JPS6360150A - Manufacture of high permittivity ceramic composition - Google Patents
Manufacture of high permittivity ceramic compositionInfo
- Publication number
- JPS6360150A JPS6360150A JP61199962A JP19996286A JPS6360150A JP S6360150 A JPS6360150 A JP S6360150A JP 61199962 A JP61199962 A JP 61199962A JP 19996286 A JP19996286 A JP 19996286A JP S6360150 A JPS6360150 A JP S6360150A
- Authority
- JP
- Japan
- Prior art keywords
- dielectric constant
- ceramic composition
- temperature
- producing
- high dielectric
- 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims description 32
- 239000000919 ceramic Substances 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 239000000843 powder Substances 0.000 claims description 17
- 229910002113 barium titanate Inorganic materials 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 10
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 6
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 238000010304 firing Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 238000009413 insulation Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000003985 ceramic capacitor Substances 0.000 description 5
- 229910052573 porcelain Inorganic materials 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 229910052712 strontium Inorganic materials 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 239000003989 dielectric material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- -1 ZrO Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- NKTZYSOLHFIEMF-UHFFFAOYSA-N dioxido(dioxo)tungsten;lead(2+) Chemical compound [Pb+2].[O-][W]([O-])(=O)=O NKTZYSOLHFIEMF-UHFFFAOYSA-N 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 150000003891 oxalate salts Chemical class 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- GGCILSXUAHLDMF-CQSZACIVSA-N 2-[[2-[(3r)-3-aminopiperidin-1-yl]-5-bromo-6-oxopyrimidin-1-yl]methyl]benzonitrile Chemical compound C1[C@H](N)CCCN1C1=NC=C(Br)C(=O)N1CC1=CC=CC=C1C#N GGCILSXUAHLDMF-CQSZACIVSA-N 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- 229910019704 Nb2O Inorganic materials 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 201000003373 familial cold autoinflammatory syndrome 3 Diseases 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920002545 silicone oil Polymers 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
- 239000002904 solvent Substances 0.000 description 1
- 229940071182 stannate Drugs 0.000 description 1
- 125000005402 stannate group Chemical group 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 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) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
〔発明の目的〕
（産業上の利用分野）
本発明は高誘電率磁器組成物の製造方法に係り、特に広
範囲な温度領域にわたって誘電率の温度変化の小さい高
誘電率磁器組成物の製造方法に関する。Detailed Description of the Invention [Objective of the Invention] (Industrial Field of Application) The present invention relates to a method for producing a high dielectric constant ceramic composition, and particularly relates to a method for producing a high dielectric constant ceramic composition with a small temperature change in dielectric constant over a wide temperature range. The present invention relates to a method for producing a porcelain composition.
（従来の技術）
誘電体材料として要求される電気的特性としては、誘電
率、誘電率温度係数、誘電損失、誘電率バイアス電界依
存性、容量抵抗積等があげられる。(Prior Art) Electrical properties required for dielectric materials include dielectric constant, temperature coefficient of dielectric constant, dielectric loss, dependence of dielectric constant on electric field, and capacitance-resistance product.
特に容量抵抗積（ＣＲ値）は、十分高い値を取る必要が
あり、ＥＩＡＪ （日本電子機械工業会）の電子機器用
積層磁器コンデンサ（チップ型）規格ＲＣ−３６９８Ｂ
に常温で５００ＭΩ・μＦ以上と規定されている。さら
により厳しい条件でも使用できるように。In particular, the capacitance-resistance product (CR value) needs to take a sufficiently high value.
It is specified to be 500 MΩ・μF or more at room temperature. It can also be used under even more severe conditions.
高温（例えば米国防省規格Ｎ几−Ｃ−５５６８１Ｂでは
１２５℃でのＣＲ値が定められている。）でも高い容量
抵抗積を維持することが要求される。It is required to maintain a high capacitance-resistance product even at high temperatures (for example, the US Department of Defense standard N-C-55681B specifies a CR value at 125° C.).
また、特に広範囲な湿度領域にわたって安定な温度特性
を要求される場合があり、たとえばＥＩＡ（米国電子工
業会）規格のＸ７Ｒ特性には一５５℃〜＋１２５℃の温
度領域における容量の変化が±１５％以内と規定されて
いる。In addition, there are cases in which stable temperature characteristics are required over a particularly wide range of humidity. For example, the EIA (Electronic Industries Association) standard for X7R characteristics requires a capacitance change of ±15°C in the temperature range of -55°C to +125°C. % or less.
さらに積層タイプの素子を考えた場合、電極層と誘電体
層とは一体的に焼成されるため、電極材料としては誘電
体材料の焼成温度でも安定なものを用いる必要がある。Furthermore, when considering a laminated type element, since the electrode layer and the dielectric layer are fired integrally, it is necessary to use an electrode material that is stable even at the firing temperature of the dielectric material.
