JPH10158059A - Ceramics for electronic parts, powdery ceramic material and their production - Google Patents
Ceramics for electronic parts, powdery ceramic material and their productionInfo
- Publication number
- JPH10158059A JPH10158059A JP8331397A JP33139796A JPH10158059A JP H10158059 A JPH10158059 A JP H10158059A JP 8331397 A JP8331397 A JP 8331397A JP 33139796 A JP33139796 A JP 33139796A JP H10158059 A JPH10158059 A JP H10158059A
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- JP
- Japan
- Prior art keywords
- powder
- elements
- ceramic material
- compound
- material powder
- 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.)
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、特に電子部品用セ
ラミックス、これに用いるセラミックス材料粉末及びこ
れらの製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a ceramic for electronic parts, a ceramic material powder used for the same, and a method for producing the same.
【０００２】[0002]
【従来の技術】現在、セラミックスは電子部品に幅広く
用いられている。例えば、セラミック基板、セラミック
コンデンサー、インダクターのコア、セラミックフィル
ター、セラミック発振子、各種センサー、高周波部品等
が挙げられる。これら部品に用いられるセラミックス誘
電体材料、セラミックス磁性体材料は、その組成のほと
んどが金属酸化物により占められている。例えばセラミ
ックス誘電体材料は、例えば炭酸バリウム、酸化チタ
ン、酸化ジルコニウム等の誘電体原料粉末を所定の比率
で混合粉砕し、ついでこれを仮焼し、Ｂａ（Ｔｉ、Ｚ
ｒ）Ｏ3 の組成の金属酸化物の材料粉末を得る。この材
料粉末に有機バインダーを加えて造粒し、この造粒物を
例えば板状に圧縮成形するいわゆる乾式成形を行ってそ
の成形物を焼成し、この焼成体に電極を形成してセラミ
ックコンデンサを作成したり、あるいはその材料粉末に
有機バインダ等を含有させて得たスラリーを用いてシー
ト状体を作成するいわゆる湿式成形を行って多数のグリ
ーンシートを形成し、それぞれのグリーンシートに内部
電極材料ペースト膜を形成して積層し、焼成することに
より積層セラミックコンデンサを作成している。2. Description of the Related Art At present, ceramics are widely used for electronic parts. For example, a ceramic substrate, a ceramic capacitor, a core of an inductor, a ceramic filter, a ceramic oscillator, various sensors, a high-frequency component and the like can be mentioned. Most of the composition of the ceramic dielectric material and ceramic magnetic material used for these components is occupied by metal oxides. For example, as a ceramic dielectric material, dielectric material powders such as barium carbonate, titanium oxide, and zirconium oxide are mixed and pulverized at a predetermined ratio, and then calcined to obtain Ba (Ti, Z
r) A metal oxide material powder having a composition of O 3 is obtained. An organic binder is added to this material powder, and granulation is performed. The granulated material is subjected to so-called dry molding, for example, compression molding into a plate shape, and the molded product is fired. A number of green sheets are formed by forming or using a slurry obtained by adding an organic binder or the like to the material powder to form a sheet-like body, thereby forming a number of green sheets, and forming an internal electrode material on each green sheet. A multilayer ceramic capacitor is produced by forming a paste film, laminating and firing.
【０００３】このようなセラミックス材料粉末を用いて
得られる焼成体の誘電体特性、磁気特性等の電気特性
は、その材料の例えば金属成分の組成に大きく依存し、
その金属成分の組成は焼成体の微細構造にも大きく影響
を及ぼすので、セラミックス材料粉末に副成分として微
量の例えば金属成分、例えば原子価制御剤、焼結助剤等
を添加し、焼成体の電気特性、微細構造を制御すること
が重要なこととして行われているが、その添加する個々
の金属成分の元素の種類によって、上記の電気特性に及
ぼす影響は異なる。例えば、セラミックスの主成分に固
溶することによりその特徴を発揮する金属成分元素と、
その固溶をせず、焼成体の結晶粒界や三重点に存在し特
徴を発揮する金属成分元素がある。いずれにせよ、微量
の金属成分はセラミックス焼成体中に均一に存在するこ
とが電気特性のバラツキを少なくし、安定のためのみな
らず、微細構造を得るためにも必要である。セラミック
ス材料粉末に副成分として例えば金属成分を添加する方
法としては、 セラミック材料の金属酸化物粉末に副
成分の金属粉末あるいはその金属の炭酸塩や酸化物を加
えてボールミル等で湿式混合し、その乾燥粉末を仮焼後
あるいはそのまま用いて作成した成形体を焼成する方
法、 セラミック材料の金属酸化物粉末のスラリーに
副成分の金属イオンを含む水溶液を添加し、この金属イ
オンをソーダ塩やアンモニウム塩のような沈澱剤により
沈澱させ、金属酸化物粉末とその沈澱物の混合物を仮焼
する方法、 セラミック材料の金属酸化物粉末に副成
分の金属化合物とバインダを加えて得たスラリーを噴霧
乾燥し、造粒した後、仮焼する方法が行われている。[0003] The electrical properties such as dielectric properties and magnetic properties of a fired body obtained using such ceramic material powder greatly depend on the composition of the metal component of the material, for example.
Since the composition of the metal component greatly affects the microstructure of the fired body, a small amount of a metal component, for example, a valence controlling agent, a sintering aid, or the like is added to the ceramic material powder as an auxiliary component, and It is important to control the electric characteristics and the microstructure, but the effect on the above electric characteristics differs depending on the type of the element of each metal component to be added. For example, a metal component element that exhibits its characteristics by forming a solid solution with the main component of ceramics,
There are metal component elements which do not form a solid solution but exist at the crystal grain boundaries and triple points of the fired body and exhibit characteristics. In any case, it is necessary that a trace amount of the metal component be uniformly present in the ceramic fired body in order to reduce the variation in the electric characteristics and to obtain not only stability but also a fine structure. As a method of adding a metal component as an auxiliary component to the ceramic material powder, for example, a metal oxide powder of the ceramic material or a carbonate or oxide of the metal is added to the metal oxide powder of the ceramic material and wet-mixed with a ball mill or the like. A method of baking the formed body after calcining or using the dry powder as it is, adding an aqueous solution containing metal ions as a sub-component to a slurry of metal oxide powder of a ceramic material, and converting the metal ions into soda salt or ammonium salt. A method of precipitating with a precipitant such as, and calcining a mixture of the metal oxide powder and the precipitate, spray-drying a slurry obtained by adding a metal compound and a binder as a sub-component to the metal oxide powder of a ceramic material. After granulation, calcining is performed.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、上記
〜のいずれの方法も、主成分のセラミック材料粉末に
必要な副成分を一度に添加して仮焼して得られるセラミ
ック材料粉末を用い、あるいは上記の方法によるセラ
ミック材料粉末に副成分を添加したセラミック材料粉末
を用い、成形を行い、焼成したものは、上述した主成分
に固溶することによりその特徴を発揮する金属成分元素
や焼成体の結晶粒界や三重点に存在し特徴を発揮する金
属成分元素の複数成分を用いると、それぞれの元素の拡
散速度が異なることにより焼成体の結晶粒子毎に固溶状
態が異なり、また、複数の元素が混在することによりそ
の粒界の状態が不均一になり易く、このように微量の副
成分が焼成体中に不均一に存在すると上述したように電
気特性の安定性が得られず、そのバラツキも小さくし難
い。特に、近年の電子部品の小型化、高性能化の進展は
めざましいものがあり、部品の小型化に対しては、セラ
ミック焼成体の微細構造、電気特性の一層高度な制御が
必要になっており、そのためには上記したように副成分
の微量の例えば金属成分はセラミック焼成体中に均一に
存在することが必要である。However, any of the above methods (1) to (3) uses a ceramic material powder obtained by adding necessary sub-components to a ceramic material powder as a main component at a time and calcining. The ceramic material powder obtained by adding a sub-component to the ceramic material powder according to the above method is molded and fired, and the metal component element or the crystal of the fired body which exhibits its characteristics by forming a solid solution with the main component described above. When a plurality of metal component elements present at grain boundaries and triple points and exhibiting characteristics are used, the solid solution state differs for each crystal particle of the fired body due to the different diffusion rate of each element, Is mixed, the state of the grain boundaries is likely to be non-uniform, and if such a small amount of sub-components are non-uniformly present in the fired body, the stability of the electrical characteristics can be obtained as described above. , It is difficult to smaller the variation. In particular, the progress of miniaturization and high performance of electronic components in recent years has been remarkable, and for the miniaturization of components, more sophisticated control of the fine structure and electrical characteristics of the ceramic fired body is required. For this purpose, as described above, it is necessary that a trace amount of a minor component, such as a metal component, be uniformly present in the ceramic fired body.
