JPS6234708B2 - - Google Patents
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- Publication number
- JPS6234708B2 JPS6234708B2 JP56156685A JP15668581A JPS6234708B2 JP S6234708 B2 JPS6234708 B2 JP S6234708B2 JP 56156685 A JP56156685 A JP 56156685A JP 15668581 A JP15668581 A JP 15668581A JP S6234708 B2 JPS6234708 B2 JP S6234708B2
- Authority
- JP
- Japan
- Prior art keywords
- capacitance
- composition
- capacitor
- resistance
- pbtio
- 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.)
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- 239000000203 mixture Substances 0.000 claims description 40
- 239000011777 magnesium Substances 0.000 claims description 23
- 229910052573 porcelain Inorganic materials 0.000 claims description 18
- 239000011572 manganese Substances 0.000 claims description 16
- 238000010586 diagram Methods 0.000 claims description 5
- FKSZLDCMQZJMFN-UHFFFAOYSA-N [Mg].[Pb] Chemical compound [Mg].[Pb] FKSZLDCMQZJMFN-UHFFFAOYSA-N 0.000 claims description 4
- LIABKAQKQSUQJX-UHFFFAOYSA-N [Mn].[Pb] Chemical compound [Mn].[Pb] LIABKAQKQSUQJX-UHFFFAOYSA-N 0.000 claims description 3
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 claims description 3
- 239000003990 capacitor Substances 0.000 description 27
- 239000000919 ceramic Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 8
- 238000009413 insulation Methods 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000005452 bending Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000003985 ceramic capacitor Substances 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- NKTZYSOLHFIEMF-UHFFFAOYSA-N dioxido(dioxo)tungsten;lead(2+) Chemical compound [Pb+2].[O-][W]([O-])(=O)=O NKTZYSOLHFIEMF-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Ceramic Capacitors (AREA)
- Inorganic Insulating Materials (AREA)
Description
本発明は磁器組成物特に1000℃以下の低温で焼
結でき誘電率と比抵抗の積が高く、しかも機械的
強度の高い誘電体磁器組成物に関するものであ
る。
従来、誘電体磁器組成物として、チタン酸バリ
ウム（BaTiO3）などを主成分とする磁器組成物が
広く実用化されていることは周知のとおりであ
る。しかしながら、BaTiO3などを主成分とする
ものは焼結温度が通常1300〜1400℃の高温であ
る。このため、これを積層形コンデンサに利用す
る場合には、内部電極としてこの焼結温度に耐え
得る材料、例えば白金、パラジウム等の高価な貴
金属を使用しなければならず、製造コストが高く
つくという欠点がある。積層形コンデンサを安く
作るためには、銀、ニツケル等を主成分とする安
価な金属が内部電極に使用できるような、できる
だけ低温、特に1000℃以下の低い温度で焼結でき
る磁器組成物が望まれている。
ところで磁器組成物を用い、実用的な積層形コ
ンデンサを作製するときに磁器組成物の電気的特
性として多くの項目が評価されなければならな
い。一般的に誘電率はできるだけ大きく、誘電損
失はできるだけ小さく、比抵抗はできるだけ大き
く、誘電率の温度変化は小さいことなどが要求さ
れる。しかしながら、実際に積層形コンデンサを
種々の機器に用いる場合においては誘電率でな
く、まず容量、次に容量の温度変化率、誘電損失
などの値が必要とされる。積層形コンデンサにお
いて、容量は磁器組成物の誘電率に比例するが、
しかし、その厚みに反比例し、電極面積、積層数
に比例するので、一定の容量を得るためには磁器
組成物の誘電率が大きいことは必ずしも絶対的な
要因でない。さらに容量の温度変化率（誘電率の
温度変化率）は用途により種々許容された範囲が
あり、磁器組成物の誘電率の温度変化率も積層形
コンデンサを作製するときの絶対的な要因でな
い。
一方、誘電損失は用途により一定の値以下でな
ければならないという規定があり、室温で最大
5.0％以下である。この値を越えると積層磁器コ
ンデンサの信頼性に問題が生じてくる。さらに比
抵抗に関しては、例えば、EIAJ規格（日本電子
機械工学会の電子機器用積層磁器コンデンサ（チ
ツプ形）RC−3698B）に述べられているごと
く、積層コンデンサの絶縁抵抗として10000MΩ
以上または容量抵抗積で、500μＦ・ＭΩ以上の
いずれか小さい方以上と規定されている。これら
いずれかの値を下回ると積層磁器コンデンサの信
頼性に問題が生じてくる。すなわち磁器組成物の
誘電率と比抵抗の積がある絶対値以上なければ、
任意の容量、特に大きな容量のコンデンサを実用
的期格に合せることができず、その用途が非常に
