JPS58190870A - High dielectric constant ceramic composition - Google Patents
High dielectric constant ceramic compositionInfo
- Publication number
- JPS58190870A JPS58190870A JP57071789A JP7178982A JPS58190870A JP S58190870 A JPS58190870 A JP S58190870A JP 57071789 A JP57071789 A JP 57071789A JP 7178982 A JP7178982 A JP 7178982A JP S58190870 A JPS58190870 A JP S58190870A
- Authority
- JP
- Japan
- Prior art keywords
- dielectric constant
- composition
- high dielectric
- ceramic composition
- capacitance
- 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 description 31
- 239000000919 ceramic Substances 0.000 title claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003990 capacitor Substances 0.000 description 6
- 229910052573 porcelain Inorganic materials 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 3
- 229910002113 barium titanate Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- PCTMTFRHKVHKIS-BMFZQQSSSA-N (1s,3r,4e,6e,8e,10e,12e,14e,16e,18s,19r,20r,21s,25r,27r,30r,31r,33s,35r,37s,38r)-3-[(2r,3s,4s,5s,6r)-4-amino-3,5-dihydroxy-6-methyloxan-2-yl]oxy-19,25,27,30,31,33,35,37-octahydroxy-18,20,21-trimethyl-23-oxo-22,39-dioxabicyclo[33.3.1]nonatriaconta-4,6,8,10 Chemical compound C1C=C2C[C@@H](OS(O)(=O)=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2.O[C@H]1[C@@H](N)[C@H](O)[C@@H](C)O[C@H]1O[C@H]1/C=C/C=C/C=C/C=C/C=C/C=C/C=C/[C@H](C)[C@@H](O)[C@@H](C)[C@H](C)OC(=O)C[C@H](O)C[C@H](O)CC[C@@H](O)[C@H](O)C[C@H](O)C[C@](O)(C[C@H](O)[C@H]2C(O)=O)O[C@H]2C1 PCTMTFRHKVHKIS-BMFZQQSSSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 244000062175 Fittonia argyroneura Species 0.000 description 1
- 229910005805 NiNb Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 210000000078 claw Anatomy 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229940071182 stannate Drugs 0.000 description 1
- 125000005402 stannate group Chemical group 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Ceramic Capacitors (AREA)
- Inorganic Insulating Materials (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】 本発明に高誘電率磁器組成物に関する。[Detailed description of the invention] The present invention relates to a high dielectric constant ceramic composition.
高誘電率磁器組成物としては、チタン酸バリウムを主体
とＬ、これにスズ酸塩、ジルコン酸塩あるいは他のチタ
ン酸塩等を固溶させたものが広く実用に供されている。As high dielectric constant ceramic compositions, compositions in which L is mainly composed of barium titanate and solid solution of stannate, zirconate, or other titanate are widely used in practical use.
しかしながら、この系の磁器利料は、誘電率が高い組成
にすると容量温度特性が悪化するばかりで々く、容量の
電圧依存性が著しく大きくなる傾向があり、これらのこ
とがコンデンザ材利として用いる場合の大きな問題とな
っていた。しかも、この系の磁器はその焼成に１３００
〜１４００℃という高い温度を必要とするため焼成コス
トが高く、さらに積層コンデンサに適用する場合には内
部電極材料として高価なパラジウムや白金を用いざるを
得す、コンデンサのコストダウンを計ることができガい
という問題があった。このようガ問題を解決するため、
Ｐｂ（Ｎｉ Ｎｂ ）０８−ＰｂＴｉ０８−Ｐｂ（
Ｃｏ １／２１／Ｂ ２／８
Ｗ１７□）０８からなる高誘電率磁器組成物が提案され
ている。この三成分系磁器組成物はチタン酸バリウム系
のものに比して、焼結性、誘電率、容量温度依存性およ
び電圧依存性において格段に優れてはいるが、未だ容量
温度特性等の点で十分満足しうるものとは言い難いのが
現状である。However, when this type of porcelain material has a composition with a high dielectric constant, its capacitance-temperature characteristics deteriorate, and the voltage dependence of the capacitance tends to become significantly large.These factors make it difficult to use it as a capacitor material. This had become a major problem. Moreover, this type of porcelain takes 1,300 yen to fire.
Because it requires a high temperature of ~1400°C, the firing cost is high, and when applied to multilayer capacitors, expensive palladium or platinum must be used as internal electrode materials.However, it is not possible to reduce the cost of capacitors. There was a problem with it. In order to solve this problem,
Pb(NiNb)08-PbTi08-Pb(
A high dielectric constant ceramic composition consisting of Co 1/21/B 2/8 W17□)08 has been proposed. Although this ternary ceramic composition is significantly superior to barium titanate-based compositions in terms of sinterability, dielectric constant, capacitance temperature dependence, and voltage dependence, it still has problems such as capacitance temperature characteristics. At present, it is difficult to say that this is completely satisfactory.
