JPS5832068A - Dielectric ceramic composition - Google Patents

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】 この清明は高誘電率系の誘電体磁器組成物に関し、（氏
ｌ黒焼結が可「止な硼器組成パ（勿を提供するものであ
る。DETAILED DESCRIPTION OF THE INVENTION This patent relates to a dielectric ceramic composition having a high dielectric constant, and provides a porcelain composition that can be easily sintered.

従来より高輝４率系の誘電体磁器組成物のうち。Among the conventional high brightness 4-factor dielectric ceramic compositions.

ＹＺ系材料としＣば％　ＢａＴｉＯ２−ＣｉＺｒＯｌ−
ＩＩ（／Ｔ１０３系に５１０２などの鉱化剤および酸化
マンガンを添／Ｊｌｌ　Ｌだものが知られ（＋へた。し
かしながらこの種材料のものはその焼結温度が１３５０
〜１４００での範囲にあり、焼；吉のだめの燃焼エネル
ギーを低減下する必要上、さらに低温焼結が可ｉヒな新
規１１） 材料が要求されＣ１へた。As YZ-based material, C% BaTiO2-CiZrOl-
II (/T103 series with mineralizing agent such as 5102 and manganese oxide added/Jll L) is known. However, the sintering temperature of this type of material is 1350
In order to reduce the combustion energy of sintering, a new 11) material that can be sintered at a lower temperature was required, and C1 was selected.

一方、誘′准体磁器を用（へ“ｃ−）！ラミックコンデ
ンサを作成する場合、コンデンサ電極として無電解ニッ
ケル；ｔ　＋ｔを用１へることが知られｒｔへるが、上
記した組成の誘電体磁器を用りて無電解ニッケル電極を
形成すると、誘１ｎ体損失が犬きく、−！た１角縁抵抗
も低くなると１ｏう間肩点が見られた。On the other hand, when making a ceramic capacitor using dielectric ceramic, it is known that electroless nickel is used as the capacitor electrode; When an electroless nickel electrode is formed using dielectric ceramic, the dielectric loss increases, and a shoulder point is observed when the edge resistance decreases.

したがつＣ１この発明は低７（４Ａ焼結が１１ＴｆｒＩ
３．な１透電体磁器組成物を提供することを目的とする
。Therefore, C1 of this invention is low 7 (4A sintered is 11TfrI)
3. An object of the present invention is to provide an electrically conductive ceramic composition.

また、この定明けたとえば電極として無電解ニッケル耐
直を形成しＣも電気的特性に間；ｌ！１１のな旨誘電体
磁器、祖酸物を提供ｒること°を目的とする。Also, after this process, for example, if electroless nickel is formed as an electrode, the electrical properties of C will change; The purpose is to provide 11 dielectric ceramics and oxidants.

つまり、この発明にかかる誘電体磁器組成物の要旨とす
るところは、Ｂ’Ｔｉ０ｓ８５〜９０ｉ’ｉ（：ｉ％。That is, the gist of the dielectric ceramic composition according to the present invention is B'Ti0s85-90i'i (:i%).

Ｃａ　Ｚ　ｒ　ＯＪ　８．５〜１２．０　、ｔ　ｉｔ％
、Ｍ９’１ｌｉＯａ　０．５．ｆｆｌｉ％以下、　Ｃａ
ｂ、　０．５　市ｉｉ１　％ＪＪ、　）’、　Ｄｉ＊０
：＋　０．１〜１．０　Ｂｆ（骨上、ＳｎＯ，Ｑ、１〜
１．Ｏｉｉ量チからなることを特徴とする。CaZrOJ 8.5-12.0, tit%
, M9'1liOa 0.5. ffli% or less, Ca
b, 0.5 City ii1 %JJ, )', Di*0
: + 0.1~1.0 Bf (on bone, SnO, Q, 1~
1. It is characterized by consisting of Oii quantity chi.

