JP3182849B2 - Method for producing raw material powder of dielectric ceramic composition - Google Patents
Method for producing raw material powder of dielectric ceramic compositionInfo
- Publication number
- JP3182849B2 JP3182849B2 JP06698592A JP6698592A JP3182849B2 JP 3182849 B2 JP3182849 B2 JP 3182849B2 JP 06698592 A JP06698592 A JP 06698592A JP 6698592 A JP6698592 A JP 6698592A JP 3182849 B2 JP3182849 B2 JP 3182849B2
- Authority
- JP
- Japan
- Prior art keywords
- raw material
- material powder
- slurry
- powder
- additive element
- 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 - Fee Related
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Description
【０００１】[0001]
【産業上の利用分野】本発明は誘電体磁器組成物原料粉
末の製造方法、特に、セラミック電子部品の誘電体材料
として有用なチタン酸バリウム系誘電体磁器組成物原料
粉末の製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a raw material powder for a dielectric ceramic composition, and more particularly to a method for producing a raw material powder for a barium titanate-based dielectric ceramic composition useful as a dielectric material for ceramic electronic components. is there.
【０００２】[0002]
【従来の技術】一般に、セラミック電子部品を製造する
場合、電気特性の改変や向上を図るため基本となる磁器
組成物に種種の元素を添加することが行なわれている。
この場合、添加元素を基本組成物に導入する手段として
は、(１)セラミック誘電体の基本組成物粉末に添加元素
の炭酸塩若しくは酸化物又はそれらの混合物を添加し、
混合、粉砕した後、１０００℃程度の温度で仮焼する伝
統的な乾式法、(２)セラミック誘電体の基本組成物粉末
のスラリー中に添加元素イオンを含む水溶液を添加し、
これに沈澱剤を加えて沈澱させ、その沈澱物を濾別、乾
燥させて仮焼する湿式法、及び(３)セラミック誘電体の
基本組成物粉末にバインダ及び添加元素化合物の水溶液
を加えてスラリー化し、これを噴霧乾燥して造粒した
後、仮焼する方法が知られている。2. Description of the Related Art In the production of ceramic electronic parts, various elements are generally added to a basic porcelain composition in order to modify or improve electrical characteristics.
In this case, the means for introducing the additive element into the basic composition include: (1) adding a carbonate or oxide of the additive element or a mixture thereof to the basic composition powder of the ceramic dielectric;
After mixing and pulverizing, a traditional dry method of calcining at a temperature of about 1000 ° C., (2) adding an aqueous solution containing an additional element ion to a slurry of a ceramic dielectric basic composition powder,
A precipitant is added thereto to precipitate the precipitate, and the precipitate is separated by filtration, dried and calcined. (3) A slurry is prepared by adding an aqueous solution of a binder and an additive element compound to the basic composition powder of the ceramic dielectric. A method is known in which the mixture is granulated, spray-dried, granulated, and calcined.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、前記
(１)の乾式法では、基本組成物粉末に対して添加した複
数の炭酸塩及び／又は酸化物をミクロ的に均一に分散さ
せることが不可能であり、添加した化合物が偏析し、基
本組成物の個々の粒子により添加効果に差が生じて、目
的とする特性を得ることが困難となるだけでなく、セラ
ミック電子部品の特性にバラツキが多いという問題があ
る。SUMMARY OF THE INVENTION
In the dry method (1), it is impossible to uniformly and microscopically disperse a plurality of carbonates and / or oxides added to the basic composition powder, and the added compounds are segregated, and There is a problem that not only does it become difficult to obtain the desired characteristics due to the difference in the effect of addition depending on the individual particles of the product, but also that the characteristics of the ceramic electronic component vary widely.
【０００４】また、(２)の湿式法は乾式法に比べて分散
性が向上しているが、十分とは言えず、しかも、複数の
添加元素を一種の沈澱剤で共沈させることが困難な場合
がある。例えば、Ｓr+2、Ｃa+2及びＭg+2はＣＯ3 -2と反
応させて複合炭酸塩として沈澱させることは可能である
が、Ｔi+4は炭酸塩として沈澱させることは不可能であ
る。また、沈澱剤としてアンモニウム塩を用いた場合、
Ｚn+2,Ｎi+2,Ｃo+2、Ｍn+2等の元素はアンミン錯体を形
成して可溶性となるため、沈澱物を生成させることがで
きないという問題がある。In the wet method (2), the dispersibility is improved as compared with the dry method, but it is not sufficient, and it is difficult to coprecipitate a plurality of additive elements with a kind of precipitant. It may be. For example, Sr +2 , Ca +2 and Mg +2 can be reacted with CO 3 -2 to precipitate as complex carbonate, while Ti +4 cannot be precipitated as carbonate. . When an ammonium salt is used as a precipitant,
Elements such as Zn +2 , Ni +2 , Co +2 , and Mn +2 have the problem that they cannot form a precipitate because they form an ammine complex and become soluble.