従って誘電体材料の焼成温度が高いとＰｔ、Ｐｄ等の高
価な材料を用いなければならず、Ａｇ等の安価な材料を
使用できるように、１１００℃以下程度の低温での焼成
が可能であることが要求される。Therefore, if the firing temperature of the dielectric material is high, expensive materials such as Pt and Pd must be used, but it is possible to fire at a low temperature of about 1100°C or less so that cheaper materials such as Ag can be used. This is required.
従来から知られている高誘電率磁器組成物としてチタン
酸バリウムをベースとして、これに錫酸塩、ジルコン酸
塩、チタン酸塩等を固溶したものがある。Conventionally known high dielectric constant ceramic compositions include barium titanate as a base and solid solutions of stannate, zirconate, titanate, etc. therein.
しかし、チタン酸バリウム系の材料の焼成温度は１２０
０〜１４００℃程度と高温であり電極材料として必然的
に白金、パラジウム等の高温で酎えうる高価な材料を用
いなければならず、コスト高の原因となる。However, the firing temperature of barium titanate-based materials is 120
Since the temperature is high at about 0 to 1400° C., expensive materials such as platinum and palladium that can be dissolved at high temperatures must be used as electrode materials, which causes high costs.
このチタン酸バリウム系の問題点を解消すべく、各種組
成物の研究がなされている０例えば、鉄・ニオブ酸鉛を
主体としたもの（特開昭５７−５７２０４号）、マグネ
シウム・ニオブ酸鉛を主体としたもの（特開昭５５−５
１７５９号）、マグネシウム・タングステン酸鉛を主体
としたもの（特開昭５５−１４４６０９号）、マグネシ
ウム・鉄・タングステン酸鉛を主体としたもの（特開昭
５８−２１７４６２号）等がある。In order to solve the problems of barium titanate, various compositions are being researched. (Japanese Unexamined Patent Publication No. 55-55
1759), one mainly composed of magnesium/lead tungstate (Japanese Patent Application Laid-open No. 144609/1982), and one mainly composed of magnesium/iron/lead tungstate (Japanese Patent Application Laid-open No. 217462/1982).
しかしながら誘電率が高く、その温度変化が例えば−５
５℃〜＋１２５℃のような広い温度範囲にわたって小さ
く、かつ絶縁抵抗が高いというような電気的諸特性に優
れ、かつ、低温焼結が可能であるという高誘電率磁器組
成物は得られていないのして平坦な温度特性を得ようと
する研究もなされている０例えば特開昭５９−２０３７
５９号にはＰｂ （ＭｇｔＮｂ、）０３−Ｐｂ（Ｍｎ１
ｖ、）ｏｉ系、Ｐｂ（Ｍｇｉ Ｎｂ、）０．− ＰｂＴ
ｉ０３Ｙ ｒ ｒ
丁 「かしなからＴ、 Ｃ，Ｃが大きく、
温度特性は十分ではない、またＪＪＡＰ、 ｗａｇ、２
４（１９８５） Ｓｕｐｐｌｅｍｅｎｔ２４の混合につ
いての開示があるが、コンデンサ材料として重要なＣＲ
値については考慮がなく、またＴ、 Ｔ、 Ｃが大きく
温度特性は十分ではない。However, the dielectric constant is high, and the temperature change is -5
A high dielectric constant ceramic composition that is small over a wide temperature range of 5°C to +125°C, has excellent electrical properties such as high insulation resistance, and can be sintered at low temperatures has not been obtained. Research has also been carried out to obtain flat temperature characteristics by
No. 59 contains Pb (MgtNb, )03-Pb(Mn1
v,)oi system, Pb(Mgi Nb,)0. -PbT
i03Y r r
Ding “T, C, and C are large from the beginning,
The temperature characteristics are not sufficient, and JJAP, wag, 2
4 (1985) There is a disclosure about the mixture of Supplement 24, but CR, which is important as a capacitor material,
There is no consideration given to the value, and T, T, and C are large, and the temperature characteristics are not sufficient.
（発明が解決しようとする問題点） 本発明は以上の点を考慮してなされたもので。(Problem to be solved by the invention) The present invention has been made in consideration of the above points.
誘電率及び絶縁抵抗が高く、かつ誘電率の温度変化が小
さく、低温で焼結することができる高誘電率磁器組成物
の製造方法を提供することを目的とする。It is an object of the present invention to provide a method for manufacturing a high-permittivity ceramic composition that has a high dielectric constant and insulation resistance, has a small temperature change in the dielectric constant, and can be sintered at a low temperature.
