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 why the ranges of the main component and the subcomponents are limited as described above in the present invention is as follows.
【００２３】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.
【００２４】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 Ｏ3
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 Ｏ3 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３３および３４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 the main component BaTiO 3 is 9
The composition ratio of 2.0 to 99.4 mol% is 92.
If it is less than 0 mol%, rare earth elements and Co 2 O 3
Since the composition ratio of is increased, as shown in sample number 4,
Insulation resistance and dielectric constant decrease, which is not preferable. Further, when the composition ratio of BaTiO 3 exceeds 99.4 mol%, there is no effect of the addition of the rare earth element and Co 2 O 3 , and as shown in Sample No. 3, the capacity of the high temperature part (around the Curie point) is The rate of temperature change is large and it shifts to the (+) side, which is not preferable. Further, the content of the alkali metal oxide in BaTiO 3 is set to 0.04% or less. When it exceeds 0.04%, as shown in sample numbers 33 and 34, the dielectric constant is lowered, and it is practical. It is not preferable.
【００２５】次に、副成分の範囲の限定理由について説
明する。Next, the reason for limiting the range of subcomponents will be described.
【００２６】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 amount of BaO added is set to 0.2 to 4.0 mol%. When the added amount is less than 0.2 mol%, as shown in Sample No. 9, the structure of the semiconductor is not changed during the atmosphere firing. Turned into
This is not preferable because it causes a significant decrease in insulation resistance. On the other hand, if the addition amount exceeds 4.0 mol%, the sinterability is deteriorated as shown in Sample No. 12, which is not preferable.
【００２７】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。Further, the MnO addition amount is set to 0.2 to 3.0 mol% if 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 lowered, which is not preferable. On the other hand, if the addition amount exceeds 3.0 mol%, the insulation resistance value will decrease as shown in Sample No. 15, which is not preferable.
【００２８】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２２および２３に示すように、容量温度変化率の曲線
がシングルピーク化する傾向があり、低温側で（−）側
にはずれ、高温側（キュリー点付近）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２７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。The amount of MgO added is set to 0.5 to 5.0 mol% when the added amount is less than 0.5 mol%, as shown in sample numbers 22 and 23, The curve tends to have a single peak, deviates to the (−) side on the low temperature side, tends to deviate to the (+) side on the high temperature side (around the Curie point), and the effect of improving the insulation resistance value is also lost, which is not preferable. .. When the added amount exceeds 5.0 mol%, as shown in sample number 27, the dielectric constant ε
Also, the insulation resistance is lowered, which is not preferable.
【００２９】また、ＣａＴｉＯ3 添加量を０．５〜４．
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３２に示すように、直流バイアス特性の
改善に効果がなくなり、静電容量の印加電圧依存性が大
きくなるので好ましくない。また、添加量が４．０モル
％を超える場合には、試料番号３０に示すように、高温
部での容積温度変化率が（−）側にはずれる傾向がある
とともに、誘電率の低下も生じるので好ましくない。The amount of CaTiO 3 added is 0.5 to 4.
0 mol% means that when the added amount is less than 0.5 mol%, there is no effect on improving the DC bias characteristics as shown in Sample No. 32, and the dependency of the capacitance on the applied voltage is large. Therefore, it is not preferable. Further, when the addition amount exceeds 4.0 mol%, as shown in Sample No. 30, the volume temperature change rate in the high temperature part tends to deviate to the (−) side, and the dielectric constant lowers. It is not preferable.
【００３０】最後に、ＢａＯ−ＳｒＯ−Ｌｉ2 Ｏ−Ｓｉ
Ｏ2 を主成分とする酸化物ガラスの添加量を０．５〜
２．５重量％とするのは、添加量が０．５重量％未満の
場合には、試料番号２１に示すように、焼結温度を低下
させる効果および耐還元性向上の効果がなくなるので好
ましくない。また、添加量が２．５重量％を超える場合
には、試料番号１９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。[0030] Finally, BaO-SrO-Li 2 O -Si
The addition amount of the oxide glass containing O 2 as a main component is 0.5 to
The amount of 2.5% by weight is preferable because when the amount added is less than 0.5% by weight, the effect of lowering the sintering temperature and the effect of improving the reduction resistance are lost as shown in Sample No. 21. Absent. On the other hand, if the addition amount exceeds 2.5% by weight, the dielectric constant ε will decrease as shown in Sample No. 19, which is not preferable.