限定され、実用的な意味がなくなる。この点を詳
しく説明すると次の様になる。積層形コンデンサ
では、ｎ＋１個の内部電極を構成して一般にｎ個
の同じ厚さの層からなる単一層コンデンサが積層
された構造になつている。この場合、単一層当り
の容量をC0、絶縁抵抗をRoとすれば、積層形コ
ンデンサの容量ＣはCoのｎ倍になり、絶縁抵抗
ＲはRoの１／ｎになる。ここで磁器組成物の誘
電率をε、真空の誘電率をεｏ、磁器組成物の比
抵抗をρ、単一層コンデンサの磁器の厚さをｄ、
重なる電極面積をｓとすれば、単一層コンデンサ
のCoは（εｏεｓ／ｄ）となりRoは（ρｄ）／
ｓとなる。従つてｎ層からなる積層コンデンサの
容量(C)と絶縁抵抗（Ｒ）の積Ｃ×Ｒは〔（ρ
ｄ）／（ns）〕×〔（ｎεｏεｓ）ｄ〕＝εｏερと
なる。すなわちどのような容量の積層コンデンサ
もその容量・抵抗積Ｃ×Ｒは、磁器組成物のεと
ρの積にεｏを乗じた一定値（εｏερ）に規格
化される。容量・抵抗積Ｃ×Ｒが500μＦ・ＭΩ
すなわち500F・Ω以上ということは、εｏ＝
8.855×10-14F／cmより、Ｃ×Ｒ＝εｏερ＝
8.855×10-14（Ｆ／cm）×ε×ρ500F・Ωよつ
てερ≧5.65×1015Ω・cmなる要求がある。例え
ばε＝10000ではρ≧5.65×1011Ω・cm、ε＝
3000ではρ≧1.88×1012Ω・cm、ε＝500ではρ
1.13×1013Ω・cmが要求される。誘電率に応じ
てこれらの値以上のρを持つ磁器組成物であれば
どのような大きな容量の積層コンデンサも容量・
抵抗積は500μＦ・ＭΩを満足する。もしεが
3000でρが要求値より１桁低い1.88×1011Ω・cm
とすればεｏερ＝50μＦ・ＭΩで500μＦ・Ｍ
Ωは満足せず、絶縁抵抗として10000MΩすなわ
ち、1010Ω以上を満足するには容量Ｃとして
0.005μＦ以下に限定されなければならない。そ
れはこの積層コンデンサの容量・抵抗積（Ｃ×
Ｒ）は常に50μＦ・ＭΩを示しているので、Ｒが
10000MΩのとき、Ｃは0.005μＦとなり、Ｃがこ
れより大きければＲは10000MΩより小さくな
り、0.005μＦが規格を満たす最高の容量となる
ためである。従つて磁器組成物の比抵抗が低いと
その材料の実用性、特に積層形コンデンサの特長
である小型大容量の特長を生かすことはできない
し、全く意味のないことにもなる。よつて磁器組
成物の誘電率と比抵抗の積がある値以上を持つこ
とが実用上極めて重要なことである。
また積層形チツプコンデンサの場合はチツプコ
ンデンサを基板に実装したときの基板とチツプコ
ンデンサが構成している磁器との熱膨張係数の違
いによりチツプコンデンサに機械的な歪みが加わ
り、クラツクの発生や、ひどい場合にはチツプコ
ンデンサが破損する場合が生じる。またエポキシ
系樹脂等を外装したデイツプコンデンサの場合も
外装樹脂の応力によつてデイツプコンデンサにク
ラツクが発生する場合がある。
いずれの場合もコンデンサを形成している磁器
の機械的強度が低いほどクラツクが生じやすく、
また破損しやすいため、信頼性が低くなる。した
がつて磁器の機械的強度をできるだけ増大させる
ことは実用上きわめて重要なことである。
本発明者の実験によれば積層磁器コンデンサに
要求される信頼性を確保するためには、磁器の抗
折強度が1000Kg／cm2以上であることが望ましい。
ところでPb（Mg1/2W1/2）O3−PbTiO3系磁
器組成物については既にエヌ・エヌ・クライニ
ク、エイアイ・アグロノフスカヤ（フイジコ ト
ベルドゴテラ Vol2、No1 70〜72ページ１月
1960年）〔Ｎ：N.Krainik and A.I.Agranovskaya
（Fiziko Tverdogo Tela、Vo.2、No.１、pp70〜
72、January1960）〕より提案があつたが、誘電
率とその温度変化についての記載のみであつた。
また（SrxPb1−xTiO3）ａ（PbMg0.5W0.5O3）
ｂ〔ただしｘ＝０〜0.10、ａは0.35〜0.5、ｂは
0.5〜0.65であり、そしてａ＋ｂ＝１〕はモノリ
シツクコンデンサおよびその製造方法として特開
昭52〜21662号に開示され、また誘電体粉末組成
物として特開昭52−21699号に開示されている。
しかしここでは誘電率（2000〜5500）と誘電損失
（2.0％〜4.4％）に関するデータの記載しかな
い。
またPb（Mg1/2W1/2）O3−PbTiO3系を含む
三成分系については特開昭55−111011において
Pb（Mg1/2W1/2）O3−PbTiO3−Pb
（Mg1/3Nb2/3）O3系が開示され、特開昭55−
117809においてPb（Mg1/2W1/2）O3−PbTiO3
−Pb（Mg1/3Ta2/3）O3系が開示されている。
これらにおいても誘電率や誘電損失、および誘電
率の温度特性についてのみ記載されている。
以上いずれも比抵抗や機械的強度に関する開示
は全くされておらずその実用性については明らか
でなかつた。
さらに本発明者達は既に910〜950℃の温度で焼
結でき、Pb（Mg1/2W1/2）O3と、PbTiO32成
分系からなり、これを〔Pb（Mg1/2W1/2）
O3〕ｘ〔PbTiO3〕1-xと表わしたときにｘが0.65
＜ｘ≦1.00の範囲にある磁器組成物を提案してい
る。この磁器組成物は誘電率と比抵抗の積が高い
値を持ち、誘電損失の小さい優れた電気的特性を
有している。しかしながら、この組成物は、機械
的強度が低いため、その用途は自ら狭い範囲に限
定せざるを得なかつた。すなわち実用的な積層磁
器コンデンサを得るためには容量抵抗積、誘電損
失、機械的強度の３つの特性が同時に所定の特性
値を示す磁器組成物が必要となる。
本発明の目的は機械的強度の大きいしかも容量
抵抗積の高く（誘電損失の小さな実用性に優れた
磁器組成物を提供することにある。すなわち本発
明は、マンガン・ニオブ酸鉛［Pb
（Mn1/3Nb2/3）O3］、マグネシウム・タングス
テン酸鉛［Pb（Mg1/2W1/2）O3］からなる組
成物を［Pb（Mn1/3Nb2/3）O3］X・［Pb
（Mg1/2W1/2）O3］1-Xと表わしたときＸが0.005
≦Ｘ≦0.08の範囲にあることを特徴とする磁器組
成物であり、マンガン・ニオブ酸鉛［Pb
（Mn1/3Nb2/3）O3］、マグネシウム・タングス
テン酸鉛［Pb（Mg1/2W1/2）O3］、およびチタ
ン酸鉛［PbTiO3］からなる組成物を［Pb
（Mn1/3Nb2/3）O3］X・［Pb（Mg1/2W1/2）
O3］Y・［PbTiO3］Zと表わしたとき（ただしＸ＋
Ｙ＋Ｚ＝1.00）、この３成分組成図において