本発明は、このような問題に鑑みてなされたものであっ
て、容量温度特性および絶縁抵抗を向上させた高誘電率
磁器組成物を提供することを目的とし、その要旨は、一
般式：
％式％
）
（但し、式中Ｘ、γ、２は各成分のモル分率を表わし、
ｘ＋ｙ＋ｚ＝１．００）で表わされ、かつ第１図に示さ
れる下記組成の点Ａ＝ Ｂ、Ｃ，Ｄｆ頂点とする多角形
ＡＢＣＤで四重れた範囲内の組成（但し、ＡＤ線上の組
成を除く）４有する三成分０〜５０ｗｔ％ とＴｉＯ２
０，０５〜２．５ｗｔ％ を含み、かつＴ ｉ ０２と
ｌ５ｉ２０Ｂのモル比（Ｔ ｉ ０２ ／ｒｓｉ２０ａ
）が０５〜３であることを特徴とする高誘電率磁器組成
物、にある。前記多角形ＡＢＣＤの各頂点における各成
分のモル分率は次の通りである。The present invention has been made in view of these problems, and aims to provide a high dielectric constant ceramic composition with improved capacitance-temperature characteristics and insulation resistance, and its gist is based on the general formula: % Formula %) (However, in the formula, X, γ, 2 represent the mole fraction of each component,
x + y + z = 1.00), and the composition within the quadrupled range of polygon ABCD with the points A = B, C, Df as vertices of the following composition shown in Figure 1 (However, the composition on the AD line (excluding composition) 0 to 50 wt% of three components having 4 and TiO2
0.05 to 2.5 wt%, and the molar ratio of T i 02 and l5i20B (T i 02 /rsi20a
) is 05 to 3. The mole fraction of each component at each vertex of the polygon ABCD is as follows.
ｘ ｙ
Ａ Ｏ，７７０，２３０，００
Ｂ Ｏ，３７０，３５０，２８
ＣＯ，３３０，４３０，２４
Ｄ Ｏ，６７０，３３０，００
本発明に係る高誘電率磁器組成物の組成を前記のように
限定１．たのＧ工法の理由による。主成分の組成範囲を
多角形Ａ ＲＣ１’）の範囲内に限定したのに、組成が
Ａｎ線より外ｔ１１１では、キュリ一点が低温側に下が
りすぎて、容量″温度変化率が悪化１−１ＲＣ線より外
側では、常温での誘電率が下がりすぎて実用上好ま１−
＜々く、ｃｎ線より外側では、キュリ一点が高温側ニ」
二かりすぎて、容量変化率（３）
が悪化するからである。副成分のＢｉ２０ｇが０．５０
ｗｔ％未満では、誘電率は高くなるものの容量温度特性
の平坦化および比抵抗を向上させる効果が充分に得られ
ず、５．ＱｗＬ％ を超えると誘雷、率の低下および誘
電正接の上昇が著しいことがらＢｉ２０ａは０．５０〜
５．Ｑｗ［％ とじた。ＴｉＯ２を０．０５〜２．５ｗ
ｔチ としたのは、０．０５ｗｔ％ より少ないと誘電
率の低下および誘電圧接の上昇が著しく、また、２．５
ｗｔ％ より多いと誘電率の低下および誘電正接の上昇
の他、−２５℃における容量温度変化率が大きくなるか
らである。また、Ｔ ｉ ０２とＢｉ２０Ｂのモル比Ｔ
ｉＯ２／Ｂｉ２０ａ を０゜５〜３としたのは、０５
より小さいと誘電率の低下および誘電正接の上昇が著し
く、３より大きいとそれらに加えて一２５℃における容
量温度変化率も大きくなるからである。x y A O,770,230,00 B O,370,350,28 CO,330,430,24 D O,670,330,00 The composition of the high dielectric constant ceramic composition according to the present invention is as described above. Limited 1. This is due to the reason for the TanoG construction method. Even though the composition range of the main component is limited to the range of the polygon A RC1'), when the composition is outside the An line at t111, the Curie point falls too low to the low temperature side, and the capacitance temperature change rate deteriorates 1-1RC. Outside the line, the dielectric constant at room temperature is too low, making it practically undesirable.
＜For a long time, outside of the CN line, one point on Curie is on the high temperature side.''