【０００５】更に、前記(３)の方法では、造粒する際、
基本組成物粉末の粒子表面に添加元素化合物を付着させ
るものであるが、スラリー形成時に共存する陰イオン及
び陽イオンの種類によっては有機バインダとの相互作用
によってゲル化し、添加元素を均一に分散付着させるこ
とができなくなるという問題がある。Further, in the method (3), when granulating,
The additive element compound adheres to the particle surface of the basic composition powder.However, depending on the type of anions and cations that coexist during the formation of the slurry, gelation occurs due to the interaction with the organic binder, and the additive element is uniformly dispersed and attached. There is a problem that it can not be made to.
【０００６】従って、本発明は、基本組成物の個々の粒
子表面に添加元素化合物を均一に担持固定させた誘電体
磁器組成物原料粉末を得ることを目的とするものであ
る。Accordingly, an object of the present invention is to obtain a raw material powder of a dielectric ceramic composition in which an additive element compound is uniformly supported and fixed on the surface of each particle of the basic composition.
【０００７】[0007]
【課題を解決するための手段】本発明は、前記課題を解
決するための手段として、チタン酸バリウムを基本組成
物とし、これに添加元素を含有させてなるチタン酸バリ
ウム系誘電体磁器組成物原料粉末を製造するに当たり、
チタン酸バリウム粉末と少なくとも一種の添加元素の化
合物の粉末とをエチレンカーボネートを含有する有機溶
剤で混合分散させてスラリー化し、該スラリーを乾燥さ
せた後、これを熱処理するようにしたものである。According to the present invention, there is provided a barium titanate-based dielectric ceramic composition comprising barium titanate as a basic composition and an additive element added thereto. In producing the raw material powder,
A barium titanate powder and a powder of a compound of at least one additional element are mixed and dispersed in an organic solvent containing ethylene carbonate to form a slurry. The slurry is dried and then heat-treated.
【０００８】添加元素の化合物としては、Ｓr、Ｐb、Ｓ
n、Ｚr、Ｃa、Ｍg、Ｃo、Ｆe、Ｎi、Ｃr、Ｍn、Ｚn、Ｓ
i、Ｃu、Ｙ、Ｎb及び希土類元素、その他変性剤、ドー
ピング剤若しくは鉱化剤として公知の任意の金属元素の
無機酸塩及び有機化合物が使用できる。添加元素の有機
化合物としては、有機酸塩、アルコキシド、アセチルア
セトネート等が挙げられるが、これらに限定されるもの
ではない。また、添加元素の無機酸塩としては、硝酸
塩、塩化物などが代表的なものとして挙げられるが、こ
れらに限定されるものではない。The compounds of the additional elements include Sr, Pb, S
n, Zr, Ca, Mg, Co, Fe, Ni, Cr, Mn, Zn, S
Inorganic acid salts and organic compounds of i, Cu, Y, Nb and rare earth elements, and any other metal element known as a modifier, doping agent or mineralizer can be used. Examples of the organic compound of the additional element include, but are not limited to, organic acid salts, alkoxides, and acetylacetonates. In addition, typical examples of the inorganic acid salt of the additive element include nitrate and chloride, but are not limited thereto.
【０００９】出発原料として使用する添加元素の化合物
が全て有機化合物であれば、有機溶剤としては、一般に
使用されている一般的な有機溶剤、例えば、メタノー
ル、エタノール、ブタノール等のアルコール類、ベンゼ
ン、トルエン、キシレン等の芳香族溶剤、メチルエチル
ケトン、メチルイソブチルケトン等のケトン類を使用す
れば良いが、本発明においては、使用する添加元素の化
合物の一部若しくは全部が無機酸塩の形態で使用される
場合、これら有機溶剤に溶解しないので、前記一般的な
有機溶剤に補助溶剤としてエチレンカーボネートを含有
させてなる混合有機溶剤を使用する。この場合、有機溶
剤中に占めるエチレンカーボネートの割合は６０重量％
以下が好ましい。If the compounds of the additional elements used as starting materials are all organic compounds, the organic solvent may be a commonly used organic solvent such as alcohols such as methanol, ethanol and butanol, benzene, Aromatic solvents such as toluene and xylene, and ketones such as methyl ethyl ketone and methyl isobutyl ketone may be used.In the present invention, some or all of the compounds of the additive elements used are used in the form of inorganic acid salts. In this case, a mixed organic solvent containing ethylene carbonate as an auxiliary solvent in the above-mentioned general organic solvent is used because it is not dissolved in these organic solvents. In this case, the proportion of ethylene carbonate in the organic solvent is 60% by weight.
