JPH0566334B2 - - Google Patents
Info
- Publication number
- JPH0566334B2 JPH0566334B2 JP60073935A JP7393585A JPH0566334B2 JP H0566334 B2 JPH0566334 B2 JP H0566334B2 JP 60073935 A JP60073935 A JP 60073935A JP 7393585 A JP7393585 A JP 7393585A JP H0566334 B2 JPH0566334 B2 JP H0566334B2
- Authority
- JP
- Japan
- Prior art keywords
- composition
- mol
- main component
- points
- present
- 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
Links
- 239000000203 mixture Substances 0.000 claims description 19
- 229910052573 porcelain Inorganic materials 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 238000010586 diagram Methods 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- PYPDMIQMPWEFHX-UHFFFAOYSA-N [Pb].[Co] Chemical compound [Pb].[Co] PYPDMIQMPWEFHX-UHFFFAOYSA-N 0.000 claims 2
- 239000000919 ceramic Substances 0.000 description 9
- 238000005245 sintering Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- 239000003985 ceramic capacitor Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- LIABKAQKQSUQJX-UHFFFAOYSA-N [Mn].[Pb] Chemical compound [Mn].[Pb] LIABKAQKQSUQJX-UHFFFAOYSA-N 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-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
- 239000011230 binding agent Substances 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 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
- 150000003891 oxalate salts Chemical class 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
（産業上の利用分野）
本発明は磁器組成物、特に1050℃以下の低温で
焼結できる誘電率の高い、積層セラミツクコンデ
ンサに適した磁器組成物に関するものである。
（従来技術）
従来積層セラミツクコンデンサに利用される誘
電体磁器組成物として、チタン酸バリウム
（BaTiO3）を主成分とするものが広く実用化さ
れていることは周知の通りである。しかしなが
ら、BaTiO3を主成分とするものは、焼結温度が
1300〜1400℃の高度であり、これを積層コンデン
サに用いる場合には内部電極としてこの焼結温度
に耐える材料、例えは白金やパラジウムなどの高
価な貴金属を使用しなければならなず、製造コス
トが高いという欠点があつた。このため銀やニツ
ケルなどを主成分とする安価な金属を使用可能と
するためには、磁器の焼結温度をできるだけ低く
することが望まれていた。
このため既に、Pb（Fe2/3Ｗ1/3）O3−Pb（Fe1/
２Nb1/2）O3（特公昭55−34962）や（Sr・Pb）
TiO3−Pb（Mg1/2Ｗ1/2）O3（特開昭52−21699）
などの提案がある。
本発明者らはこれと異なる新たな磁器組成物を
探索したところＰ（Cob1/3Nb2/3）O3とPb（Co1/
２Ｗ1/2）O3及びPbTiO3からなる３成分組成物は
1050℃以下の低温で焼結でき、高い誘電率を有す
ることを見い出した。しかしがらこの３成分磁器
組成物は誘電損失が高く、比抵抗は低く、実用上
より改良が望まれていた。
（発明の目的）
本発明の目的は1050℃以下の低温で焼結でき、
誘電率が高く、誘電損失の低いかつ比抵抗の高い
積層コンデンサ用磁器組成物を提供することにあ
る。
（発明の構成）
本発明の主成分磁器組成物は〔Pb（Co1/3Nb2/
３）O3〕x〔Pb（Co1/2Ｗ1/2）O3〕y〔PbTiO3〕zから
なり（ただしｘ＋ｙ＋ｚ＝1.00）、三元組成図に
おける点Ａ，Ｂ，Ｃ，Ｄすなわち、Ａ（ｘ＝0.89、
ｙ＝0.01、ｚ＝0.10）、Ｂ（ｘ＝0.01、ｙ＝0.74、
ｚ＝0.25）、Ｃ（ｘ＝0.01、ｙ＝0.34、ｚ＝0.65）、
Ｄ（ｘ＝0.50、ｙ＝0.05、ｚ＝0.45）からなる４点
を結す線上および４点に囲まれる主成分組成物に
副成分としてPb（Mn1/2Ne1/2）O3が0.5モル％
ないし７モル％添加されていることを特徴とする
〔ただしMeはNb、TaおよびSbのうちから一種以
上の元素が選ばれる〕。
（構成に関する説明）
本発明の磁器組成物は主成分原料と同時に、マ
ンガンニオブ酸鉛〔Pb（Mn1/2Me1/2）O3〕、マ
ンガンタンタル酸鉛〔Pb（Mn1/2TaY2）O3〕、
マンガンアンチモン酸鉛〔Pb（Mn1/2Sb1/2）
O3〕のうちから選ばれた１種以上が主成分に対
して0.5モル％ないし７モル％となるように含有
せしめうことにより、比抵抗を著るしく改良し、
誘電損失も大巾に小さくすることができる。
（実施例）
以下本発明を実施例にて詳細に説明する。
出発原料として純度99％以上の酸化鉛（PbO）、
炭酸コバルト（CoCO3）、酸化ニオブ（Nb2O5）、
酸化タンタル（Ta2O5）、酸化アンチモン
（Sb2O3）、酸化タングステン（WO3）、酸化チタ
ン（TiO2）および炭酸マンガン（MnCO3）を使
用し、所定の配合比に秤量する。次にボールミル
中で湿式混合したのち750〜800℃で予焼した。
その後ボールミルで粉砕し、別、乾燥後、有