（問題点を解決するための手段）
本発明はＡＢＯ，の一般式で表わされ、Ａ成分としてＰ
ｂ及びＢを含むペロブスカイト型の高誘電率磁器組成物
の製造方法において、原料として少なくともチタン酸バ
リウム粉を用い、かつこのチタン酸バリウム粉の５０ｗ
ｔ％以上が０．７〜３岬の粒径を有することを特徴とす
る高誘電率磁器組成物の製造方法である。(Means for Solving the Problems) The present invention is represented by the general formula ABO, where the A component is P.
In the method for producing a perovskite-type high dielectric constant ceramic composition containing B and B, at least barium titanate powder is used as a raw material, and 50 w of this barium titanate powder is used.
A method for producing a high dielectric constant ceramic composition characterized in that t% or more has a particle size of 0.7 to 3 caps.
一般に磁器組成物は出発原料としてＰｂｎ Ｂａｔ ５
ｒｔＺｎ、 Ｎｂ、 Ｔｉ等の酸化物もしくは焼成によ
り酸化物になる炭酸塩、しゅう酸塩等の塩類、水酸化物
、有機化合物等を所定の割合で秤量し、十分混合した後
に仮焼した後、この仮焼物を粉砕し原料粉末を製造する
。Generally, porcelain compositions are made using Pbn Bat 5 as the starting material.
Oxides such as rtZn, Nb, and Ti, or salts such as carbonates and oxalates that become oxides upon firing, hydroxides, organic compounds, etc. are weighed out in a predetermined proportion, thoroughly mixed, and then calcined. This calcined material is pulverized to produce raw material powder.
この様な原料粉末を用い所望の形状に成型した後、焼成
することにより、高誘電率のセラミックを得る。A ceramic having a high dielectric constant is obtained by molding such raw material powder into a desired shape and then firing it.
本発明では上述したような一般的方法に代え、原料粉と
してＢａＴｉ０．粉を少なくとも含む原料と、他の成分
とを混合して焼成する。このような方法により製造され
た高誘電率磁器組成物は、さらに誘電率の温度変化幅が
縮減される。In the present invention, instead of the general method as described above, BaTi0. A raw material containing at least powder and other ingredients are mixed and fired. In the high dielectric constant ceramic composition produced by such a method, the range of temperature change in dielectric constant is further reduced.
（作 用）
すなわち本発明製造方法は次のような工程をとる。出発
原料のうちＢａＴｉ０ｉを構成する成分であろＢａおよ
びＴ１の酸化物もしくは焼成により酸化物になる炭酸塩
、しゆう酸塩等の塩類、水酸化物、有機化合物等を、予
めＢａＴｉＯ３の化学式になるように調製し１０００〜
１３５０℃で仮焼する。この際、多少化学論比がずれて
もかまわない、この仮焼粉と、他の出発原料とを所定の
割合で秤量し、十分混合粉砕する。この場合ＢａＴｉ０
．粉を粉砕しすぎないように樹脂コーティングボール等
を用いることが好ましい、なお、この場合、Ｐｂを主体
とする他の出発原料（Ｂａ、 Ｔｉを含んでいても良い
）は別に混合し７００〜９００℃程度で仮焼しておくこ
とが望ましい。(Function) That is, the manufacturing method of the present invention takes the following steps. Among the starting materials, the components constituting BaTiOi, such as oxides of Ba and T1, salts such as carbonates and oxalates, hydroxides, organic compounds, etc., which become oxides by calcination, are prepared in advance to form the chemical formula of BaTiO3. Prepared as follows: 1000 ~
Calcinate at 1350℃. At this time, this calcined powder and other starting materials, which may differ slightly in stoichiometric ratio, are weighed out in a predetermined ratio, and thoroughly mixed and pulverized. In this case BaTi0
．． It is preferable to use a resin-coated ball or the like to avoid crushing the powder too much. In this case, other starting materials mainly consisting of Pb (which may also contain Ba and Ti) are mixed separately and It is desirable to calcinate at around ℃.
またＢａＴｉＯ３を構成する成分の粉末に少量の他の元
素が含まれていても構わない。Further, the powder of the components constituting BaTiO3 may contain a small amount of other elements.
十分混合粉砕した粉末を用い所望の形状に成型した後、
焼成することにより、高誘電率磁器組成物を得る。After thoroughly mixing and pulverizing the powder and molding it into the desired shape,
By firing, a high dielectric constant ceramic composition is obtained.
