JP3376468B2 - Manufacturing method of ceramic material powder - Google Patents
Manufacturing method of ceramic material powderInfo
- Publication number
- JP3376468B2 JP3376468B2 JP33139796A JP33139796A JP3376468B2 JP 3376468 B2 JP3376468 B2 JP 3376468B2 JP 33139796 A JP33139796 A JP 33139796A JP 33139796 A JP33139796 A JP 33139796A JP 3376468 B2 JP3376468 B2 JP 3376468B2
- Authority
- JP
- Japan
- Prior art keywords
- powder
- elements
- component
- section
- compound
- 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
Links
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Ceramic Capacitors (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、セラミックス材料
粉末の製造方法に関する。The present invention relates to relates to a method of manufacturing a ceramics material <br/> Powder.
【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 Currently, ceramics are widely used in electronic parts. Examples thereof include ceramic substrates, ceramic capacitors, inductor cores, ceramic filters, ceramic oscillators, various sensors, and high frequency components. Most of the compositions of ceramic dielectric materials and ceramic magnetic materials used for these parts are occupied by metal oxides. For example, a ceramics dielectric material is prepared by mixing and pulverizing dielectric material powders such as barium carbonate, titanium oxide, zirconium oxide, etc. at a predetermined ratio, and then calcining the mixture to form 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 to granulate, and the granulated material is subjected to so-called dry molding, for example, compression molding into a plate shape, and the molded material is fired, and electrodes are formed on the fired body to form a ceramic capacitor. A large number of green sheets are formed by performing so-called wet molding, in which a sheet-like body is formed by using a slurry obtained by making an organic binder or the like in the material powder, and forming an internal electrode material on each green sheet. A laminated ceramic capacitor is created by forming and laminating a paste film 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。The electrical properties such as dielectric properties and magnetic properties of the fired body obtained by using such a ceramic material powder greatly depend on the composition of the material, for example, the metal component,
Since the composition of the metal component has a great influence on the fine structure of the fired body, a small amount of a metal component such as a valency control agent or a sintering aid is added as an auxiliary component to the ceramic material powder, and It is important to control the electric characteristics and the fine structure, but the influence on the electric characteristics is different depending on the kind of the element of each metal component added. For example, a metal component element that exhibits its characteristics by forming a solid solution in the main component of ceramics,
There is a metal component element that does not form a solid solution and is present at the crystal grain boundary or triple point of the fired body and exerts a characteristic. In any case, it is necessary that a small amount of metal component be uniformly present in the ceramic fired body in order to reduce variations in electrical characteristics and stabilize, and also to obtain a fine structure. As a method of adding, for example, a metal component as a sub-component to the ceramic material powder, a metal oxide powder of the ceramic material is mixed with a sub-component metal powder or a carbonate or oxide of the metal and wet-mixed with a ball mill or the like. A method of firing a formed body after calcination of the dry powder or using it as it is, adding an aqueous solution containing a metal ion as a subcomponent to a slurry of a metal oxide powder of a ceramic material, and adding the metal ion to a soda salt or an ammonium salt. A method of precipitating a mixture of the metal oxide powder and the precipitate by precipitating with a precipitating agent such as, a slurry obtained by adding a metal compound and a binder as subcomponents to the metal oxide powder of the ceramic material and spray drying. The method of calcination after granulating is used.