機バインダーを入れ整粒し、0.7ton／cm2プレスし
た。直径16mm、厚さ約２mmの円板を４枚作成し
た。次に空気中で880℃〜1040℃で１時間焼結し
た。焼結した円板の上下面に銀電極を600℃で焼
付け、デジタルLCRメーターで周波数1KHz、電
流1Vrmsで容量と誘電損失（tanδ）を測定し、
誘電率を算出した。次に超絶縁計で50Vの電圧を
１分間印加し絶縁抵抗を測定し、比抵抗を算出し
た。いずれも４個の試料を室温で測定し、平均値
を代表値とした。
このようにして得られた特性と配合比の関係を
次表に示す。
(Field of Industrial Application) The present invention relates to a ceramic composition, particularly a ceramic composition having a high dielectric constant that can be sintered at a low temperature of 1050° C. or lower and is suitable for a laminated ceramic capacitor. (Prior Art) It is well known that dielectric ceramic compositions containing barium titanate (BaTiO 3 ) as a main component have been widely put into practical use as conventional dielectric ceramic compositions used in laminated ceramic capacitors. However, for those whose main component is BaTiO3 , the sintering temperature is
The temperature is 1,300 to 1,400 degrees Celsius, and if this is used in a multilayer capacitor, a material that can withstand this sintering temperature must be used for the internal electrodes, for example, expensive noble metals such as platinum or palladium, which increases manufacturing costs. The disadvantage was that it was expensive. For this reason, it has been desired to lower the sintering temperature of porcelain as low as possible in order to make it possible to use inexpensive metals mainly composed of silver or nickel. Therefore, Pb(Fe2/3W1/3)O 3 −Pb(Fe1/
2Nb1/2) O 3 (Special Publication No. 1983-34962) and (Sr/Pb)
TiO 3 −Pb(Mg1/2W1/2)O 3 (Japanese Patent Application Laid-Open No. 1983-21699)
There are other suggestions. The present inventors searched for a new ceramic composition different from this, and found that P(Cob1/3Nb2/3)O 3 and Pb(Co1/
The three-component composition consisting of 2W1/2) O 3 and PbTiO 3 is
It was discovered that it can be sintered at low temperatures below 1050°C and has a high dielectric constant. However, this three-component ceramic composition has a high dielectric loss and a low resistivity, and improvements have been desired for practical purposes. (Object of the invention) The object of the present invention is to enable sintering at a low temperature of 1050°C or lower,
An object of the present invention is to provide a ceramic composition for a multilayer capacitor that has a high dielectric constant, low dielectric loss, and high specific resistance. (Structure of the Invention) The main component ceramic composition of the present invention is [Pb(Co1/3Nb2/
3) It consists of O 3 ] x [Pb(Co1/2W1/2)O 3 ] y [PbTiO 3 ] z (however, x+y+z=1.00), and points A, B, C, and D in the ternary composition diagram, that is, A( x=0.89,
y=0.01, z=0.10), B(x=0.01, y=0.74,
z=0.25), C(x=0.01, y=0.34, z=0.65),
0.5 mol% of Pb(Mn1/2Ne1/2)O 3 as a subcomponent is added to the main component composition on the line connecting the four points consisting of D (x=0.50, y=0.05, z=0.45) and surrounded by the four points.