この発明におＩｎてｔの、＠酸物のｌ１ＩＩ成範囲を退
定しに４由は次のとおシである。In this invention, there are four reasons for retiring the l1II composition range of the @ acid in the following manner.

（２） Ｂ　ａ　Ｔｉ　Ｏ３が８５重ｔ％未満では誘電率温度特
性が悪くなるとともに誘電率が低下し、また９０ｄ（を
優を越えると、−２５′ｃｌでおける誘電率温度特性が
悪く々る。Ｃａ、ＺｒＯ３が８．５重敏係末／）１々で
は−２５′ｃにおけろ誘電率温度特性が！くなり、蜂だ
１２．０重陥Ｙチを１戊えると誘電率温度特性が悪くな
るとともに誘’Ｆｔｆ率が低下する。Ｍ　ｑ　Ｔ　ｉ　
Ｏ３１寸誘電率温度特性を改善する効果を有するが、０
５重量％を越え７）と誘電率が極端に低下する。０００
２１寸誘電損失の改善に効果がちるが、０５重量幅を４
戦えると焼結温度が一ヒ昇ｌ〜、また誘電率も１代丁す
る。(2) If B a Ti O3 is less than 85% by weight, the dielectric constant-temperature characteristics deteriorate and the dielectric constant decreases, and if it exceeds 90 d (well), the dielectric constant-temperature characteristics at -25'cl become worse. Ca, ZrO3 have a dielectric coefficient of 8.5/) and the dielectric constant temperature characteristics at -25'c! When the 12.0-fold Y-chi is exceeded, the dielectric constant-temperature characteristics worsen and the dielectric constant Ftf decreases. M q Ti
It has the effect of improving the dielectric constant temperature characteristics of O31, but 0
When it exceeds 5% by weight 7), the dielectric constant decreases extremely. 000
Although it is effective in improving the dielectric loss of 21 dimensions, the weight width of 05 is 4
If it can be used, the sintering temperature will rise by one inch, and the dielectric constant will also drop by one order of magnitude.

Ｂｉ、Ｏｌが０．１重り係圭・１！Ａｉでは、焼結温度
の大福な低下が困１１１１であり、また１０重重量上越
えろと、誘電率が極端に低下する。５ｎ０２が０．１重
１辻係未、１（白では、焼結温度の大幅な低下が１難で
あり、また１、０重肴メを１場えると、誘電率温度特性
が悪くなるとともにｊｊ”Ｊ　’ｆｔｆ１率が低下−１
ろ。Bi, Ol is 0.1 weight Kei 1! With Ai, it is difficult to reduce the sintering temperature by a large amount, and when the weight exceeds 10%, the dielectric constant decreases extremely. 5n02 is 0.1 layer, 1 layer, 1 (with white, it is difficult to significantly reduce the sintering temperature, and if 1, 0 layer is added, the dielectric constant temperature characteristics will deteriorate and jj"J 'ftf1 rate decreased -1
reactor.

以下この発明を実施例（（従って詳細に説明する。The present invention will be described in detail below with reference to examples.

原料として、ＢａＴｉＯ３，ＣａＺｒＯ２，ＭｇＴｉＯ
３，ＣｅＯ２゜Ｂｉ、　０３．５ｎ０２　を用意し、各
原料を第１友１に示す組成の磁器が得られろように調合
した。調合原１′、］をこの調合原料と開瞼の水と、Ｉ
−もにボール（ル中で湿式粉砕？ＩＲ（′ｉＬ　’／：
＝。（’）：　ｌｑ　（、’混合１ｒ：Ｃ４：Ｉ　Ｔｃ
　＋ｌＲ，水、乾水上乾燥ち、有！浅バインダを加え′
Ｃ造粒し、成Ｊｌニ圧力１００ＱＩ＋り／Ｃ）で加圧成
形しＡ０成形物を１３（］０での温度で１時間空気中で
焼ｉ’＋！ｔ　Ｌ　’Ｃｍ　！Ｆｌ径ｉａ、。As raw materials, BaTiO3, CaZrO2, MgTiO
3, CeO2°Bi, 03.5n02 were prepared, and each raw material was mixed so as to obtain a porcelain having the composition shown in the first example 1. Mixture raw material 1',] with this blended raw material, water from open eyelids, and I
-Moni ball (wet grinding in Le?IR('iL'/:
=. ('): lq (,'Mixture 1r:C4:I Tc
+lR, water, dry water, dry, yes! Add shallow binder′
C granulation, pressure molding at a forming pressure of 100QI+/C), and baking the A0 molded product in air at a temperature of 13(]0 for 1 hour i'+!t L'Cm !Fl diameter ia, .