【０００５】本発明の第１の目的は、主成分に副成分が
均一に固溶し、その均一性をより高めることができる焼
成体のセラミックス、これが得られるセラミックス材料
粉末及びこれらの製造方法を提供することにある。本発
明の第２の目的は、副成分による主成分の粒界が均一に
なる焼成体のセラミックス、これが得られるセラミック
ス材料粉末及びこれらの製造方法を提供することにあ
る。本発明の第３の目的は、誘電率の温度特性等の電気
特性の安定性が良く、そのバチツキが小さい焼成体のセ
ラミックス、これが得られるセラミックス材料粉末及び
これらの製造方法を提供することにある。本発明の第４
の目的は、最近の小型化、高性能化の電子部品の製造を
可能にする焼成体のセラミックス、これが得られるセラ
ミックス材料粉末及びこれらの製造方法を提供すること
にある。本発明の第５の目的は、特別に新たな設備を必
要とすることなく、生産性が良く、コスト的に有利なセ
ラミック材料粉末の製造方法を提供することにある。A first object of the present invention is to provide a ceramic of a fired body in which subcomponents are uniformly dissolved in a main component and the uniformity thereof can be further improved, a ceramic material powder obtained therefrom, and a method for producing these. To provide. A second object of the present invention is to provide a fired body ceramic in which the grain boundaries of the main component due to the sub-components are uniform, a ceramic material powder obtained therefrom, and a method for producing these. A third object of the present invention is to provide a fired ceramic having good stability of electric characteristics such as temperature characteristics of a dielectric constant and a small stickiness, a ceramic material powder obtained therefrom, and a method for producing these. . Fourth Embodiment of the Present Invention
SUMMARY OF THE INVENTION An object of the present invention is to provide a fired body ceramic which enables the manufacture of recent miniaturized and high-performance electronic components, a ceramic material powder obtained therefrom, and a method of manufacturing these. A fifth object of the present invention is to provide a method for producing a ceramic material powder which has good productivity and is economically advantageous without requiring special new equipment.
【０００６】[0006]
【課題を解決するための手段】本発明は、上記課題を解
決するために、（１）、セラミックス原料粉末から得ら
れる主成分としての無機化合物粉末粒子表面に副成分と
して複数の元素を区分して各区分ごとに層状に担持させ
たセラミックス材料粉末を提供するものである。また、
本発明は、（２）、複数の元素を各区分ごとに層状に担
持させた構成は副成分の複数の元素の各区分の元素が主
成分となる無機化合物粉末粒子に対して拡散速度の小さ
い元素から大きい元素の順に内側から外側に順次担持さ
れている構成である請求項１に記載のセラミックス材料
粉末、（３）、副成分の複数の元素の各区分の元素は主
成分としての無機化合物粉末粒子の粒径の１／５より大
きくない粒径で担持されている上記（１）又は（２）の
セラミックス材料粉末、（４）、上記（１）ないし
（３）のいずれかのセラミックス材料粉末を用いた電子
部品用セラミックス、（５）、副成分の複数の元素の各
区分の元素の担持は主成分としての無機化合物粉末粒子
に副成分の１の区分の元素又は該１の区分の元素の化合
物の粉末を湿式混合した後熱処理を行なう工程と、この
工程で得られた粉末に他の１の区分の元素又は該他の１
の区分の元素の化合物の粉末を湿式混合した後熱処理を
行ない、順次これを繰り返す工程を有することにより上
記（１）ないし（３）のいずれかのセラミックス材料粉
末を製造するセラミックス材料粉末の製造方法、
（６）、副成分の複数の元素の各区分の元素の担持は主
成分としての無機化合物粉末粒子に副成分の１の区分の
元素又は該１の区分の元素の化合物の粉末を湿式混合し
た後熱処理を行なう工程と、この工程で得られた粉末に
他の１の区分の元素又は該他の１の区分の元素の化合物
の粉末を湿式混合した後熱処理を行ない、順次これを繰
り返す工程を有し、かつ最後の区分の元素又は該最後の
区分の元素の化合物の粉末については湿式混合を行った
のち熱処理を行わないことにより上記（１）ないし
（３）のいずれかのセラミックス材料粉末を製造するセ
ラミックス材料粉末の製造方法、（７）、副成分の複数
の元素の各区分の元素の担持は液中において主成分とし
ての無機化合物粉末粒子に副成分の１の区分の元素又は
該１の区分の元素の化合物の表面イオン交換反応及び／
又は沈殿反応を用いて付着させる工程と、この工程で得
られた粉末に液中において他の１の区分の元素又は該他
の１の区分の元素の化合物のイオン交換反応及び／又は
沈殿反応を用いて付着させ、順次これを繰り返す工程を
有することにより上記（１）ないし（３）のいずれかの
セラミックス材料粉末を製造するセラミックス材料粉末
の製造方法、（８）、副成分の複数の元素の各区分の元
素の担持は主成分としての無機化合物粉末粒子に副成分
の１の区分の元素又は該１の区分の元素の化合物を気化
させて付着させる工程と、この工程で得られた粉末に他
の１の区分の元素又は該他の１の区分の元素の化合物を
気化させて付着させ、順次これを繰り返す工程を有する
ことにより上記（１）ないし（３）のいずれかのセラミ
ックス材料粉末を製造するセラミックス材料粉末の製造
方法、（９）、副成分の複数の元素の各区分の元素の担
持は主成分としての無機化合物粉末粒子に副成分の１の
区分の元素又は該１の区分の元素の化合物を主成分と副
成分の粒子に対する機械的な力に基づいて起こる両者の
化学反応であるメカノケミカル反応により付着させる工
程と、この工程で得られた粉末に他の１の区分の元素又
は該他の１の区分の元素の化合物を該メカノケミカル反
応により付着させ、順次これを繰り返す工程を有するこ
とにより上記（１）ないし（３）のいずれかのセラミッ
クス材料粉末を製造するセラミックス材料粉末の製造方
法、（１０）、上記（１）ないし（３）のいずれかのセ
ラミックス材料粉末又は該セラミックス材料粉末を仮焼
した仮焼粉末を用いて成形体を得る工程と、該成形体を
焼成する工程を有する電子部品用セラミックスの製造方
法、（１１）、セラミックス材料粉末が上記（５）ない
し（９）のいずれかのセラミックス材料粉末の製造方法
により製造された上記（１０）に記載の電子部品用セラ
ミックスの製造方法を提供するものである。上記におい
て「各区分ごとに層状に担持」は、「各区分ごとに積層
して層状に担持」としてもよい。また、「１の区分の元
素又は該１の区分の元素の化合物」、「他の１の区分の
元素又は該他の１の区分の元素の化合物」とは、その区
分の元素が単数の場合と複数の場合があることを意味
し、その元素を構成成分とする化合物が一般的である
が、単体であっても良いことを示す。上記（１）その他
のこれを引用する発明において、「各区分毎に層状に担
持させ」は「各区分毎に層状に少なくとも２層担持さ
せ」とするこが好ましい。In order to solve the above-mentioned problems, the present invention provides (1) dividing a plurality of elements as subcomponents on the surface of inorganic compound powder particles as main components obtained from ceramic raw material powder. To provide a ceramic material powder supported in layers for each section. Also,
According to the present invention, (2) the configuration in which a plurality of elements are supported in layers in each section has a low diffusion rate with respect to inorganic compound powder particles in which the elements of each section of the plurality of subcomponents are the main components. 2. The ceramic material powder according to claim 1, wherein the element in each of the plurality of subcomponents is an inorganic compound as a main component. The ceramic material powder according to the above (1) or (2), which is supported at a particle size not larger than 1/5 of the particle size of the powder particles, (4), the ceramic material according to any of the above (1) to (3) The ceramics for electronic parts using powder, (5), the support of the elements of each category of a plurality of elements of the sub-components, the particles of the inorganic compound powder as the main component, the elements of the category of the sub-component or the Wet mixing of elemental compound powders A step of performing a post heat treatment, an element or said other one other first divided into powder obtained by this process
A method for producing a ceramic material powder according to any one of the above (1) to (3), comprising a step of performing a heat treatment after wet-mixing powders of the compounds of the elements of the category and sequentially repeating the heat treatment. ,
(6) The supporting of the elements of each of the plurality of sub-components is performed by wet-mixing the inorganic compound powder particles as the main component with the powder of the element of the sub-component or the compound of the element of the one sub-component. A step of performing a post-heat treatment, and a step of wet-mixing the powder obtained in this step with a powder of another one of the elements of the element or a compound of the compound of the other one of the elements, performing the heat treatment, and sequentially repeating the steps. The powder of the element of the last category or the compound of the element of the last category is subjected to wet mixing and then not subjected to heat treatment, so that the ceramic material powder of any of the above (1) to (3) is obtained. The method for producing a ceramic material powder to be produced, (7), the supporting of the elements of each of the plurality of sub-elements in the liquid is carried out in the liquid of the inorganic compound powder as a main component by the element of one of the sub-components or the one of the sub-components. Of the elements of the classification Object surface ion exchange reaction and /
Or a step of adhering using a precipitation reaction, and performing an ion exchange reaction and / or a precipitation reaction of another one of the elements in the liquid or a compound of the other one of the elements in the liquid on the powder obtained in this step. A method for producing a ceramic material powder according to any one of the above (1) to (3), wherein the method comprises the steps of: The supporting of the elements of each category is performed by vaporizing and attaching the element of the category 1 or the compound of the element of the category 1 to the inorganic compound powder particles as the main component, and the powder obtained in this step. The step of vaporizing and adhering the element of the other one category or the compound of the element of the other one category, and sequentially repeating this, makes it possible to obtain the ceramic material powder of any of the above (1) to (3). The method for producing a ceramic material powder to be produced, (9), the supporting of the elements of each of the plurality of sub-elements is carried out by adding the element of the sub-component to the inorganic compound powder particles as the main component or the element of the sub-component. Attaching a compound of the element by a mechanochemical reaction, which is a chemical reaction between the main component and the subcomponent, which is based on a mechanical force on the particles; Alternatively, a ceramic material powder for producing the ceramic material powder according to any one of the above (1) to (3), comprising a step of attaching a compound of the other one of the elements by the mechanochemical reaction and sequentially repeating the steps. (10) A molded body is obtained by using the ceramic material powder of any of the above (1) to (3) or a calcined powder obtained by calcining the ceramic material powder. And (11), wherein the ceramic material powder is produced by the method for producing a ceramic material powder according to any one of the above (5) to (9). Another object of the present invention is to provide a method for producing the ceramic for electronic parts according to the above (10). In the above, “supported in layers for each section” may be referred to as “laminated for each section and supported in layers”. Further, “an element of one category or a compound of an element of the one category” and “a compound of an element of another one category or a compound of an element of the other category” mean that the element of the category is singular. Means that there are a plurality of cases, and a compound containing the element as a component is generally used, but it may be a single compound. In the above (1) and other cited inventions, the phrase "supported in layers for each section" preferably means "at least two layers supported for each section."