The present invention relates to a porcelain composition, particularly a dielectric porcelain composition that can be sintered at a low temperature of 1000° C. or lower, has a high product of dielectric constant and specific resistance, and has high mechanical strength. It is well known that ceramic compositions containing barium titanate (BaTiO 3 ) as a main component have been widely put into practical use as dielectric ceramic compositions. However, the sintering temperature of materials whose main component is BaTiO 3 or the like is usually as high as 1300 to 1400°C. Therefore, when using this material in a multilayer capacitor, a material that can withstand this sintering temperature must be used for the internal electrodes, such as an expensive noble metal such as platinum or palladium, which increases manufacturing costs. There are drawbacks. In order to manufacture multilayer capacitors at low cost, it is desirable to have a porcelain composition that can be sintered at as low a temperature as possible, especially at a temperature below 1000°C, so that inexpensive metals mainly composed of silver, nickel, etc. can be used for the internal electrodes. It is rare. By the way, when producing a practical multilayer capacitor using a ceramic composition, many items must be evaluated as the electrical properties of the ceramic composition. Generally, it is required that the dielectric constant be as large as possible, the dielectric loss as small as possible, the resistivity as large as possible, and the temperature change in the dielectric constant as small as possible. However, when multilayer capacitors are actually used in various devices, values such as capacitance, temperature change rate of capacitance, dielectric loss, etc. are required first, rather than dielectric constant. In multilayer capacitors, the capacitance is proportional to the dielectric constant of the ceramic composition;
However, since it is inversely proportional to the thickness and proportional to the electrode area and the number of laminated layers, a high dielectric constant of the ceramic composition is not necessarily an absolute factor in obtaining a certain capacity. Further, the temperature change rate of the capacitance (temperature change rate of the dielectric constant) has various allowable ranges depending on the application, and the temperature change rate of the dielectric constant of the ceramic composition is not an absolute factor when manufacturing a multilayer capacitor. On the other hand, there are regulations that dielectric loss must be below a certain value depending on the application, and the maximum
5.0% or less. If this value is exceeded, problems will arise in the reliability of the multilayer ceramic capacitor. Furthermore, regarding specific resistance, for example, as stated in the EIAJ standard (Multilayer ceramic capacitor (chip type) RC-3698B for electronic equipment by the Japan Electronics Engineers Society), the insulation resistance of a multilayer capacitor is 10000MΩ.