【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, in any of the above methods, the ceramic material powder obtained by adding the necessary subcomponents to the main material ceramic material powder at one time and calcining is used, or Using the ceramic material powder obtained by adding a sub-component to the ceramic material powder by the method described in 1 above, molding and firing, the metal component element that exhibits its characteristics by forming a solid solution with the above-mentioned main component or the crystal of the fired body When using multiple components of metal component elements that are present at grain boundaries and triple points and exhibit characteristics, the solid solution state differs for each crystal grain of the fired body due to the difference in diffusion rate of each element, and more than one element Due to the presence of a mixture of particles, the state of the grain boundaries is likely to be non-uniform, and if a trace amount of subcomponents are non-uniformly present in the fired body, the stability of electrical characteristics can be obtained as described above. , It is difficult to smaller the variation. In particular, there have been remarkable advances in miniaturization and high performance of electronic parts in recent years, and for miniaturization of parts, it is necessary to control the fine structure of the ceramic fired body and the electrical properties more sophisticatedly. For that purpose, as described above, it is necessary that a trace amount of the auxiliary component, for example, the metal component is 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 a subcomponent is uniformly solid-dissolved in the main component and the uniformity thereof can be further improved, a ceramic material powder capable of obtaining the same, and a manufacturing method thereof. To provide. A second object of the present invention is to provide a ceramic of a fired body in which the grain boundaries of the main component due to the subcomponents are uniform, a ceramic material powder from which it can be obtained, and a method for producing these. A third object of the present invention is to provide a ceramic of a fired body which has good stability of electric characteristics such as temperature characteristics of permittivity and has small fluttering, a ceramic material powder capable of obtaining the same, and a manufacturing method thereof. . Fourth of the present invention
It is an object of the present invention to provide a ceramic of a fired body that enables the recent manufacture of electronic components with smaller size and higher performance, a ceramic material powder that can obtain the same, 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 cost effective without requiring any special 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製造する方法において、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仮焼を行
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
合した後仮焼を行なう工程を有するセラミックス材料粉
末の製造方法を提供するものである。また、本発明は、
（２）、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
材料粉末を製造する方法において、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仮焼を行なう工程と、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仮焼を
行なわない工程を有するセラミックス材料粉末の製造方
法、（３）、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
クス材料粉末を製造する方法において、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る工程を有するセラミックス材
料粉末の製造方法、（４）、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製造する方法において、
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セラミックス材料
粉末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。なお、上記（１）〜（４）におい
て、「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
であるセラミックス材料粉末の製造方法」、「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
ているセラミックス材料粉末の製造方法」の少なくとも
一つの限定を設けてもよい。 In order to solve the above-mentioned problems, the present invention (1) divides a plurality of elements as sub-components on the surface of an inorganic compound powder particle as a main component obtained from a ceramic raw material powder. In the method of manufacturing ceramic material powder supported in layers for each section ,
Of each element of the multiple elements of
Inorganic compound powder particles include elements belonging to one of the sub-components or the one
Calcination is performed after the powders of the compounds of the
The step of rinsing and the powder obtained in this step
Wet-mix powder of compound of element or other 1st class element
Ceramic material powder having a step of calcining after combination
The present invention provides a method for manufacturing a powder . Further, the present invention is
( 2 ) As a main component obtained from ceramic raw material powder
Inorganic compound powder with multiple elements as sub-components on the particle surface
Ceramics that are divided into layers and supported in layers for each category
In the method for producing the material powder, the loading of the element of each section of the plurality of elements of the sub-component is carried out by the powder of the inorganic compound powder particles as the main component, the element of the one section of the sub-component or the compound of the element of the first section. Is wet-mixed and then calcined , and the powder obtained in this step is wet-mixed with powder of another element of the other category or a compound of the other one category of element and then calcinated.
The method of manufacturing ceramics material powder having a step is not performed, (3), obtained from the ceramic raw material powder composed mainly
Inorganic compound powder as a plurality of secondary components on the surface
Ceramics in which elements are divided and supported in layers for each division
In the method for producing a powder material, the supporting of the element of each section of the plurality of elements of the subcomponent is carried out in the liquid by the inorganic compound powder particles as the main ingredient A step of attaching the compound of the present invention by a surface ion exchange reaction and / or a precipitation reaction, and the powder obtained in this step, in the liquid, of another group of elements or a compound of the other group of elements. the method of manufacturing Rousset La mix material powder having a step of adhering using an ion exchange reaction and / or precipitation reactions, (4), the ceramic raw material powder
By-product on the surface of the obtained inorganic compound powder particles
Multiple elements are divided into parts and carried in layers for each classification
In the method for producing the ceramic material powder,
Supporting the elements of each sub-component of the plurality of sub-components is carried out by using an inorganic compound powder particle as the main component, the sub-component 1 sub-element or a compound of the one sub-element as a machine for the main component and sub-component particles. And a compound of another element of the other section is attached to the powder obtained in this step by a mechanochemical reaction, which is a chemical reaction of the two occurring based on the physical force. deposited by mechanochemical reaction, there is provided a sequentially manufactured how the ruse La mix material powder having a step of repeating this. In the above description, “supporting in layers for each section” may be “supporting in layers by stacking for each section”. In addition, "an element of the 1st category or a compound of the element of the 1st category" and "an element of the other 1 category or a compound of the element of the 1st category" mean that the element of the category is singular And there are multiple cases,
A compound containing the element as a constituent is generally used, but it is shown that it may be a simple substance. In the above (1) and other inventions that cite this, it is preferable that "carry in layers in each section" means "carry at least two layers in layers in each section". In addition, the above (1) to (4) smell
, "Multiple elements are supported in layers for each section
Indicates that the element of each category of multiple elements of the subcomponents is the main component.