【０００７】本発明において、「セラミック原料粉末か
ら得られる無機化合物粉末粒子」とは、例えばセラミッ
ク誘電体材料粉末粒子を得る場合には、例えば炭酸バリ
ウム、炭酸ストロンチウム等の炭酸塩、酸化チタン、酸
化ジルコニウム等の酸化物等の誘電体原料粉末をそれぞ
れの材料の組成に応じて選択し、所定の比率で混合粉砕
し、ついでこれを仮焼して得られる、Ｂａ（Ｔｉ、Ｚ
ｒ）Ｏ3 、ＳｒＴｉＯ3等の組成の金属酸化物粉末粒子
が挙げられる。また、「主成分としての無機化合物粉末
粒子表面に副成分として複数の元素を区分して各区分ご
とに層状に担持させ」の元素としては、Ｃｏ、Ｎｂ、Ａ
ｌ、Ｓｉ、Ｍｎ、希土類金属、アルカリ土類金属等が挙
げられ、これらは１種のみならず複数でも良い。一般に
は原子価制御剤、焼結助剤等として用いられる。「複数
の元素を区分して各区分ごとに層状に担持させ」とは、
主成分の粒子に同心円的に１又は複数の元素を区分して
担持させることをいうが、その元素としては主成分の粒
子に拡散速度が大きいものほど外側にし、拡散速度の小
さいものほど内側にすることが好ましく、例えばＢａ
（Ｔｉ、Ｚｒ）Ｏ3 の粒子に対しては内側から外側に順
に、例えばＮｂ、Ｃｏ、Ｓｉを担持させる。このように
すると、焼成を行うときに中心の粒子に対して副成分の
各成分の拡散量を均すことができ、それだけ副成分の固
溶状態を均一にでき好ましいが、このような構造は核に
複数の層からなる殻を形成した、いわゆるコアシェル構
造の粒子と呼ばれ、その効果を大きく発現することがで
きる。なお、複数の元素の各元素を区分して各元素ごと
に層状に担持させる場合のみならず、複数の元素の内の
複数の元素を１区分とし、その区分された複数の元素を
１つの層状に担持させる場合も含まれ、さらにこれらの
場合を組み合わせた場合も含まれる。In the present invention, "inorganic compound powder particles obtained from ceramic raw material powder" means, for example, when obtaining ceramic dielectric material powder particles, for example, carbonates such as barium carbonate and strontium carbonate, titanium oxide, and oxides. Dielectric raw material powders such as oxides of zirconium and the like are selected according to the composition of each material, mixed and pulverized at a predetermined ratio, and then calcined to obtain Ba (Ti, Z).
r) Metal oxide powder particles having a composition such as O 3 and SrTiO 3 . The elements of “a plurality of elements are divided as subcomponents on the surface of the inorganic compound powder particles as the main component and supported in layers for each division” include Co, Nb, and A.
l, Si, Mn, rare earth metals, alkaline earth metals, etc., and not only one kind but also plural kinds. Generally, it is used as a valence controlling agent, a sintering aid and the like. "Several elements are divided and supported in layers for each division"
This means that one or more elements are concentrically separated and supported on the particles of the main component, and the elements are set such that the higher the diffusion rate of the main component particles is, the more the element is placed outside, and the lower the diffusion rate is, the more the element is placed inside. Preferably, for example, Ba
For example, Nb, Co, and Si are loaded on the (Ti, Zr) O 3 particles in order from inside to outside. This makes it possible to equalize the diffusion amount of each of the sub-components with respect to the central particle when performing the firing, and to make the solid solution state of the sub-components uniform accordingly, which is preferable. It is called a particle having a so-called core-shell structure in which a shell composed of a plurality of layers is formed in a nucleus, and the effect can be greatly exhibited. In addition to the case where each element of the plurality of elements is divided and supported in a layer form for each element, a plurality of elements among the plurality of elements are divided into one section, and the divided elements are classified into one layer. And the case where these cases are combined.
【０００８】本発明において、副成分の複数の元素の各
区分の元素を主成分の無機化合物粉末粒子に担持させる
には、固相法、液相法、気相法及びメカノケミカル法が
あり、これらを複数併用してもよい。固相法は、主成分
の無機化合物粉末に副成分の複数の元素の１の区分の元
素又は該１の区分の元素の化合物の粉末、例えば上記金
属の酸化物粉末等を水等の媒体とボールミル等で攪拌
し、粉末同志を湿式混合し、熱処理を行うことによりそ
の副成分を無機化合物粉末粒子に付着させて担持させ、
ついでこの副成分を担持した粉末粒子に副成分の複数の
元素の他の１の区分の元素の例えば上記と同様な化合物
の粉末を同様にボールミル等で攪拌し、粉末同志を湿式
混合し、熱処理を行うことによりその副成分を第１の副
成分の元素の成分の層上に担持させ、以下各元素を順次
同様にして担持させ、セラミックス材料粉末を得る方法
である。最後の区分の元素の例えば上記と同様な化合物
の粉末については熱処理を行わず、湿式混合した後乾燥
させてセラミックス材料粉末とすることができる。この
とき適性な熱処理温度を選定する必要があり、例えば９
００〜１１００℃、１〜６０分を挙げることができ、こ
れは仮焼とも言える。このようにすると、副成分の元素
の成分は主成分の無機化合物粉末粒子表面に拡散するの
でその担持は容易である。[0008] In the present invention, there are a solid phase method, a liquid phase method, a gas phase method and a mechanochemical method for supporting the elements of each of the plurality of subcomponents on the inorganic compound powder particles as the main component. These may be used in combination. In the solid phase method, a powder of an element of one of a plurality of subcomponents or a powder of a compound of an element of the one of the elements, for example, an oxide powder of the above-mentioned metal is mixed with an inorganic compound powder of a main component with a medium such as water. Stir with a ball mill etc., wet mix the powders together, and carry out heat treatment to make the auxiliary components adhere to the inorganic compound powder particles and carry them,
Then, the powder of the sub-component is mixed with a powder of the same compound as above, for example, a compound of the same one of the above-mentioned sub-components, by a ball mill or the like, and the powders are wet-mixed. Is carried out on the layer of the component of the element of the first subcomponent, and thereafter, the respective elements are successively carried in the same manner to obtain a ceramic material powder. The powder of the last element, for example, a compound similar to the above, is not heat-treated, but is wet-mixed and then dried to obtain a ceramic material powder. At this time, it is necessary to select an appropriate heat treatment temperature.
00 to 1100 ° C for 1 to 60 minutes, which can be said to be calcination. In this case, the component of the subcomponent element is diffused to the surface of the inorganic compound powder particles of the main component, so that the supporting is easy.