or more, or the capacitance-resistance product, whichever is smaller, is specified as 500μF/MΩ or more. If it falls below any of these values, a problem will arise in the reliability of the multilayer ceramic capacitor. In other words, if the product of the dielectric constant and resistivity of the porcelain composition is not greater than a certain absolute value,
Capacitors of any capacitance, especially large capacitances, cannot be made to meet practical requirements, and their uses are extremely limited, rendering them useless in practical terms. This point will be explained in detail as follows. A multilayer capacitor has a structure in which single-layer capacitors are stacked, generally consisting of n layers of the same thickness and forming n+1 internal electrodes. In this case, if the capacitance per single layer is C 0 and the insulation resistance is Ro, the capacitance C of the multilayer capacitor will be n times Co, and the insulation resistance R will be 1/n of Ro. Here, the permittivity of the ceramic composition is ε, the permittivity of vacuum is εo, the specific resistance of the ceramic composition is ρ, the thickness of the ceramic of the single layer capacitor is d,
If the overlapping electrode area is s, Co of a single layer capacitor is (εoεs/d) and Ro is (ρd)/
It becomes s. Therefore, the product C×R of the capacitance (C) and insulation resistance (R) of a multilayer capacitor consisting of n layers is [(ρ
d)/(ns)]×[(nεoεs)d]=εoερ. That is, the capacitance/resistance product C×R of a multilayer capacitor of any capacity is normalized to a constant value (εoερ) obtained by multiplying the product of ε and ρ of the ceramic composition by εo. Capacitance/resistance product C×R is 500μF・MΩ
In other words, 500F・Ω or more means εo=
From 8.855×10 -14 F/cm, C×R=εoερ=
8.855×10 -14 (F/cm)×ε×ρ500F・Ω, so there is a requirement that ερ≧5.65×10 15 Ω・cm. For example, when ε=10000, ρ≧5.65×10 11 Ω・cm, ε=
For 3000, ρ≧1.88×10 12 Ω・cm, for ε=500, ρ
1.13×10 13 Ω・cm is required. Depending on the dielectric constant, any large capacitance multilayer capacitor will have a capacitance of
The resistance product satisfies 500μF・MΩ. If ε
At 3000, ρ is 1.88×10 11 Ω・cm, which is one order of magnitude lower than the required value.
Then, εoερ=50μF・MΩ and 500μF・M
Ω is not satisfied, and in order to satisfy the insulation resistance of 10000MΩ, that is, 10 10 Ω or more, the capacitance C must be
Must be limited to 0.005 μF or less. It is the capacitance/resistance product (C×
R) always shows 50μF・MΩ, so R
This is because when C is 10,000 MΩ, C is 0.005 μF, and if C is larger than this, R is smaller than 10,000 MΩ, and 0.005 μF is the highest capacitance that satisfies the standard. Therefore, if the specific resistance of the ceramic composition is low, the practicality of the material, especially the small size and large capacity that is a feature of multilayer capacitors, cannot be taken advantage of, and it is completely meaningless. Therefore, it is extremely important in practice that the product of the dielectric constant and specific resistance of the porcelain composition has a certain value or more. In addition, in the case of multilayer chip capacitors, when the chip capacitor is mounted on a board, mechanical distortion is applied to the chip capacitor due to the difference in thermal expansion coefficient between the board and the porcelain that the chip capacitor is made of, which can cause cracks, In severe cases, the chip capacitor may be damaged. Also, in the case of dip capacitors coated with epoxy resin or the like, cracks may occur in the dip capacitor due to the stress of the coating resin. In either case, the lower the mechanical strength of the porcelain that forms the capacitor, the more likely it is that cracks will occur.