The following is preferred.
【００１０】[0010]
【作用】誘電体磁器組成物の基本組成物及び添加元素化
合物をエチレンカーボネートを含有する有機溶剤で混
合、分散処理を行うと、補助溶剤として使用されるエチ
レンカーボネートが非プロトン性極性溶媒で、極性の有
機化合物及び無機化合物を良く溶解し、無機酸塩に対し
ても非常に良好な溶解性を示すため、添加元素化合物と
して無機酸塩を単独で若しくは有機化合物と併用しても
個々の粒子表面に添加元素化合物を均一に付着させ、こ
れを乾燥(好ましくは、噴霧乾燥)させることにより個々
の粒子の表面に添加元素化合物を均一に担持固定させ
る。このように粒子表面に添加元素化合物を均一に担持
固定させた基本組成物粉末を仮焼若しくは焼成すること
により均一な組成の誘電体磁器組成物原料粉末が得られ
る。When the basic composition of the dielectric ceramic composition and the additive element compound are mixed and dispersed with an organic solvent containing ethylene carbonate, ethylene carbonate used as an auxiliary solvent is an aprotic polar solvent, Dissolves organic compounds and inorganic compounds well, and shows very good solubility in inorganic acid salts. Therefore, even if inorganic acid salts are used alone or in combination with organic compounds as additive element compounds, the surface of individual particles The additive element compound is uniformly adhered to the particles, and is dried (preferably, spray-dried) to uniformly support and fix the additive element compound on the surface of each particle. By calcining or baking the basic composition powder in which the additive element compound is uniformly supported and fixed on the particle surface in this way, a dielectric ceramic composition raw material powder having a uniform composition is obtained.
【００１１】[0011]
【実施例】チタン酸バリウム５０gに硝酸コバルト、塩
化錫、オクチル酸バリウム、硝酸マンガン及びエチルシ
リケートを各添加元素の酸化物換算でチタン酸バリウム
１００モルに対してＣo2Ｏ3１０.３８モル、ＳnＯ2２.
５９モル、ＢaＯ１．２１モル、ＭnＯ１．３１モル、Ｓ
iＯ2４．６１モルの割合で添加し、その混合物に溶媒と
してトルエン３５mlとエチレンカーボネート５wt％を加
えた後、ボールミルに投入し、５mm径の部分安定化ジル
コニア玉石１５０gを用いて１６時間混合分散処理を行
い、更にチタン酸バインダ粉末に対してアクリル系バイ
ンダ７．５％とジオクチルフタレート２．５％を添加
し、５時間分散処理を行いスラリーを得た。EXAMPLE Cobalt nitrate, tin chloride, barium octylate, manganese nitrate, and ethyl silicate were added to 50 g of barium titanate, and 10.38 mol of Co 2 O 3 with respect to 100 mol of barium titanate in terms of oxide of each additive element. SnO 2 2.
59 mol, BaO 1.21 mol, MnO 1.31 mol, S
To the mixture was added 4.61 mol of SiO 2, 35 ml of toluene and 5 wt% of ethylene carbonate were added as a solvent to the mixture, and the mixture was charged into a ball mill. After the treatment, 7.5% of an acrylic binder and 2.5% of dioctyl phthalate were added to the titanate binder powder, and dispersion treatment was performed for 5 hours to obtain a slurry.
【００１２】得られたスラリーを用いて、このスラリー
を脱気した後、ドクターブレード法で４０μm厚のシー
トを成形し、これを所定の形状に打ち抜き、そのグリー
ンシートを積層し、圧着成形して１mm厚の単板を得た。
この単板を５mm角のチップに切断し、Ｈ2／Ｎ2の体積比
が３／１０００の還元雰囲気ガス気流中で１２５０℃で
３時間焼成して焼結体を得た。得られた焼結体の表裏両
面にＡg電極を焼き付けて電気的特性を測定した。その
結果を表１に示す。After degassing the slurry by using the obtained slurry, a sheet having a thickness of 40 μm is formed by a doctor blade method, the sheet is punched into a predetermined shape, the green sheets are laminated, and compression molded. A 1 mm thick veneer was obtained.
This single plate was cut into 5 mm square chips, and fired at 1250 ° C. for 3 hours in a reducing atmosphere gas stream having a volume ratio of H 2 / N 2 of 3/1000 to obtain a sintered body. Ag electrodes were baked on both the front and back surfaces of the obtained sintered body, and the electrical characteristics were measured. Table 1 shows the results.