このようにして得られた磁器組成物は基本的にＢａＴｉ
０ｉ主体の第１の成分とＰｂを構成元素とするベロブス
カカイト構造のｆ５２の成分との混合焼結体となる。
ＢａＴｉ０ｊは１２５℃近傍のキュリー点をもち、第２
の成分との相乗効果で良好な温度特性を得ることができ
る。また誘電率、ＣＲ値も高く、コンデンサ用として好
適となる。焼結の際ＢａＴｉＯ３粉が細かすぎると、第
１成分と第２成分との拡散がすすみすぎてしまい、温度
特性向上の効果を得ることが困難となる。The porcelain composition thus obtained is basically BaTi.
This results in a mixed sintered body of the first component mainly composed of Oi and the f52 component having a belobuskite structure containing Pb as a constituent element.
BaTi0j has a Curie point near 125°C,
Good temperature characteristics can be obtained by the synergistic effect with the components. Furthermore, the dielectric constant and CR value are high, making it suitable for use in capacitors. If the BaTiO3 powder is too fine during sintering, the first component and the second component will diffuse too much, making it difficult to obtain the effect of improving temperature characteristics.
また、大きすぎると焼結体中のボア・クラックが極端に
増加するために、 ＣＲ値が低下するとともに機械的強
度が低下し、特に積層タイプの素子を作成する場合に組
成のかたよりを起こし、歩留り低下の原因となる。In addition, if it is too large, the number of bores and cracks in the sintered body will increase significantly, resulting in a decrease in CR value and mechanical strength, which will cause compositional deviation, especially when creating a laminated type element. This causes a decrease in yield.
従って用いるＢａＴｉ０．粉はその５０ｗｔ％以上が０
．７〜３１ＪＭの粒径さらに好ましくは、０．８〜２−
を有するものを用いる。Therefore, BaTi0. More than 50wt% of powder is 0
．． Particle size of 7 to 31 JM, more preferably 0.8 to 2-
Use one with
本発明で用いる高誘電率磁器組成物はＰｂＴＬＯｉ ｔ
を含有する系、さらにＰｂをＳｒ、 Ｃａ等で置換する
系等が挙げられ、特に限定されるものではない、しかし
ながらＰｂＯ換算で鉛を２５ｗｔ％以上、さらには３０
ｗｔ％以上含有することが焼成温度低下の効果上好まし
い、なお、前述の第２成分としてのキュリー点は温度特
性を考慮しＢａＴｉＯ３との関係で、１２５℃以下、好
ましくは室温以下のものを用いることが好ましい。また
キュリー点を変更するため、ＢａＴｉＯ３粉においてＨ
ａの一部をＳｒ、 Ｃａ、 Ｃａで置換したり、Ｔｉの
一部をＺｒ、 Ｓｎで置換したりすることは可能である
。The high dielectric constant ceramic composition used in the present invention is PbTLOi t
Examples include systems containing Pb and systems in which Pb is replaced with Sr, Ca, etc., and are not particularly limited.
It is preferable to contain more than wt% in terms of the effect of lowering the firing temperature.The Curie point of the second component mentioned above is 125°C or less, preferably room temperature or less, in relation to BaTiO3 in consideration of temperature characteristics. It is preferable. In addition, in order to change the Curie point, H
It is possible to replace a part of a with Sr, Ca, or Ca, or to replace a part of Ti with Zr or Sn.
特にＰｂ（Ｚｎ１Ｎｂ、）０．−ＰｂＴｉＯ，系が好ま
しく、鉛。Especially Pb(Zn1Nb,)0. -PbTiO, system is preferred, and lead.
Ｔ 丁
パリ、ラム、ストロンチウム、亜鉛、ニオブ及びチタン
を夫々酸化物に換算して、
ＰｂＯ３２，１４〜４９．９４ ｗｔ％Ｂａ０ １
５．４６〜２Ｌ３４ ｗｔ％Ｓｒ３ １．７４〜５
．８０ ｗｔ％Ｚｎ０ ４．０１〜５．９１ ｔ
ｚｔ％Ｎｂ２Ｏ，１３，１０〜１９．３２ リｔ％Ｔ
ｉｅ、 １０．７４〜１７．８８ ｗｔ％含有する
系が好適である。この範囲で誘電率が大きく、かつ広範
囲な温度領域にわたって誘電率の変化が小さく、絶縁抵
抗が高く、しかも１１５０℃以下程度の低温で焼結でき
る磁器組成物が得られる。T Paris, rum, strontium, zinc, niobium and titanium are each converted into oxides, PbO32,14~49.94 wt%Ba01
5.46~2L34 wt%Sr3 1.74~5
．． 80 wt%Zn0 4.01-5.91 t
zt%Nb2O, 13,10~19.32 lit%T
ie, a system containing 10.74 to 17.88 wt% is suitable. In this range, a ceramic composition can be obtained which has a large dielectric constant, small change in dielectric constant over a wide temperature range, high insulation resistance, and can be sintered at a low temperature of about 1150° C. or lower.