Furthermore, it is easily damaged, resulting in low reliability. Therefore, it is of practical importance to increase the mechanical strength of porcelain as much as possible. According to experiments conducted by the present inventors, in order to ensure the reliability required for a multilayer ceramic capacitor, it is desirable that the bending strength of the ceramic be 1000 Kg/cm 2 or more. By the way, Pb (Mg 1/2 W 1/2 ) O 3 -PbTiO 3 -based porcelain compositions have already been published by N.N. Kleinik and A.I.
1960) [N: N. Krainik and AIAgranovskaya
(Fiziko Tverdogo Tela, Vo.2, No.1, pp70~
72, January 1960)], but only the dielectric constant and its temperature change were described. Also (SrxPb 1 −xTiO 3 ) a(PbMg 0.5 W 0.5 O 3 )
b [However, x = 0 to 0.10, a is 0.35 to 0.5, b is
0.5 to 0.65 and a+b=1] is disclosed in JP-A-52-21662 as a monolithic capacitor and its manufacturing method, and as a dielectric powder composition in JP-A-52-21699. .
However, only data regarding dielectric constant (2000 to 5500) and dielectric loss (2.0% to 4.4%) are listed here. In addition, a ternary system including Pb(Mg 1/2 W 1/2 )O 3 -PbTiO 3 system is described in Japanese Patent Application Laid-open No. 111011/1983.
Pb(Mg 1/2 W 1/2 )O 3 −PbTiO 3 −Pb
(Mg 1/3 Nb 2/3 )O 3 system was disclosed in Japanese Patent Application Laid-Open No. 1986-
Pb(Mg 1/2 W 1/2 )O 3 −PbTiO 3 in 117809
-Pb(Mg 1/3 Ta 2/3 ) O 3 system is disclosed.
These documents only describe the dielectric constant, dielectric loss, and temperature characteristics of the dielectric constant. None of the above discloses specific resistance or mechanical strength, and their practicality is unclear. Furthermore, the present inventors have already found that sintering can be performed at a temperature of 910 to 950°C, which consists of a two-component system of Pb(Mg 1/2 W 1/2 ) O 3 and PbTiO 3 , which can be sintered at a temperature of 910 to 950 °C. W 1/2 )
O 3 ] x [PbTiO 3 ] When expressed as 1-x , x is 0.65
We propose a porcelain composition in the range <x≦1.00. This ceramic composition has a high product of dielectric constant and specific resistance, and has excellent electrical properties with low dielectric loss. However, since this composition has low mechanical strength, its use has had to be limited to a narrow range. That is, in order to obtain a practical laminated ceramic capacitor, a ceramic composition is required that simultaneously exhibits predetermined characteristic values for the three properties of capacitance-resistance product, dielectric loss, and mechanical strength. An object of the present invention is to provide a highly practical porcelain composition that has high mechanical strength and a high capacitance-resistance product (low dielectric loss).
(Mn 1/3 Nb 2/3 ) O 3 ] and magnesium lead tungstate [Pb (Mg 1/2 W 1/2 ) O 3 ]. )O 3 ] X・[Pb
(Mg 1/2 W 1/2 )O 3 ] When expressed as 1-X, X is 0.005
It is a porcelain composition characterized by being in the range of ≦X≦0.08, and contains manganese lead niobate [Pb
(Mn 1/3 Nb 2/3 ) O 3 ], magnesium lead tungstate [Pb (Mg 1/2 W 1/2 ) O 3 ], and lead titanate [PbTiO 3 ].
