JP2902926B2 - Dielectric porcelain composition - Google Patents
Dielectric porcelain compositionInfo
- Publication number
- JP2902926B2 JP2902926B2 JP5335569A JP33556993A JP2902926B2 JP 2902926 B2 JP2902926 B2 JP 2902926B2 JP 5335569 A JP5335569 A JP 5335569A JP 33556993 A JP33556993 A JP 33556993A JP 2902926 B2 JP2902926 B2 JP 2902926B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- temperature coefficient
- dielectric constant
- tcc
- tio
- 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 title claims description 27
- 229910052573 porcelain Inorganic materials 0.000 title claims description 10
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 15
- 239000000919 ceramic Substances 0.000 claims description 11
- 239000012535 impurity Substances 0.000 claims description 9
- 229910052718 tin Inorganic materials 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 claims description 8
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 2
- 238000005259 measurement Methods 0.000 claims description 2
- 239000011734 sodium Substances 0.000 description 18
- 230000007423 decrease Effects 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 6
- 239000011572 manganese Substances 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000003985 ceramic capacitor Substances 0.000 description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000007606 doctor blade method Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- -1 sodium carboxylate Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Insulating Materials (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、誘電体磁器組成物に関
するものであり、例えば、温度補償用の磁器コンデンサ
に用いられる誘電体磁器組成物に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dielectric ceramic composition, for example, a dielectric ceramic composition used for a ceramic capacitor for temperature compensation.
【０００２】[0002]
【従来の技術】従来から、温度補償用磁器コンデンサは
各種電気機器の中で、同調、共振用等として広く用いら
れ、小型でかつ誘電損失が小さく、誘電特性の安定した
コンデンサが求められている。2. Description of the Related Art Conventionally, ceramic capacitors for temperature compensation have been widely used in various electric devices for tuning, resonance, etc., and there has been a demand for a capacitor having a small size, a small dielectric loss, and a stable dielectric characteristic. .
【０００３】このため誘電体磁器の条件としては、小型
化の要求に対して比誘電率が大きいこと、誘電損失が小
さいこと（言い換えればＱ値が大きいこと）、比誘電率
の温度に対する変化が小さいこと等が主として挙げら
れ、また信頼性に対しては、化学的に安定であること、
機械的強度が高いこと、熱衝撃に対する強度が高いこと
等が挙げられる。For this reason, the conditions of the dielectric porcelain include a large relative dielectric constant, a small dielectric loss (in other words, a large Q value), and a change in the relative dielectric constant with respect to temperature in response to a demand for miniaturization. It is mainly small, and it is chemically stable for reliability.
High mechanical strength, high strength against thermal shock and the like can be mentioned.
【０００４】そして、従来、この種の誘電体磁器として
は、比誘電率が５５〜９５程度と高く、静電容量の温度
係数ＴＣＣが０±２００ｐｐｍ／℃程度のＢａＯ−ＲＥ
2 Ｏ3 −ＴｉＯ2 （但し、ＲＥ2 Ｏ3 は希土類元素酸化
物、以下同様）系材料が知られていた（特公昭５０−２
０２８０号公報参照）。Conventionally, as this type of dielectric porcelain, a BaO-RE having a relative dielectric constant as high as about 55 to 95 and a temperature coefficient of capacitance TCC of about 0 ± 200 ppm / ° C.
A 2 O 3 —TiO 2 (where RE 2 O 3 is a rare earth oxide, the same applies hereinafter) -based material has been known (Japanese Patent Publication No. Sho 50-2).
No. 0280).
【０００５】[0005]
【発明が解決しようとする問題点】しかしながら、最近
の誘電体磁器は、例えば、移動体通信機器等に使用され
るものでは、より高周波化と小型化のために比誘電率と
Ｑ値が高いだけではなく、温度特性の安定とともに、静
電容量の温度係数ＴＣＣが０±３０ｐｐｍ／℃以内であ
ること等が要求されるようになり、前記ＢａＯ−ＲＥ2
Ｏ3 −ＴｉＯ2 系材料では、高い比誘電率を維持した状
態で静電容量の温度係数ＴＣＣを前記範囲内に制御しよ
うとすると、磁器の焼結性が不安定になるという欠点が
あり、従来より焼結性を安定させるために、例えば、Ｓ
ｉＯ2 等の助剤を添加すること等が行われていたが、前
記助剤の添加は、比誘電率の低下や温度特性の悪化を起
こす他、高周波領域ではＱ値を劣化する恐れがあり、誘
電特性自体を損なう恐れがあるという課題があった。However, recent dielectric porcelains used in mobile communication equipment, for example, have a high relative dielectric constant and a high Q value for higher frequency and smaller size. not only stable with temperature characteristic, now that such a temperature coefficient TCC of the capacitance is within 0 ± 30 ppm / ° C. are required, the BaO-RE 2
The O 3 —TiO 2 based material has a drawback that if the temperature coefficient TCC of the capacitance is controlled within the above range while maintaining a high relative dielectric constant, the sinterability of the porcelain becomes unstable. Conventionally, in order to stabilize sinterability, for example, S
Addition of an auxiliary agent such as iO 2 has been performed. However, the addition of the auxiliary agent may cause a decrease in relative dielectric constant and a deterioration in temperature characteristics, and may deteriorate a Q value in a high frequency region. However, there is a problem that the dielectric properties may be impaired.