なお、この組成物は、
（Ｐｂｔ−（＋ｔ＋ｙ＋ ＢａｘＳｒｙ） ［（Ｚｎｉ
Ｎｂｌ）ｔ−ｚ ＴｉｚｌＯｖｌ 丁
を主体とするものであるが、多少化学量論比がずれても
構わないため、上記の如く酸化物換算で表示した。In addition, this composition is (Pbt-(+t+y+ BaxSry) [(Zni
Nbl)t-z TizlOvl Although it is mainly composed of TizlOvl, the stoichiometric ratio may be slightly different, so it is expressed in terms of oxide as described above.
一般式で表示した場合Ｐｂの置換元素Ｂａ及びＳｒであ
るが、少量の置換でペロブスカイト構造を形成できるが
、（ｘ＋ｙ）が０．３５未満では広い温度範囲で誘電率
の温度変化を小さくすることが困難である。また（：ｃ
＋ｙ）が０．６を超えてしまうと焼成温度が高くなって
しまうｅＸｐ ｙについてはこの範囲をはずれろと誘電
率の温度変化が大きくなってしまう、２が０．６を超え
ると焼成温度が高くなってしまい、０．４未満では誘電
率の温度変化が大きくなってしまう。When represented by the general formula, the substitution elements Ba and Sr for Pb can form a perovskite structure with a small amount of substitution, but if (x+y) is less than 0.35, the temperature change in dielectric constant will be small over a wide temperature range. is difficult. Also (:c
If +y) exceeds 0.6, the firing temperature will become high.If y is outside this range, the temperature change in the dielectric constant will become large.If 2 exceeds 0.6, the firing temperature will increase. If it is less than 0.4, the change in dielectric constant with temperature will become large.
また本発明の効果を損わない範囲での不純物、添加物等
の含有も猜わない１例えばＣａｂ、 ＬａｚＯｉｔＭｎ
Ｏ，、Ｃｏｄ、 Ｎｉｐ、 Ｍｇｏ、 ｓｂ、ｏ、 、
ＺｒＯ，、Ｓｉｎ、等の遷移金属、ランタンド元素が
あげられる。これらの添加物の含有量は、多くてもｌｗ
ｔ％程度である。Further, impurities, additives, etc. may not be contained within a range that does not impair the effects of the present invention. For example, Cab, LazOitMn
O,, Cod, Nip, Mgo, sb, o, ,
Examples include transition metals such as ZrO, Sin, and lanthanide elements. The content of these additives is at most lw
It is about t%.
積層タイプの素子を製造する場合は、前述の原料粉末ま
たは混合粉砕後の粉末にバインダー、溶剤等を加えスラ
リー化して、グリーンシートを形成しこのグリーンシー
ト上に内部電極を印刷した後、所定の枚数を積層・圧着
し、焼成することにより製造する。この時、本発明の誘
電体材料は低温で焼結ができるため、内部電極材料とし
て例えばＡｇ主体の安価な材料を用いることができる。When manufacturing a laminated type element, a binder, a solvent, etc. are added to the raw material powder or mixed and pulverized powder to form a slurry, a green sheet is formed, internal electrodes are printed on this green sheet, and then the predetermined Manufactured by laminating and crimping several sheets and firing them. At this time, since the dielectric material of the present invention can be sintered at a low temperature, an inexpensive material mainly composed of Ag, for example, can be used as the internal electrode material.
また、このように低温で焼成が可能であることから、回
路基板−Ｅ等に印刷・焼成する厚膜誘電体ペーストの材
料としても有効である。Furthermore, since it can be fired at such a low temperature, it is also effective as a material for thick film dielectric paste printed and fired on circuit boards-E and the like.
この様な本発明磁器組成物は、高誘電率かつ、その温度
特性が良好である。また、ＣＲ値も大きく、特に高温で
も十分な値を有し、高温での信頼性に優れている。Such a ceramic composition of the present invention has a high dielectric constant and good temperature characteristics. In addition, the CR value is large, particularly sufficient even at high temperatures, and has excellent reliability at high temperatures.
さらに誘［率バイアス電界依存性も優れており、２にｖ
／１ｍｍでも１０％以下程度の材料を得ることもできる
。したがって、高圧用の材料として有効である。また誘
電損失が小さく、交流用、高周波用として有効である。Furthermore, the dielectric bias electric field dependence is also excellent, with v
/1 mm, it is also possible to obtain material with a ratio of about 10% or less. Therefore, it is effective as a material for high pressure. Furthermore, it has low dielectric loss and is effective for AC and high frequency applications.
