JPH06283378A - Manufacture of lead series ceramic electronic component - Google Patents
Manufacture of lead series ceramic electronic componentInfo
- Publication number
- JPH06283378A JPH06283378A JP5095245A JP9524593A JPH06283378A JP H06283378 A JPH06283378 A JP H06283378A JP 5095245 A JP5095245 A JP 5095245A JP 9524593 A JP9524593 A JP 9524593A JP H06283378 A JPH06283378 A JP H06283378A
- Authority
- JP
- Japan
- Prior art keywords
- lead
- electronic component
- wasp
- ceramic electronic
- based ceramic
- 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.)
- Withdrawn
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、鉛系セラミック電子部
品の製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a lead-based ceramic electronic component.
【０００２】[0002]
【従来の技術】鉛系セラミック電子部品とは、鉛化合物
を主成分とするセラミック組成物を原料に用いる電子部
品をいう。2. Description of the Related Art A lead-based ceramic electronic component refers to an electronic component using a ceramic composition containing a lead compound as a main component as a raw material.
【０００３】従来、セラミック体の焼成は次のように行
なわれていた。先ず、被焼成物がディスク状の単板の場
合、セッタと称されるセラミック製の支持板上に、被焼
成物の両面と支持板の支持表面とが平行になるように被
焼成物を積み重ね、または被焼成物の両面が支持板の支
持表面に垂直になるように被焼成物を立てて配置する。
次いで、このように多数の被焼成物を配置した支持板
を、アルミナまたはマグネシア製のサヤと呼ばれる容器
に収容し、この容器を炉に入れて焼成する。Conventionally, firing of a ceramic body has been performed as follows. First, when the object to be fired is a disk-shaped single plate, the objects to be fired are stacked on a ceramic support plate called a setter so that both surfaces of the object to be fired and the supporting surface of the support plate are parallel to each other. Alternatively, the object to be fired is placed upright so that both sides of the object to be fired are perpendicular to the supporting surface of the support plate.
Next, the support plate on which a large number of objects to be fired are arranged is housed in a container called alumina or magnesia sheath, and the container is put in a furnace to be fired.
【０００４】また、被焼成物が積層型セラミックチップ
コンデンサ等の積層体の場合には、一般に、積み重ねる
ことなく支持板上に配置し、ディスク状の単板と同様に
容器中で焼成する。When the material to be fired is a laminated body such as a laminated ceramic chip capacitor, it is generally placed on a support plate without being stacked and fired in a container like a disk-shaped single plate.
【０００５】以上のように、被焼成物を容器中に収容
し、実質的に密閉状態で焼成する理由は、焼成中に、セ
ラミックからのセラミック成分の蒸発をできる限り抑
え、セラミックの出発組成からのズレを少なくするとと
もに、セラミック自体の焼結を促進するためである。As described above, the reason why the material to be fired is contained in a container and fired in a substantially closed state is that evaporation of the ceramic component from the ceramic is suppressed as much as possible during firing, and the starting composition of the ceramic This is because the deviation of the ceramics is reduced and the sintering of the ceramic itself is promoted.
【０００６】特に、焼成中に液相が生成される鉛系セラ
ミックにおいては、その焼成温度が９００〜１２００℃
であり、ＰｂＯの融点〜８８０℃よりかなり高く、従っ
て、Ｐｂ成分の蒸発が生じてしまう。これを防止するた
め、鉛系セラミックでは、実質的に密閉状態の容器内で
焼成することが必要である。Particularly, in a lead-based ceramic in which a liquid phase is generated during firing, the firing temperature is 900 to 1200 ° C.
Which is considerably higher than the melting point of PbO up to 880 ° C., so that evaporation of the Pb component occurs. In order to prevent this, it is necessary for the lead-based ceramic to be fired in a substantially closed container.