【０００６】[0006]
【発明の目的】本発明は、前記欠点に鑑み案出されたも
ので、コンデンサの小型化、高容量化、高信頼性化を可
能とするため、測定周波数１ＭＨｚにおける比誘電率ε
ｒが５０以上と高く、Ｑ値が３０００以上と高く、温度
特性が安定で静電容量の温度係数ＴＣＣが０±３０ｐｐ
ｍ／℃以内と小さい誘電体磁器組成物を提供することを
目的とするものである。SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned drawbacks, and has been developed in view of the above-mentioned drawbacks.
r is as high as 50 or more, Q value is as high as 3000 or more, temperature characteristics are stable, and temperature coefficient of capacitance TCC is 0 ± 30 pp.
It is an object of the present invention to provide a dielectric ceramic composition as small as m / ° C. or less.
【０００７】[0007]
【問題点を解決するための手段】本発明者等はＢａ−Ｎ
ｄ−（Ｔｉ＋Ｍｅ）系に対して検討を加えた結果、Ｂａ
−Ｎｄ−Ｔｉ系にさらにＺｒまたはＳｎのいずれか一種
以上を配合することにより、誘電率を高く維持しながら
マイナス側に大きな静電容量の温度係数ＴＣＣをプラス
側にシフトさせて諸特性を満足させることができること
を見出した。[Means for Solving the Problems] The present inventors have proposed Ba-N
As a result of examining the d- (Ti + Me) system,
Satisfaction of various characteristics by shifting the temperature coefficient TCC of the large capacitance to the minus side to the plus side while maintaining a high dielectric constant by blending one or more of Zr and Sn with the -Nd-Ti system. I found that I can do that.
【０００８】更に、Ｎａの含有量が小さい原料を用いる
等の手段によりＮａ量を低減すると、ＳｉＯ2 等の助剤
を添加することなく安定した焼結性を示すことを見出し
本発明に至った。Further, it has been found that when the amount of Na is reduced by means such as using a raw material having a small amount of Na, stable sinterability is exhibited without adding an auxiliary agent such as SiO 2 and the like, and the present invention has been achieved. .
【０００９】即ち、ＴｉＯ2 原料（工業的に多く用いら
れる硫酸法で作成したＴｉＯ2 原料）には、０．０５重
量％程度のＮａが含有されており、また、例えば、ドク
ターブレード法によりグリーンシートを作成する際に、
原料粉を泥漿中に分散させるために用いられるカルボン
酸ソーダ系の分散剤には、５．００重量％程度のＮａが
含まれていることから、総量として誘電体磁器中には
０．２０重量％程度のＮａが混入することになるが、こ
のＮａ量が０．１重量％よりも多く存在すると、焼結性
が悪化することを見出しものである。That is, a TiO 2 raw material (a TiO 2 raw material prepared by a sulfuric acid method, which is widely used in industry) contains about 0.05% by weight of Na. When creating a sheet,
Since the sodium carboxylate dispersant used to disperse the raw material powder in the slurry contains about 5.00% by weight of Na, the total amount in the dielectric porcelain is 0.20% by weight. % Of Na is mixed in, but it has been found that when the amount of Na is more than 0.1% by weight, the sinterability deteriorates.
【００１０】本発明の誘電体磁器組成物は、金属元素と
して少なくともＢａ、Ｎｄ、ＴｉとＺｒまたはＳｎのい
ずれか一種以上からなる主成分に対してＭｎを添加して
なる複合酸化物であって、前記主成分を金属元素のモル
比による組成式をｘＢａＯ・ｙＮｄ2 Ｏ3 ・ｚ〔（１−
ｃ）ＴｉＯ2 ＋ｃＭｅＯ2 〕（但し、ｘ＋ｙ＋ｚ＝１０
０、０．０１≦ｃ≦０．１０、ＭｅはＺｒまたはＳｎの
いずれか一種以上の元素）と表した時、前記ｘ、ｙ、ｚ
が下記Ａ、Ｂ、Ｃ、Ｄ、Ｅで囲まれた範囲内にあり、前
記ＭｎがＭｎＣＯ3 換算で前記主成分に対して０．０１
〜０．５重量％の割合で存在するとともに、不純物成分
としてのＮａが全量中０．１０重量％以下であり、か
つ、測定周波数１ＭＨｚにおける比誘電率が５０以上、
静電容量の温度係数Ｔｃｃが０±３０ｐｐｍ／℃を有す
るものである。The dielectric porcelain composition of the present invention is a composite oxide obtained by adding Mn to a main component comprising at least one of Ba, Nd, Ti and Zr or Sn as a metal element. the main component molar ratio according to the composition formula xBaO · yNd 2 O 3 · z of the metal element [(1-
c) TiO 2 + cMeO 2 ] (where x + y + z = 10
0, 0.01 ≦ c ≦ 0.10, and Me is at least one element of Zr or Sn).