朋φ、厚み０．５　ｒｐ、ｒｎの円板状の磁？ｇ水体を
？！Ｊ　／ね。A disc-shaped magnet with a diameter of 0.5 and a thickness of 0.5 rp and rn? g water body? ! J / Right.

得られた磁器素体の＋１乎面に無電ｑｉｆニック゛ル電
極を形成１−１これを試料とし／ζ、。試料の誘電率（
ε）、誘電損失（ｔａｎδ）、誘電率温度特性（ＴＣ’
）、お・よび絶、緑抵抗（ＴＲ）を測定し、その清用も
ｌ■１ｋに合わせＣ示した。なお、＠電飢１）か電損失
は周波数１ＫＨ２、温度２０′ｃで測定した値である。An electroless qif nickel electrode was formed on the +1 side of the obtained porcelain body. 1-1 This was used as a sample /ζ. Dielectric constant of sample (
ε), dielectric loss (tanδ), dielectric constant temperature characteristic (TC'
), and the green resistance (TR) was measured, and its value was also shown as C according to l 1 k. It should be noted that the electric power loss is a value measured at a frequency of 1KH2 and a temperature of 20'C.

また誘電率温度特性は＋２０′ｃを基１１（とじて−２
５Ｃ〜十８５′ｃの温度範囲で測定した値である。さら
に絶縁抵抗は直流電圧５００Ｖを４０抄間印１Ｊ１１シ
たのち測定した値である。また表中、※印をイ・ｉｌ、
／ｒものはこの発明範囲外のものであり、それ以外ｒ↓
イｄ明範囲内のものである。In addition, the dielectric constant temperature characteristics are based on +20'c and -2
This value was measured in a temperature range of 5C to 185'C. Furthermore, the insulation resistance is a value measured after applying a DC voltage of 500 V for 40 years. In addition, in the table, *marks are
/r items are outside the scope of this invention, and other r↓
It is within the bright range.

第１表から明らかなように、この全開にかかる誘心体磁
器組成物によれば、高誘電率を維持しながら、　　ｔａ
ｎδは１慢以下、ＩＩＪｉ／、Ｏ×ＩＱ”’　０以上の
特性が得られＣおり、またＩ’ＣにつＩＡ’？ｌｌｄ・
［［）ｌ規格のＥ特性（２０℃を基準としたときｆｆｌ
Ｒ度範囲−２５′ｃ〜→−８５′ｃで変化率が→−２０
チ〜−５５係以１：のもの）を満足するものも得られて
１へる。As is clear from Table 1, according to this fully dielectric ceramic composition, while maintaining a high dielectric constant, ta
nδ is less than 1, IIJi /, O
[[)l Standard E characteristics (ffl when referenced to 20°C
The rate of change is →-20 in the R degree range -25'c to →-85'c
Items that satisfy the conditions (1) for -55 and below are also obtained and go to 1.