【０００７】ところが、鉛系セラミックの被焼成物を支
持板上に直接配置し、実質的に密閉状態で上記容器内に
収めて焼成を行なうと、次のような問題が生ずる。However, when a lead-based ceramic article to be fired is directly placed on a support plate and is housed in the above-mentioned container in a substantially sealed state for firing, the following problems occur.
【０００８】すなわち、ＰｂＯは、焼成中に蒸発し、容
器内にＰｂＯ雰囲気を形成するが、ＰｂＯは分子量が大
きいため通常容器の底に滞留し、このため、容器の底で
ＰｂＯ濃度が過剰に高くなり、過剰のＰｂＯ雰囲気に被
われた被焼成物やその部分に、素子表面あるいは粒界に
おいてＰｂＯが析出してしまうという問題である。That is, PbO evaporates during firing to form a PbO atmosphere in the container, but since PbO has a large molecular weight, it usually stays at the bottom of the container. Therefore, the PbO concentration becomes excessive at the bottom of the container. There is a problem that PbO is deposited on the surface of the device or at the grain boundaries on the object to be fired or the portion thereof that is exposed to an excessive PbO atmosphere.
【０００９】このような問題点を解消するため、特開平
４−２０２０４４号公報においては、次のようなセラミ
ックス又はセラミックス複合材料の製造方法が提案され
ている。In order to solve such a problem, Japanese Patent Application Laid-Open No. 4-202044 proposes the following method for producing a ceramic or a ceramic composite material.
【００１０】上記特開平４−２０２０４４号公報におい
て提案されたセラミックス又はセラミックス複合材料の
製造方法は、ＰｂＯ系ペロブスカイト化合物を主成分と
するセラミックス又はその複合材料からなる被焼成体
を、容器底部から所定の高さ以上に保持して該容器に収
容し、焼成炉内で焼成するものである。In the method of manufacturing a ceramics or ceramics composite material proposed in the above-mentioned Japanese Patent Laid-Open No. 4-202044, an object to be fired made of ceramics or a composite material thereof containing PbO-based perovskite compound as a main component is predetermined from the bottom of the container. Is held in the container while being held at a height of at least 1, and fired in a firing furnace.
【００１１】この公開公報に開示された製造方法によれ
ば、被焼成体を炉内に収容される容器底部から所定の高
さ以上に保持した状態で焼成を行なっているため、Ｐｂ
Ｏの蒸気は、容器底部に滞留し、被焼成体は、ＰｂＯ蒸
気雰囲気に曝されることがなく、その結果、素子表面又
は粒界に過剰なＰｂＯが析出することが防止される。According to the manufacturing method disclosed in this publication, since the material to be fired is fired while being held at a predetermined height or more from the bottom of the container housed in the furnace, Pb
O vapor stays at the bottom of the container, and the body to be fired is not exposed to the PbO vapor atmosphere, and as a result, excessive PbO is prevented from precipitating on the device surface or grain boundaries.
【００１２】[0012]
【発明が解決しようとする課題】しかしながら、上記公
開公報に開示された従来のセラミック体の製造方法で
は、過剰のＰｂＯを滞留させるための所定容積以上の空
間が必要となり、余分なスペースが必要となるととも
に、上記ＰｂＯ滞留用空間が大き過ぎると、反対にＰｂ
Ｏが蒸発し過ぎてしまうという問題がある。However, in the conventional method for manufacturing a ceramic body disclosed in the above publication, a space of a predetermined volume or more for accumulating excess PbO is required, and an extra space is required. In addition, if the PbO retention space is too large, PbO
There is a problem that O is excessively evaporated.
【００１３】また、電極として、Ｃｕを用い、同時焼成
する場合には、焼成を還元性雰囲気内で行なわなければ
ならないが、この場合には、上記密閉容器を用いたので
は、脱バインダが充分に行なえず、焼結された電子部品
の電気的特性が低下してしまうという問題が生じてしま
う。Further, when Cu is used as the electrode and the simultaneous firing is carried out, the firing must be carried out in a reducing atmosphere. In this case, however, the use of the above-mentioned closed container is sufficient for removing the binder. However, there is a problem in that the electrical characteristics of the sintered electronic component deteriorate.