【０００９】また、液相法は、副成分の複数の元素の１
の区分の元素又は該１の区分の元素の化合物を構成成分
に有する塩及びアルコキシド、キレート化合物その他の
金属の有機化合物等の少なくとも１種を溶媒に溶解し、
その溶液を主成分の無機化合物粉末を含有する有機溶媒
等の液に加え、その無機化合物粉末粒子表面に表面イオ
ン交換反応及び沈殿反応の少なくとも１種を起こさせて
その元素又はそれぞれの元素（前者は単数の場合、後者
は複数の場合、以下同様）を担持させ、ついでこの副成
分を担持した粉末粒子を含有する液に副成分の複数の元
素の他の１の区分の元素又は該他の１の区分の化合物を
構成成分に有する塩及びアルコキシド、キレート化合物
その他の金属の有機化合物等の少なくとも１種を溶媒に
溶解した溶液を加えて第１の副成分の元素の成分の層上
に表面イオン交換反応及び沈殿反応の少なくともも１種
を起こさせてその元素又はそれぞれの元素の成分を担持
させ、以下各元素を順次同様にして担持させる方法であ
る。溶解の代わりに分散でもよい。なお、表面イオン交
換反応は、粒子表面のＯＨ基のプロトンを金属イオンが
置換する反応をいい、沈殿反応は、沈殿剤により金属イ
オンを水酸化物として表面に吸着させる反応をいう。い
ずれにせよ、副成分の元素の成分を所望の組成にて担持
させるには反応条件の適性化が必要となるが、その適性
化を行なえば副成分の元素の成分の析出は主成分の無機
化合物粉末粒子表面やこれに担持された他の副成分の元
素の成分の析出膜上で起こるので各元素又は複数の元素
の成分の均一な被膜が形成できる。その適性化として
は、例えば上記反応を起こさせる液のｐＨ、加水分解剤
の使用の有無、その濃度、反応温度等の条件の選択が挙
げられる。例えば沈殿反応において、加水分解剤を使用
する場合には、その反応を起こさせる溶媒は中性からア
ルカリ性の領域内の水性液が好ましく、例えばアンモニ
ア水が好ましく、これに限らないが、アルカリ金属等の
後のセラミック材料を得る際、あるいはその材料を用い
た成形体の焼成の際残留するようなものよりは、揮発又
は分解し残留しないものが好ましい。水性液とは溶媒が
水のみの場合のみならず、水とこれに混ざる有機溶媒の
混合液でも良い。上記加水分解剤として水のみでも良い
ことがあるが、アンモニア水を用いる場合には、上記無
機化合物粉末を含有する有機溶媒等の液中におけるアン
モニア水（ＮＨ4 ＯＨ）の濃度としては、０．０１〜１
０ｍｏｌ／ｌが好ましく、より好ましくは０．１〜５ｍ
ｏｌ／ｌである。０．０１ｍｏｌ／ｌより小さければア
ンモニア水の量が増加し、生産性が悪化し易く、また、
１０ｍｏｌ／ｌより大きければアンミン錯体が生成し易
く、所望の組成の無機化合物の被覆が不可能となり易
い。また、加えるＮＨ4 ＯＨの量は、金属の有機化合物
に対して、１〜２当量であることが生産性、被覆する無
機化合物の組成制御の点から好ましく、この範囲外では
生産性の悪化を起こし易い。より好ましくは１当量であ
る。In the liquid phase method, one of a plurality of subcomponents is used.
Dissolving at least one of a salt and an alkoxide having a compound of the element of the category or the compound of the element of the category 1 as a component, an organic compound of a chelate compound and other metals, in a solvent,
The solution is added to a liquid such as an organic solvent containing an inorganic compound powder as a main component, and at least one of a surface ion exchange reaction and a precipitation reaction is caused on the surface of the inorganic compound powder particles to cause the element or each element (the former) Is a singular case, the latter is a plural case, the same applies hereinafter), and then the liquid containing the powder particles supporting the sub-components has a plurality of elements of the sub-components in another one of the elements or the other. A solution in which at least one kind of a salt having a compound of Class 1 as a constituent component and an alkoxide, a chelate compound, or another organic compound of a metal is dissolved in a solvent is added, and the surface is formed on the layer of the first subcomponent element. This is a method in which at least one of the ion exchange reaction and the precipitation reaction is caused to support the element or the component of each element, and thereafter, the respective elements are sequentially and similarly supported. Dispersion may be used instead of dissolution. The surface ion exchange reaction refers to a reaction in which a proton of an OH group on the particle surface is replaced by a metal ion, and the precipitation reaction refers to a reaction in which a metal ion is adsorbed on the surface as a hydroxide by a precipitant. In any case, it is necessary to optimize the reaction conditions in order to support the component of the subcomponent element in a desired composition. However, if the optimization is performed, the precipitation of the component of the subcomponent element becomes an inorganic component of the main component. Since it occurs on the surface of the compound powder particles or on the deposited film of the components of the other subcomponents carried on the compound powder particles, a uniform coating of the components of each or a plurality of elements can be formed. Examples of the suitability include selection of conditions such as the pH of the solution causing the reaction, the use of a hydrolyzing agent, the concentration thereof, and the reaction temperature. For example, in the case of using a hydrolyzing agent in the precipitation reaction, the solvent causing the reaction is preferably an aqueous liquid in a neutral to alkaline region, for example, ammonia water is preferable, and the solvent is not limited thereto. It is more preferable that the material does not remain after being volatilized or decomposed than the material remaining when a subsequent ceramic material is obtained or when a molded body using the material is fired. The aqueous liquid is not limited to the case where the solvent is only water, but may be a mixed liquid of water and an organic solvent mixed with water. Although only water may be used as the hydrolyzing agent, when ammonia water is used, the concentration of aqueous ammonia (NH 4 OH) in a liquid such as an organic solvent containing the inorganic compound powder is set to 0.1. 01-1
0 mol / l is preferable, and more preferably 0.1 to 5 m
ol / l. If the amount is less than 0.01 mol / l, the amount of aqueous ammonia increases, and the productivity tends to deteriorate.
If it is larger than 10 mol / l, an ammine complex is easily formed, and it becomes difficult to coat an inorganic compound having a desired composition. Further, the amount of NH 4 OH to be added is preferably 1 to 2 equivalents with respect to the metal organic compound from the viewpoint of productivity and control of the composition of the inorganic compound to be coated. Easy to wake up. More preferably, it is 1 equivalent.
【００１０】有機溶媒としては、エタノール、プロパノ
ール等のアルコール系溶媒、エタノールアミン等の上記
加水分解剤を溶解できる溶媒、すなわち極性溶媒が好ま
しいが、この極性溶媒を他の有機溶媒、例えばベンゼ
ン、トルエン等の少なくとも１種を０〜４０％を混合し
たある程度極性を持った有機溶媒でも、上記加水分解剤
を溶解できるものであれば良い。上記無機化合物粉末を
有機溶媒に分散させる際には、界面活性剤を使用し、有
機溶剤に無機化合物粉末が分散し易くしても良く、陰イ
オンの界面活性剤を使用すれば、無機化合物粉末に吸着
されたその陰イオンに加水分解剤やこれによる金属の有
機化合物の加水分解物の陽イオンが吸着され易いように
することもでき、界面活性剤に有機物を使用すれば後の
セラミック材料を得る際、あるいはその材料を用いた成
形体の焼成の際、分解除去できるので好ましい。The organic solvent is preferably an alcoholic solvent such as ethanol or propanol, or a solvent capable of dissolving the above hydrolyzing agent such as ethanolamine, that is, a polar solvent. This polar solvent is preferably replaced with another organic solvent such as benzene or toluene. Even a solvent having a certain degree of polarity, which is obtained by mixing at least one kind of such as 0 to 40%, may be any as long as it can dissolve the hydrolyzing agent. When dispersing the above inorganic compound powder in an organic solvent, a surfactant may be used, and the inorganic compound powder may be easily dispersed in the organic solvent. A hydrolyzing agent or a cation of a hydrolyzate of a metal organic compound thereby can be easily adsorbed to the anion adsorbed on the surface of the ceramic material. It is preferable because it can be decomposed and removed when it is obtained or when a molded body using the material is fired.
【００１１】上記において、元素又は元素の化合物を構
成成分に有する塩及びアルコキシド、キレート化合物そ
の他の金属の有機化合物等の少なくとも１種とは、塩の
１種、金属の有機化合物の少なくとも１種、塩及び金属
の有機化合物のそれぞれ少なくとも１種が挙げられる。
金属の有機化合物の少なくとも１種は、上記例示した金
属の例えば加水分解可能なアルコキシド類及びキレート
化合物類の少なくとも１つの類に属する少なくとも１
種、すなわちアルコキシド類の少なくとも１種、キレー
ト化合物類の少なくとも１種、両者のそれぞれの少なく
とも１種が挙げられるが、具体的にはアルコキシドとし
てはエトキシド、プロポキシド等の低級アルコキシド、
ジケトン系、また、キレート化合物としてはアセチルア
セトナート、ＤＰＭ等が好ましいものとして例示され
る。塩としては具体的には上記例示した金属の塩化物、
硝酸塩等が挙げられる。これらの例えば金属の有機化合
物は、金属イオンが親水性の無機化合物粉末粒子の表面
の吸着水に配位するため、その金属の有機化合物の加水
分解剤による加水分解はその表面で選択的に行われ、そ
の析出した水酸化物あるいは酸化物も親水的であるので
分解析出及び吸着によりその成長が行われ、金属酸化物
粉末粒子に対する被膜が形成される。上記金属の有機化
合物の上記有機溶媒中の濃度は、０．００１〜０．１ｍ
ｏｌ／ｌが好ましく、低過ぎると生産性が悪くなり易
く、多過ぎると溶解でき難くなる。これらの塩や金属の
有機化合物の主成分である無機化合物粉末に対する添加
量は塩としては０．０１〜５ｍｏｌ％が好ましい。In the above, at least one of a salt having an element or a compound of the element as a constituent component, an alkoxide, a chelate compound, and other metal organic compounds, etc., refers to one kind of salt, at least one kind of metal organic compound, At least one of each of a salt and an organic compound of a metal is exemplified.