【００１３】[0013]
【比較例】実施例の出発原料からエチレンカーボネート
を除去した以外は、同実施例と同じ成分組成でスラリー
を調製し、該スラリーを用いて実施例と同様にして焼結
体を得、その表裏両面にＡg電極を焼き付けて電気的特
性を測定した。その結果を表１に示す。Comparative Example A slurry was prepared with the same composition as in the example except that ethylene carbonate was removed from the starting material of the example, and a sintered body was obtained using the slurry in the same manner as in the example. Ag electrodes were baked on both sides and electrical characteristics were measured. Table 1 shows the results.
【００１４】[0014]
【表１】 ε tan δ 静電容量温度特性（％） log ＩＲ (％) −５５℃ １２５℃ 実施例 ２６００ １．１ −６ １０ １２.９ 比較例 ２０００ ３．７ −１８ ３０ １０.７ [Table 1] ε tan δ Capacitance temperature characteristics (%) log IR (%) −55 ° C. 125 ° C. Example 2600 1.1 −6 10 12.9 Comparative Example 2000 3.7 −18 30 10.7
【００１５】表１に示す結果から明らかなように、添加
元素化合物としてトルエンには溶解しない硝酸コバル
ト、塩化錫及び硝酸マンガンを溶解させるためにエチレ
ンカーボネートを補助溶剤として用いた実施例の試料
は、ＥＩＡに規定するＸ７Ｒ特性を満足し、しかも、ta
n δも１．５％以下と優れた特性を示している。これ
に対し、比較例のものは、実施例のものと同じ成分組成
であるにも拘わらず、εが２０００と低く、静電容量温
度特性もＸ７Ｒを満足せず、log ＩＲは実施例のもの
に比べて１桁も低くなっている。As is clear from the results shown in Table 1, the samples of the examples using ethylene carbonate as an auxiliary solvent for dissolving cobalt nitrate, tin chloride and manganese nitrate which do not dissolve in toluene as additive element compounds are as follows: Satisfies the X7R characteristics specified in EIA, and
n δ also shows excellent characteristics of 1.5% or less. On the other hand, in the case of the comparative example, despite having the same component composition as that of the example, ε was as low as 2000, the capacitance temperature characteristic did not satisfy X7R, and the log IR was that of the example. It is one digit lower than.
【００１６】このような相異を生じるのは、実施例のも
のでは、有機溶剤に溶解しない無機酸塩が存在していて
もエチレンカーボネートの作用により均一に分散され、
基本組成物粉末の個々の粒子表面に均一に担持固定され
るのに対し、比較例のものでは有機溶剤に溶解しない添
加元素の無機酸塩が基本組成物粉末の個々の粒子表面に
均一に担持固定されないことに起因するためである。こ
れは、前記実施例及び比較例の試料の表面及び４０μm
厚のグリーンシートの表面の添加元素の分布状態をＸ線
マイクロアナライザによるマッピング分析により裏付け
られるところである。即ち、実施例のグリーンシート及
び試料では、添加元素であるＣo、Ｓn、Ｍn及びＳiの偏
析が認められず、表面に均一に分散していたのに対し、
比較例のものではグリーンシート及び試料のいづれの場
合もＣo、Ｍn及びＳnの偏析が認められた。In the case of the embodiment, such a difference is caused by the action of ethylene carbonate even when an inorganic acid salt which is insoluble in an organic solvent is present,
In contrast to the comparative example, the inorganic acid salt of the additive element which is not dissolved in the organic solvent is uniformly supported on the individual particle surfaces of the basic composition powder, whereas the comparative example is uniformly supported and fixed on the individual particle surfaces of the basic composition powder. This is because it is not fixed. This is the surface of the samples of the above Examples and Comparative Examples and 40 μm
The distribution of added elements on the surface of the thick green sheet is justified by mapping analysis using an X-ray microanalyzer. That is, in the green sheets and the samples of the examples, the segregation of the additive elements Co, Sn, Mn and Si was not recognized, and the elements were uniformly dispersed on the surface.
In the case of the comparative example, segregation of Co, Mn and Sn was recognized in both the green sheet and the sample.