Is in a range surrounded by the following A, B, C, D, and E, and the Mn is 0.01% with respect to the main component in terms of MnCO 3.
0.5% by weight, Na as an impurity component is 0.10% by weight or less in the total amount, and the relative dielectric constant at a measurement frequency of 1 MHz is 50 or more,
It has a temperature coefficient of capacitance Tcc of 0 ± 30 ppm / ° C.
【００１１】 ｘ ｙ ｚ Ａ １５．５０ １７．５０ ６７．００ Ｂ １０．５０ ２２．５０ ６７．００ Ｃ ７．５０ ２２．５０ ７０．００ Ｄ ９．１７ １９．１７ ７１．６６ Ｅ １２．５０ １７．５０ ７０．００ 更に、不純物成分としてのＳｉがＳｉＯ2 換算で全量中
０．０５重量％以下であることが望ましい。Xyz A 15.50 17.50 67.00 B 10.50 22.50 67.00 C 7.50 22.50 70.00 D 9.17 19.17 71.66 E 12.50 17.50 70.00 Further, it is desirable that the content of Si as an impurity component is 0.05% by weight or less in the total amount in terms of SiO 2 .
【００１２】本発明の誘電体磁器組成物において、不純
物成分としてのＮａを全量中０．１０重量％以下とした
のは、Ｎａが全量中０．１０重量％よりも多いと焼結性
の悪化を生じ、比誘電率，Ｑ値，静電容量の温度係数
等、各種誘電率特性の悪化を招くからであり、Ｎａは全
量中０．０５重量％以下であることがより望ましい。In the dielectric ceramic composition of the present invention, the content of Na as an impurity component is set to 0.10% by weight or less in the total amount because the sinterability deteriorates when Na is more than 0.10% by weight in the total amount. This causes deterioration of various dielectric constant characteristics such as relative dielectric constant, Q value, temperature coefficient of capacitance, etc., and it is more preferable that Na is 0.05% by weight or less in the total amount.
【００１３】前記Ｎａ量を低減するには、原料であるＢ
ａＯ（またはＢａＣＯ3 ）、Ｎｄ2Ｏ3 、ＴｉＯ2 、Ｚ
ｒＯ2 及びＳｎＯ2 粉末を高純度のものを使用したり、
低ソーダの原料を用いたり、繰り返し仮焼を行ってＮａ
を蒸発させたり、粉砕や成形時に用いる分散剤や有機系
粘結剤（バインダー）等の薬品にＮａ含有量の少ないも
のを使用する等が適用できる。In order to reduce the amount of Na, the raw material B
aO (or BaCO 3 ), Nd 2 O 3 , TiO 2 , Z
Use high purity rO 2 and SnO 2 powder,
Use low soda raw materials or repeatedly calcine
It is possible to apply a chemical such as a dispersant or an organic binder (binder) used at the time of pulverization or molding, which has a low Na content, or the like.
【００１４】次に、モル比による組成式を、ｘＢａＯ・
ｙＮｄ2 Ｏ3 ・ｚ〔（１−ｃ）ＴｉＯ2 ＋ｃＭｅＯ2 〕
（但し、ｘ＋ｙ＋ｚ＝１００、０．０１≦ｃ＜０．１
０、ＭｅはＺｒまたはＳｎのいずれか一種以上の元素）
と表した時、ＢａＯ量ｘを７．５０≦ｘ≦１５．５０に
限定したのは、ｘが７．５０よりも小さいと比誘電率が
５０より小さくなり、ｘが１５．５０よりも大きくなる
と、温度係数ＴＣＣが悪化するからである。尚、比誘電
率はＢａＯ量を増加させることにより大きくなる傾向を
示す。Next, the composition formula based on the molar ratio is expressed as xBaO ·
yNd 2 O 3 .z [(1-c) TiO 2 + cMeO 2 ]
(However, x + y + z = 100, 0.01 ≦ c <0.1
0 and Me are at least one element of Zr or Sn)
When the BaO amount x is limited to 7.50 ≦ x ≦ 15.50, when x is smaller than 7.50, the relative dielectric constant becomes smaller than 50, and x is larger than 15.50. If so, the temperature coefficient TCC deteriorates. The relative permittivity tends to increase as the amount of BaO increases.
【００１５】また、Ｎｄ2 Ｏ3 量ｙを１７．５０≦ｙ≦
２２．５０としたのは、ｙが１７．５０よりも小さい場
合や２２．５０よりも大きい場合には、温度係数ＴＣＣ
が悪化するからである。The amount y of Nd 2 O 3 is defined as 17.50 ≦ y ≦
The reason for setting 22.50 is that when y is smaller than 17.50 or larger than 22.50, the temperature coefficient TCC
Is worse.