At least one of the organic compounds of the metal is at least one of at least one of the above-listed metals, for example, at least one of hydrolyzable alkoxides and chelate compounds.
Species, that is, at least one of alkoxides, at least one of chelate compounds, and at least one of each of them, specifically, alkoxides include lower alkoxides such as ethoxide and propoxide;
Acetone acetonate, DPM and the like are preferable examples of the diketone compound and the chelate compound. As the salt, specifically, the metal chloride exemplified above,
Nitrates and the like. In these organic compounds of a metal, for example, the metal ions are coordinated with the water adsorbed on the surface of the hydrophilic inorganic compound powder particles, so that the hydrolysis of the organic compound of the metal by the hydrolyzing agent is selectively performed on the surface. Since the precipitated hydroxide or oxide is also hydrophilic, its growth is carried out by decomposition precipitation and adsorption, and a film is formed on the metal oxide powder particles. The concentration of the organic compound of the metal in the organic solvent is 0.001 to 0.1 m.
ol / l is preferred. If it is too low, the productivity tends to deteriorate, and if it is too high, it becomes difficult to dissolve. The amount of the salt or the metal added to the inorganic compound powder, which is the main component of the organic compound, is preferably 0.01 to 5 mol% as the salt.
【００１２】上記無機化合物粉末粒子に対して担持した
被膜の成長と結晶性の向上には、有機溶媒中に金属の有
機化合物を溶解し、その溶液と無機化合物粉末を分散さ
せた分散液に、さらに加水分解剤を加えて得たスラリー
の熱処理を行うことが、金属の有機化合物を良く溶解す
ることによりその分子レベルの吸着を可能にし、その状
態で加水分解剤により加水分解されるので、その加水分
解物である水酸化物あるいは酸化物の析出反応が促進さ
れ、効果的である。その加熱温度はその金属化合物の被
膜を強固にする点から８０℃が好ましいが、その結晶化
が促進されるためには６０℃以上に加熱することが好ま
しい。最も適当な熟成温度は６０〜８０℃である。ま
た、その被覆膜の均一性を向上させるには、加水分解剤
による加水分解をスラリー中で均一に行わせることが重
要であり、そのためには上記スラリーを撹拌することが
有効である。その速度は１００〜１０００ｒｐｍ（毎分
の回転数）が好ましく、１００ｒｐｍより遅いと得られ
る被覆膜の均一性は十分ではなく、１０００ｒｐｍより
大きくすると生産設備のコスト増になり易い。In order to grow and improve the crystallinity of the film supported on the inorganic compound powder particles, an organic compound of a metal is dissolved in an organic solvent, and a solution obtained by dissolving the solution of the metal and the inorganic compound powder is dispersed in an organic solvent. Heat treatment of the slurry obtained by further adding a hydrolyzing agent enables adsorption at the molecular level by dissolving the organic compound of the metal well, and is hydrolyzed by the hydrolyzing agent in that state. The precipitation reaction of the hydroxide or oxide, which is a hydrolyzate, is promoted, which is effective. The heating temperature is preferably 80 ° C. in order to strengthen the coating of the metal compound, but it is preferable to heat it to 60 ° C. or higher in order to promote the crystallization. The most suitable aging temperature is 60-80 ° C. Further, in order to improve the uniformity of the coating film, it is important that the hydrolysis with the hydrolyzing agent is uniformly performed in the slurry, and for that purpose, it is effective to stir the slurry. The speed is preferably 100 to 1000 rpm (rotation speed per minute). If the speed is lower than 100 rpm, the uniformity of the coating film obtained is not sufficient. If the speed is higher than 1000 rpm, the cost of production equipment tends to increase.
【００１３】このようにして金属の水酸化物あるいは酸
化物を担持したセラミック材料粉末が得られるが、これ
をその含有液から分離するには、フィルタープレス等の
濾過を行うことで十分であるが、この含有液を噴霧する
噴霧乾燥によっても陰イオンの残留はなく、生産設備等
を考慮して使用できる。噴霧乾燥の場合陰イオンの残留
をなくすため４００℃以上の温度で加熱することが好ま
しいが、生産設備を考慮すると６００℃以下が好まし
い。その最も適当な加熱温度は４００〜６００℃であ
る。[0013] In this way, a ceramic material powder supporting a metal hydroxide or oxide is obtained. To separate this from a liquid containing the same, it is sufficient to perform filtration using a filter press or the like. No anions remain even by spray-drying by spraying the contained liquid, and it can be used in consideration of production facilities and the like. In the case of spray drying, it is preferable to heat at a temperature of 400 ° C. or higher in order to eliminate residual anions. However, in consideration of production equipment, 600 ° C. or lower is preferable. Its most suitable heating temperature is 400-600 ° C.
【００１４】また、気相法は、副成分の複数の元素の１
の区分の元素又は該１の区分の元素の化合物として比較
的蒸気圧の高い物質を用い、これを気化させてその気化
物を主成分の無機化合物粉末粒子表面に析出させて担持
させ、ついでこの副成分を担持した粉末粒子表面に副成
分の複数の元素の他の１の区分の元素又は該他の１の区
分の元素の化合物として比較的蒸気圧の高い物質を用
い、これを気化させてその気化物を第１の副成分の元素
の成分の層上に析出させて担持させ、以下各元素を順次
同様にして担持させる方法である。この場合、副成分の
元素の化合物は２０００℃以下、すなわち２０００℃よ
り高くない温度で気化する物質が製造設備の経済性の点
で好ましい。この場合、減圧下の場合も含まれる。In the gas phase method, one of a plurality of subcomponent elements is used.
A substance having a relatively high vapor pressure is used as the element of the category or the compound of the element of the category, and the substance is vaporized, and the vaporized substance is precipitated and supported on the surface of the inorganic compound powder particles of the main component. A substance having a relatively high vapor pressure is used as a compound of the other one of the plurality of elements of the sub-components or the compound of the other one of the sub-components on the surface of the powder particle supporting the sub-component, and this is vaporized. This is a method in which the vaporized substance is deposited on a layer of the first subcomponent element and supported, and each element is subsequently carried out in the same manner. In this case, the compound of the subcomponent element is preferably a substance that vaporizes at a temperature of 2000 ° C. or less, that is, a temperature not higher than 2000 ° C., from the viewpoint of economical efficiency of the manufacturing equipment. In this case, a case under reduced pressure is also included.
【００１５】また、メカノケミカル反応を用いる方法
は、主成分の無機化合物粉末と副成分の複数の元素の１
の区分の元素又は該１の区分の元素の化合物の粉末とを
乾式で混合し、両者の粉末の粒子表面でメカノケミカル
反応、すなわち粒子表面に例えばライカイ機を用いた場
合のように機械的力を加えることにより両者の間に化学
反応を起こさせて（剪断力により粒子を摩擦しその新た
な表面が化学的に活性であり、化学反応を起こさせるこ
とができる）副成分の元素の成分を担持させ、ついでこ
の副成分を担持した粉末と副成分の複数の元素の他の１
の区分の元素又は該他の１の区分の元素の化合物の粉末
とを乾式で混合し、両者の粉末の粒子表面でメカノケミ
カル反応させ上記と同様にその元素の成分を担持させ、
以下副成分の元素を順次同様にして担持させる方法であ
る。In addition, the method using the mechanochemical reaction is based on a method in which an inorganic compound powder as a main component and one of a plurality of subcomponents are used.
The powder of the element of the category or the compound of the element of the category is dry-mixed, and a mechanochemical reaction occurs on the particle surfaces of both powders, that is, a mechanical force such as when a raikai machine is used on the particle surface. To cause a chemical reaction between the two (the friction of the particles by the shearing force causes the new surface to be chemically active and can cause a chemical reaction). Supported, and then the powder supporting the sub-component and the other one of the plurality of elements of the sub-component.
The powder of the element of the category or the compound of the element of the other category is dry-mixed, and a mechanochemical reaction is carried out on the particle surfaces of the two powders, and the components of the element are supported as described above,
The following is a method in which the elements of the subcomponents are successively carried in the same manner.