【００３１】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。The characteristic data shown in Table 2 are the data obtained for the single plate capacitor, but even for the laminated capacitor in which the same composition is sheet-formed and chip-processed, it is almost the same as the present data. The result is obtained.
【図１】直流印加電界強度を変化させたときの容量変化
率を示すグラフである。FIG. 1 is a graph showing a rate of change in capacitance when a DC applied electric field strength is changed.
Claims (1)
物の含有量が０．０４重量％以下のＢａＴｉＯ3 と、Ｔ
ｂ2 Ｏ3 ，Ｄｙ2 Ｏ3 ，Ｈｏ2 Ｏ3 ，Ｅｒ2 Ｏ3 の中か
ら選ばれる少なくとも１種類の希土類酸化物（Ｒｅ2 Ｏ
3 ）と、Ｃｏ2 Ｏ3 との配合比が、 ＢａＴｉＯ3 ９２．０〜９９．４モル％、 Ｒｅ2 Ｏ3 ０．３〜４．０モル％、および Ｃｏ2 Ｏ3 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％、 ＭｇＯ ０．５〜５．０モル％、および ＣａＴｉＯ3 ０．５〜４．０モル％を含有し、さらに
上記成分を１００重量部として、ＢａＯ−ＳｒＯ−Ｌｉ
2 Ｏ−ＳｉＯ2 を主成分とする酸化物ガラスを０．５〜
２．５重量部含有する、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 and T
b 2 O 3 , Dy 2 O 3 , Ho 2 O 3 , and Er 2 O 3 , at least one rare earth oxide (Re 2 O 3)
And 3) blending ratio of Co 2 O 3 is, BaTiO 3 92.0-99.4 mol%, Re 2 O 3 0.3 to 4.0 mol%, and Co 2 O 3 0.3 to 4 As a subcomponent, BaO 0.2 to 4.0 mol%, MnO 0.2 to 3.0 mol%, MgO 0.5 to 5% with respect to 100 mol% of the main component in the range of 0.0 mol%. 0 mol%, and CaTiO 3 containing 0.5 to 4.0 mol%, 100 parts by weight of further above components, BaO-SrO-Li
2 O-SiO 2 containing 0.5-
A non-reducing dielectric ceramic composition containing 2.5 parts by weight.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03258318A JP3109171B2 (en) | 1991-09-09 | 1991-09-09 | 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. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03258318A JP3109171B2 (en) | 1991-09-09 | 1991-09-09 | Non-reducing dielectric porcelain composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0570221A true JPH0570221A (en) | 1993-03-23 |
| JP3109171B2 JP3109171B2 (en) | 2000-11-13 |
Family
ID=17318582
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03258318A Expired - Lifetime JP3109171B2 (en) | 1991-06-27 | 1991-09-09 | Non-reducing dielectric porcelain composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3109171B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002231560A (en) * | 2001-01-31 | 2002-08-16 | Murata Mfg Co Ltd | Dielectric ceramic and laminated ceramic capacitor |
| JP2010180116A (en) * | 2009-02-09 | 2010-08-19 | Tdk Corp | Dielectric ceramic composition, and electronic component |
-
1991
- 1991-09-09 JP JP03258318A patent/JP3109171B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002231560A (en) * | 2001-01-31 | 2002-08-16 | Murata Mfg Co Ltd | Dielectric ceramic and laminated ceramic capacitor |
| JP2010180116A (en) * | 2009-02-09 | 2010-08-19 | Tdk Corp | Dielectric ceramic composition, and electronic component |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3109171B2 (en) | 2000-11-13 |
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