【００１６】更に、〔（１−ｃ）ＴｉＯ2 ＋ｃＭｅ
Ｏ2 〕量ｚを６７．００≦ｚ≦７１．６６としたのは、
ｚが６７．００よりも小さい場合には、焼結性および温
度係数ＴＣＣが悪化し、ｚが７１．６６よりも大きい場
合には、温度係数ＴＣＣが悪化するからである。Further, [(1-c) TiO 2 + cMe
O 2 ] The amount z was set to 67.00 ≦ z ≦ 71.66 because
When z is smaller than 67.00, the sinterability and the temperature coefficient TCC deteriorate, and when z is larger than 71.66, the temperature coefficient TCC deteriorates.
【００１７】また、ＴｉＯ2 とＭｅＯ2 の全体のモル量
に対するＭｅＯ2 の割合ｃは、０．０１≦ｃ≦０．１０
であることが望ましい。これは、ｃが０．０１よりも小
さいと、ＺｒＯ2 添加による効果である静電容量の温度
係数ＴＣＣのプラス側への移動が殆どなくなり、ｃが
０．１０より大きくなると誘電率の低下が大となるから
である。Further, the ratio c of MeO 2 to the total molar amount of TiO 2 and MeO 2 is, 0.01 ≦ c ≦ 0.10
It is desirable that This is because when c is smaller than 0.01, the temperature coefficient of capacitance TCC, which is an effect of the addition of ZrO 2 , hardly moves to the positive side, and when c is larger than 0.10. Because it will be great.
【００１８】そして、モル比による組成式を、ｘＢａＯ
・ｙＮｄ2 Ｏ3 ・ｚ〔（１−ｃ）ＴｉＯ2 ＋ｃＭｅ
Ｏ2 〕（但し、ｘ＋ｙ＋ｚ＝１００、０．０１≦ｃ≦
０．１０、ＭｅはＺｒまたはＳｎのいずれか一種以上の
元素）と表した時、下記ａ、ｂ、ｃ、ｄ、ｅで囲まれた
範囲内である場合には、静電容量の温度係数ＴＣＣが０
±３０ｐｐｍ／℃（Ｃ０Ｇ特性）以内を有し、且つ、比
誘電率が６０以上と高く、更に好ましい。The composition formula based on the molar ratio is represented by xBaO
・ YNd 2 O 3 .z [(1-c) TiO 2 + cMe
O 2 ] (however, x + y + z = 100, 0.01 ≦ c ≦
0.10, and Me is at least one element of Zr or Sn), and if it is within the range surrounded by the following a, b, c, d, and e, the temperature coefficient of capacitance TCC is 0
It is more preferable that the temperature is within ± 30 ppm / ° C. (COG characteristics) and the relative dielectric constant is as high as 60 or more.
【００１９】 ｘ ｙ ｚ ａ １５．５０ １７．５０ ６７．００ ｂ １０．５０ ２２．５０ ６７．００ ｃ １０．００ ２２．５０ ７０．００ ｄ １０．００ ２０．００ ７０．００ ｅ １５．００ １７．５０ ６７．５０ また、マンガンをＭｎＣＯ3 換算で０．０１〜０．５０
重量％の割合で含有させたのは、０．０１重量％よりも
少ない場合や０．５０重量％よりも多い場合にはＱ値が
低下するからである。Xyz a 15.50 17.50 67.00 b 10.50 22.50 67.00 c 10.00 22.50 70.00 d 10.00 20.00 70.00 e 15.00 17.50 67.50 Further, manganese is converted to 0.01 to 0.50 in terms of MnCO 3.
The reason for the content by weight is that when the content is less than 0.01% by weight or more than 0.50% by weight, the Q value decreases.
【００２０】そして、Ｓｉ量は、ＳｉＯ2 換算で０．０
５重量％よりも多くなるとＱ値が低下するため、全量中
０．０５重量％以下であることが好ましく、更に０．０
３重量％以下であることが特に好ましい。The Si content is 0.02 in terms of SiO 2.
When the content is more than 5% by weight, the Q value decreases. Therefore, the content is preferably 0.05% by weight or less of the total amount, and more preferably 0.0% by weight.
It is particularly preferred that the content be 3% by weight or less.