(Mn 1/3 Nb 2/3 ) O 3 ] X・[Pb (Mg 1/2 W 1/2 )
O 3 ] Y・[PbTiO 3 ] Z (where X+
Y + Z = 1.00), in this three-component composition diagram
【表】
の各点を結ぶ線上（ただしＺ＝０の部分は除
く。）およびこの範囲内にあることを特徴とする
磁器組成物である。本発明の磁器組成物は積層形
コンデンサに利用する場合、銀、ニツケル等を主
成分とする安価な内部電極が使用可能な、900℃
〜1000℃の温度で焼結でき容量、抵抗積が500μ
Ｆ・ＭΩ以上で、しかも誘電損失が小さく、機械
的強度が高く、また誘電率も前記の範囲内で300
〜6000程度の値を持つ優れた材料である。
次に本発明を実施例によつて詳細に説明する。
実施例
出発原料として純度99.9％以上の酸化鉛
（PbO）、酸化マグネシウム（MgO）、炭酸マンガ
ン（MnCO3）酸化ニオブ（Nb2O5）、酸化タング
ステン（WO3）および酸化チタン（TiO2）を使用
し、所定の配合比に秤量した。次にボールミル中
で湿式混合した後750℃〜800℃で予焼した。その
後、ボールミルで粉砕し、口別、乾燥後、有機バ
インダーを入れ整粒後プレスし、直径16mm、厚さ
約２mmの円板を４枚と直径16mm、厚さ約10mmの円
柱を作製した。次に空気中において900℃〜1000
℃で１時間焼結した。焼結した円板の上下面に
600℃で銀電極を焼付け、デジタルLCRメーター
で周波数1KHz、電圧1Vr.m.s.で容量と誘電損失
（tanδ）を測定し、誘電率を算出した。次に超絶
縁抵抗計で50Vの電圧を１分間印加して絶縁抵抗
を測定した。４個の試料の平均値をとり、その値
を各配分比の代表値とした。
また機械的強度を抗折強度で評価するため円柱
試料から厚さ0.5mm、幅２mm、長さ約13mmの矩形
板を切り出した。支点間の距離を９mmにとり、３
点法で破壊荷重Pm〔Kg〕を測定し、τ＝３Ｐｍｌ／２Ｗ
Ｔ２
〔Kg／cm2〕なる式により抗折強度τ（Kg／cm2）を
求めた。ただしｌは支点間距離、ｔは試料の厚
み、ｗは試料の巾である。値は試料10点の平均値
より求めた。
試作した磁器組成物の成分配合比を表に示す。
また磁器組成物配合比と容量・抵抗積、誘電損
失、抗折強度との関係を第１図から第３図に示
す。なお図中の曲線上の番号は表の各番号に対応
している。さらに第４図に本発明の請求範囲と成
分配合比を示す。これらの図においてPb
（Mg1/2W1/2）O3−PbTiO3系組成物、あるいは
Pb（Mg1/2W1/2）O3に対してPb
（Mn1/3Nb2/3）O3を固溶させると、誘電損失は
Pb（Mn1/3Nb2/3）O3が３〜４モル％付近で極
小になり、その後増加する。また容量抵抗積は
Pb（Mn1/3Nb2/3）Ｏが１〜２モル％付近で極
大になり、その後減少し、抵折強度はPb
（Mn1/3Nb2/3）O3を固溶せせると急激に増加し
１モル％付近で1200〜1400Kg／cm2の値になり、そ
の後1000〜1100Kg／cm2のほぼ一定した値になる。[Table] This is a porcelain composition characterized by being on the line connecting each point (excluding the part where Z=0) and within this range. When used in a multilayer capacitor, the ceramic composition of the present invention can be heated to 900°C, allowing the use of inexpensive internal electrodes mainly composed of silver, nickel, etc.
Can be sintered at a temperature of ~1000℃, with a capacity and resistance product of 500μ
F・MΩ or more, with low dielectric loss, high mechanical strength, and a dielectric constant of 300 within the above range.
It is an excellent material with a value of about ~6000. Next, the present invention will be explained in detail by way of examples. Examples Lead oxide (PbO), magnesium oxide (MgO), manganese carbonate (MnCO 3 ), niobium oxide (Nb 2 O 5 ), tungsten oxide (WO 3 ), and titanium oxide (TiO 2 ) with a purity of 99.9% or more are used as starting materials. were weighed to a predetermined blending ratio. Next, after wet mixing in a ball mill, the mixture was pre-baked at 750°C to 800°C. Thereafter, it was ground in a ball mill, divided into slivers, dried, and then mixed with an organic binder, sized, and pressed to produce four discs with a diameter of 16 mm and a thickness of about 2 mm, and a cylinder with a diameter of 16 mm and a thickness of about 10 mm. Then in the air at 900℃~1000℃
Sintered at ℃ for 1 hour. on the top and bottom surfaces of the sintered disk.
The silver electrode was baked at 600°C, and the capacitance and dielectric loss (tan δ) were measured using a digital LCR meter at a frequency of 1 KHz and a voltage of 1 Vr.ms, and the dielectric constant was calculated. Next, a voltage of 50V was applied for 1 minute using a super insulation resistance meter to measure the insulation resistance. The average value of the four samples was taken, and that value was used as the representative value for each distribution ratio. In addition, in order to evaluate the mechanical strength in terms of bending strength, a rectangular plate with a thickness of 0.5 mm, a width of 2 mm, and a length of approximately 13 mm was cut out from the cylindrical sample. Set the distance between the fulcrums to 9mm, and
Measure the breaking load Pm [Kg] using the point method, and find τ=3Pml/2W
The bending strength τ (Kg/cm 2 ) was determined using the formula T 2 [Kg/cm 2 ]. However, l is the distance between the supporting points, t is the thickness of the sample, and w is the width of the sample. The value was determined from the average value of 10 samples. The table shows the component composition ratio of the prototype porcelain composition.
Further, the relationship between the blending ratio of the porcelain composition and the capacitance/resistance product, dielectric loss, and bending strength is shown in FIGS. 1 to 3. Note that the numbers on the curves in the figure correspond to the numbers in the table. Further, FIG. 4 shows the claimed scope and component blending ratio of the present invention. In these figures Pb
(Mg 1/2 W 1/2 )O 3 −PbTiO 3 based composition, or
Pb(Mg 1/2 W 1/2 ) Pb for O3
(Mn 1/3 Nb 2/3 ) When O 3 is dissolved in solid solution, the dielectric loss is
Pb(Mn 1/3 Nb 2/3 )O 3 reaches a minimum around 3 to 4 mol%, and then increases. Also, the capacitance-resistance product is
Pb(Mn 1/3 Nb 2/3 )O reaches a maximum around 1 to 2 mol%, then decreases, and the bending strength is
(Mn 1/3 Nb 2/3 ) When O 3 is made into a solid solution, it increases rapidly to a value of 1200 to 1400 Kg/cm 2 at around 1 mol%, and then becomes an almost constant value of 1000 to 1100 Kg/cm 2 Become.
【表】【table】
【表】
また第３図を第１，２図と比べるとPbTiO3の
モル比が増加すると、誘電損失が大きくなり、容
量抵抗値は減少してゆくことが判かる。
ここで本発明の組成物はマンガン・ニオブ酸鉛
［Pb（Mn1/3Nb2/3）O3］、マグネシウム・タン
グステン酸鉛［Pb（Mg1/2W1/2）O3］からな
る組成物を［Pb（Mn1/3Nb2/3）O3］X・［Pb
（Mg1/2W1/2）O3］1-Xと表わしたときＸが0.005
≦Ｘ≦0.08の範囲であり、マンガン・ニオブ酸鉛
［Pb（Mn1/3Nb2/3）O3］、マグネシウム・タン
グステン酸鉛［Pb（Mg1/2W1/2）O3］、および
チタン酸鉛［PbTiO3］からなる組成物を［Pb
（Mn1/3Nb2/3）O3］X・［Pb（Mg1/2W1/2）
O3］Y・［PbTiO3］と表わしたとき（ただしＸ＋
Ｙ＋Ｚ＝1.00）、この３成分組成図において[Table] Comparing Figure 3 with Figures 1 and 2, it can be seen that as the molar ratio of PbTiO 3 increases, the dielectric loss increases and the capacitance resistance value decreases. Here, the composition of the present invention is made from manganese/lead niobate [Pb(Mn 1/3 Nb 2/3 )O 3 ] and magnesium/lead tungstate [Pb(Mg 1/2 W 1/2 )O 3 ]. [Pb( Mn 1/3 Nb 2/3 )O 3 ]
(Mg 1/2 W 1/2 )O 3 ] When expressed as 1-X, X is 0.005
≦X≦0.08, manganese/lead niobate [Pb (Mn 1/3 Nb 2/3 ) O 3 ], magnesium/lead tungstate [Pb (Mg 1/2 W 1/2 ) O 3 ] , and lead titanate [PbTiO 3 ].
(Mn 1/3 Nb 2/3 ) O 3 ] X・[Pb (Mg 1/2 W 1/2 )
O 3 ] Y・[PbTiO 3 ] (where X+
Y + Z = 1.00), in this three-component composition diagram
【表】
の各点を結ぶ線上（ただしＺ＝０の部分は除
く。）およびこの範囲内に限定される。
その理由はＸ＞0.08で、しかも本発明の請求範
囲に含まれない範囲、及びＺ＞0.46で、しかも本
発明の請求範囲に含まれない範囲では容量抵抗積
が500μＦ・ＭΩより小さくなり、実用上の規格
値より劣る。
またＸ＜0.005の範囲では抵折強度が低くなつ
てしまう。
以上、本発明の磁器組成物は1000℃以上の低温
で焼成でき銀やニツケル等を主成分とする低価格
金属を内部電極として使用できると共に、省エネ
ルギーや炉材の節約という経済的な面で極めて有
用な材料である。さらに特性面においては容量抵
抗積は十分に実用上の規格値より大きく、また機
械的強度が高いため高信頼性が得られ、さらに誘
電損失が小さく、非常に優れた材料である。[Table] Limited to the line connecting each point (excluding the part where Z=0) and within this range. The reason for this is that in the range where X > 0.08 and not included in the claimed scope of the present invention, and in the range where Z > 0.46 and not included in the claimed scope of the present invention, the capacitance-resistance product becomes smaller than 500μF・MΩ, making it impractical. Inferior to the above standard value. Moreover, in the range of X<0.005, the refraction strength becomes low. As described above, the porcelain composition of the present invention can be fired at a low temperature of 1000°C or higher, and low-cost metals containing silver, nickel, etc. as main components can be used as internal electrodes, and it is extremely economical in terms of saving energy and furnace materials. It is a useful material. Furthermore, in terms of characteristics, the capacitance-resistance product is sufficiently larger than the practical standard value, the mechanical strength is high, so high reliability can be obtained, and the dielectric loss is small, making it an extremely excellent material.