Organic compound powder particles to small to large diffusion rate
A structure in which the threshold elements are sequentially loaded from the inside to the outside.
In a method of manufacturing a ceramic material powder "," accessory ingredients
Inorganic compounds as the main component of each category of multiple elements
Supported with a particle size not larger than 1/5 of the particle size of powder particles
Of the method for producing ceramics material powder "
There may be one limitation.
【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, in the case of obtaining ceramic dielectric material powder particles, for example, carbonates such as barium carbonate and strontium carbonate, titanium oxide, and oxides. Ba (Ti, Z) obtained by selecting a dielectric material powder such as an oxide such as zirconium according to the composition of each material, mixing and pulverizing at a predetermined ratio, and then calcining this.
r) Metal oxide powder particles having a composition such as O 3 and SrTiO 3 can be mentioned. In addition, as the elements of “dividing a plurality of elements as sub-components on the surface of the inorganic compound powder particles as the main component and supporting them in layers in each division”, Co, Nb, A
1, Si, Mn, rare earth metals, alkaline earth metals and the like are mentioned, and these may be one kind or plural kinds. Generally, it is used as a valence control agent, a sintering aid and the like. "Dividing multiple elements and loading each element in layers"
It means to carry one or more elements concentrically on the particles of the main component in a concentric manner. As for the element, those having a higher diffusion rate on the particles of the main component are placed on the outer side, and those having a lower diffusion rate are placed on the inner side. Preferably, for example Ba
For (Ti, Zr) O 3 particles, Nb, Co, and Si are carried in order from the inside to the outside. This makes it possible to even out the diffusion amount of each of the subcomponents with respect to the central particle when performing firing, which is preferable because the solid solution state of the subcomponent can be made uniform by that much. It is called a particle having a so-called core-shell structure in which a shell having a plurality of layers is formed in the nucleus, and the effect can be greatly exhibited. Not only when each element of a plurality of elements is divided and each layer is supported in a layered manner, but also a plurality of elements among a plurality of elements is defined as one division, and the divided plurality of elements are formed into one layered shape. It is also included in the case of being supported on, and also in the case of combining these cases.
【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。In the present invention, there are a solid phase method, a liquid phase method, a vapor phase method and a mechanochemical method for supporting the elements of the respective subdivided plural elements on the powder of the inorganic compound powder as the main ingredient. You may use these in combination. In the solid-phase method, an inorganic compound powder as a main component is mixed with a powder of an element of one group of a plurality of sub-components or a compound of the element of the one group, such as an oxide powder of the above metal and a medium such as water. Stir with a ball mill or the like, wet mix the powders, and heat-treat them to attach their subcomponents to the inorganic compound powder particles and carry them,
Then, the powder particles carrying the sub-components are mixed with powders of the compound of the other one of the sub-components, for example, compounds similar to the above by a ball mill or the like in the same manner, the powders are wet mixed, and heat treated. Is carried out on the layer of the component of the element of the first subcomponent by carrying out, and thereafter each element is sequentially carried in the same manner to obtain a ceramic material powder. The powder of the compound of the last category, for example, a compound similar to the above, may be wet-mixed and then dried to obtain a ceramic material powder without heat treatment. At this time, it is necessary to select an appropriate heat treatment temperature.
The temperature can be from 0 to 1100 ° C. for 1 to 60 minutes, which can be said to be calcination. By doing so, the component of the subordinate element diffuses to the surface of the inorganic compound powder particles of the main component, so that it can be easily carried.