【００２１】本発明の誘電体磁器組成物は、例えば以下
のようにして作成される。先ず、純度９９％以上のＢａ
ＣＯ3 （ＢａＯ）、ＴｉＯ2 、ＺｒＯ2 及びＭｎＣＯ3
と純度９５％以上のＮｄ2 Ｏ3 （希土類酸化物の不純物
としてＰｒ等が混入する場合がある）の各粉末を用いる
とともに、組成物中のＮａの含有量およびＳｉのＳｉＯ
2 換算での含有量が本発明の範囲内となるようにＢａＣ
Ｏ3 （ＢａＯ）、ＴｉＯ2 、Ｎｄ2 Ｏ3 、ＺｒＯ2 およ
びＭｎＣＯ3 粉末を調整し、焼結体の組成が後述する表
１及び表２となるように秤量後混合し、この混合物を乾
燥後、１０００〜１２００℃で１〜３時間仮焼する。The dielectric ceramic composition of the present invention is prepared, for example, as follows. First, Ba of 99% or more purity
CO 3 (BaO), TiO 2 , ZrO 2 and MnCO 3
And Nd 2 O 3 powder having a purity of 95% or more (Pr or the like may be mixed as an impurity of the rare earth oxide), and the content of Na in the composition and the SiO of Si are used.
BaC so that the content in 2 conversion falls within the range of the present invention.
O 3 (BaO), TiO 2 , Nd 2 O 3 , ZrO 2, and MnCO 3 powders were prepared, weighed so that the composition of the sintered body would be as shown in Tables 1 and 2 described below, and mixed, and the mixture was dried. Then, it is calcined at 1000 to 1200 ° C for 1 to 3 hours.
【００２２】この仮焼粉を用いてボールミルにて粉砕し
た後、Ｎａ含有量の少ない有機系粘結剤（バインダー）
を添加して撹拌後、例えば、ドクターブレード法により
グリーンシートに成形し、これらのグリーンシートを積
層し、脱バインダー処理をした後、１２８０〜１３４０
℃の温度で１〜３時間空気中において焼成することによ
り本発明の誘電体磁器組成物が得られる。After the calcined powder is pulverized with a ball mill, an organic binder having a low Na content (binder) is obtained.
After adding and stirring, for example, green sheets are formed by a doctor blade method, these green sheets are laminated, and after debinding treatment, 1280 to 1340
The dielectric ceramic composition of the present invention is obtained by firing in air at a temperature of 1 to 3 hours.
【００２３】[0023]
【作用】本発明の誘電体磁器組成物によれば、静電容量
の温度係数を向上させ、高比誘電率および高Ｑ値を得る
ことが可能となり、更にＢａ−Ｎｄ−Ｔｉ系に対してＴ
ｉの一部をＺｒまたはＳｎのいずれか一種以上に置換す
ることにより、前記Ｂａ−Ｎｄ−Ｔｉ系で比誘電率は大
きいがマイナス側に大きな静電容量の温度係数ＴＣＣ
を、プラス側にシフトさせて使用可能な組成を拡大でき
る。According to the dielectric porcelain composition of the present invention, it is possible to improve the temperature coefficient of capacitance, obtain a high relative dielectric constant and a high Q value, and further improve the Ba-Nd-Ti system. T
By substituting a part of i with one or more of Zr or Sn, the relative permittivity of the Ba-Nd-Ti system is large, but the temperature coefficient TCC of the capacitance is large on the negative side.
Can be shifted to the plus side to expand the usable composition.
【００２４】また、不純物としてのＮａを全量中０．１
０重量％以下とすることにより、焼結性の改善が可能と
なり、比誘電率、Ｑ値、温度係数ＴＣＣを向上すること
が可能となる。Further, Na as an impurity is contained in the total amount of 0.1%.
When the content is 0% by weight or less, the sinterability can be improved, and the relative dielectric constant, the Q value, and the temperature coefficient TCC can be improved.
【００２５】また、マンガンをＭｎＣＯ3 換算で０．０
１〜０．５重量％の割合で含有することにより、高Ｑ値
を得ることが可能となる。In addition, manganese is converted to MnCO 3 by 0.0
A high Q value can be obtained by containing 1 to 0.5% by weight.
【００２６】さらに、ＳｉをＳｉＯ2 換算で全量中０．
０５重量％以下とすることにより、Ｑ値をさらに向上す
ることが可能となる。Further, Si is contained in a total amount of 0.1% in terms of SiO 2 .
By setting the content to 05% by weight or less, the Q value can be further improved.
【００２７】[0027]
【実施例】出発原料として、純度９９％以上のＢａＣＯ
3 、ＴｉＯ2 、ＺｒＯ2 、ＳｎＯ2 及びＭｎＣＯ3 と純
度９５％以上のＮｄ2 Ｏ3 （希土類酸化物の不純物とし
てＰｒ等が混入する場合がある）の各粉末を用いるとと
もに、原料の不純物量を制御することによって組成物中
のＮａおよびＳｉの含有量を調整し、それらを表１，表
２および表３となるように秤量後、純水を加え樹脂ボー
ルを用いて一昼夜ボールミル混合を行った。EXAMPLE As a starting material, BaCO having a purity of 99% or more was used.