【００１６】このように固相法等の方法により主成分と
しての無機化合物粉末粒子に副成分の複数の元素を担持
させて得られるセラミック材料粉末は、そのまま成形
し、あるいは仮焼した後その仮焼粉体を成形し、それぞ
れの成形品を焼成することにより上記各種電子部品のセ
ラミック焼成体とすることができ、その電気特性を向上
し、その安定性を向上させ、そのバラツキを少なくする
ことができる。The ceramic material powder obtained by supporting a plurality of subcomponent elements on the inorganic compound powder particles as a main component by a method such as a solid phase method or the like is directly molded or calcined, By forming a sintered powder and firing each molded product, it is possible to obtain a ceramic fired body of the above various electronic components, to improve its electric characteristics, to improve its stability, and to reduce its variation. Can be.
【００１７】[0017]
【発明の実施の形態】詳細は以下の実施例により説明す
るが、主成分の無機質化合物粉末粒子に副成分の複数の
元素を区分して各区分ごとの元素を層状に担持させる
と、各元素の主成分に対する作用をその性質に応じて制
御することができ、例えば拡散速度の相違に応じてその
速度の大きいものほど外側に担持させ、外側の層を形成
するようにすると、このようにして得られるセラミック
ス材料粉末を用いた焼成体の主成分の結晶粒子に拡散す
る各元素の量を均すことができ、副成分のように微量添
加する添加剤のその添加の効果を最大限に発揮させるこ
とができる。BEST MODE FOR CARRYING OUT THE INVENTION The details of the present invention will be described with reference to the following examples. The action on the main component can be controlled according to its properties.For example, depending on the difference in diffusion rate, the larger the rate is, the more it is carried outside and the outer layer is formed. The amount of each element diffused into the crystal grains of the main component of the fired body using the obtained ceramic material powder can be equalized, and the effect of the addition of a small amount of additive such as a sub-component is maximized. Can be done.
【００１８】[0018]
【実施例】次に本発明の実施例を説明する。 実施例１（液相法の例） ＢａＴｉＯ3 粉末１００ｇと純水２００ｍｌのスラリー
に、１．５ａｔｏｍ％のＮｂＣｌ5 を溶解したエチレン
グリコール５０ｍｌを加え、８０℃、３時間加熱した。
その後、その一部を濾過し、その粉末をＩＣＰ発光分析
装置（Ｉｎｄｕｃｔｉｖｅｌｙ Ｃｏｕｐｌｅｄ Ｐｌ
ａｓｍａ）で確認したところ、ＢａＴｉＯ3 粉末粒子表
面にＮｂが担持されていることが確認された。なお、濾
液からはＮｂは検出されなかった。ついで、Ｃｏ（ＮＯ
3 ）2 を０．５ａｔｏｍ％上記加熱処理したスラリーに
加えて溶解し、さらに１．５Ｎアンモニア水５０ｍｌを
加えた。その一部を濾過し、その濾液を調べたところＣ
ｏは検出されず、この元素の成分は上記のＢａＴｉＯ3
粉末粒子表面に担持されたＮｂの被膜の上に担持されて
いることが確認された。さらに、エタノール２５ｍｌと
純水５０ｍｌを混合し、Ｓｉ（ＯＣ2 Ｈ5 ）4を１．５
ｍｏｌ％溶解した溶液を、上記のアンモニア水を加えた
スラリーを攪拌しながら滴下した。その後、そのスラリ
ーを８０℃、５時間加熱した。その一部を濾過し、その
濾液を調べたところＳｉは検出されず、この元素の成分
は上記ＢａＴｉＯ3 粉末粒子表面に担持されたＮｂの被
膜の上に形成されたＣｏの被膜の上に担持されているこ
とが確認された。得られたスラリーを乾燥した。このよ
うにして得られたセラミックス誘電体材料粉末を用いて
成形し、その成形体を１２００℃で焼成した。その焼成
体の誘電率の温度特性をインピーダンスアナライザーで
測定したところ、ＥＩＡ規格のＸ７Ｒ特性を満足し、そ
のバラツキが小さく、その性能が安定していることが分
かった。この実施例は、主成分のＢａＴｉＯ3 粉末に、
副成分として３つの元素を区分して第１区分をＮｂ、第
２区分をＣｏ、第３区分をＳｉとし、各区分ごと、すな
わち各元素ごとに層状に担持させた場合である。Next, embodiments of the present invention will be described. Example 1 (Example of Liquid Phase Method) To a slurry of 100 g of BaTiO 3 powder and 200 ml of pure water, 50 ml of ethylene glycol in which 1.5 atom% of NbCl 5 was dissolved was added, and the mixture was heated at 80 ° C. for 3 hours.
Thereafter, a part of the powder was filtered, and the powder was filtered using an ICP emission spectrometer (Inductively Coupled Pl).
(asma), it was confirmed that Nb was supported on the surface of the BaTiO 3 powder particles. Note that Nb was not detected from the filtrate. Then, Co (NO
3 ) 2 was added to 0.5 atom% of the slurry subjected to the heat treatment and dissolved, and 50 ml of 1.5N ammonia water was further added. A part thereof was filtered, and the filtrate was examined.
o was not detected, and the component of this element was BaTiO 3
It was confirmed that the particles were supported on the Nb film supported on the surface of the powder particles. Furthermore, 25 ml of ethanol and 50 ml of pure water were mixed, and Si (OC 2 H 5 ) 4 was added to 1.5 ml.
The solution in which the mol% was dissolved was added dropwise while stirring the slurry to which the above-mentioned ammonia water was added. Thereafter, the slurry was heated at 80 ° C. for 5 hours. When a part thereof was filtered and the filtrate was examined, no Si was detected, and the component of this element was supported on the Co film formed on the Nb film supported on the surface of the BaTiO 3 powder particles. It was confirmed that it was. The obtained slurry was dried. The ceramic dielectric material powder thus obtained was molded, and the molded body was fired at 1200 ° C. When the temperature characteristic of the dielectric constant of the fired body was measured with an impedance analyzer, it was found that the X7R characteristic of the EIA standard was satisfied, the variation was small, and the performance was stable. In this example, the main component BaTiO 3 powder
This is a case where three elements are divided as subcomponents, the first division is Nb, the second division is Co, and the third division is Si, and each division, that is, each element is supported in a layer.
【００１９】実施例２（気相法の例） ＢａＴｉＯ3 粉末１００ｇを反応容器に入れ、真空状態
にし、初めにＮｂのアルコキシドを気化させ、その気化
物を反応容器に導入し、ついでＣｏのアルコキシドを気
化させ、その気化物を反応容器に導入した。得られた粉
末をＩＣＰで組成分析したところ、ＢａＴｉＯ3 に対し
Ｎｂが０．５ｍｏｌ％、Ｃｏが１．５ｍｏｌ％含まれて
いることが分かり、ＢａＴｉＯ3 粉末粒子の表面にＮｂ
が担持され、その被膜の上にＣｏが担持されてその被膜
が形成され、積層被膜が形成されていることが分かっ
た。このようにして得られたセラミックス誘電体材料粉
末を用いて成形し、その成形体を１２００℃で焼成し
た。その焼成体の誘電率の温度特性をインピーダンスア
ナライザーで測定したところ、ＥＩＡ規格のＸ７Ｒ特性
を満足し、そのバラツキが小さく、その性能が安定して
いることが分かった。この実施例は、主成分のＢａＴｉ
Ｏ3 粉末に、副成分として２つの元素を区分して第１区
分をＮｂ、第２区分をＣｏとし、各区分ごと、すなわち
各元素ごとに層状に担持させた場合である。Example 2 (Example of Gas Phase Method) 100 g of BaTiO 3 powder was placed in a reaction vessel, a vacuum was applied, Nb alkoxide was first vaporized, the vapor was introduced into the reaction vessel, and then Co alkoxide was introduced. Was vaporized, and the vaporized product was introduced into a reaction vessel. When the composition of the obtained powder was analyzed by ICP, it was found that 0.5 mol% of Nb and 1.5 mol% of Co were contained in BaTiO 3 , and Nb was added to the surface of the BaTiO 3 powder particles.
It was found that Co was carried on the film, the film was formed, and a laminated film was formed. The ceramic dielectric material powder thus obtained was molded, and the molded body was fired at 1200 ° C. When the temperature characteristic of the dielectric constant of the fired body was measured with an impedance analyzer, it was found that the X7R characteristic of the EIA standard was satisfied, the variation was small, and the performance was stable. In this embodiment, the main component BaTi
In this case, the O 3 powder is divided into two elements as subcomponents, the first division is Nb, and the second division is Co, and each of the divisions, that is, each element, is supported in layers.