【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 addition, the liquid phase method uses one of a plurality of subordinate elements.
At least one of a salt and an alkoxide having an element of the category 1 or a compound of the element of the category 1 as a constituent component, a chelate compound and other organic compounds of metals, etc. is dissolved 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 to occur on the surface of the inorganic compound powder particles, and the element or each element (the former Is a singular case, the latter case is a plural case, the same shall apply hereinafter), and then the liquid containing the powder particles carrying the sub-components is added to the element of the other one of the plurality of sub-components or the other element. A solution having at least one kind of a salt and an alkoxide having a compound of the first category as a constituent, a chelate compound, and an organic compound of a metal, etc., dissolved in a solvent is added to form a surface on the layer of the component of the first subcomponent. This is a method in which at least one of an ion exchange reaction and a precipitation reaction is caused to carry the element or a component of each element, and then each element is sequentially carried in the same manner. Dispersion may be used instead of dissolution. The surface ion exchange reaction is a reaction in which a metal ion replaces a proton of an OH group on the particle surface, and the precipitation reaction is a reaction in which a metal ion is adsorbed on the surface as a hydroxide by a precipitating agent. 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, but if the optimization is performed, the precipitation of the component of the subcomponent element will be the inorganic component of the main component. Since this occurs on the surface of the compound powder particles or on the deposited film of the component of the element of the other subcomponent supported on this, a uniform coating film of each element or a plurality of elements can be formed. Examples of the optimization include selection of conditions such as pH of the liquid causing the above reaction, presence or absence of a hydrolyzing agent, its concentration, and reaction temperature. For example, in the precipitation reaction, when a hydrolyzing agent is used, the solvent in which the reaction is caused is preferably an aqueous liquid in a neutral to alkaline range, for example, ammonia water is preferable, but not limited to this, alkali metal, etc. Those that volatilize or decompose and do not remain are preferable to those that remain when obtaining the subsequent ceramic material or when firing a molded body using the material. 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 water alone may be used as the hydrolyzing agent, when ammonia water is used, the concentration of ammonia water (NH 4 OH) in a liquid such as an organic solvent containing the inorganic compound powder is 0. 01 to 1
0 mol / l is preferred, more preferably 0.1-5 m
ol / l. If it is less than 0.01 mol / l, the amount of aqueous ammonia increases, and the productivity tends to deteriorate.
If it is more than 10 mol / l, an ammine complex is likely to be formed, and it becomes difficult to coat the inorganic compound having a desired composition. Further, the amount of NH 4 OH added is preferably 1 to 2 equivalents with respect to the organic compound of the metal from the viewpoint of productivity and composition control 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 alcohol solvent such as ethanol or propanol, or a solvent capable of dissolving the above-mentioned hydrolyzing agent such as ethanolamine, that is, a polar solvent, but this polar solvent is used as another organic solvent such as benzene or toluene. An organic solvent having a certain degree of polarity, in which 0 to 40% of at least one of the above is mixed, may be used as long as it can dissolve the hydrolyzing agent. When dispersing the inorganic compound powder in the organic solvent, a surfactant is used, and the inorganic compound powder may be easily dispersed in the organic solvent. If an anionic surfactant is used, the inorganic compound powder It is also possible to make it easier for the cation of the hydrolyzate and the hydrolyzate of the organic compound of the metal by this to be adsorbed to the anion adsorbed on the It is preferable because it can be decomposed and removed when it is obtained or when a molded product 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 kind of salt or alkoxide having an element or a compound of an element as a constituent, an organic compound of a metal such as a chelate compound and the like means at least one kind of salt, at least one kind of organic compound of metal, At least one of each of a salt and an organic compound of a metal can be mentioned.
At least one of the organic compounds of the metal is at least one belonging to at least one of the above-exemplified metals such as hydrolyzable alkoxides and chelate compounds.
Species, that is, at least one kind of alkoxides, at least one kind of chelate compounds, and at least one kind of both of them, and specific examples of the alkoxides include lower alkoxides such as ethoxide and propoxide.
Preferred examples of diketone-based compounds and chelate compounds include acetylacetonate and DPM. As the salt, specifically, the metal chlorides exemplified above,
Examples include nitrates and the like. In these metal organic compounds, for example, metal ions are coordinated with the adsorbed water on the surface of the hydrophilic inorganic compound powder particles, so that the hydrolysis of the metal organic compound by the hydrolyzing agent is selectively performed on the surface. Since the precipitated hydroxide or oxide is also hydrophilic, its growth is performed 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.
It is preferably ol / l. If it is too low, the productivity tends to deteriorate, and if it is too high, it becomes difficult to dissolve it. The amount of the salt or 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 above-mentioned inorganic compound powder particles, a metal organic compound is dissolved in an organic solvent, and the solution and the inorganic compound powder are dispersed in a dispersion liquid. Further, heat treatment of the slurry obtained by adding a hydrolyzing agent makes it possible to adsorb the organic compound of the metal well at its molecular level, and in that state, it is hydrolyzed by the hydrolyzing agent. This is effective because it accelerates the precipitation reaction of hydroxide or oxide that is a hydrolyzate. The heating temperature is preferably 80 ° C. from the viewpoint of strengthening the coating film of the metal compound, but it is preferably heated to 60 ° C. or higher in order to promote the crystallization. The most suitable aging temperature is 60 to 80 ° C. Further, in order to improve the uniformity of the coating film, it is important to carry out hydrolysis by a hydrolyzing agent uniformly in the slurry, and for that purpose, stirring the slurry is effective. The speed is preferably 100 to 1000 rpm (revolutions per minute), and if it is slower than 100 rpm, the uniformity of the obtained coating film is not sufficient, and if it is higher than 1000 rpm, the cost of the 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。In this way, a ceramic material powder carrying a metal hydroxide or an oxide can be obtained. To separate this from the liquid containing it, filtration with a filter press or the like is sufficient. The anion does not remain even when spray-dried by spraying this contained liquid, and it can be used in consideration of production equipment. 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, but 600 ° C. or lower is preferable in consideration of production equipment. The 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。Further, the vapor phase method uses one of a plurality of subordinate elements.
A substance having a relatively high vapor pressure is used as the element of the category 1 or the compound of the element of the category 1, and the substance is vaporized to deposit the vaporized substance on the surface of the inorganic compound powder particles of the main component and carry it. A substance having a relatively high vapor pressure is used as a compound of the element of the other one of the plurality of elements of the subcomponent or the compound of the other one of the elements of the plurality of subcomponents on the surface of the powder particles supporting the subcomponent, and vaporizes the substance. In this method, the vaporized substance is deposited and supported on the layer of the component of the element of the first subcomponent, and then each element is sequentially supported in the same manner. In this case, it is preferable that the compound of the subordinate element is a substance that vaporizes at 2000 ° C. or less, that is, at a temperature not higher than 2000 ° C., from the viewpoint of economical efficiency of manufacturing equipment. In this case, the 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。Further, the method using the mechanochemical reaction is carried out by using one of the inorganic compound powder as the main component and a plurality of sub-elements.
Powder of a compound of the element of the first category or a compound of the element of the first category is dry-mixed, and a mechanochemical reaction occurs on the particle surfaces of the two powders, that is, a mechanical force is applied to the particle surface, for example, when using a Reiki machine. By adding a chemical reaction between them (the particles are rubbed by the shearing force and the new surface is chemically active, the chemical reaction can occur) The powder carrying this subcomponent and then the other one of the plurality of subcomponent elements
Powder of a compound of the element of the section 1 or the element of the other section 1 is dry-mixed, and a mechanochemical reaction is carried out on the particle surfaces of both powders, and the component of the element is supported in the same manner as above,
Hereinafter, it is a method of sequentially supporting the subordinate elements 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。As described above, the ceramic material powder obtained by supporting the plural particles of the subcomponents on the inorganic compound powder particles as the main component by a method such as the solid phase method is molded or calcined as it is, and then the provisional By molding a fired powder and firing each molded product, it is possible to obtain a ceramic fired body of the above various electronic components, improve its electrical characteristics, improve its stability, and reduce its variation. You can
【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 will be described with reference to the following examples. When a plurality of sub-component elements are divided into particles of an inorganic compound powder as a main component and the elements of each division are supported in layers, each element The action on the main component of can be controlled according to its property, and for example, the one having a higher diffusion rate can be supported on the outer side according to the difference in the diffusion rate, and the outer layer can be formed in this way. The amount of each element diffused into the crystal particles of the main component of the fired body using the obtained ceramic material powder can be leveled, and the effect of the addition of a small amount of additive such as an auxiliary component is maximized. Can be made.
【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。EXAMPLES Examples of the present invention will be described below. 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 heated at 80 ° C. for 3 hours.
Then, a part of the powder was filtered, and the powder was mixed with an ICP emission spectrometer (Inductively Coupled Pl).
As a result of confirmation by asma), it was confirmed that Nb was supported on the surface of the BaTiO 3 powder particles. Nb was not detected in the filtrate. Then Co (NO
3 ) 2 was dissolved by adding 0.5 atom% to the above-mentioned heat-treated slurry, and 50 ml of 1.5N ammonia water was further added. When a part of it was filtered and the filtrate was examined, C
o was not detected, and the elemental component was BaTiO 3
It was confirmed that the powder was carried on the Nb film carried on the surface of the powder particles. Furthermore, 25 ml of ethanol and 50 ml of pure water are mixed, and Si (OC 2 H 5 ) 4 is added to 1.5 ml.
The mol% dissolved solution was added dropwise while stirring the slurry containing the above ammonia water. Then, the slurry was heated at 80 ° C. for 5 hours. When a part of it was filtered and the filtrate was examined, Si was not detected, and the component of this element was carried on the Co film formed on the Nb film carried on the surface of the BaTiO 3 powder particles. It was confirmed that it was done. The resulting slurry was dried. The ceramic dielectric material powder thus obtained was used for molding, and the molded body was fired at 1200 ° C. When the temperature characteristic of the dielectric constant of the fired body was measured by 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 is BaTiO 3 powder,
This is a case where three elements are divided as sub-components, the first division is Nb, the second division is Co, and the third division is Si, and each element, that is, each element is supported in a layered manner.
【００１９】参考例１（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。 Reference Example 1 ( Example of vapor phase method) 100 g of BaTiO 3 powder was placed in a reaction vessel, a vacuum was applied, Nb alkoxide was first vaporized, the vaporized product was introduced into the reaction vessel, and then Co alkoxide was introduced. Was vaporized and the vaporized product was introduced into the reaction vessel. When the composition of the obtained powder was analyzed by ICP, it was found that Nb was contained in an amount of 0.5 mol% and Co was contained in an amount of 1.5 mol% with respect to BaTiO 3 , and Nb was contained on the surface of the BaTiO 3 powder particles.
Was found to be supported, Co was supported on the coating to form the coating, and a laminated coating was formed. The ceramic dielectric material powder thus obtained was used for molding, and the molded body was fired at 1200 ° C. When the temperature characteristic of the dielectric constant of the fired body was measured by 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 of BaTi is
This is a case where two elements are divided into O 3 powder as a sub-component, the first division is Nb, the second division is Co, and each of the divisions, that is, each element is supported in a layered manner.
【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 of utilizing mechanochemical reaction) BaTiO 3 powder and 0.75 mol% Nb 2 O 5 fine powder were mixed for 10 hours by a liquor machine, and then 0.5 mol.
% CoO fine powder was added and mixed for another 24 hours. TEM-EDS analysis of the obtained powder showed that BaTi
1.5 mol% of Nb and 0.5 mol of Co with respect to O 3.
%, It was found that Nb was supported on the surface of the BaTiO 3 powder particles, Co was supported on the coating to form the coating, and a laminated coating was formed. It was confirmed to be the result of the methanochemical reaction. The ceramic dielectric material powder thus obtained was used for molding,
Baked at ° C. When the temperature characteristic of the dielectric constant of the fired body was measured by 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 divided into a main component of BaTiO 3 powder as a sub-component, the first division was Nb and the second division was Co, and each division, that is, each element was supported in a layered manner. This 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 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 is filtered and the powder obtained is 100
Heat treatment (calcination) was performed at 0 ° C. for 1 hour. 0.5 mol% of CoO and 1.5 mol% of S with respect to this heat-treated powder
After adding iO 2 and crushing and dispersing with a ball mill in the same manner as above, the mixture was filtered and dried. The ceramic dielectric material powder thus obtained was used for molding, 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 by 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, BaTiO 3 powder as the main component is divided into three elements as sub-components, the first segment being Nb and the second segment being C.