3 , each powder of TiO 2 , ZrO 2 , SnO 2, MnCO 3 and Nd 2 O 3 having a purity of 95% or more (Pr etc. may be mixed as impurities of rare earth oxide) is used, and the amount of impurities in the raw material is used. Was adjusted to control the contents of Na and Si in the composition, and after weighing them so as to be as shown in Tables 1, 2 and 3, pure water was added, and ball milling was performed day and night using a resin ball. Was.
【００２８】次いで、この混合物を乾燥後、１１８０℃
で２時間仮焼し、この仮焼粉をボールミルにて２０時間
粉砕した後、有機系粘結剤を添加して混合撹拌し、ドク
ターブレード法によって肉厚５０μｍのグリーンシート
に成形した。Next, after drying this mixture,
After calcining for 2 hours with a ball mill, the calcined powder was pulverized with a ball mill for 20 hours, an organic binder was added thereto, mixed and stirred, and formed into a green sheet having a thickness of 50 μm by a doctor blade method.
【００２９】得られたグリーンシートを２５枚重ねてホ
ットプレスしてグリーン成形板を作製し、直径２０ｍ
ｍ、厚さ約１ｍｍの円板状に打ち抜いた後、これらの成
形体を３００℃で２時間脱バインダー処理をし、引き続
いて１２８０〜１３４０℃の温度で２時間空気中におい
て焼成した。The green sheets thus obtained were stacked on each other and hot-pressed to form a green molded plate having a diameter of 20 m.
After punching into a disc having a thickness of about 1 mm and a thickness of about 1 mm, these compacts were subjected to a binder removal treatment at 300 ° C. for 2 hours, and subsequently fired at a temperature of 1280 to 1340 ° C. for 2 hours in air.
【００３０】[0030]
【表１】 [Table 1]
【００３１】[0031]
【表２】 [Table 2]
【００３２】[0032]
【表３】 [Table 3]
【００３３】かくして得られた円板形状の磁器の上下全
面に、銀電極を形成して単層の円板型コンデンサとし、
これを評価試料とした。Silver electrodes are formed on the entire upper and lower surfaces of the disk-shaped porcelain thus obtained to form a single-layer disk-shaped capacitor.
This was used as an evaluation sample.
【００３４】次に、前記評価用の各試料を周波数１ＭＨ
ｚ、入力電力レベル１Ｖｒｍｓにて静電容量（Ｃ）及び
品質係数（Ｑ値）を測定し、周波数１ＭＨｚに於いて−
５５℃〜１２５℃の範囲での静電容量の温度係数ＴＣＣ
を測定した。Next, each sample for evaluation was subjected to a frequency of 1 MHz.
z, the capacitance (C) and the quality factor (Q value) were measured at an input power level of 1 Vrms, and at a frequency of 1 MHz,
Temperature coefficient of capacitance TCC in the range of 55 ° C to 125 ° C
Was measured.
【００３５】また、試料の直径（Ｄ）、厚み（Ｔ）の寸
法を±５μｍの精度で、重量（ｍ）を±５ｍｇの精度で
それぞれ測定し、比誘電率εｒを算出した。以上の結果
を表４、表５及び表６に示す。The diameter (D) and thickness (T) dimensions of the sample were measured with an accuracy of ± 5 μm, and the weight (m) was measured with an accuracy of ± 5 mg, and the relative permittivity εr was calculated. The above results are shown in Tables 4, 5 and 6.
【００３６】また、焼結体を原子吸光、ＩＣＰ等で定量
分析した結果、Ｂａ，Ｎｄ，Ｔｉ，Ｚｒ，Ｓｎ等の組成
は、調合組成と基本的に変わらないことを確認した。Further, as a result of quantitative analysis of the sintered body by means of atomic absorption, ICP, etc., it was confirmed that the composition of Ba, Nd, Ti, Zr, Sn, etc. was basically the same as the prepared composition.
【００３７】[0037]
【表４】 [Table 4]
【００３８】[0038]
【表５】 [Table 5]
【００３９】[0039]
【表６】 [Table 6]
【００４０】表４、表５および表６から明らかなよう
に、図１のαの領域では静電容量の温度係数ＴＣＣがマ
イナス側に大きいため、またγの領域では同ＴＣＣがプ
ラス側に大きいため、またβの領域では比誘電率が低い
ためにいずれも特性を満足しない。更にδの領域では焼
結性が悪化し、緻密な磁器を得ることが困難であること
が判る。As is clear from Tables 4, 5 and 6, the temperature coefficient TCC of the capacitance is large on the minus side in the region α in FIG. 1, and the TCC is large on the plus side in the region γ. Therefore, in the region of β, the characteristics are not satisfied because the relative dielectric constant is low. Further, it can be seen that the sinterability deteriorates in the region of δ, and it is difficult to obtain a dense porcelain.
【００４１】一方、ＭｎがＭｎＣＯ3 換算で０．０１重
量％未満及び０．５重量％を越えるとＱ値が低くなった
り、誘電特性が劣化することが判る。On the other hand, when Mn is less than 0.01% by weight or more than 0.5% by weight in terms of MnCO 3 , it can be seen that the Q value decreases and the dielectric properties deteriorate.
【００４２】更に、Ｎａの混入により焼結性の悪化が見
られ、それに伴って比誘電率及びＱ値が低下し、温度係
数ＴＣＣも悪化することが判る。Further, it can be seen that the sinterability deteriorates due to the incorporation of Na, and the relative dielectric constant and Q value decrease, and the temperature coefficient TCC also worsens.
【００４３】また、Ｓｉ量が増加することにより比誘電
率が低下し、静電容量の温度係数ＴＣＣの絶対値が大き
くなり、Ｑ値が低下することが判る。It can also be seen that the relative dielectric constant decreases as the amount of Si increases, the absolute value of the temperature coefficient of capacitance TCC increases, and the Q value decreases.
【００４４】それらに対して、本発明の誘電体磁器組成
物では、比誘電率が５０以上、Ｑ値も３０００以上と高
く、更に温度係数ＴＣＣが０±３０ｐｐｍ／℃以内と優
れた特性を有しており、また、Ｓｉの混入を防ぐことに
より、温度係数の安定した高い比誘電率の磁器を作製で
きることが判る。On the other hand, the dielectric ceramic composition of the present invention has excellent characteristics such as a relative dielectric constant of 50 or more, a Q value of 3000 or more, and a temperature coefficient TCC of 0 ± 30 ppm / ° C. or less. In addition, it can be seen that by preventing the incorporation of Si, a ceramic having a high relative dielectric constant with a stable temperature coefficient can be manufactured.
【００４５】[0045]
【発明の効果】以上記述した通り、本発明の誘電体磁器
組成物は、ＳｉＯ2 等の焼結助剤を用いることなく１３
４０℃以下で焼成が可能であり、静電容量の温度変化が
小さく、比誘電率及びＱ値が高いため、Ｐｄを内部電極
とする温度補償用磁器コンデンサ用の誘電体磁器組成物
に好適に用いることができる。As described above, the dielectric ceramic composition of the present invention can be used without using a sintering aid such as SiO 2.
It can be fired at 40 ° C or lower, has a small capacitance temperature change, and has a high relative dielectric constant and a high Q value. Therefore, it is suitable for a dielectric ceramic composition for a temperature compensating ceramic capacitor having Pd as an internal electrode. Can be used.
【図１】本発明の組成範囲を示すＢａＯ−Ｎｄ2 Ｏ3 −
（ＴｉＯ2 ＋ＭｅＯ2 ）系の３元図である。FIG. 1 shows the composition range of the present invention, BaO—Nd 2 O 3 −.
FIG. 3 is a ternary diagram of a (TiO 2 + MeO 2 ) system.
フロントページの続き (56)参考文献 特開 平２−49307（ＪＰ，Ａ) 特開 平２−106810（ＪＰ，Ａ) 特開 昭62−243207（ＪＰ，Ａ) 特開 平４−334809（ＪＰ，Ａ) 特開 平７−192531（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) C04B 35/42 - 35/49 C04B 35/00 - 35/22 H01B 3/00 - 3/14 Continuation of the front page (56) References JP-A-2-49307 (JP, A) JP-A-2-106810 (JP, A) JP-A-62-243207 (JP, A) JP-A-4-334809 (JP) , A) JP-A-7-192531 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) C04B 35/42-35/49 C04B 35/00-35/22 H01B 3/00 -3/14
Claims (2)
ｉとＺｒまたはＳｎのいずれか一種以上からなる主成分
に対してＭｎを添加してなる複合酸化物であって、前記
主成分を金属元素のモル比による組成式をｘＢａＯ・ｙ
Ｎｄ2 Ｏ3 ・ｚ〔（１−ｃ）ＴｉＯ2 ＋ｃＭｅＯ2 〕
（但し、ｘ＋ｙ＋ｚ＝１００、０＜ｃ、ＭｅはＺｒまた
はＳｎのいずれか一種以上の元素）と表した時、前記
ｘ、ｙ、ｚが下記Ａ、Ｂ、Ｃ、Ｄ、Ｅで囲まれた範囲内
にあり、前記ＭｎがＭｎＣＯ3 換算で前記主成分に対し
て０．０１〜０．５重量％の割合で存在するとともに、
不純物成分としてのＮａが全量中０．１０重量％以下で
あり、かつ、測定周波数１ＭＨｚにおける比誘電率が５
０以上、静電容量の温度係数Ｔｃｃが０±３０ｐｐｍ／
℃であることを特徴とする誘電体磁器組成物。 ｘ ｙ ｚ Ａ １５．５０ １７．５０ ６７．００ Ｂ １０．５０ ２２．５０ ６７．００ Ｃ ７．５０ ２２．５０ ７０．００ Ｄ ９．１７ １９．１７ ７１．６６ Ｅ １２．５０ １７．５０ ７０．００1. At least Ba, Nd, T
A composite oxide obtained by adding Mn to a main component consisting of i and one or more of Zr and Sn, wherein the main component is represented by a composition formula of xBaO · y based on a molar ratio of a metal element.
Nd 2 O 3 .z [(1-c) TiO 2 + cMeO 2 ]
(Where x + y + z = 100, 0 <c, and Me is at least one element of Zr or Sn), the x, y, and z are surrounded by the following A, B, C, D, and E. Mn is present in a range of 0.01 to 0.5% by weight based on the main component in terms of MnCO 3 , and
Na as an impurity component is 0.10% by weight or less in the total amount, and the relative dielectric constant at a measurement frequency of 1 MHz is 5%.
0 or more, the temperature coefficient of capacitance Tcc of 0 ± 30 ppm /
A dielectric porcelain composition characterized in that the temperature is ℃. xyz A 15.50 17.50 67.00 B 10.50 22.50 67.00 C 7.50 22.50 70.00 D 9.17 19.17 71.66 E 12.50 17.50 70.00
全量中０．０５重量％以下である請求項１記載の誘電体
磁器組成物。2. The dielectric ceramic composition according to claim 1, wherein the content of Si as an impurity component is 0.05% by weight or less in the total amount in terms of SiO 2 .
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5335569A JP2902926B2 (en) | 1993-12-28 | 1993-12-28 | Dielectric porcelain composition |
| GB9424540A GB2284416B (en) | 1993-12-02 | 1994-12-02 | Dielectric ceramic composition |
| US08/686,482 US5650368A (en) | 1993-12-02 | 1996-07-26 | Dielectric ceramic composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5335569A JP2902926B2 (en) | 1993-12-28 | 1993-12-28 | Dielectric porcelain composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07187771A JPH07187771A (en) | 1995-07-25 |
| JP2902926B2 true JP2902926B2 (en) | 1999-06-07 |
Family
ID=18290055
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5335569A Expired - Lifetime JP2902926B2 (en) | 1993-12-02 | 1993-12-28 | Dielectric porcelain composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2902926B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4890683B2 (en) * | 2001-03-28 | 2012-03-07 | 財団法人ファインセラミックスセンター | Porcelain composition |
| JP2007112689A (en) * | 2005-10-24 | 2007-05-10 | Tdk Corp | Dielectric powder manufacturing method, composite electronic component and manufacturing method thereof |
| US9487445B2 (en) | 2013-03-28 | 2016-11-08 | Tdk Corporation | Ceramic composition |
-
1993
- 1993-12-28 JP JP5335569A patent/JP2902926B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07187771A (en) | 1995-07-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3028503B2 (en) | Non-reducing dielectric porcelain composition | |
| EP0087004B1 (en) | Ceramic composition and capacitor made from this ceramic composition | |
| EP0605904B1 (en) | Nonreducible dielectric ceramic composition | |
| EP0534378A1 (en) | Non-reducible dielectric ceramic composition | |
| EP0192779A1 (en) | Perovskite-type ceramic material and a process for producing the same | |
| JPH0831232A (en) | Non-reducing dielectric ceramic composition | |
| JP2902926B2 (en) | Dielectric porcelain composition | |
| JP3450913B2 (en) | Dielectric porcelain composition | |
| JP2974829B2 (en) | Microwave dielectric porcelain composition | |
| JP3435039B2 (en) | Dielectric ceramics and multilayer ceramic capacitors | |
| JP3595090B2 (en) | Dielectric porcelain composition | |
| JP3250917B2 (en) | Dielectric porcelain composition | |
| JP2902925B2 (en) | Dielectric porcelain composition | |
| JP3793548B2 (en) | Dielectric porcelain and multilayer ceramic capacitor | |
| JPH11219844A (en) | Dielectric porcelain and multilayer ceramic capacitors | |
| JP3450919B2 (en) | Dielectric ceramic composition for temperature compensation | |
| JP3193157B2 (en) | Dielectric porcelain composition for low-temperature firing, dielectric resonator or dielectric filter obtained using the same, and methods for producing them | |
| JP3469910B2 (en) | Dielectric porcelain composition | |
| JP3250927B2 (en) | Dielectric porcelain composition | |
| JP2531548B2 (en) | Porcelain composition for temperature compensation | |
| KR970005883B1 (en) | High Frequency Dielectric Self Composition and Manufacturing Method Thereof | |
| JP4553301B2 (en) | Dielectric porcelain composition and electronic component | |
| JP3469911B2 (en) | Dielectric porcelain composition | |
| JP3377915B2 (en) | Dielectric porcelain composition and electronic component | |
| JP3699598B2 (en) | Dielectric porcelain composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090319 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090319 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100319 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110319 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110319 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120319 Year of fee payment: 13 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120319 Year of fee payment: 13 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130319 Year of fee payment: 14 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140319 Year of fee payment: 15 |
|
| EXPY | Cancellation because of completion of term |