【００１７】[0017]
【発明の効果】以上説明したように、本発明によれば、
チタン酸バリウム系誘電体磁器組成物を製造するにあた
り、原料として添加元素の無機酸塩を使用する場合に、
エチレンカーボネートを補助溶剤として用いて混合分散
処理を行いスラリー化することにより、一般の有機溶剤
に不溶な無機酸塩を可溶化させ基本組成物粉末の個々の
粒子表面に添加元素化合物を均一に担持固定させること
ができ、仮焼若しくは焼成することにより均一な組成の
誘電体磁器組成物原料粉末を製造することができる。ま
た、有機化合物に比べて安価な無機酸塩を使用し、特性
のバラツキの無い誘電体磁器を製造することができ、低
コスト化を図ることができる。As described above, according to the present invention,
In producing a barium titanate-based dielectric porcelain composition, when using an inorganic acid salt of an additive element as a raw material,
By mixing and dispersing using ethylene carbonate as an auxiliary solvent to make a slurry, solubilize inorganic acid salts that are insoluble in general organic solvents and uniformly carry the additive element compound on the surface of each particle of the basic composition powder It can be fixed and calcined or fired to produce a dielectric ceramic composition raw material powder having a uniform composition. Further, a dielectric porcelain having no variation in characteristics can be manufactured by using an inorganic acid salt which is cheaper than an organic compound, and the cost can be reduced.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭64−65063（ＪＰ，Ａ) 特開 平１−257158（ＪＰ，Ａ) 特開 平５−78162（ＪＰ，Ａ) 特開 平４−272107（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C04B 35/00 - 35/22 C04B 35/42 - 35/49 ＣＡ（ＳＴＮ) ＪＩＣＳＴファイル（ＪＯＩＳ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-64-65063 (JP, A) JP-A-1-257158 (JP, A) JP-A-5-78162 (JP, A) JP-A-4- 272107 (JP, A) (58) Fields studied (Int. Cl. 7 , DB name) C04B 35/00-35/22 C04B 35/42-35/49 CA (STN) JICST file (JOIS) REGISTRY (STN )
Claims (2)
れに添加元素を含有させてなるチタン酸バリウム系誘電
体磁器組成物原料粉末を製造する方法において、チタン
酸バリウム粉末と少なくとも一種の添加元素の化合物の
粉末とをエチレンカーボネートを含有する有機溶剤で混
合分散させてスラリー化し、該スラリーを乾燥させた
後、これを熱処理することを特徴とする誘電体磁器組成
物原料粉末の製造方法。1. A method for producing a barium titanate-based dielectric porcelain composition raw material powder comprising barium titanate as a basic composition and an additive element added thereto, wherein the barium titanate powder and at least one additive element A method for producing a raw material powder for a dielectric porcelain composition, comprising mixing and dispersing a powder of the compound (1) with an organic solvent containing ethylene carbonate to form a slurry, drying the slurry, and subjecting the slurry to a heat treatment.
r、Ｃa、Ｍg、Ｃo、Ｆe、Ｎi、Ｃr、Ｍn、Ｚn、Ｓi、Ｃ
u、Ｙ、Ｎb及び希土類元素からなる群から選ばれた少な
くとも一種の元素からなり、かつ、これらの一部または
全部が無機酸塩である請求項１に記載の誘電体磁器組成
物原料粉末の製造方法。2. The compound of an additional element is Sr, Pb, Sn, Z
r, Ca, Mg, Co, Fe, Ni, Cr, Mn, Zn, Si, C
The dielectric ceramic composition raw material powder according to claim 1, comprising at least one element selected from the group consisting of u, Y, Nb, and a rare earth element, and a part or all of these are inorganic acid salts. Production method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06698592A JP3182849B2 (en) | 1992-03-25 | 1992-03-25 | Method for producing raw material powder of dielectric ceramic composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06698592A JP3182849B2 (en) | 1992-03-25 | 1992-03-25 | Method for producing raw material powder of dielectric ceramic composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05270903A JPH05270903A (en) | 1993-10-19 |
| JP3182849B2 true JP3182849B2 (en) | 2001-07-03 |
Family
ID=13331824
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06698592A Expired - Fee Related JP3182849B2 (en) | 1992-03-25 | 1992-03-25 | Method for producing raw material powder of dielectric ceramic composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3182849B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7904300B2 (en) | 2005-08-10 | 2011-03-08 | Nuance Communications, Inc. | Supporting multiple speech enabled user interface consoles within a motor vehicle |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4691977B2 (en) * | 2004-12-13 | 2011-06-01 | Ｔｄｋ株式会社 | Method for manufacturing dielectric composition |
-
1992
- 1992-03-25 JP JP06698592A patent/JP3182849B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7904300B2 (en) | 2005-08-10 | 2011-03-08 | Nuance Communications, Inc. | Supporting multiple speech enabled user interface consoles within a motor vehicle |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05270903A (en) | 1993-10-19 |
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