[However, Me is one or more elements selected from Nb, Ta, and Sb]. (Explanation regarding composition) The porcelain composition of the present invention contains lead manganese niobate [Pb (Mn1/2Me1/2) O 3 ] and lead manganese tantalate [Pb (Mn1/2TaY 2 ) O 3 ] at the same time as the main component raw materials. ,
Manganese lead antimonate [Pb (Mn1/2Sb1/2)
By containing one or more selected from O 3 in an amount of 0.5 mol % to 7 mol % based on the main component, the specific resistance is significantly improved,
Dielectric loss can also be significantly reduced. (Example) The present invention will be described in detail below with reference to Examples. Lead oxide (PbO) with a purity of over 99% as a starting material,
Cobalt carbonate (CoCO 3 ), niobium oxide (Nb 2 O 5 ),
Tantalum oxide (Ta 2 O 5 ), antimony oxide (Sb 2 O 3 ), tungsten oxide (WO 3 ), titanium oxide (TiO 2 ), and manganese carbonate (MnCO 3 ) are used and weighed to a predetermined mixing ratio. Next, after wet mixing in a ball mill, the mixture was pre-baked at 750-800°C. Thereafter, it was ground in a ball mill, separated, and after drying, an organic binder was added thereto to size it, and it was pressed at 0.7 ton/cm 2 . Four disks with a diameter of 16 mm and a thickness of about 2 mm were created. It was then sintered in air at 880°C to 1040°C for 1 hour. Silver electrodes were baked on the top and bottom surfaces of the sintered disk at 600℃, and the capacitance and dielectric loss (tanδ) were measured using a digital LCR meter at a frequency of 1KHz and a current of 1Vrms.
The dielectric constant was calculated. Next, a voltage of 50V was applied for 1 minute using a super megohmmeter to measure the insulation resistance and calculate the specific resistance. In each case, four samples were measured at room temperature, and the average value was taken as the representative value. The relationship between the properties thus obtained and the blending ratio is shown in the following table.