In this case, two elements, i.e., o and Si, are carried in each section, that is, one element is carried in the first section and a plurality of elements are carried in the second section in layers.
【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%
SiO 2 is pure water 200 ml, diameter 1.5 mm ZrO
Wet-mixed with a ball mill using 300 g of 2 beads and dried to obtain a ceramics dielectric material powder. The ceramic dielectric material powder thus obtained was used for molding, 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, the X7R characteristic of the EIA standard was not satisfied. In this comparative example, BaTiO 3 powder as a main component is a case where three elements are supported as a subcomponent without dividing the three elements.
【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 subcomponents can be uniformly solid-dissolved in the main component obtained from the ceramic raw material powder, and the uniformity can be further improved. It is possible to provide a ceramic of a fired body having a uniform temperature, a ceramic material powder for obtaining the same, and a method for producing the same, which improves stability of electric characteristics such as temperature characteristics of dielectric constant of the ceramics for electronic parts. , To make it possible to manufacture the electronic components of recent miniaturization and higher performance by reducing the variation, and to provide good productivity and cost advantage without requiring special new equipment. You can
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｈ０１Ｇ 4/12 ３６４ Ｈ０１Ｇ 4/12 ４１８ ４１５ Ｃ０４Ｂ 35/00 Ａ ４１８ Ｂ (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 −２ (56)参考文献 特開 平１−317154（ＪＰ，Ａ) 特開 昭64−38924（ＪＰ，Ａ) 特開 昭64−38925（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C04B 35/42 - 35/50 C04B 35/00 - 35/22 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI H01G 4/12 364 H01G 4/12 418 415 C04B 35/00 A 418 B (72) Inventor Shinichi Hirano Higashiura Town, Chita District, Aichi Prefecture Ogawa character Maruikedai 3 -2 (56) References JP-A-1-317154 (JP, A) JP-A 64-38924 (JP, A) JP-A 64-38925 (JP, A) (58) Field (Int.Cl. 7 , DB name) C04B 35/42-35/50 C04B 35/00-35/22
Claims (4)
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
ックス材料粉末を製造する方法において、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仮焼を行なう工程
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
仮焼を行なう工程を有するセラミックス材料粉末の製造
方法。 1. A method for producing a ceramic material powder in which a plurality of elements as subcomponents are sectioned on a surface of an inorganic compound powder particle as a main component obtained from a ceramic raw material powder and each layer is carried in a layered manner. Multiple of ingredients
The support of the elements of each category of the
Substance powder particles to the sub-components of the 1st category of elements or the 1st category of
A step of calcination after wet mixing the powders of elemental compounds
And the powder obtained in this step contains another element of
After wet-mixing the powder of the compound of the element of the other one category
Manufacture of ceramic material powder having a step of calcination
Method.
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
ックス材料粉末を製造する方法において、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仮焼を行なう工程
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
仮焼を行なわない工程を有するセラミックス材料粉末の
製造方法。2. Main composition obtained from ceramic raw material powder
Inorganic compound powder as a component
Ceramics that are divided into different elements and supported in layers in each section
In the method for producing a powder material powder, the loading of the element of each section of the plurality of elements of the sub-component is carried out by the powder of the inorganic compound powder as the main component of the element of the one section of the sub-component or the compound of the element of the one section. After wet-mixing the powders, calcining, and after wet-mixing the powders obtained in this step with the powders of the element of the other section or the compound of the element of the other section
Method for producing a ceramics material powder having a step is not performed calcination.