第１図から第３図は磁器組成物の配合比と諸特
性との関係を示した図である。第１図は表のNo.１
〜13、第２図は表のNo.14〜27、第３図は表のNo.28
〜40のそれぞれの特性値である。各図中の曲線ａ
は抗折強度、ｂは容量抵抗値、ｃは誘電損失の特
性をそれぞれ示している。また図中の番号は表の
各組成配合比の番号に対応している。第４図は本
発明の請求の範囲と表に示した各配合比の組成点
を示した図である。
FIGS. 1 to 3 are diagrams showing the relationship between the blending ratio of the porcelain composition and various properties. Figure 1 is No. 1 in the table.
~13, Figure 2 is No. 14 to 27 in the table, Figure 3 is No. 28 in the table
~40 respective characteristic values. Curve a in each figure
indicates the bending strength, b indicates the capacitance resistance value, and c indicates the dielectric loss characteristic. Further, the numbers in the figure correspond to the numbers of each composition/blending ratio in the table. FIG. 4 is a diagram showing the scope of claims of the present invention and composition points for each compounding ratio shown in the table.
Claims (1)
（Mn1/3Nb2/3）O3］、マグネシウム・タングス
テン酸鉛［Pb（Mg1/2W1/2）O3］からなる組
成物を［Pb（Mn1/3Nb2/3）O3］X・［Pb
（Mg1/2W1/2）O3］1-Xと表わしたときＸが0.005
≦Ｘ≦0.08の範囲にあることを特徴とする磁器組
成物。 ２ マンガン・ニオブ酸鉛［Pb
（Mn1/3Nb2/3）O3］、マグネシウム・タングス
テン酸鉛［Pb（Mg1/2W1/2）O3］、およびチタ
ン酸鉛［PbTiO3］からなる組成物を［Pb
（Mn1/3Nb2/3）O3］X・［Pb（Mg1/2W1/2）
O3］Y・［PbTiO3］Zと表わしたとき（ただしＸ＋
Ｙ＋Ｚ＝1.00）、この３成分組成図において 【表】 の各点を結ぶ線上（ただしＺ＝０の部分は除
く。）およびこの範囲内にあることを特徴とする
磁器組成物。[Claims] 1 Manganese lead niobate [Pb
(Mn 1/3 Nb 2/3 ) O 3 ] and magnesium lead tungstate [Pb (Mg 1/2 W 1/2 ) O 3 ]. )O 3 ] X・[Pb
(Mg 1/2 W 1/2 )O 3 ] When expressed as 1-X, X is 0.005
A porcelain composition characterized in that it is in the range of ≦X≦0.08. 2 Manganese lead niobate [Pb
(Mn 1/3 Nb 2/3 ) O 3 ], magnesium lead tungstate [Pb (Mg 1/2 W 1/2 ) O 3 ], and lead titanate [PbTiO 3 ].
(Mn 1/3 Nb 2/3 ) O 3 ] X・[Pb (Mg 1/2 W 1/2 )
O 3 ] Y・[PbTiO 3 ] Z (where X+
Y+Z=1.00), on the line connecting each point of [Table] in this three-component composition diagram (excluding the part where Z=0), and within this range.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56156685A JPS5860670A (en) | 1981-10-01 | 1981-10-01 | Ceramic composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56156685A JPS5860670A (en) | 1981-10-01 | 1981-10-01 | Ceramic composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5860670A JPS5860670A (en) | 1983-04-11 |
| JPS6234708B2 true JPS6234708B2 (en) | 1987-07-28 |
Family
ID=15633082
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56156685A Granted JPS5860670A (en) | 1981-10-01 | 1981-10-01 | Ceramic composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5860670A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6033256A (en) * | 1983-07-28 | 1985-02-20 | 日本電気株式会社 | Ceramic composition |
| JPH09208312A (en) | 1996-01-26 | 1997-08-12 | Murata Mfg Co Ltd | Dielectric ceramic composition |
-
1981
- 1981-10-01 JP JP56156685A patent/JPS5860670A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5860670A (en) | 1983-04-11 |
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