【００２０】実施例３（メカノケミカル反応を利用する
例） ＢａＴｉＯ3 粉末と０．７５ｍｏｌ％のＮｂ2 Ｏ5 微粉
末をライカイ機で１０時間混合し、この後０．５ｍｏｌ
％のＣｏＯ微粉末を加え、さらに２４時間混合した。得
られた粉末をＴＥＭ−ＥＤＳ分析したところ、ＢａＴｉ
Ｏ3 に対しＮｂが１．５ｍｏｌ％、Ｃｏが０．５ｍｏｌ
％含まれていることが分かり、ＢａＴｉＯ3粉末粒子の
表面にＮｂが担持され、その被膜の上にＣｏが担持され
てその被膜が形成され、積層被膜が形成されていること
が分かり、これらはメタノケミカル反応の結果であるこ
とが確認された。このようにして得られたセラミックス
誘電体材料粉末を用いて成形し、その成形体を１２００
℃で焼成した。その焼成体の誘電率の温度特性をインピ
ーダンスアナライザーで測定したところ、ＥＩＡ規格の
Ｘ７Ｒ特性を満足し、そのバラツキが小さく、その性能
が安定していることが分かった。この実施例は、主成分
のＢａＴｉＯ3 粉末に、副成分として２つの元素を区分
して第１区分をＮｂ、第２区分をＣｏとし、各区分ご
と、すなわち各元素ごとに層状に担持させた場合であ
る。Example 3 (Example utilizing mechanochemical reaction) BaTiO 3 powder and 0.75 mol% of Nb 2 O 5 fine powder were mixed for 10 hours by a raikai machine, and then 0.5 mol
% CoO fine powder was added and mixed for an additional 24 hours. TEM-EDS analysis of the resulting powder showed that BaTi
1.5 mol% of Nb and 0.5 mol of Co based on O 3
%, The Nb is supported on the surface of the BaTiO 3 powder particles, the Co is supported on the film to form the film, and the laminated film is formed. It was confirmed that this was the result of the methanochemical reaction. The ceramic dielectric material powder obtained in this manner is molded using the powder,
Fired at ℃. When the temperature characteristic of the dielectric constant of the fired body was measured with an impedance analyzer, it was found that the X7R characteristic of the EIA standard was satisfied, the variation was small, and the performance was stable. In this example, two elements were subdivided into BaTiO 3 powder as a main component, the first division was Nb, and the second division was Co, and each of the divisions, that is, each element was supported in layers. Is the case.
【００２１】実施例４（固相法の例） ＢａＴｉＯ3 粉末１００ｇに０．７５ｍｏｌ％のＮｂ2
Ｏ5 粉末を加えて、純水２００ｍｌ、直径１．５ｍｍの
ＺｒＯ2 ビーズ３００ｇを用いたボールミルで湿式混合
した。その混合分散体を濾過し、得られた粉末を１００
０℃で１時間熱処理（仮焼）した。この熱処理した粉末
に対して０．５ｍｏｌ％のＣｏＯと１．５ｍｏｌ％のＳ
ｉＯ2 を加え、上記と同様にボールミルで解砕・分散さ
せた後、濾過し、乾燥した。このようにして得られたセ
ラミックス誘電体材料粉末を用いて成形し、その成形体
を１３００℃、２時間焼成した。その焼成体の誘電率の
温度特性をインピーダンスアナライザーで測定したとこ
ろ、ＥＩＡ規格のＸ７Ｒ特性を満足し、そのバラツキが
小さく、その性能が安定していることが分かった。この
実施例は、主成分のＢａＴｉＯ3 粉末に、副成分として
３つの元素を区分して第１区分をＮｂ、第２区分をＣ
ｏ、Ｓｉの２つとし、各区分ごと、すなわち第１区分に
ついては１つの元素、第２の区分については複数の元素
を層状に担持させた場合である。Example 4 (Example of solid phase method) 0.75 mol% of Nb 2 was added to 100 g of BaTiO 3 powder.
O 5 powder was added, and the mixture was wet-mixed with a ball mill using 200 ml of pure water and 300 g of ZrO 2 beads having a diameter of 1.5 mm. The mixed dispersion was filtered, and the resulting powder was
Heat treatment (calcination) was performed at 0 ° C. for 1 hour. 0.5 mol% of CoO and 1.5 mol% of S
After adding iO 2 and crushing and dispersing in a ball mill in the same manner as described above, the mixture was filtered and dried. The ceramic dielectric material powder thus obtained was molded, and the molded body was fired at 1300 ° C. for 2 hours. When the temperature characteristic of the dielectric constant of the fired body was measured with an impedance analyzer, it was found that the X7R characteristic of the EIA standard was satisfied, the variation was small, and the performance was stable. In this embodiment, three elements are divided as subcomponents into BaTiO 3 powder as a main component, the first section is Nb, and the second section is C.
o and Si, and each section, that is, one element in the first section and a plurality of elements in the second section in a layered manner.
【００２２】比較例１ ＢａＴｉＯ3 粉末１００ｇと０．７５ｍｏｌ％のＮｂ2
Ｏ5 粉末と０．５ｍｏｌ％ＣｏＯ粉末と１．５ｍｏｌ％
ＳｉＯ2 を、純水２００ｍｌ、直径１．５ｍｍのＺｒＯ
2 ビーズ３００ｇを用いたボールミルで湿式混合し、乾
燥してセラミックス誘電体材料粉末を得た。このように
して得られたセラミックス誘電体材料粉末を用いて成形
し、その成形体を１３００℃、２時間焼成した。その焼
成体の誘電率の温度特性をインピーダンスアナライザー
で測定したところ、ＥＩＡ規格のＸ７Ｒ特性を満足しな
かった。この比較例は、主成分のＢａＴｉＯ3 粉末に副
成分として３つの元素を区分せず３者を一緒に担持させ
た場合である。Comparative Example 1 100 g of BaTiO 3 powder and 0.75 mol% of Nb 2
O 5 powder and 0.5 mol% CoO powder and 1.5 mol%
The SiO 2, pure water 200ml, ZrO with a diameter of 1.5mm
The mixture was wet-mixed in a ball mill using 300 g of 2 beads and dried to obtain a ceramic dielectric material powder. The ceramic dielectric material powder thus obtained was molded, and the molded body was fired at 1300 ° C. for 2 hours. When the temperature characteristics of the dielectric constant of the fired body were measured with an impedance analyzer, the temperature characteristics did not satisfy the EIA standard X7R characteristics. This comparative example is a case in which three elements are supported together without dividing three elements as subcomponents on BaTiO 3 powder as a main component.
【００２３】[0023]
【発明の効果】本発明によれば、セラミックス原料粉末
から得られる主成分に副成分を均一に固溶し、さらにそ
の均一性をより高めることができ、また、副成分による
主成分の粒界が均一になる焼成体のセラミックス、これ
が得られるセラミックス材料粉末及びこれらの製造方法
を提供することができ、これにより、電子部品用セラミ
ックスについて誘電率の温度特性等の電気特性の安定性
を向上し、そのバラツキを小さくし、最近の小型化、高
性能化の電子部品の製造を可能にし、しかも特別に新た
な設備を必要とすることなく、生産性が良く、コスト的
に有利に提供することができる。According to the present invention, the sub-component can be uniformly dissolved in the main component obtained from the ceramic raw material powder, and the uniformity thereof can be further improved. It is possible to provide a fired body ceramic having uniformity, a ceramic material powder obtained therefrom, and a method for producing the same, thereby improving the stability of electrical characteristics such as temperature characteristics of dielectric constant of ceramics for electronic components. , Which makes it possible to manufacture electronic components of smaller size and higher performance in recent years, and at the same time offers good productivity and cost advantage without requiring special new equipment. Can be.
フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｈ０１Ｇ 4/12 ４１８ Ｈ０１Ｇ 4/12 ４１８ (72)発明者 平野 眞一 愛知県知多郡東浦町大字緒川字丸池台３− ２Continuation of the front page (51) Int.Cl. 6 Identification symbol FI H01G 4/12 418 H01G 4/12 418 (72) Inventor Shinichi Hirano 3-2 Maruikedai Ogawa, Higashiura-cho, Chita-gun, Aichi Prefecture
Claims (11)
分としての無機化合物粉末粒子表面に副成分として複数
の元素を区分して各区分ごとに層状に担持させたセラミ
ックス材料粉末。1. A ceramic material powder in which a plurality of elements are divided as subcomponents on the surface of an inorganic compound powder particle as a main component obtained from a ceramic raw material powder and supported in layers for each of the divisions.
せた構成は副成分の複数の元素の各区分の元素が主成分
となる無機化合物粉末粒子に対して拡散速度の小さい元
素から大きい元素の順に内側から外側に順次担持されて
いる構成である請求項１に記載のセラミックス材料粉
末。2. A structure in which a plurality of elements are supported in a layered manner in each section is formed from an element having a small diffusion rate to an inorganic compound powder particle whose main component is an element in each section of a plurality of subcomponents. The ceramic material powder according to claim 1, wherein the ceramic material powder is configured to be sequentially supported from inside to outside in the order of elements.