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
ックス材料粉末を製造する方法において、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る工程を有するセラミックス
材料粉末の製造方法。3. Main composition obtained from ceramic raw material powder
Inorganic compound powder as a component
Ceramics that are divided into different elements and supported in layers in each section
In the method for producing powder material powder, the loading of the elements of each section of the plurality of elements of the sub-component is carried out in the liquid by the inorganic compound powder particles as the main ingredient Ion exchange reaction of compounds of
Or a step of attaching using a precipitation reaction, and an ion exchange reaction and / or a precipitation reaction of the powder of the powder obtained in this step with the element of the other one group or the compound of the other one group of the element in the liquid. method for producing Rousset La mix material powder having a step of depositing using.
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
ックス材料粉末を製造する方法において、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セラミックス材料粉末の製造方
法。4. Main composition obtained from ceramic raw material powder
Inorganic compound powder as a component
Ceramics that are divided into different elements and supported in layers in each section
In the method for producing the powder material for powder, the supporting of the elements of each section of the plurality of elements of the sub-component is carried out by adding the element of the one section or the compound of the element of the one section of the inorganic compound powder particles as the main component. A step of attaching by a mechanochemical reaction, which is a chemical reaction of the main component and the subcomponent, which is a chemical reaction of the two caused on the basis of mechanical force, and the powder obtained in this step is provided with another element or another element the compound of an element of the first segment is adhered by the mechanochemical reaction, Rousset La mix material production method of a powder having a step of sequentially repeated.
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 JPH10158059A (en) | 1998-06-16 |
| JP3376468B2 true 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) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JP6517012B2 (en) * | 2014-12-18 | 2019-05-22 | 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． | Method of manufacturing dielectric ceramic particles and dielectric ceramic |
| JP6773381B2 (en) * | 2019-01-28 | 2020-10-21 | 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． | Dielectric Ceramic Particle Manufacturing Method and Dielectric Ceramic |
-
1996
- 1996-11-28 JP JP33139796A patent/JP3376468B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH10158059A (en) | 1998-06-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4310318B2 (en) | Method for producing dielectric ceramic powder, and multilayer ceramic capacitor produced using the ceramic powder | |
| KR100431213B1 (en) | Perovskite type composite oxide containing titanium | |
| US20010046603A1 (en) | Dispersible, metal oxide-coated, barium titanate materials | |
| CA2282503A1 (en) | Dispersible, metal oxide-coated, barium titanate materials | |
| KR100845216B1 (en) | Spherical tetragonal barium titanate particles and process for producing the same | |
| CN103214235B (en) | A kind of preparation method of microwave dielectric ceramic materials | |
| JP2006096652A (en) | Barium titanate and its manufacturing method as well as capacitor | |
| US20160035490A1 (en) | Composite oxide-coated metal powder, production method therefor, conductive paste using composite oxide-coated metal powder, and multilayer ceramic electronic component | |
| JP3376468B2 (en) | Manufacturing method of ceramic material powder | |
| KR20030059189A (en) | Production of dielectric barium titanate particles | |
| JP3306614B2 (en) | Method for producing ceramic material powder | |
| KR20150032999A (en) | Perovskite powder, manufacturing method thereof and paste composition for internal electrode comprising the same | |
| JPH0665603B2 (en) | Method for producing composite oxide ceramic powder | |
| JPH0580427B2 (en) | ||
| JPH0210089B2 (en) | ||
| JP3550498B2 (en) | Manufacturing method of ceramic powder | |
| CN103224393B (en) | A kind of preparation method of microwave dielectric ceramic materials | |
| JP2007091549A (en) | Shell component-containing perovskite composite oxide powder and its manufacturing method | |
| JPH0210091B2 (en) | ||
| JPH0826833A (en) | Production of ceramic raw material | |
| JP3531047B2 (en) | Method for producing titanate compound-based ceramic material powder | |
| KR100695760B1 (en) | Particle of barium titanate powder coated with magnesium oxide and preparation method thereof using ultrasonication | |
| KR100716124B1 (en) | Coated barium titanate particle and preparation method thereof | |
| CN109456053A (en) | A kind of high dielectric coating material of high-performance barium strontium titanate and preparation method thereof | |
| JP3182849B2 (en) | Method for producing raw material powder of dielectric ceramic composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20021022 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20071206 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081206 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091206 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091206 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101206 Year of fee payment: 8 |
|
| LAPS | Cancellation because of no payment of annual fees |