This is because the capacitance change rate (3) deteriorates if the capacitance change rate (3) is too high. Bi20g of subcomponent is 0.50
If it is less than wt%, although the dielectric constant becomes high, the effect of flattening the capacitance-temperature characteristics and improving the specific resistance cannot be sufficiently obtained; 5. Bi20a is 0.50 to
5. Qw [% Closed. TiO2 0.05~2.5w
The reason for setting tchi is that if it is less than 0.05wt%, the dielectric constant will decrease significantly and the dielectric voltage junction will increase.
This is because if the amount exceeds wt%, the dielectric constant decreases, the dielectric loss tangent increases, and the capacitance temperature change rate at -25° C. increases. Moreover, the molar ratio T of T i 02 and Bi20B
The reason why iO2/Bi20a was set to 0°5~3 was 05
This is because if it is smaller, the dielectric constant decreases and the dielectric loss tangent increases significantly, and if it is larger than 3, in addition to these, the capacitance temperature change rate at -25° C. increases.
本発明に係る前記組成の高誘電率組成物は、誘電率が高
いにもかかわらず、容量温度特性において従来のチタン
酸バリウム系のものに比べて著しく優れ、ＪＩＳ［規定
されるＤ特性を満足し、まＣ４）
た高い比抵抗値を示す。しかも、本発明に係る高誘電率
磁器組成物に約９００〜１１００℃と従来のものに比べ
て低い温度で焼結させることができるので、焼成コスト
ヲ低下させることができるだけでなく、積層コンデンサ
を製造する場合に内部電極月利として従来のＩ” ｒｌ
やＰｔに比べてはるかに安価な銀糸合金、例えば、Ａ
ｇ −１’ ｄ合金、Ａｇ−Ｐｃ 合金などを使用でき
、コンデンサのコストダウンを削ることができるなど、
優れた効果を奏する。Although the high dielectric constant composition of the present invention has a high dielectric constant, it has significantly superior capacitance-temperature characteristics compared to conventional barium titanate-based compositions, and satisfies the D characteristics specified by JIS. However, C4) shows a high specific resistance value. Moreover, since the high dielectric constant ceramic composition according to the present invention can be sintered at a temperature of approximately 900 to 1100°C, which is lower than that of conventional compositions, it is possible not only to reduce the firing cost but also to manufacture multilayer capacitors. If the internal electrode monthly rate as conventional I”rl
Silver thread alloys, such as A and Pt, are much cheaper than Pt.
g-1'd alloy, Ag-Pc alloy, etc. can be used, and the cost of capacitors can be reduced.
It has excellent effects.
次に、本発明の実施例について説明する。Next, examples of the present invention will be described.
原料と１．てＩ’ｂＯ１ＮｉＯ１Ｎ１３２０５、Ｔ ｉ
０２、ＣｏＣ０ａ、ＷＯａおよび１１ｉ２０ａ’ｉ用
い、これら全第１表に示す組成割合になるように秤爪１
−、メノウ石を用いたボールミルにて５〜２０時間湿式
混合１−だ。Raw materials and 1. TeI'bO1NiO1N13205, T i
02, CoC0a, WOa and 11i20a'i were used, and the scale claw 1 was adjusted to have the composition ratio shown in Table 1.
-, wet mixing 1- for 5 to 20 hours in a ball mill using agate stone.
得られた各混合物を脱水、乾燥後、６５０〜８００°Ｃ
で２時間保持して仮焼Ｌ、再びボールミルにて粉砕１−
た。得られた粉末をバインダとしてのポリビニルアルコ
ール３重ｉ１％ （ｗｔ％ ’ｒ と混練し、造粒し
た後、２０００ ｋｇ／ｃｍ の圧力で直径］５關、
厚さ１漉の円板に成形した。この円板を電気炉にて鉛雰
囲気中９００〜１１００℃で２時間焼成して磁器を得た
。After dehydrating and drying each of the obtained mixtures, heat at 650 to 800°C.
Hold for 2 hours and calcinate L, then grind again using a ball mill 1-
Ta. The obtained powder was kneaded with polyvinyl alcohol triple i1% (wt% 'r) as a binder, granulated, and then granulated with a pressure of 2000 kg/cm to a diameter of 5 mm,
It was molded into a disk with a thickness of 1. This disk was fired in an electric furnace at 900 to 1100° C. for 2 hours in a lead atmosphere to obtain porcelain.
得られた磁器円板の両面に銀電極を焼付けてコンデンサ
となし、その誘電率Ｃε）、誘電正接Ｃｔａｎδ）、容
量温度特性および比抵抗（ρ）を測定した。その結果を
第２表に示す。A capacitor was prepared by baking silver electrodes on both sides of the obtained ceramic disc, and its dielectric constant Cε), dielectric loss tangent Ctan δ), capacitance temperature characteristics, and specific resistance (ρ) were measured. The results are shown in Table 2.
々お、εおよびｔａｎδは温度２０℃、周波数ｌ ＫＨ
ｚ で測定し、容量温度特性について（工、２０℃で
の容量を基準とし、−２５℃および＋８５℃での容量の
変化率を求めた。また、比抵抗は２０℃で試ＩＲｖＣ５
００Ｖ ／ｙｎｍ）直流Ｎ圧’ｔ 印７ＪＩＩ Ｌ、１
分後の電流値から計算により求めた。ε and tanδ are at a temperature of 20℃ and a frequency of l KH.
The capacitance-temperature characteristics were measured at -25°C and +85°C with the capacitance at 20°C as the standard. Also, the resistivity was measured at 20°C with the test IRvC5.
00V/ynm) DC N pressure't Mark 7JII L, 1
It was calculated from the current value after minutes.
表中、＊は本発明の範囲外の組成の磁器を示す。In the table, * indicates porcelain whose composition is outside the scope of the present invention.
（７）
（８）
第２表に示す結果から明らかなように、本発明に係る磁
器は誘電率が約６８００以上と著しく高いにもかかわら
ず、静電容昆変化率は一３０％以下でＪＩＳに規定する
Ｉ）特性を満足し、また比抵抗も１０ Ωｏｎ以」−の
高い値を示す他、１１００℃以下の温度で焼結させるこ
とができる。(7) (8) As is clear from the results shown in Table 2, although the porcelain according to the present invention has a significantly high dielectric constant of about 6,800 or more, the electrostatic capacitance change rate is less than -30%, which meets the JIS standard. It satisfies the characteristics I) specified in 1), exhibits a high specific resistance of 10 Ω or higher, and can be sintered at a temperature of 1100° C. or lower.
４図面の簡ｒ、１（な説明
図は本発明に係る高誘電率磁器組成物の主成分の組成範
囲を示す三角図である。The explanatory diagrams in Figures 4 and 1 are triangular diagrams showing the composition range of the main components of the high dielectric constant ceramic composition according to the present invention.
Claims (1)
Ｘ＋Ｙ＋Ｚ＝１．ＯＯ）で表わされ、かつ第１図に示さ
れる下記組成の点Ａ、Ｂ、Ｃ，Ｄｆ頂点とする多角形Ａ
ＢＣＤで囲まれた範囲内の組成（但し、ＡＤ線上の組成
を除く）を有する三成分系組成物を主成分とし、副成分
としてＢｉ ２０８０．５０〜５．Ｑｗｌ ％と、Ｔｉ
０２０．０５〜２．５ｗｔ％ を含み、かつＴｉＯ２と
Ｂｉ２０ｇのモル比（Ｔ ｉ Ｏ２／Ｂｉ２０ｇ）が０
．５〜３であることを特徴とする高誘電率磁器組成物。 Ｘ ｙ ｚＡ
Ｏ，７７０，２３０，００Ｂ Ｏ，３７０，３５
０，２８ ＣＯ，３３０，４３０，２４ Ｄ Ｏ，６７０，３３０，００(1) General formula: % formula %) (However, in the formula, x, y, z represent the mole fraction of each component,
X+Y+Z=1. OO) and has the following composition points A, B, C, Df vertices shown in FIG.
The main component is a three-component composition having a composition within the range surrounded by BCD (excluding the composition on the AD line), and Bi 2080.50 to 5.0 as a subcomponent. Qwl% and Ti
020.05 to 2.5 wt%, and the molar ratio of TiO2 and Bi20g (T i O2/Bi20g) is 0.
．． A high dielectric constant ceramic composition having a dielectric constant of 5 to 3. X y zA
O,770,230,00B O,370,35
0,28 CO,330,430,24 DO,670,330,00
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57071789A JPS58190870A (en) | 1982-04-27 | 1982-04-27 | High dielectric constant ceramic composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57071789A JPS58190870A (en) | 1982-04-27 | 1982-04-27 | High dielectric constant ceramic composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58190870A true JPS58190870A (en) | 1983-11-07 |
| JPS6238316B2 JPS6238316B2 (en) | 1987-08-17 |
Family
ID=13470688
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57071789A Granted JPS58190870A (en) | 1982-04-27 | 1982-04-27 | High dielectric constant ceramic composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58190870A (en) |
-
1982
- 1982-04-27 JP JP57071789A patent/JPS58190870A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6238316B2 (en) | 1987-08-17 |
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