成分としての無機化合物粉末粒子の粒径の１／５より大
きくない粒径で担持されている請求項１又は２に記載の
セラミックス材料粉末。3. The method according to claim 1, wherein the elements in each of the plurality of subcomponents are supported with a particle size not larger than 1/5 of the particle size of the inorganic compound powder particles as the main component. Ceramic material powder.
ラミックス材料粉末を用いた電子部品用セラミックス。4. A ceramic for electronic parts using the ceramic material powder according to claim 1.
持は主成分としての無機化合物粉末粒子に副成分の１の
区分の元素又は該１の区分の元素の化合物の粉末を湿式
混合した後熱処理を行なう工程と、この工程で得られた
粉末に他の１の区分の元素又は該他の１の区分の元素の
化合物の粉末を湿式混合した後熱処理を行ない、順次こ
れを繰り返す工程を有することにより請求項１ないし３
のいずれかに記載のセラミックス材料粉末を製造するセ
ラミックス材料粉末の製造方法。5. The method of carrying an element of each of a plurality of sub-elements by wet mixing a powder of an element of one of the sub-components or a powder of a compound of the one of the sub-elements with inorganic compound powder particles as a main component. And then heat-treating the powder obtained in this step with a powder of another one of the elements of the class or a compound of the compound of the other one of the classes, heat-treating the powder, and sequentially repeating the steps. Claims 1 to 3
A method for producing a ceramic material powder according to any one of the above.
持は主成分としての無機化合物粉末粒子に副成分の１の
区分の元素又は該１の区分の元素の化合物の粉末を湿式
混合した後熱処理を行なう工程と、この工程で得られた
粉末に他の１の区分の元素又は該他の１の区分の元素の
化合物の粉末を湿式混合した後熱処理を行ない、順次こ
れを繰り返す工程を有し、かつ最後の区分の元素又は該
最後の区分の元素の化合物の粉末については湿式混合を
行ったのち熱処理を行わないことにより請求項１ないし
３のいずれかに記載のセラミックス材料粉末を製造する
セラミックス材料粉末の製造方法。6. The method of carrying a plurality of sub-elements in each category by wet-mixing the inorganic compound powder particles as a main component with the powder of the element of the first category or the compound of the first category. And then heat-treating the powder obtained in this step with a powder of another one of the elements of the class or a compound of the compound of the other one of the classes, heat-treating the powder, and sequentially repeating the steps. The powder of the element of the last category or the compound of the element of the last category is subjected to wet mixing and then not subjected to heat treatment, whereby the ceramic material powder according to any one of claims 1 to 3 is obtained. Manufacturing method of ceramic material powder to be manufactured.
持は液中において主成分としての無機化合物粉末粒子に
副成分の１の区分の元素又は該１の区分の元素の化合物
の表面イオン交換反応及び／又は沈殿反応を用いて付着
させる工程と、この工程で得られた粉末に液中において
他の１の区分の元素又は該他の１の区分の元素の化合物
のイオン交換反応及び／又は沈殿反応を用いて付着さ
せ、順次これを繰り返す工程を有することにより請求項
１ないし３のいずれかに記載のセラミックス材料粉末を
製造するセラミックス材料粉末の製造方法。7. The support of an element of each category of a plurality of elements of a sub-component is carried out in the liquid of the inorganic compound powder particles as a main component in the liquid by the surface of the element of the one category of the sub-component or the compound of the element of the one category. Adhering using an ion exchange reaction and / or a precipitation reaction, and performing ion exchange reaction of another one of the elements or a compound of the other one of the elements in a liquid on the powder obtained in this step; The method for producing a ceramic material powder according to any one of claims 1 to 3, further comprising a step of depositing and / or sequentially repeating the deposition using a precipitation reaction.
持は主成分としての無機化合物粉末粒子に副成分の１の
区分の元素又は該１の区分の元素の化合物を気化させて
付着させる工程と、この工程で得られた粉末に他の１の
区分の元素又は該他の１の区分の元素の化合物を気化さ
せて付着させ、順次これを繰り返す工程を有することに
より請求項１ないし３のいずれかに記載のセラミックス
材料粉末を製造するセラミックス材料粉末の製造方法。8. The supporting of the elements of each of the plurality of sub-components is carried out by vaporizing the sub-component of the one-part element or the compound of the one-part element onto the inorganic compound powder particles as the main component. And a step of vaporizing and adhering another one of the elements of the element or a compound of the other one of the elements to the powder obtained in this step, and sequentially repeating the steps. 3. A method for producing a ceramic material powder according to any one of the above items 3.
持は主成分としての無機化合物粉末粒子に副成分の１の
区分の元素又は該１の区分の元素の化合物を主成分と副
成分の粒子に対する機械的な力に基づいて起こる両者の
化学反応であるメカノケミカル反応により付着させる工
程と、この工程で得られた粉末に他の１の区分の元素又
は該他の１の区分の元素の化合物を該メカノケミカル反
応により付着させ、順次これを繰り返す工程を有するこ
とにより請求項１ないし３のいずれかに記載のセラミッ
クス材料粉末を製造するセラミックス材料粉末の製造方
法。9. The support of the element of each category of the plurality of elements of the auxiliary ingredient is carried out by adding the element of the category of the auxiliary ingredient or the compound of the element of the same category to the inorganic compound powder particles as the main ingredient. Adhering by a mechanochemical reaction, which is a chemical reaction of the two based on the mechanical force on the particles of the component, and adding another element of the class or the other class to the powder obtained in this step. The method for producing a ceramic material powder according to any one of claims 1 to 3, comprising a step of attaching a compound of an element by the mechanochemical reaction and sequentially repeating the steps.
セラミックス材料粉末又は該セラミックス材料粉末を仮
焼した仮焼粉末を用いて成形体を得る工程と、該成形体
を焼成する工程を有する電子部品用セラミックスの製造
方法。10. A step of obtaining a molded body using the ceramic material powder according to claim 1 or a calcined powder obtained by calcining the ceramic material powder, and a step of firing the molded body. Manufacturing method of ceramics for electronic parts.
し９のいずれかに記載のセラミックス材料粉末の製造方
法により製造された請求項１０に記載の電子部品用セラ
ミックスの製造方法。11. The method for producing a ceramic for electronic parts according to claim 10, wherein the ceramic material powder is produced by the method for producing a ceramic material powder according to any one of claims 5 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33139796A JP3376468B2 (en) | 1996-11-28 | 1996-11-28 | Manufacturing method of ceramic material powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33139796A JP3376468B2 (en) | 1996-11-28 | 1996-11-28 | Manufacturing method of ceramic material powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10158059A true JPH10158059A (en) | 1998-06-16 |
| JP3376468B2 JP3376468B2 (en) | 2003-02-10 |
Family
ID=18243246
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33139796A Expired - Fee Related JP3376468B2 (en) | 1996-11-28 | 1996-11-28 | Manufacturing method of ceramic material powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3376468B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001326132A (en) * | 2000-05-18 | 2001-11-22 | Matsushita Electric Ind Co Ltd | Reduction-resistant dielectric composition and laminated ceramic capacitor using the same |
| JP2007091549A (en) * | 2005-09-29 | 2007-04-12 | Showa Denko Kk | Shell component-containing perovskite composite oxide powder and its manufacturing method |
| JP2008162817A (en) * | 2006-12-27 | 2008-07-17 | Samsung Electro Mech Co Ltd | Dielectric ceramic material and its manufacturing method as well as ceramic capacitor |
| JP2016117599A (en) * | 2014-12-18 | 2016-06-30 | 株式会社サムスン日本研究所 | Method for production of dielectric ceramic particle, and dielectric ceramic particle |
| JP2019089705A (en) * | 2019-01-28 | 2019-06-13 | サムソン エレクトロ−メカニックス カンパニーリミテッド． | Manufacturing method for dielectric ceramic particle and dielectric ceramic |
-
1996
- 1996-11-28 JP JP33139796A patent/JP3376468B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001326132A (en) * | 2000-05-18 | 2001-11-22 | Matsushita Electric Ind Co Ltd | Reduction-resistant dielectric composition and laminated ceramic capacitor using the same |
| JP4552272B2 (en) * | 2000-05-18 | 2010-09-29 | パナソニック株式会社 | Multilayer ceramic capacitor |
| JP2007091549A (en) * | 2005-09-29 | 2007-04-12 | Showa Denko Kk | Shell component-containing perovskite composite oxide powder and its manufacturing method |
| JP2008162817A (en) * | 2006-12-27 | 2008-07-17 | Samsung Electro Mech Co Ltd | Dielectric ceramic material and its manufacturing method as well as ceramic capacitor |
| JP2016117599A (en) * | 2014-12-18 | 2016-06-30 | 株式会社サムスン日本研究所 | Method for production of dielectric ceramic particle, and dielectric ceramic particle |
| JP2019089705A (en) * | 2019-01-28 | 2019-06-13 | サムソン エレクトロ−メカニックス カンパニーリミテッド． | Manufacturing method for dielectric ceramic particle and dielectric ceramic |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3376468B2 (en) | 2003-02-10 |
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