【表】【table】
【表】
（発明の効果）
表に示した結果から明らかなように本発明は
Pb（Co1/3Nb2/3）O3−Pb（Co1/2Ｗ1/2）O3−
PbTiO33成分系に副成分としてPb（Mn1/2Nb1/
２）O3、Pb（Mn1/2Ta1/2）O3、Pb（Mn1/2Sb1/
２）O3のうちから選ばれた１種以上を含有せしめ
て、誘電損失、（tanδ）を大巾に改良し、比抵抗
を著るしく高め、しかも高誘電率でありかつ低温
焼結できる。このため積層コンデンサ用磁器組成
物として優れた材料を提供している。
なお主成分配合比が本発明の範囲外では誘電率
が低くなるか焼結温度が1050℃より高くなる。副
成分の添加量が0.5モル％未満では比抵抗や誘電
損失（tanδ）の改善効果が少ない。７モル％を越
えると誘電損失の改善効果が少なくなる。
マンガンを化合物として本実施例では炭酸マン
ガンを使用したがマンガンの酸化物や高温で分解
し、酸化物になるしゆう酸塩、硫酸塩、水酸化物
など使用してもよい。[Table] (Effects of the invention) As is clear from the results shown in the table, the present invention
Pb(Co1/3Nb2/3)O 3 −Pb(Co1/2W1/2)O 3 −
Pb ( Mn1 /2Nb1/
2) O 3 , Pb (Mn1/2Ta1/2) O 3 , Pb (Mn1/2Sb1/
2) Contains one or more selected from O 3 to greatly improve dielectric loss (tan δ), significantly increases specific resistance, and has a high dielectric constant and can be sintered at low temperatures. . Therefore, it provides an excellent material as a ceramic composition for multilayer capacitors. Note that if the blending ratio of the main components is outside the range of the present invention, the dielectric constant will be low or the sintering temperature will be higher than 1050°C. If the amount of the subcomponents added is less than 0.5 mol%, the effect of improving specific resistance and dielectric loss (tan δ) will be small. If it exceeds 7 mol%, the effect of improving dielectric loss will be reduced. In this embodiment, manganese carbonate was used as a manganese compound, but manganese oxides, oxalates, sulfates, hydroxides, etc., which decompose at high temperatures to form oxides, may also be used.
Claims (1)
O3〕とコバルト・タングステン酸鉛〔Pb（Co1/2
Ｗ1/2）O3〕とチタン酸鉛〔PbTiO3〕からなる
組成物を〔Pb（Co1/3Nb2/3）O3〕x〔Pb（Co1/2Ｗ
１／２）O3〕y〔PbTiO3〕zと表わしたときに（ただし
ｘ＋ｙ＋ｚ＝1.00）、三元組成図における点、Ａ，
Ｂ，Ｃ，Ｄすなわち Ａ（ｘ＝0.89、ｙ＝0.01、ｚ＝0.10） Ｂ（ｘ＝0.01、ｙ＝0.74、ｚ＝0.25） Ｃ（ｘ＝0.01、ｙ＝0.34、ｚ＝0.65） Ｄ（ｘ＝0.50、ｙ＝0.05、ｚ＝0.45） からなる４点を結ぶ線上、および４点に囲まれる
主成分組成物に副成分としてPb（Mn1/2Me1/2）
O3を0.5モル％ないし７モル％添加含有せしめる
ことを特徴とする磁器組成物〔ただしMeはNb、
TaおよびSbのうちから一種以上の元素が選ばれ
る〕。[Claims] 1 Cobalt lead niobate [Pb (Co1/3Nb2/3)
O 3 ] and cobalt-lead tungstate [Pb (Co1/2
A composition consisting of [Pb(Co1/3Nb2/ 3 )O 3 ] x [Pb(Co1/2W
1/2) O 3 ] y [PbTiO 3 ] When expressed as z (however, x+y+z=1.00), the points in the ternary composition diagram, A,
B, C, D i.e. A(x=0.89, y=0.01, z=0.10) B(x=0.01, y=0.74, z=0.25) C(x=0.01, y=0.34, z=0.65) D( x=0.50, y=0.05, z=0.45), and Pb (Mn1/2Me1/2) as a subcomponent in the main component composition surrounded by the four points.
A porcelain composition characterized by additionally containing 0.5 mol % to 7 mol % of O 3 [where Me is Nb,
One or more elements are selected from Ta and Sb].
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60073935A JPS61232262A (en) | 1985-04-08 | 1985-04-08 | Ceramic composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60073935A JPS61232262A (en) | 1985-04-08 | 1985-04-08 | Ceramic composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61232262A JPS61232262A (en) | 1986-10-16 |
| JPH0566334B2 true JPH0566334B2 (en) | 1993-09-21 |
Family
ID=13532474
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60073935A Granted JPS61232262A (en) | 1985-04-08 | 1985-04-08 | Ceramic composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61232262A (en) |
-
1985
- 1985-04-08 JP JP60073935A patent/JPS61232262A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61232262A (en) | 1986-10-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |