JP2009249244A - Dielectric ceramic composition, method for producing the same and dielectric ceramic capacitor - Google Patents
Dielectric ceramic composition, method for producing the same and dielectric ceramic capacitor Download PDFInfo
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- 229910052788 barium Inorganic materials 0.000 claims abstract description 16
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 16
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- 239000003990 capacitor Substances 0.000 abstract description 7
- 229910052758 niobium Inorganic materials 0.000 abstract description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 abstract description 2
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- 239000002994 raw material Substances 0.000 description 12
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- 229910052761 rare earth metal Inorganic materials 0.000 description 7
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- 229910052693 Europium Inorganic materials 0.000 description 5
- 229910052688 Gadolinium Inorganic materials 0.000 description 5
- 229910052689 Holmium Inorganic materials 0.000 description 5
- 229910052779 Neodymium Inorganic materials 0.000 description 5
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- 229910052775 Thulium Inorganic materials 0.000 description 5
- 229910052769 Ytterbium Inorganic materials 0.000 description 5
- 230000005684 electric field Effects 0.000 description 5
- 229910052746 lanthanum Inorganic materials 0.000 description 5
- 229910052573 porcelain Inorganic materials 0.000 description 5
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- 239000002253 acid Substances 0.000 description 3
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- 229910052745 lead Inorganic materials 0.000 description 3
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- 238000005516 engineering process Methods 0.000 description 2
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- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- 229910002367 SrTiO Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 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
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
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- 239000000758 substrate Substances 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
Description
本発明は、誘電体磁器組成物、特に、鉛を含有しないニオブ酸系の誘電体磁器組成物、その製造方法、及びその誘電体磁器組成物を用いたコンデンサ関する。 The present invention relates to a dielectric ceramic composition, in particular, a niobic acid-based dielectric ceramic composition containing no lead, a method for producing the same, and a capacitor using the dielectric ceramic composition.
従来、誘電体磁器組成物及び誘電体磁器コンデンサとしては、例えば主成分として（Ｂａ,Ｓｒ,Ｃａ,Ｐｂ）（Ｔｉ,Ｚｒ）Ｏ３を含む磁器組成物が用いられてきた（例えば、特許文献１〜３参照）。
これらの組成物において、例えばＢａＴｉＯ３はキュリー点が１２５℃付近であり、１５０℃以上の高温領域では、室温の比誘電率に比較して大きく低下してしまい、また、１００℃以上の領域では、キュリー点近傍となるために、室温に比べて比誘電率が著しく増大してしまうために、単体では比誘電率の温度依存性が極めて高く実用に耐えず、主成分にＰｂを導入することや副成分として例えば希土類元素を混入することによって、磁器コンデンサとして実用領域である−５５℃〜１５０℃における比誘電率の温度依存性を制御し、広く産業分野で用いられてきた。
In these compositions, for example, BaTiO 3 has a Curie point of around 125 ° C., and in a high temperature region of 150 ° C. or higher, it is greatly reduced compared to the relative dielectric constant at room temperature, and in a region of 100 ° C. or higher. Because the relative permittivity increases remarkably compared to the room temperature because it is in the vicinity of the Curie point, the temperature dependence of the relative permittivity is extremely high by itself and it cannot withstand practical use, and Pb is introduced into the main component. For example, by mixing rare earth elements as subcomponents, the temperature dependence of the relative permittivity at −55 ° C. to 150 ° C., which is a practical range of a ceramic capacitor, is controlled and widely used in the industrial field.
また、例えば、ＰｂＴｉＯ３−ＢａＺｒＯ３で示されるような２成分系の誘電体磁器組成物は、ＰｂＴｉＯ３のキュリー点が４９０℃前後であることを利用して、３００℃程度まで比誘電率の温度依存性を比較的少なくできるが、組成にＰｂを用いなくてはならない。 Further, for example, a two-component dielectric ceramic composition represented by PbTiO 3 —BaZrO 3 has a relative dielectric constant of about 300 ° C. by utilizing the Curie point of PbTiO 3 around 490 ° C. Although temperature dependence can be made relatively small, Pb must be used for the composition.
一方、鉛を含有しないニオブ酸系の圧電磁器組成物が周知である（例えば、特許文献４〜８参照）が、いずれの文献にも、誘電体磁器組成物について広い温度域における比誘電率の温度依存性を少なくすることについては開示されていない。
また、組成の面からみた場合、特許文献４に記載された発明は、（１−ｎ）（Ａｇ1-a-b-cＬｉaＮａbＫc）（Ｎｂ1-x-y-zＴａxＳｂyＶz）Ｏ3を主成分とする圧電／電歪磁器組成物であり、Ａｇが必須成分であり、特許文献５に記載された発明は、Ｌｉx（Ｋ1-yＮａy）1-x｝（Ｎｂ1-z-nＴａz（Ｍｎ0.5Ｗ0.5）n）Ｏ3を主成分とする圧電磁器組成物であり、Ｍｎ及びＷが必須成分であるから、高価な元素を使用しなければならないという問題がある。 Also, when viewed from the surface of the composition, the invention described in Patent Document 4, (1-n) ( Ag 1-abc Li a Na b K c) (Nb 1-xyz Ta x Sb y V z) O 3 Is a piezoelectric / electrostrictive porcelain composition containing Ag as a main component, Ag is an essential component, and the invention described in Patent Document 5 describes Li x (K 1-y Na y ) 1-x } (Nb 1- zn Ta z (Mn 0.5 W 0.5 ) n ) A piezoelectric ceramic composition mainly composed of O 3 , and since Mn and W are essential components, there is a problem that expensive elements must be used.
特許文献６及び７には、（Ｎａ1-x-y Ｋx Ｌｉy）（Ｎｂ1-w Ｔａw ）Ｏ3 を主成分とし、Ｍｇ、Ｃａ、Ｓｒ及びＢａからなる元素群のうちの少なくとも１種を含む圧電磁器が記載されているが、これらの圧電磁器は、ＭｇとＣａ、Ｓｒ及びＢａからなる元素群のうちの少なくとも１種とを組み合わせて含有するものではないため、後述の実施例（比較例）に示されるように、比誘電率の温度依存性は改善されていない。 Patent Documents 6 and 7 include at least one element group consisting of (Na 1-xy K x Li y ) (Nb 1-w Ta w ) O 3 and consisting of Mg, Ca, Sr and Ba. However, since these piezoelectric ceramics do not contain a combination of Mg and at least one element group consisting of Ca, Sr and Ba, examples described later ( As shown in Comparative Example), the temperature dependence of the dielectric constant is not improved.
特許文献８に記載された発明は、Ｋ１-ｘＮａｘＮｂＯ３にＣｕＯ、又はＬｉ及びＴａの両者を添加して圧電材料組成物とすることにより、温度変化に対する誘電率（％／−５０〜１００℃）変化を小さくするものではあるが、広い温度域（−５５℃〜１５０℃）における比誘電率の温度依存性を少なくする点では十分ではなかった。 In the invention described in Patent Document 8, the dielectric constant (% / − 50) with respect to temperature change is obtained by adding CuO or both Li and Ta to K 1-x Na x NbO 3 to obtain a piezoelectric material composition. (˜100 ° C.) Although the change is reduced, it is not sufficient in reducing the temperature dependence of the relative dielectric constant in a wide temperature range (−55 ° C. to 150 ° C.).
一方、例えば車載用途などの電子部品においては、従来においては、例えばＥＩＡ規格Ｘ８Ｒ（−５５℃〜１５０℃において静電容量の変化率が±１５％以内（ΔＣ／Ｃ＝±１５％以内））を満たす誘電体磁器コンデンサが必要とされているが、例えば車載用途の電子部品をよりいっそう自動車エンジン周域に近づけて配備し、自動車内のスペースをより広くし、より快適な操縦環境を得ようとする場合は、さらに高い温度である１５０℃以上においても、ΔＣ／Ｃ＝±１５％を満たす誘電体磁器コンデンサであることが望ましい。 On the other hand, for example, in the case of electronic parts such as in-vehicle applications, conventionally, for example, EIA standard X8R (capacitance change rate within −15% at −55 ° C. to 150 ° C. (ΔC / C = within ± 15%)) Dielectric porcelain capacitors that satisfy the requirements are required. For example, electronic components for on-vehicle use will be placed closer to the car engine periphery, allowing more space in the car and a more comfortable driving environment. In this case, it is desirable that the dielectric ceramic capacitor satisfy ΔC / C = ± 15% even at a higher temperature of 150 ° C. or higher.
また、ＥＩＡ規格Ｘ８Ｒを満たすことのできる誘電体磁器コンデンサで、例えば、ＢａＴｉＯ３、ＳｒＴｉＯ３、ＣａＴｉＯ３などを主成分とする誘電体磁器コンデンサは、希土類元素である、Ｓｃ、Ｙ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕなどの希土類金属元素を使用することによって、その特性を達成している。これらのレアアースを用いずとも従来のＥＩＡ規格Ｘ８Ｒ特性を達成しすることができれば、希少元素を使用せずとも従来の特性を達成することができ、近年の希少元素の高騰など、市場原理に依存することを防ぐことができる。 In addition, dielectric ceramic capacitors that can satisfy the EIA standard X8R, for example, dielectric ceramic capacitors mainly composed of BaTiO 3 , SrTiO 3 , CaTiO 3, etc., are rare earth elements such as Sc, Y, La, Ce. The characteristics are achieved by using rare earth metal elements such as Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. If the conventional EIA standard X8R characteristics can be achieved without using these rare earth elements, the conventional characteristics can be achieved without using rare elements, depending on market principles such as the recent rise in rare elements. Can be prevented.
さらには、ＥＩＡ規格Ｘ８Ｒに囚われなくとも、例えば、低温側で−５５℃を満たさなくても、１５０℃以上の高い温度でΔＣ／Ｃ＝±１５％以内を満たす誘電体磁器コンデンサを作ることができるのであれば、周囲の環境が例えば１５０℃〜３００℃になるような環境においても、大きく静電容量が低下することのない、まったく新規の誘電体磁器コンデンサとなる。 Furthermore, even without being bound by the EIA standard X8R, for example, a dielectric ceramic capacitor satisfying ΔC / C = ± 15% at a high temperature of 150 ° C. or higher can be made without satisfying −55 ° C. on the low temperature side. If possible, even in an environment where the surrounding environment is, for example, 150 ° C. to 300 ° C., a completely new dielectric ceramic capacitor that does not greatly decrease the capacitance is obtained.
また、従来、例えばＰｂＴｉＯ３を主成分とすることによって、１５０℃以上の高い温度でΔＣ／Ｃ＝±１５％以内を満たす誘電体磁器コンデンサは存在するが、組成にＰｂが存在するために、原料として例えばＰｂＯ、ＰｂＯ２、Ｐｂ３Ｏ４などを用いなければならず、生産工程において、これら原料の環境への拡散が起こりうるため、これを解決することは、近年の環境との調和が求められる技術として有望である。 Conventionally, for example, there is a dielectric ceramic capacitor satisfying ΔC / C = ± 15% at a high temperature of 150 ° C. or higher by using, for example, PbTiO 3 as a main component. However, because Pb exists in the composition, For example, PbO, PbO 2 , Pb 3 O 4 or the like must be used as a raw material, and in the production process, these raw materials may diffuse into the environment. It is promising as a required technology.
本発明は、上記のような観点から、比誘電率の変化率が広い温度域において小さく、比誘電率が大きく、誘電損失が小さい、鉛を含有しないニオブ酸系の誘電体磁器組成物、その製造方法、及びその誘電体磁器組成物を用いた、静電容量の容量変化率（ΔＣ／Ｃ）が広い温度域において小さいコンデンサを提供することを課題とする。 In view of the above, the present invention is a niobic acid-based dielectric ceramic composition containing no lead, containing a low relative dielectric constant change rate in a wide temperature range, a high relative dielectric constant, and a low dielectric loss. It is an object of the present invention to provide a capacitor having a small capacitance change rate (ΔC / C) using a manufacturing method and its dielectric ceramic composition in a wide temperature range.
本発明は、上記の課題を解決するために、以下の手段を採用する。
（１）一般式［Ｎａ１−ｘＫｘ］１−ｙＬｉｙ［Ｎｂ１−ｚＴａｚ］Ｏ３（但し、ｘ、ｙ、ｚは、０≦ｘ≦１．０、０≦ｙ≦０．３０、０≦ｚ≦０．４０）で示される主成分と、副成分として、主成分に対するモル％で１．０〜８．０モル％のＮｂ２Ｏ５、１．０〜８．０モル％のＭｇＯ、３．０〜１６．０モル％のＲＯ（但しＲはＣａ、Ｓｒ、Ｂａの内、少なくとも１種）を含むことを特徴とする誘電体磁器組成物である。
（２）比誘電率の変化率が、−５５℃〜１５０℃の範囲内で±１５％以内であることを特徴とする前記（１）の誘電体磁器組成物である。
（３）比誘電率の変化率が、さらに、−５５℃〜２５０℃の範囲内で±１５％以内であることを特徴とする前記（２）の誘電体磁器組成物である。
（４）比誘電率の変化率が、０℃〜４００℃の範囲で±１５％以内であることを特徴とする前記（１）の誘電体磁器組成物である。
（５）誘電損失が５％以内であることを特徴とする前記（１）〜（４）のいずれか１項の誘電体磁器組成物である。
（６）平均粒子径が２μｍ以下であることを特徴とする前記（１）〜（５）のいずれか１項の誘電体磁器組成物である。
（７）一般式［Ｎａ１−ｘＫｘ］１−ｙＬｉｙ［Ｎｂ１−ｚＴａｚ］Ｏ３（但し、ｘ、ｙ、ｚは、０≦ｘ≦１．０、０≦ｙ≦０．３０、０≦ｚ≦０．４０） で示される主成分と、副成分として、主成分に対するモル％で１．０〜８．０モル％のＮｂ２Ｏ５、１．０〜８．０モル％のＭｇＯ、３．０〜１６．０モル％のＲＯ（但しＲはＣａ、Ｓｒ、Ｂａの内、少なくとも１種）を含む粉末を成形し、焼成することによって誘電体磁器組成物を得ること特徴とする誘電体磁器組成物の製造方法である。
（８）前記（１）〜（６）のいずれか１項の誘電体磁器組成物よりなる誘電体を有することを特徴とする誘電体磁器コンデンサである。
（９）静電容量の容量変化率（ΔＣ／Ｃ）が、−５５℃〜１５０℃の範囲内で±１５％以内であることを特徴とする前記（８）の誘電体磁器コンデンサである。
（１０）静電容量の容量変化率（ΔＣ／Ｃ）が、さらに、−５５℃〜２５０℃の範囲内で±１５％以内であることを特徴とする前記（９）の誘電体磁器コンデンサである。
（１１）静電容量の容量変化率（ΔＣ／Ｃ）が、０℃〜４００℃の範囲で±１５％以内であることを特徴とする前記（８）の誘電体磁器コンデンサである。
The present invention employs the following means in order to solve the above problems.
(1) General formula [Na 1-x K x ] 1-y Li y [Nb 1-z Ta z ] O 3 (where x, y, z are 0 ≦ x ≦ 1.0, 0 ≦ y ≦ 0.30, 0 ≦ z ≦ 0.40) and, as subcomponents, 1.0 to 8.0 mol% of Nb 2 O 5 , 1.0 to 8. A dielectric ceramic composition comprising 0 mol% MgO and 3.0 to 16.0 mol% RO (wherein R is at least one of Ca, Sr, and Ba).
(2) The dielectric ceramic composition according to (1), wherein a change rate of a relative dielectric constant is within ± 15% within a range of −55 ° C. to 150 ° C.
(3) The dielectric ceramic composition according to (2), wherein the change rate of the relative dielectric constant is further within ± 15% within a range of −55 ° C. to 250 ° C.
(4) The dielectric ceramic composition according to (1), wherein a change rate of a relative dielectric constant is within ± 15% in a range of 0 ° C. to 400 ° C.
(5) The dielectric ceramic composition according to any one of (1) to (4), wherein the dielectric loss is within 5%.
(6) The dielectric ceramic composition according to any one of (1) to (5), wherein an average particle diameter is 2 μm or less.
(7) General formula [Na 1-x K x ] 1-y Li y [Nb 1-z Ta z ] O 3 (where x, y, z are 0 ≦ x ≦ 1.0, 0 ≦ y ≦ 0.30, 0 ≦ z ≦ 0.40) and, as subcomponents, 1.0 to 8.0 mol% of Nb 2 O 5 , 1.0 to 8. A dielectric ceramic composition is formed by molding and firing a powder containing 0 mol% MgO and 3.0 to 16.0 mol% RO (wherein R is at least one of Ca, Sr, and Ba). This is a method for producing a dielectric ceramic composition.
(8) A dielectric ceramic capacitor comprising a dielectric made of the dielectric ceramic composition according to any one of (1) to (6).
(9) The dielectric ceramic capacitor according to (8), wherein the capacitance change rate (ΔC / C) is within ± 15% within a range of −55 ° C. to 150 ° C.
(10) The dielectric ceramic capacitor according to (9), wherein the capacitance change rate (ΔC / C) is further within ± 15% within a range of −55 ° C. to 250 ° C. is there.
(11) The dielectric ceramic capacitor according to (8), wherein the capacitance change rate (ΔC / C) is within ± 15% in the range of 0 ° C. to 400 ° C.
本発明によれば、その主成分に、Ｐｂ、Ｂｉ、Ｓｂなどの重金属元素を使用することなく広い温度域における比誘電率の変化率が±１５％以内となる誘電体磁器組成物、その製造方法、前記誘電体磁器組成物よりなる誘電体を有する、静電容量の容量変化率（ΔＣ／Ｃ）が±１５％以内となる誘電体磁器コンデンサが得られるという効果を奏する。特に、−５５℃〜２５０℃という、従来の誘電体磁器組成物では達成することのできなかった広い温度域において、ΔC／C＝±１５％以内を満たす誘電体磁器コンデンサを得ることが可能となる。 According to the present invention, a dielectric ceramic composition in which the rate of change in relative permittivity in a wide temperature range is within ± 15% without using heavy metal elements such as Pb, Bi, and Sb as its main component, and its production The method has an effect that a dielectric ceramic capacitor having a dielectric made of the dielectric ceramic composition and having a capacitance change rate (ΔC / C) within ± 15% is obtained. In particular, it is possible to obtain a dielectric ceramic capacitor satisfying ΔC / C = ± 15% in a wide temperature range of −55 ° C. to 250 ° C. that cannot be achieved by the conventional dielectric ceramic composition. Become.
また、誘電体磁器組成物の主成分および副成分として、Ｓｃ、Ｙ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕなどの希土類金属元素を使用しなくても、従来のＥＩＡ規格Ｘ８Ｒ特性（−５５℃〜１５０℃におけるΔC／C＝±１５％以内）を達成することができる。 Moreover, rare earth metals such as Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu as the main component and subcomponent of the dielectric ceramic composition Even if no element is used, the conventional EIA standard X8R characteristic (ΔC / C = within ± 15% at −55 ° C. to 150 ° C.) can be achieved.
さらに、２５℃における比誘電率（ε）が８００以上、誘電損失、すなわち誘電分散（tanδ）が５％以内、相対密度にして９５％以上の密度、表面粒子径の平均が２μｍ以下という特性を有する誘電体磁器組成物、誘電体磁器コンデンサが得られる。 Furthermore, the specific dielectric constant (ε) at 25 ° C. is 800 or more, dielectric loss, that is, dielectric dispersion (tan δ) is within 5%, relative density is 95% or more, and the average surface particle diameter is 2 μm or less. A dielectric ceramic composition and a dielectric ceramic capacitor are obtained.
本発明において、主成分である誘電体組成物は、一般式［Ｎａ１−ｘＫｘ］１−ｙＬｉｙ［Ｎｂ１−ｚＴａｚ］Ｏ３で表され、且つ、ｘ、ｙ、ｚが０≦ｘ≦１．０、０≦ｙ≦０．３０、０≦ｚ≦０．４０で示される。
ここで、y＞０．３０においては、比誘電率が極端に低下してしまい、誘電体磁器組成物として実用に耐えない。また、ｚ＞０．４０においては、キュリー点が１５０℃以下まで低下してしまい、１５０℃以上における比誘電率の低下を防ぐことができないために、本発明を満たす特性を得ることができない。
In the present invention, dielectric composition is a main component represented by the general formula [Na 1-x K x] is represented by 1-y Li y [Nb 1 -z Ta z] O 3, and, x, y, z Are expressed as 0 ≦ x ≦ 1.0, 0 ≦ y ≦ 0.30, and 0 ≦ z ≦ 0.40.
Here, when y> 0.30, the relative dielectric constant is extremely lowered and cannot be practically used as a dielectric ceramic composition. In addition, when z> 0.40, the Curie point is lowered to 150 ° C. or lower, and a decrease in the dielectric constant at 150 ° C. or higher cannot be prevented, so that the characteristics satisfying the present invention cannot be obtained.
また、主成分である誘電体組成物のキュリー点は、１５０℃以上にあることが好ましい。この場合には、１５０℃以上における比誘電率の低下を防ぐことが可能であり、１５０℃以上でも高い比誘電率を確保することが可能となる。 Moreover, it is preferable that the Curie point of the dielectric composition which is a main component is 150 ° C. or higher. In this case, it is possible to prevent a decrease in relative dielectric constant at 150 ° C. or higher, and a high relative dielectric constant can be secured even at 150 ° C. or higher.
副成分の含有量は、Ｎｂ２Ｏ５を１．０モル％以上、ＭｇＯを１．０モル％以上、ＲＯ（但しＲはＣａ、Ｓｒ、Ｂａの内、少なくとも１種） を３．０モル％以上とする必要がある。以下の比較例に示されるように、１．０モル％未満のＮｂ２Ｏ５含有量、１．０モル％未満のＭｇＯ含有量、又は３．０モル％未満のＲＯ含有量である場合は、主成分のキュリー点近傍における比誘電率の上昇によって、１５０℃以上の温度において、ΔＣ／Ｃ＝±１５％以内に留めることが困難であり、実用上問題がある。 The content of subcomponents is 1.0 mol% or more of Nb 2 O 5 , 1.0 mol% or more of MgO, and RO (provided that R is at least one of Ca, Sr and Ba) is 3.0 mol. % Or more is necessary. When the Nb 2 O 5 content is less than 1.0 mol%, the MgO content is less than 1.0 mol%, or the RO content is less than 3.0 mol%, as shown in the following comparative examples Due to the increase of the relative dielectric constant in the vicinity of the Curie point of the main component, it is difficult to keep it within ΔC / C = ± 15% at a temperature of 150 ° C. or more.
また、副成分の含有量は、Ｎｂ２Ｏ５を８．０モル％以下、ＭｇＯを８．０モル％以下、ＲＯ（但しＲはＣａ、Ｓｒ、Ｂａの内、少なくとも１種） を１６．０モル％以下とする必要がある。８.０モル％を超えるＮｂ２Ｏ５含有量、８.０モル％を超えるＭｇＯ含有量であり、１６．０モル％を超えるＲＯ(但しＲはＣａ,Ｓｒ,Ｂａの内、少なくとも1種)含有量である場合は、２５℃における比誘電率（ε）が８００以下に著しく低下してしまい、実用上問題がある。 Further, the contents of subcomponents are Nb 2 O 5 of 8.0 mol% or less, MgO of 8.0 mol% or less, and RO (wherein R is at least one of Ca, Sr, and Ba). It is necessary to make it 0 mol% or less. Nb 2 O 5 content exceeding 8.0 mol%, MgO content exceeding 8.0 mol%, and RO exceeding 16.0 mol% (where R is at least one of Ca, Sr, Ba) ) Content, the relative dielectric constant (ε) at 25 ° C. is remarkably lowered to 800 or less, which causes a practical problem.
本発明において、２５℃における比誘電率（ε）は８００以上が望ましく、誘電損失、すなわち誘電分散（tanδ）は５％以内が好ましい。この場合は、本発明の誘電体磁器組成物を、磁器コンデンサとして用いた場合、高電界を印加した場合の発熱を抑制することが可能であり、本発明の誘電体磁器組成物を、コンデンサとして有用に用いることができる。 In the present invention, the relative dielectric constant (ε) at 25 ° C. is desirably 800 or more, and the dielectric loss, that is, dielectric dispersion (tan δ) is preferably within 5%. In this case, when the dielectric ceramic composition of the present invention is used as a ceramic capacitor, it is possible to suppress heat generation when a high electric field is applied, and the dielectric ceramic composition of the present invention is used as a capacitor. It can be usefully used.
本発明において、主成分である誘電体組成物は、一般式［Ｎａ１−ｘＫｘ］１−ｙＬｉｙ［Ｎｂ１−ｚＴａｚ］Ｏ３で表され、且つ、ｘ、ｙ、ｚが０≦ｘ≦１．０、０≦ｙ≦０．１０、０≦ｚ≦０．２０で示される誘電体組成物のキュリー点が３００℃以上にあることが好ましい。この範囲内においては、以下の実施例に示されるように、主成分に対する副成分の含有量において、１．０モル％〜３．０モル％のＮｂ２Ｏ５含有量であり、１．０モル％〜３．０モル％のＭｇＯ含有量であり、３．０モル％〜９．０モル％のＲＯ（但し、Ｃａ、Ｓｒ、Ｂａの内、少なくとも１種）含有量である場合は、０℃〜４００℃においてΔＣ／Ｃ＝±１５．０％を達成できる。 In the present invention, dielectric composition is a main component represented by the general formula [Na 1-x K x] is represented by 1-y Li y [Nb 1 -z Ta z] O 3, and, x, y, z Of the dielectric composition represented by 0 ≦ x ≦ 1.0, 0 ≦ y ≦ 0.10, and 0 ≦ z ≦ 0.20 is preferably 300 ° C. or higher. Within this range, as shown in the following examples, the content of subcomponents relative to the main component is 1.0 to 3.0 mol% of Nb 2 O 5 content, and 1.0% When the content of MgO is from mol% to 3.0 mol%, and the content of RO is from 3.0 mol% to 9.0 mol% (at least one of Ca, Sr, and Ba), ΔC / C = ± 15.0% can be achieved at 0 ° C. to 400 ° C.
また、例えば−５５℃〜２５０℃においてΔＣ／Ｃ＝±１５％以内の特性を求める場合には、副成分の含有量を以下の実施例に示されるように、適宜調節することによって、１５０℃以上におけるΔＣ／Ｃ＝±１５％以内を満たす上限温度を上昇させ、０℃以下におけるΔＣ／Ｃ＝±１５％以内を満たす下限温度を、さらに下げるという方法を採用することができ、副成分の含有量によって、ΔＣ／Ｃ＝±１５％以内となる温度領域を有益に制御することが可能である。 Further, for example, in the case of obtaining a characteristic within ΔC / C = ± 15% at −55 ° C. to 250 ° C., the content of subcomponents is appropriately adjusted to 150 ° C. as shown in the following examples. It is possible to employ a method of increasing the upper limit temperature that satisfies ΔC / C = ± 15% or less and further lowering the lower limit temperature that satisfies ΔC / C = ± 15% or less at 0 ° C. or less. Depending on the content, it is possible to beneficially control the temperature range where ΔC / C = within ± 15%.
次に、本発明における誘電体磁器組成物の製造方法については、原料粉末を準備し、主成分が一般式［Ｎａ１−ｘＫｘ］１−ｙＬｉｙ［Ｎｂ１−ｚＴａｚ］Ｏ３(但し、ｘ、ｙ、ｚは、０≦ｘ≦１．０、０≦ｙ≦０．３０、０≦ｚ≦０．４０)となり、副成分が、主成分に対するモル％で１．０〜８．０モル％のＮｂ２Ｏ５、１．０〜８．０モル％のＭｇＯ、３．０〜１６．０モル％のＲＯ（但しＲはＣａ、Ｓｒ、Ｂａの内、少なくとも１種）となるように各原料粉末の配合を行い、常法により、原料混合物を仮焼して、粉砕した後、バインダーを添加して成形し、焼成するという方法を採用することができる。焼成温度は、１１００〜１２８０℃が好ましい。 Next, the production method of a dielectric ceramic composition of the present invention, preparing a raw material powder, the main component is the general formula [Na 1-x K x] 1-y Li y [Nb 1-z Ta z] O 3 (where x, y, z are 0 ≦ x ≦ 1.0, 0 ≦ y ≦ 0.30, 0 ≦ z ≦ 0.40), and the subcomponent is 1.0% by mol% with respect to the main component. 8.0 mol% of Nb 2 O 5, 1.0~8.0 mol% of MgO, 3.0-16.0 mole% of RO (wherein R is Ca, Sr, among Ba, at least one The raw material powders are blended so as to be, and the raw material mixture is calcined and pulverized by a conventional method, and then added with a binder, molded, and fired. The firing temperature is preferably 1100 to 1280 ° C.
さらには、本発明は、ＥＩＡ規格Ｘ８Ｒ特性を、Ｓｃ、Ｙ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕなどの希土類金属元素を用いなくとも達成することが可能であり、原料の原価を低下させることが可能である。 In addition, the present invention provides EIA standard X8R characteristics with rare earth metal elements such as Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. This can be achieved without using it, and the cost of raw materials can be reduced.
また、誘電体磁器組成物を製造するための原料となる材料には、Ｋ（カリウム）を含有する材料としては、Ｋ２ＣＯ３ないし、ＫＨＣＯ３であり、Ｎａ（ナトリウム）を含有する材料としては、Ｎａ２ＣＯ３ないしＮａＨＣＯ３であり、Ｌｉ（リチウム）を含有する材料としては、Ｌｉ２ＣＯ３であり、Ｎｂ（ニオブ）を含有する材料としては、Ｎｂ２Ｏ５であり、Ｔａ（タンタル）を含有する材料としては、Ｔａ２Ｏ５であり、Ｂａ（バリウム）を含有する材料としてはＢａＣＯ３であり、Ｓｒ（ストロンチウム）を含有する材料としてはＳｒＣＯ３であり、Ｃａ（カルシウム）を含有する材料としてはＣａＣＯ３であり、Ｍｇ（マグネシウム）を含有する材料としてはＭｇＯないし、ＭｇＣＯ３ないし、Ｍｇ（ＯＨ）２であることが好ましい。この場合には、上記の誘電体組成物を容易に製造することが可能となる。 In addition, as a material that is a raw material for manufacturing the dielectric ceramic composition, K (potassium) -containing material is K 2 CO 3 or KHCO 3 and Na (sodium) -containing material. Is Na 2 CO 3 to NaHCO 3 , Li 2 CO 3 is a material containing Li (lithium), Nb (niobium) is a material containing Nb 2 O 5 , and Ta ( The material containing tantalum) is Ta 2 O 5 , the material containing Ba (barium) is BaCO 3 , the material containing Sr (strontium) is SrCO 3 , and Ca (calcium) The material containing Ca is CaCO 3 , and the material containing Mg (magnesium) is MgO or MgCO 3 or Mg (OH) 2 . Preferably there is. In this case, the above dielectric composition can be easily manufactured.
さらに、本発明における誘電体磁器組成物には、第一遷移元素であるＳｃ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎを少なくとも１種類一定量混入させることによって、焼結温度を制御したり粒子の成長を制御したり、高電界化における寿命を延ばしたりすることが可能であるが、これらの元素は、用いても、用いなくてもよい。 Furthermore, the dielectric ceramic composition according to the present invention is mixed with a predetermined amount of at least one of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn as the first transition elements. Although it is possible to control the sintering temperature, to control the growth of particles, and to extend the lifetime in increasing the electric field, these elements may or may not be used.
また、本発明における誘電体磁器組成物には、第二遷移元素であるＹ、Ｚｒ、Ｍｏ、Ｒｕ、Ｒｈ、Ｐｄ、Ａｇを少なくとも１種類一定量混入させることによって、焼結温度を制御したり粒子の成長を制御したり、高電界化における寿命を延ばしたりすることが可能であるが、これらの元素は、用いても、用いなくてもよい。 In addition, the dielectric ceramic composition according to the present invention can control the sintering temperature by mixing a certain amount of at least one kind of second transition elements Y, Zr, Mo, Ru, Rh, Pd, and Ag. Although it is possible to control the growth of particles and extend the lifetime in increasing the electric field, these elements may or may not be used.
また、本発明における誘電体磁器組成物には、第三遷移元素であるＬａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ、Ｈｆ、Ｗ、Ｒｅ、Ｏｓ、Ｉｒ、Ｐｔ、Ａｕを少なくとも１種類一定量混入させることによって、焼結温度を制御したり粒子の成長を制御したり、高電界化における寿命を延ばしたりすることが可能であるが、これらの元素は、用いても、用いなくてもよい。 Further, the dielectric ceramic composition of the present invention includes La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, W, which are third transition elements. , Re, Os, Ir, Pt, Au can be mixed in a certain amount so that the sintering temperature can be controlled, the growth of particles can be controlled, and the life in high electric field can be extended. However, these elements may or may not be used.
上記の第一遷移元素、第二遷移元素、第三遷移元素の内、少なくとも１種類一定量混入させることによって、焼結温度を制御したり粒子の成長を制御したり、高電界化における寿命を延ばしたりすることが可能であるが、これらを複合させても、させなくても同様の効果が得られる。 By mixing a certain amount of at least one of the first transition element, second transition element, and third transition element described above, the sintering temperature can be controlled, the growth of particles can be controlled, and the lifetime in increasing the electric field can be increased. Although it can be extended, the same effect can be obtained with or without combining these.
さらには、本発明によって得られる誘電体磁器は、焼結体の相対密度が９５％以上であることが望ましい。これ以下である場合には、誘電分散（ｔａｎδ）が室温、通常大気雰囲気においても、大きく分散してしまい、実用に耐えない。 Further, in the dielectric ceramic obtained by the present invention, it is desirable that the relative density of the sintered body is 95% or more. If it is less than this, the dielectric dispersion (tan δ) will be greatly dispersed even at room temperature and in the normal atmosphere, which is not practical.
また、本発明によって得られる誘電体磁器における表面粒子径の平均は、２μｍ以下となることが好ましい。この場合、例えば積層セラミックスコンデンサなどにおいて、電極間隔を狭めることが容易となり、工業的に応用することが容易となる。 The average surface particle diameter in the dielectric ceramic obtained by the present invention is preferably 2 μm or less. In this case, for example, in a multilayer ceramic capacitor, it is easy to narrow the electrode interval, and industrial application is facilitated.
本発明の誘電体磁器コンデンサは、本発明の誘電体磁器組成物よりなる誘電体を用いることを特徴とするものであり、従来の積層セラミックコンデンサと同様の製造方法、例えば、未焼成誘電体層に内部電極層を形成したものを積層して、焼成後、外部電極を形成するか、外部電極を形成後、焼成を同時に行う方法で製造することができる。 The dielectric ceramic capacitor of the present invention is characterized by using a dielectric made of the dielectric ceramic composition of the present invention, and a manufacturing method similar to that of a conventional multilayer ceramic capacitor, for example, an unfired dielectric layer It is possible to manufacture the substrate by laminating the layers having the internal electrode layer formed thereon and forming an external electrode after firing, or by simultaneously firing after forming the external electrode.
本発明の誘電体磁器組成物の製造方法と評価した結果について説明する。
実施例における誘電体磁器組成物は、主成分が、一般式［Ｎａ１−ｘＫｘ］１−ｙＬｉｙ［Ｎｂ１−ｚＴａｚ］Ｏ３で示され、かつｘ、ｙ、ｚがそれぞれ０≦ｘ≦１．０、０≦y≦０．３０、０≦ｚ≦０．４０の範囲内にあり、さらに副成分が、主成分に対するモル％として、１．０〜８．０モル％のＮｂ２Ｏ５、１．０〜８．０モル％のＭｇＯ、３．０〜１６．０モル％のＲＯ（但しＲはＣａ、Ｓｒ、Ｂａの内、少なくとも１種）の範囲内にある。
The production method of the dielectric ceramic composition of the present invention and the evaluation results will be described.
The dielectric ceramic composition in the examples, the main component has the general formula represented by [Na 1-x K x] 1-y Li y [Nb 1-z Ta z] O 3, and x, y, z is Each of them is in the range of 0 ≦ x ≦ 1.0, 0 ≦ y ≦ 0.30, 0 ≦ z ≦ 0.40, and the subcomponent is 1.0 to 8.0 mol as mol% with respect to the main component. % Nb 2 O 5 , 1.0 to 8.0 mol% MgO, 3.0 to 16.0 mol% RO (wherein R is at least one of Ca, Sr and Ba) is there.
本発明の範囲内にある誘電体磁器組成物の原料として、純度が９９％以上のＫ２ＣＯ３（又はＫＨＣＯ３）、Ｎａ２ＣＯ３（又はＮａＨＣＯ３）、Ｎｂ２Ｏ５、ＳｒＣＯ３、ＭｇＯ（又はＭｇＣＯ３、Ｍｇ（ＯＨ）２）を準備し、これらの原料を上記の主成分が一般式［Ｎａ１−ｘＫｘ］１−ｙＬｉｙ［Ｎｂ１−ｚＴａｚ］Ｏ３において、ｘ＝０．５、ｙ＝０、ｚ＝０となるように配合を行い、副成分としては、次の実験No.１から１９のような主成分に対するモル％となるように配合を行った。
なお、実験No.１、５、６、７は、本発明の組成範囲外にある比較例である。
As a raw material of the dielectric ceramic composition within the scope of the present invention, K 2 CO 3 (or KHCO 3 ), Na 2 CO 3 (or NaHCO 3 ), Nb 2 O 5 , SrCO 3 , having a purity of 99% or more, MgO (or MgCO 3 , Mg (OH) 2 ) is prepared, and the above main components are represented by the general formula [Na 1−x K x ] 1−y Li y [Nb 1−z Ta z ] O 3. In this case, the blending was performed so that x = 0.5, y = 0, z = 0, and the subcomponents were blended so as to be mol% with respect to the main component as in the following experiments No. 1 to 19. went.
Experiments Nos. 1, 5, 6, and 7 are comparative examples outside the composition range of the present invention.
実験No.１．（比較例）
主成分がＮａ０．５Ｋ０．５ＮｂＯ３となり、副成分が、ＳｒＣＯ３を２.０モル％、ＭｇＯを０．７モル％、Ｎｂ２Ｏ５を０．７モル％となるように配合を行った。
Experiment No.1. (Comparative example)
The main component is Na 0.5 K 0.5 NbO 3 , and the subcomponents are 2.0 mol% SrCO 3 , 0.7 mol% MgO and 0.7 mol% Nb 2 O 5. Blended.
実験No.２．
主成分がＮａ０．５Ｋ０．５ＮｂＯ３となり、副成分が、ＳｒＣＯ３を５.０モル％、ＭｇＯを１．７モル％、Ｎｂ２Ｏ５を１．７モル％となるように配合を行った。
Experiment No.2.
The main component is Na 0.5 K 0.5 NbO 3 , and the subcomponents are 5.0 mol% of SrCO 3 , 1.7 mol% of MgO, and 1.7 mol% of Nb 2 O 5. Blended.
実験No.３．
主成分がＮａ０．５Ｋ０．５ＮｂＯ３となり、副成分が、ＳｒＣＯ３を８．０モル％、ＭｇＯを２．７モル％、Ｎｂ２Ｏ５を２．７モル％となるように配合を行った。
Experiment No.3.
The main component is Na 0.5 K 0.5 NbO 3 , and the subcomponents are 8.0 mol% SrCO 3 , 2.7 mol% MgO, and 2.7 mol% Nb 2 O 5. Blended.
実験No.４．
主成分がＮａ０．５Ｋ０．５ＮｂＯ３となり、副成分が、ＳｒＣＯ３を１０．０モル％、ＭｇＯを３．３モル％、Ｎｂ２Ｏ５を３．３モル％となるように配合を行った。
Experiment No.4.
The main component is Na 0.5 K 0.5 NbO 3 , and the subcomponents are 10.0 mol% of SrCO 3 , 3.3 mol% of MgO, and 3.3 mol% of Nb 2 O 5. Blended.
実験No.５．（比較例）
主成分がＮａ０．５Ｋ０．５ＮｂＯ３となり、副成分が、ＳｒＣＯ３を２．５モル％、Ｎｂ２Ｏ５を２．５モル％となるように配合を行った。
Experiment No.5. (Comparative example)
The main component was Na 0.5 K 0.5 NbO 3 , and the subcomponents were blended so that SrCO 3 was 2.5 mol% and Nb 2 O 5 was 2.5 mol%.
実験No.６．（比較例）
主成分がＮａ０．５Ｋ０．５ＮｂＯ３となり、副成分が、ＳｒＣＯ３を４．０モル％、Ｎｂ２Ｏ５を４．０モル％となるように配合を行った。
Experiment No. 6. (Comparative example)
The main component was Na 0.5 K 0.5 NbO 3 , and the subcomponents were blended so that SrCO 3 was 4.0 mol% and Nb 2 O 5 was 4.0 mol%.
実験No.７．（比較例）
主成分がＮａ０．５Ｋ０．５ＮｂＯ３となり、副成分が、ＳｒＣＯ３を５．０モル％、Ｎｂ２Ｏ５を５．０モル％となるように配合を行った。
Experiment No.7. (Comparative example)
The main component was Na 0.5 K 0.5 NbO 3 , and the subcomponents were blended so that SrCO 3 was 5.0 mol% and Nb 2 O 5 was 5.0 mol%.
実験No.８．
主成分がＮａ０．５Ｋ０．５ＮｂＯ３となり、副成分が、ＣａＣＯ３を５.０モル％、ＭｇＯを１．７モル％、Ｎｂ２Ｏ５を１．７モル％となるように配合を行った。
Experiment No.8.
The main component is Na 0.5 K 0.5 NbO 3 , and the secondary components are 5.0 mol% CaCO 3 , 1.7 mol% MgO, and 1.7 mol% Nb 2 O 5. Blended.
実験No.９．
主成分がＮａ０．５Ｋ０．５ＮｂＯ３となり、副成分が、ＣａＣＯ３を８.０モル％、ＭｇＯを２．７モル％、Ｎｂ２Ｏ５を２．７モル％となるように配合を行った。
Experiment No. 9.
The main component is Na 0.5 K 0.5 NbO 3 , and the auxiliary components are 8.0 mol% CaCO 3 , 2.7 mol% MgO and 2.7 mol% Nb 2 O 5. Blended.
実験No.１０．
主成分がＮａ０．５Ｋ０．５ＮｂＯ３となり、副成分が、ＣａＣＯ３を１０.０モル％、ＭｇＯを３．３モル％、Ｎｂ２Ｏ５を３．３モル％となるように配合を行った。
Experiment No. 10.
The main component is Na 0.5 K 0.5 NbO 3 , and the auxiliary components are 10.0 mol% CaCO 3 , 3.3 mol% MgO, and 3.3 mol% Nb 2 O 5. Blended.
実験No.１１．
主成分がＮａ０．５Ｋ０．５ＮｂＯ３となり、副成分が、ＢａＣＯ３を５.０モル％、ＭｇＯを１．７モル％、Ｎｂ２Ｏ５を１．７モル％となるように配合を行った。
Experiment No.11.
The main component is Na 0.5 K 0.5 NbO 3 , and the subcomponents are BaCO 3 of 5.0 mol%, MgO of 1.7 mol%, and Nb 2 O 5 of 1.7 mol%. Blended.
実験No.１２．
主成分がＮａ０．５Ｋ０．５ＮｂＯ３となり、副成分が、ＢａＣＯ３を８.０モル％、ＭｇＯを２．７モル％、Ｎｂ２Ｏ５を２．７モル％となるように配合を行った。
Experiment No. 12.
The main component is Na 0.5 K 0.5 NbO 3 , and the subcomponents are BaCO 3 8.0 mol%, MgO 2.7 mol%, and Nb 2 O 5 2.7 mol%. Blended.
実験No.１３．
主成分がＮａ０．５Ｋ０．５ＮｂＯ３となり、副成分が、ＢａＣＯ３を１０.０モル％、ＭｇＯを３．３モル％、Ｎｂ２Ｏ５を３．３モル％となるように配合を行った。
Experiment No. 13.
The main component is Na 0.5 K 0.5 NbO 3 , and the subcomponents are BaCO 3 10.0 mol%, MgO 3.3 mol%, and Nb 2 O 5 3.3 mol%. Blended.
実験No.１４．
主成分がＮａ０．５Ｋ０．５ＮｂＯ３となり、副成分が、ＳｒＣＯ３を２.５モル％、ＣａＣＯ３を２．５モル％、ＭｇＯを１．７モル％、Ｎｂ２Ｏ５を１．７モル％となるように配合を行った。
Experiment No.14.
The main component is Na 0.5 K 0.5 NbO 3 , and the subcomponents are 2.5 mol% of SrCO 3 , 2.5 mol% of CaCO 3 , 1.7 mol% of MgO and Nb 2 O 5 . Formulation was performed so that the amount was 1.7 mol%.
実験No.１５．
主成分がＮａ０．５Ｋ０．５ＮｂＯ３となり、副成分が、ＳｒＣＯ３を４．０モル％、ＣａＣＯ３を４．０モル％、ＭｇＯを２．７モル％、Ｎｂ２Ｏ５を２．７モル％となるように配合を行った。
Experiment No. 15.
The main component is Na 0.5 K 0.5 NbO 3 , and the subcomponents are 4.0 mol% of SrCO 3 , 4.0 mol% of CaCO 3 , 2.7 mol% of MgO, and Nb 2 O 5 . Formulation was performed so as to be 2.7 mol%.
実験No.１６．
主成分がＮａ０．５Ｋ０．５ＮｂＯ３となり、副成分が、ＳｒＣＯ３を５．０モル％、ＣａＣＯ３を５．０モル％、ＭｇＯを３．３モル％、Ｎｂ２Ｏ５を３．３モル％となるように配合を行った。
Experiment No. 16.
The main component is Na 0.5 K 0.5 NbO 3 , and the subcomponents are 5.0 mol% of SrCO 3 , 5.0 mol% of CaCO 3 , 3.3 mol% of MgO, and Nb 2 O 5 . The blending was performed so as to be 3.3 mol%.
実験No.１７．
主成分がＮａ０．５Ｋ０．５ＮｂＯ３となり、副成分が、ＳｒＣＯ３を２.５モル％、ＢａＣＯ３を２．５モル％、ＭｇＯを１．７モル％、Ｎｂ２Ｏ５を１．７モル％となるように配合を行った。
Experiment No. 17.
The main component is Na 0.5 K 0.5 NbO 3 , and the subcomponents are 2.5 mol% SrCO 3 , 2.5 mol% BaCO 3 , 1.7 mol% MgO and Nb 2 O 5 . Formulation was performed so that the amount was 1.7 mol%.
実験No.１８．
主成分がＮａ０．５Ｋ０．５ＮｂＯ３となり、副成分が、ＳｒＣＯ３を４．０モル％、ＢａＣＯ３を４．０モル％、ＭｇＯを２．７モル％、Ｎｂ２Ｏ５を２．７モル％となるように配合を行った。
Experiment No. 18.
The main component is Na 0.5 K 0.5 NbO 3 , and the subcomponents are 4.0 mol% SrCO 3 , 4.0 mol% BaCO 3 , 2.7 mol% MgO and Nb 2 O 5 . Formulation was performed so as to be 2.7 mol%.
実験No.１９．
主成分がＮａ０．５Ｋ０．５ＮｂＯ３となり、副成分が、ＳｒＣＯ３を５．０モル％、ＢａＣＯ３を５．０モル％、ＭｇＯを３．３モル％、Ｎｂ２Ｏ５を３．３モル％となるように配合を行った。
Experiment No. 19.
The main component is Na 0.5 K 0.5 NbO 3 , and the subcomponents are 5.0 mol% SrCO 3 , 5.0 mol% BaCO 3 , 3.3 mol% MgO and Nb 2 O 5 . The blending was performed so as to be 3.3 mol%.
上記のように配合を行った原料をボールミルによって、エタノール中で２４時間混合をし、１００℃の乾燥機の中でエタノールを揮発させることによって、目的となる原料混合物を得た。次にこの原料混合物を１０００℃、３時間仮焼を行った後、ボールミルによりエタノール中で２４時間粉砕を行った。続いて、バインダーとしてポリビニルアルコールを添加して、造粒を行った。 The raw materials blended as described above were mixed in ethanol for 24 hours by a ball mill, and ethanol was volatilized in a dryer at 100 ° C. to obtain a target raw material mixture. Next, this raw material mixture was calcined at 1000 ° C. for 3 hours and then pulverized in ethanol by a ball mill for 24 hours. Subsequently, granulation was performed by adding polyvinyl alcohol as a binder.
造粒した粉体を厚さ０．６ｍｍ、直径１０ｍｍの円盤状に加圧成形を行った後、成形体を常圧、大気雰囲気で１１００℃から１２８０℃の温度範囲にて２時間、一定温度に保つことによって焼成を行った。
ここにおいて、実験No.１〜１９の全ての試料は相対密度９５％以上に緻密化した。次に、焼成後の円盤試料における直径方向の両面にＡｇ電極を塗布し、８００℃で電極を焼き付けた。
The granulated powder is pressure-molded into a disk shape with a thickness of 0.6 mm and a diameter of 10 mm, and then the molded body is kept at a constant temperature for 2 hours in a temperature range from 1100 ° C. to 1280 ° C. under atmospheric pressure. Firing was carried out by keeping
Here, all the samples of Experiment Nos. 1 to 19 were densified to a relative density of 95% or more. Next, Ag electrodes were applied to both surfaces in the diameter direction of the fired disc sample, and the electrodes were baked at 800 ° C.
そして、実験No.１〜１９における円盤試料の比誘電率（ε）、誘電分散（ｔａｎδ）、静電容量の容量変化率（ΔＣ／Ｃ）の評価を行った。測定は、１ｋＨｚ、１Ｖの交流電圧によって行った。なお、計測には恒温槽として、Despatch社製の環境試験用恒温槽を、ε、ｔａｎδ、 ΔＣ／Ｃの評価には、YHP４１９２Ａインピーダンスアナライザを用いた。結果を表１に示す。また、ΔＣ／Ｃに関しては、図１に−５５℃〜４５０℃に渡って測定を行った結果を示す。 Then, evaluation of the relative dielectric constant (ε), dielectric dispersion (tan δ), and capacitance change rate (ΔC / C) of the disk samples in Experiment Nos. 1 to 19 was performed. The measurement was performed with an alternating voltage of 1 kHz and 1V. For measurement, a constant temperature bath for environmental testing manufactured by Despatch was used as a thermostat, and YHP4192A impedance analyzer was used for evaluation of ε, tan δ, and ΔC / C. The results are shown in Table 1. Regarding ΔC / C, FIG. 1 shows the results of measurement over −55 ° C. to 450 ° C.
実験No.１は、室温におけるεが１３８０と高く、tanδも２．０％と実用に耐え得る誘電体磁器組成物であるが、ＳｒＣＯ３、ＭｇＯ、Ｎｂ２Ｏ５といった副成分がいずれも一定以上存在しないので、温度特性が芳しくなく、本発明を満たす特性の誘電体磁器組成物を得ることができなかった。 Experiment No. 1 is a dielectric porcelain composition that can withstand practical use with a high ε of 1380 at room temperature and a tan δ of 2.0%, but the subcomponents such as SrCO 3 , MgO, and Nb 2 O 5 are all constant. Since it does not exist, the temperature characteristics are not good, and a dielectric ceramic composition satisfying the present invention cannot be obtained.
実験No.２の誘電体磁器組成物は、０℃から４００℃の間でΔＣ／Ｃ＝±１５％を満たし、εも１２３０と高く、tanδも２．３％であり、０℃〜４００℃の幅広い温度変化が見込まれる環境化で動作させる各種電子部品において、高いεと低いtanδとΔＣ／Ｃ＝±１５％以内を達成でき、工業的に極めて有益である。 The dielectric ceramic composition of Experiment No. 2 satisfies ΔC / C = ± 15% between 0 ° C. and 400 ° C., ε is as high as 1230, tan δ is 2.3%, and 0 ° C. to 400 ° C. In various electronic parts operated in an environment where a wide range of temperature changes are expected, high ε, low tan δ, and ΔC / C = within ± 15% can be achieved, which is extremely useful industrially.
実験No.３の誘電体磁器組成物は、−５５℃から２５０℃の間でΔＣ／Ｃ＝±１５％以内を満たし、εも１１１０と高く、tanδも１．８％と低く、例えばＥＩＡ規格Ｘ８Ｒ特性である−５５℃から１５０℃の範囲内でΔＣ／Ｃ＝±１５％以内という現在のコンデンサにおける静電容量の容量変化率の範囲以上における高い温度での保障を達成し、工業的に極めて有益である。 The dielectric ceramic composition of Experiment No. 3 satisfies ΔC / C = ± 15% between −55 ° C. and 250 ° C., ε is high as 1110, and tan δ is as low as 1.8%. For example, EIA standard Achieved a high temperature guarantee over the range of the capacitance change rate of the current capacitor within ΔC / C = ± 15% within the range of -55 ° C to 150 ° C, which is the X8R characteristic, and industrially Very beneficial.
実験No.４の誘電体磁器組成物は、−５５℃から１５０℃の間でΔＣ／Ｃ＝±１５％以内を満たし、εも１０９０と高く、tanδも１．６％と低い。本組成は、Ｓｃ、Ｙ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕなどの希土類金属元素を用いることなく、従来のＥＩＡ規格Ｘ８Ｒ特性を達成しているので、原料の原価を低下させることが可能であり、工業的に極めて有益である。 The dielectric ceramic composition of Experiment No. 4 satisfies ΔC / C = within ± 15% between −55 ° C. and 150 ° C., ε is as high as 1090, and tan δ is as low as 1.6%. This composition is a conventional EIA standard X8R without using rare earth metal elements such as Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. Since the characteristics are achieved, it is possible to reduce the cost of raw materials, which is extremely useful industrially.
実験No.５からNo.７は、副成分としてＳｒＣＯ３、Ｎｂ２Ｏ５が配合された特許４００１３６６号（特許文献６）の組成範囲内にある誘電体磁器組成物であるが、ＭｇＯが配合されていないため、表１にあるように、−５５℃から１５０℃の間でΔＣ／Ｃ＝±１５％以内、あるいは、０℃から４００℃の間でΔＣ／Ｃ＝±１５％以内を満たす特性の誘電体磁器組成物を得ることはできなかった。 Experiments No. 5 to No. 7 are dielectric porcelain compositions within the composition range of Patent No. 4001366 (Patent Document 6) in which SrCO 3 and Nb 2 O 5 are blended as subcomponents, but MgO is blended As shown in Table 1, ΔC / C is within ± 15% between −55 ° C. and 150 ° C., or ΔC / C is within ± 15% between 0 ° C. and 400 ° C. A characteristic dielectric ceramic composition could not be obtained.
実験No.１０、No.１３、No.１６、No.１９の誘電体磁器組成物は、−５５℃から１５０℃の間でΔＣ／Ｃ＝±１５％以内を満たし、実験No.９、No.１２、No.１５、No.１８の誘電体磁器組成物は、−５５℃から２５０℃の間でΔＣ／Ｃ＝±１５％以内を満たし、実験No.８、No.１４、No.１７の誘電体磁器組成物は、０℃から４００℃の間でΔＣ／Ｃ＝±１５％以内を満たし、いずれもεは８００以上であり、tanδは５％以内であるから、静電容量の容量変化率（ΔＣ／Ｃ）が広い温度域において小さく、比誘電率が大きく、誘電損失が小さいことが確認された。 The dielectric ceramic compositions of Experiment No. 10, No. 13, No. 16, and No. 19 satisfy ΔC / C = ± 15% or less between −55 ° C. and 150 ° C. The dielectric ceramic compositions of No. 12, No. 15, and No. 18 satisfy ΔC / C = ± 15% or less between −55 ° C. and 250 ° C., and Experiment No. 8, No. 14, No. 17 The dielectric porcelain composition of the present invention satisfies ΔC / C = ± 15% between 0 ° C. and 400 ° C., and in both cases, ε is 800 or more and tan δ is within 5%. It was confirmed that the rate of change (ΔC / C) was small in a wide temperature range, the relative dielectric constant was large, and the dielectric loss was small.
また、実験No.２からNo.４、No.８からNo.１９における誘電体磁器組成物においては、Ｐｂ、Ｂｉ、Ｓｂといった重金属元素を含まないために、これらの元素の環境への拡散が問題とならず、環境に調和した技術として極めて有望である。 In addition, since the dielectric ceramic compositions in Experiments No. 2 to No. 4 and No. 8 to No. 19 do not contain heavy metal elements such as Pb, Bi, and Sb, diffusion of these elements into the environment is prevented. This is not a problem and is extremely promising as a technology that is in harmony with the environment.
さらに、実験No.２からNo.４、No.８からNo.１９における組成において、走査型電子顕微鏡による焼結体の表面観察においては、その平均粒子径が２μｍ以下となっていることを確認し、均一な微細構造であることを確認した。図２に、左から順に、実験No.２、No.３、No.４における走査型電子顕微鏡による焼結体の表面観察結果を示す。よって、これらの誘電体磁器組成物を用いて、例えば積層コンデンサなどにおいて、電極間隔を狭めることが容易となり、工業的に既存の生産工程と親和性が高く、応用することは容易である。 Furthermore, in the compositions of Experiment No. 2 to No. 4 and No. 8 to No. 19, it was confirmed that the average particle diameter was 2 μm or less in the surface observation of the sintered body with a scanning electron microscope. And confirmed to have a uniform fine structure. FIG. 2 shows the results of surface observation of the sintered body by a scanning electron microscope in Experiment No. 2, No. 3, and No. 4 in order from the left. Therefore, using these dielectric ceramic compositions, for example, in a multilayer capacitor, it is easy to narrow the electrode interval, and it is highly compatible with existing industrial production processes and is easy to apply.
また、実験No.２からNo.４、No.８からNo.１９における組成の誘電体磁器組成物は、主成分であるＫ０．５Ｎａ０．５ＮｂＯ３は、９５％以上の相対密度を得ることが困難な組成ではあるが、副成分の効果によって容易に緻密化することが可能である。 Further, the dielectric ceramic compositions having the compositions in Experiments No. 2 to No. 4 and No. 8 to No. 19 have a relative density of 95% or more of K 0.5 Na 0.5 NbO 3 as the main component. Is difficult to obtain, but can be easily densified by the effect of subcomponents.
また、本発明における、一般式［Ｎａ１−ｘＫｘ］１−ｙＬｉｙ［Ｎｂ１−ｚＴａｚ］Ｏ３(但し、ｘ、ｙ、ｚは、０≦ｘ≦１．０、０≦ｙ≦０．３０、０≦ｚ≦０．４０) で示される主成分と、副成分として、主成分に対するモル％で１．０〜８．０モル％のＮｂ２Ｏ５、１．０〜８．０モル％のＭｇＯ、３．０〜１６．０モル％のＲＯ（但しＲは、Ｃａ、Ｓｒ、Ｂａの内、少なくとも1種）を含む誘電体磁器組成物において、上記本発明品とは異なる組成範囲について、実験No.２からNo.４において計測したように、ε、tanδ、ΔＣ／Ｃを計測し、例えば実験No.８からNo.１９について、さらに、それら以外の本発明の組成範囲内の誘電体磁器組成物についても同様の効果があることを確認した。 In the present invention, the general formula [Na 1-x K x ] 1-y Li y [Nb 1-z Ta z ] O 3 (where x, y, and z are 0 ≦ x ≦ 1.0, 0 ≦ y ≦ 0.30,0 ≦ z ≦ 0.40 ) and the main component represented by, as an auxiliary component, Nb 2 O 5 of 1.0 to 8.0 mol% in mol% based on the main component, 1.0 A dielectric ceramic composition comprising ˜8.0 mol% MgO and 3.0 to 16.0 mol% RO (wherein R is at least one of Ca, Sr, and Ba). Ε, tan δ, and ΔC / C were measured for composition ranges different from those in Experiments No. 2 to No. 4, for example, No. 8 to No. 19 and the present invention other than those. It was confirmed that the dielectric ceramic composition within the composition range had the same effect.
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