ちなみに、従来の組成物（ａａＴｌｏ、　８　Ｂ、８取
降％、ＣａＺｒＯｓ　１０．９重ｆｆｔ４．　　ＭｇＴ
ｉＯ！０．３　ｔ〕重ｌチ）につ（八て、上記した実殉
例と同様にし、てコンデンサ試料を作成したとき、その
各電気的特性を測定したところ、次のとおりであった。By the way, the conventional composition (aaTlo, 8 B, 8 withdrawal%, CaZrOs 10.9 weight fft4. MgT
iO! When a capacitor sample was prepared in the same manner as in the above-mentioned actual case, its electrical characteristics were measured as follows.

な粋、焼結温度は１４００’Ｃ’であった。Actually, the sintering temperature was 1400'C'.

誘電率？　　６５００ 誘電損失：　　１．５５チ 誘電率温度特性：　　　−２５−（？−４５．４チ十８
５−ｃ−５２．５％ 絶縁抵抗？　　　１．５ＸＩＤｎ 従来組成物との比較から明らかなように、コンデンサ電
極として無電解ニッケル電甑を形成した１易合、この発
明にかかるものは銹電損失が小さく４・す、絶縁抵抗に
つＩｎ’Ｃは約３倍院度改善されて１ｏることがｉ’ｆ
ｈう￥できる。Dielectric constant? 6500 Dielectric loss: 1.55cm Dielectric constant temperature characteristics: -25-(?-45.4cm 18
5-c-52.5% Insulation resistance? 1.5XIDn As is clear from the comparison with the conventional composition, when an electroless nickel electrode is formed as a capacitor electrode, the one according to the present invention has a small galvanic loss and a high insulation resistance. 'C can be improved by about 3 times and become 1o if
I can do it.

以」−このノ’６１Ｊ］ｌてかかる誘況体磁２（組成物
によれば、従〕ｌ（例にくらべ°Ｃ約１００で程度焼１
清温度を下げることができ、低瀞焼＋？−１が可１走と
なる。寸た、コンデンザ’ｔ１極としＣ無「理解ニッケ
ル電（・返金形成しでも電気的Ｉｌ＆性の劣化が見られ
ず、安定した電気的特性をイｊするセラミックコンｆン
ザを１供することができる。According to the composition, the dielectric magnet 2 (compared to the example)
Can the temperature be lowered, resulting in a lower temperature? -1 is one possible run. In short, it is possible to provide a ceramic capacitor with stable electrical characteristics without any deterioration in electrical properties even after forming a nickel capacitor (with a single pole and no capacitor). .

なＩ？、この発明にかかる誘電体７訂器組成゛吻１ｃさ
らにＳ　ｊ、　０２．　Ｍ　ｎ　Ｏ、など２添加すれば
磁器化を容易にすることができる。またコンデンサｉ程
極としては無電解ニッケル電極に限られるものではなく
。Na I? , Dielectric 7th grader composition according to the present invention 1c and S j, 02. By adding MnO, etc., it is possible to easily form the material into porcelain. Further, the electrode of the capacitor is not limited to an electroless nickel electrode.

その他倶焼例−，Ｉｆ極、無電解銅電極などを用（０て
も同様な電気的特性が得られ乙。Other firing examples, If electrodes, electroless copper electrodes, etc. can be used (same electrical characteristics can be obtained even with 0).

特許出願人 昧戊会社村田製作所patent applicant Murata Manufacturing Co., Ltd.

Claims (1)

【特許請求の範囲】[Claims] ＢａＴｉ０．８５−９Ｑ重１１７１％、　ＣａＺｒＯｓ
　ａ、ｓ〜１２．０重丑グ、ＭｇＴｉ、Ｏ，Ｑ、５重用
：係以ド、　ＣａＯ２［１，５重−計係にｉＬ　　Ｂｉ
、０３Ｑ、１〜１．０重ｔ％　、　　Ｓ　ｎ　Ｏ２０，
１〜１゜０重化ヂからなることを特徴とする誘電体磁器
組成物。BaTi0.85-9Q weight 1171%, CaZrOs
a.
, 03Q, 1-1.0 wt%, S n O20,
A dielectric porcelain composition characterized in that it consists of 1 to 1°0 overlap.