さらに前述のごとく誘電率の温度特性に優れているため
、電歪素子へ応用した場合でも変位量の温度変化の小さ
い素子を得ることができる。Furthermore, as described above, since the dielectric constant has excellent temperature characteristics, even when applied to an electrostrictive element, an element with small temperature change in displacement can be obtained.
さらに焼成時のグレインサイズも１〜３／ｆｆｉと均一
化されるため耐圧性にも優れている。Furthermore, since the grain size during firing is made uniform at 1 to 3/ffi, it also has excellent pressure resistance.
以上電気的特性について述べたが、機械的強度も十分に
優れたものである。Although the electrical properties have been described above, the mechanical strength is also sufficiently excellent.
（実施例） 以下に本発明の詳細な説明する。(Example) The present invention will be explained in detail below.
出発原料のうちＢａＴｉ０．を構成する成分であるＢａ
Ｃ０，とＴｉｅ、を予めｌ１ａＴｉＯ，の化学式になる
ように秤量し、ボールミル等で混合し、１０００〜１３
５０℃で仮焼し、さらにボールミルを用いて粉砕した。Among the starting materials, BaTi0. Ba, which is a component of
C0, and Tie are weighed in advance so that they have the chemical formula l1aTiO, and mixed in a ball mill etc. to give a
It was calcined at 50°C and further ground using a ball mill.
この場合、ボールミルの粉砕条件を変えて得られたＢａ
Ｔｉ０．の粉末の粒径を制御した。なお、粒径はブレー
ン法を用いて平均粒径を測定した。In this case, Ba obtained by changing the grinding conditions of the ball mill
Ti0. The particle size of the powder was controlled. Note that the particle size was determined by measuring the average particle size using the Blaine method.
一方、ＢａＴｉ０．以外のＰｂ、 Ｓｒ、 Ｚｎ、 Ｎ
ｂ、 Ｔｉなどの酸化物もしくは炭酸化物等を別にボー
ルミル等で混合し、７００〜９００℃で仮焼し粉砕した
６次いで、これらの仮焼体を所定の割合になるように拝
承し、ポットを用して混合した。乾燥の後、バインダー
を加え造粒し、プレスして、直径１７ｍｍ、厚さ約２ｍ
の円板状素体を形成した。On the other hand, BaTi0. Other than Pb, Sr, Zn, N
b. Oxides or carbonates such as Ti are mixed separately in a ball mill, etc., calcined at 700 to 900°C, and crushed.6 Next, these calcined bodies are mixed in a predetermined ratio, and the pot is poured. Mixed using After drying, add a binder, granulate it and press it to a diameter of 17mm and a thickness of about 2m.
A disc-shaped element body was formed.
混合、粉砕用のボールは、不純物の混入を防止するため
、部分安定化ジルコニアボール等の硬度が大きく、かつ
靭性の高いボールを用いることが好ましい、またＢａＴ
ｉ０．を主体とする第１の成分とＰｂの構成元素とする
ペロブスカイト構造の第２の成分とを混合する場合には
、ＢａＴｉ０．を粉砕しすぎないように、樹脂コーティ
ングボール等を用いることが好ましい。For mixing and grinding balls, in order to prevent the mixing of impurities, it is preferable to use balls with high hardness and high toughness, such as partially stabilized zirconia balls.
i0. When mixing the first component mainly consisting of BaTi0. It is preferable to use a resin-coated ball or the like to avoid crushing too much.
この素体を空気中１０００〜１１００℃２時間の条件で
焼結し１両主面に銀電極を焼付は各特性を測定した。、
誘電損失、容量はＩ ＫＨｚ 、 Ｉ Ｖｒｍｓ、２５
℃の条件でのデジタルＬＣＲメーターによる測定値であ
り。This element body was sintered in air at 1000 to 1100°C for 2 hours, silver electrodes were baked on both main surfaces, and various characteristics were measured. ,
Dielectric loss, capacitance is I KHz, I Vrms, 25
This is a value measured by a digital LCR meter at ℃ conditions.
この値から誘電率を算出した。また、絶縁抵抗は１００
ｖの電圧を２分間印加した後、絶縁抵抗計を用いて測定
した値から算出した。なお、誘電率の温度特性は２５℃
の値を基準とし、−５５℃〜＋１２５℃の温度範囲にお
ける変化幅の最大値で表わした。The dielectric constant was calculated from this value. Also, the insulation resistance is 100
It was calculated from the value measured using an insulation resistance meter after applying a voltage of v for 2 minutes. In addition, the temperature characteristic of dielectric constant is 25℃
It is expressed as the maximum value of the width of change in the temperature range of -55°C to +125°C based on the value of .
容量抵抗積（ＣＲ値）は、２５℃および１２５℃での（
誘電率）×（絶縁抵抗）Ｘ（真空の誘電率）から求めた
。The capacitance-resistance product (CR value) is (
It was determined from dielectric constant) x (insulation resistance) x (vacuum permittivity).
絶縁抵抗の測定は、空気中の湿気の効果を除くため、シ
リコンオイル中で行なった。Insulation resistance measurements were performed in silicone oil to eliminate the effects of atmospheric moisture.
一般式
で表わされる組成について行なった結果を第１表に示す
。比較のため、粒径の小さなりａＴｉＯ，を用いた例を
参考例１として第１表に示す。さらに比較のため粒径の
大きなりａＴｉＯ，を用いた例を参考例２として第１表
に示す。Table 1 shows the results for the composition represented by the general formula. For comparison, an example using aTiO having a small particle size is shown in Table 1 as Reference Example 1. Furthermore, for comparison, an example using aTiO having a large particle size is shown in Table 1 as Reference Example 2.
第１表から明らかなように、本発明の製造方法による磁
器組成物は１５ｖＩ電車（Ｋ ＝ ３０００以上）かつ
温度特性が良好（−５５〜＋１２５℃で±１５％以内）
である、 ＣＲ値も４０００ＭΩμＦ（２５℃）以上と
大きく。As is clear from Table 1, the porcelain composition produced by the manufacturing method of the present invention has a 15vI electric current (K = 3000 or more) and good temperature characteristics (within ±15% at -55 to +125°C).
The CR value is also large, over 4000MΩμF (25℃).
特に、１２５℃でも１０００ＭΩμＦ以上であり、高温
のイＷＭ性に優れている。In particular, the resistance is 1000 MΩμF or more even at 125° C., and it has excellent high-temperature IWM properties.
参考例１は粒径の小さなりａＴｉＯ，を用いた例である
が、ｖＩ誘電率値が小さく、また温度変化幅も大きくな
ってしまうことを示している。Reference Example 1 is an example using aTiO having a small particle size, but it shows that the vI dielectric constant value is small and the temperature change range is also large.
また参考例２は粒径の大きなりａＴ４０ｉを用いた例で
あるが、ＣＲ値がいちじるしく低下し、また誘電率の温
度変化幅も大きくなってしまう。Further, although Reference Example 2 is an example using aT40i having a large particle size, the CR value is significantly lowered and the temperature change width of the dielectric constant is also increased.
次いで実施例３にさらに０．２５ｖｏｊ！％のＭｎＯお
よびＣｏＯを添加含有した組成を用いて積層セラミック
コンデンサを作成した実施例を説明する。まず、この様
な組成を有するＢａＴｉ０Ｊ及びその他の焙焼粉をよく
混合して有機溶剤を加えてスラリー化した後ドクタープ
レイド型キャスターを用いて３０ｍのグリーンシートを
作成した。このグリーンシート上に８ＯＡ／２０Ｐｄの
ｆｆ１ｔ１ペーストを所定のパターンで印刷し、この様
な電極パターンを有するシートを２０層積層圧着した。Next, an additional 0.25 voj in Example 3! An example will be described in which a multilayer ceramic capacitor was manufactured using a composition containing % MnO and CoO. First, BaTi0J having such a composition and other roasted powders were thoroughly mixed and an organic solvent was added to form a slurry, and then a 30 m green sheet was created using a doctor plaid type caster. On this green sheet, 8OA/20Pd ff1t1 paste was printed in a predetermined pattern, and 20 sheets having such an electrode pattern were laminated and pressure-bonded.
その後、所定の形状に切断し。Then cut into the desired shape.
脱脂を行い１０８０℃、２Ｈの条件で焼成を行った。焼
結後、外部電極としてＡｇペーストを焼付け、積層セラ
ミックコンデンサを製造した。その電気的特性を第２表
に示す。It was degreased and fired at 1080° C. for 2 hours. After sintering, Ag paste was baked as an external electrode to produce a multilayer ceramic capacitor. Its electrical characteristics are shown in Table 2.
得られた積層セラミックコンデンサの誘電率は約４００
０であり、また、第２表に示したごとく各特性が十分に
優れていることが分る。特に温度特性は一５５℃〜＋１
２５℃で±１５％以内であり、Ｅ工ＡのＸ７Ｒ特性を満
足するものである。The dielectric constant of the obtained multilayer ceramic capacitor is approximately 400.
0, and as shown in Table 2, it can be seen that each property is sufficiently excellent. In particular, the temperature characteristics are -55℃ to +1
It is within ±15% at 25°C and satisfies the X7R characteristics of E-A.
このように、本発明による高誘電率磁器組成物の製造方
法は、誘電率が大きく、かつ広範囲な温度領域にわたっ
て誘電率の変化が小さいなど各種特性に優れた高誘電率
磁器組成物を提供することができるので、特に積層セラ
ミックコンデンサの製法として有効である。また、本発
明の製造方法においては亜鉛ニオブ酸鉛およびチタン酸
バリウムを主体としたものを用いたが、他の成分でこれ
らに替わるものを用いても本発明と同様の効果が得られ
る場合がある。As described above, the method for producing a high-permittivity ceramic composition according to the present invention provides a high-permittivity ceramic composition that has various excellent properties such as a large dielectric constant and a small change in dielectric constant over a wide temperature range. Therefore, it is particularly effective as a method for manufacturing multilayer ceramic capacitors. In addition, although zinc lead niobate and barium titanate were used as main ingredients in the manufacturing method of the present invention, the same effects as the present invention may be obtained by using other ingredients in place of these. be.
以上説明したように１本発明の製造方法によれば、高１
ｉｆｔ率でかつ温度特性に優れた高誘電率磁器組成物を
得ることができる。特に、この様な各種特性に優れた磁
器を低温焼成で得ることができるため、積層セラミック
コンデンサ、積層型セラミック変位素子等の積層タイプ
のセラミック素子への応用に適している。As explained above, according to the manufacturing method of the present invention,
A high dielectric constant ceramic composition having a high ift ratio and excellent temperature characteristics can be obtained. In particular, since porcelain with such excellent various properties can be obtained by firing at low temperatures, it is suitable for application to multilayer ceramic elements such as multilayer ceramic capacitors and multilayer ceramic displacement elements.
代理人 弁理士 則 近 憲 倍 量 竹 花 喜久男Agent Patent Attorney Norihiro Kenji Quantity Bamboo Flower Kikuo
Claims (3)
ｂ及びＢａを含むペロブスカイト型の高誘電率磁器組成
物の製造方法において、原料として少なくともチタン酸
バリウム粉を用い、かつこのチタン酸バリウム粉の５０
ｗｔ％以上が０．７〜３μｍの粒径を有することを特徴
とする高誘電率磁器組成物の製造方法。(1) Represented by the general formula ABO_3, with P as the A component
In a method for producing a perovskite-type high-permittivity ceramic composition containing B and Ba, at least barium titanate powder is used as a raw material, and 50% of this barium titanate powder is
A method for producing a high dielectric constant ceramic composition, characterized in that at least % by weight has a particle size of 0.7 to 3 μm.
特徴とする特許請求の範囲第１項記載の高誘電率磁器組
成物の製造方法。(2) The method for producing a high dielectric constant ceramic composition according to claim 1, characterized in that it contains 25 wt% or more of lead in terms of PbO.
３−ＰｂＴｉＯ＿３系であることを特徴とする特許請求
の範囲第１項記載の高誘電率磁器組成物の製造方法。 （Ａ）鉛、バリウム、ストロンチウム、亜鉛、ニオブ及
びチタンを夫々酸化物に換算して ＰｂＯ ３２．１４〜４９．９４ｗｔ％ ＢａＯ １５．４６〜２８．３４ｗｔ％ ＳｒＯ １．７４〜５．８０ｗｔ％ ＺｎＯ ４．０１〜５．９１ｗｔ％ Ｎｂ＿２Ｏ＿５ １３．１０〜１９．３２ｗｔ％ＴｉＯ
＿２ １０．７４〜１７．８８ｗｔ％含有することを特
徴とする特許請求の範囲第１項記載の高誘電率磁器組成
物の製造方法。(3) Pb(Zn_1_/_3Nb_2_/_3)O_
2. The method for producing a high dielectric constant ceramic composition according to claim 1, wherein the composition is 3-PbTiO_3 based. (A) PbO 32.14-49.94 wt% BaO 15.46-28.34 wt% SrO 1.74-5.80 wt% ZnO 4.01~5.91wt% Nb_2O_5 13.10~19.32wt%TiO
_2 10.74 to 17.88 wt% of the manufacturing method of the high dielectric constant ceramic composition according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61199962A JPS6360150A (en) | 1986-08-28 | 1986-08-28 | Manufacture of high permittivity ceramic composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61199962A JPS6360150A (en) | 1986-08-28 | 1986-08-28 | Manufacture of high permittivity ceramic composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6360150A true JPS6360150A (en) | 1988-03-16 |
Family
ID=16416500
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61199962A Pending JPS6360150A (en) | 1986-08-28 | 1986-08-28 | Manufacture of high permittivity ceramic composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6360150A (en) |
-
1986
- 1986-08-28 JP JP61199962A patent/JPS6360150A/en active Pending
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