【００１４】そこで、本発明は、還元性雰囲気内でも焼
結でき、しかもＰｂＯの蒸気圧が過剰になることを防止
することができる鉛系セラミック電子部品の製造方法を
提供することを目的とするものである。Therefore, an object of the present invention is to provide a method for producing a lead-based ceramic electronic component which can be sintered even in a reducing atmosphere and can prevent the vapor pressure of PbO from becoming excessive. It is a thing.
【００１５】[0015]
【課題を解決するための手段】このような目的は、下記
（１）〜（１２）の本発明により達成される。 （１）鉛化合物を主成分とするセラミック組成物を原料
に用いる電子部品の製造方法において、その焼成工程
を、少なくとも一部が開放したコウバチを用い、還元性
ガスを該コウバチ内に供給しつつ行い、焼成中に発生す
るバインダの分解ガスおよび鉛蒸気の余剰分をコウバチ
から排出するようにしたことを特徴とする鉛系セラミッ
ク電子部品の製造方法。 （２）前記コウバチが、被焼成物を支持する支持板と、
上部が開放した状態で、前記セラミック電子部品を取り
囲む枠状体とを備えている上記（１）の鉛系セラミック
電子部品の製造方法。 （３）前記枠状体の高さが、前記被焼成物の高さ以上で
ある上記（２）の鉛系セラミック電子部品の製造方法。 （４）前記枠状体の高さが、前記被焼成物の高さ以上、
５０ｍｍ以下の範囲である上記（３）の鉛系セラミック
電子部品の製造方法。 （５）前記枠状体の上に、スペーサを介して上蓋を配置
してコウバチを構成し、前記枠状体とスペーサの間に、
コウバチ内外を連通する間隙を形成するようにした上記
（１）ないし（４）のいずれかの鉛系セラミック電子部
品の製造方法。 （６）前記スペーサが前記枠状体に一体に形成されてい
る上記（５）の鉛系セラミック電子部品の製造方法。 （７）上記（５）のコウバチを上方に積み重ねて焼成工
程を行なう鉛系セラミック電子部品の製造方法。 （８）１つのコウバチの開放率が、全表面積当たりで、
２％以上である上記（１）ないし（７）のいずれかの鉛
系セラミック電子部品の製造方法。 （９）コウバチの全上面が開放している上記（１）ない
し（８）のいずれかの鉛系セラミック電子部品の製造方
法。 （１０）焼成前における１つのコウバチにおける被焼成
物の体積のコウバチ内容積に対する占有率が６０〜１０
０％の範囲である上記（１）ないし（９）のいずれかの
鉛系セラミック電子部品の製造方法。 （１１）前記コウバチ内に還元性雰囲気を導入しつつ焼
成を行なう上記（１）ないし（１０）のいずれかの鉛系
セラミック電子部品の製造方法。 （１２）前記コウバチ内への前記還元性雰囲気の導入量
が、線速度で１〜１２０ｃｍ／ｍｉｎである上記（１
１）の鉛系セラミック電子部品の製造方法。The above objects are achieved by the present invention described in (1) to (12) below. (1) In a method of manufacturing an electronic component using a ceramic composition containing a lead compound as a main component as a raw material, the firing step is performed by using a big bee at least a part of which is supplied with reducing gas into the big bee. A method for producing a lead-based ceramic electronic component, characterized in that the binder decomposition gas and the excess lead vapor generated during firing are discharged from the wasp. (2) A support plate for supporting the object to be fired,
The method for producing a lead-based ceramic electronic component according to (1), further comprising: a frame-shaped body that surrounds the ceramic electronic component in a state in which an upper portion is opened. (3) The method for manufacturing a lead-based ceramic electronic component according to the above (2), wherein the height of the frame-shaped body is not less than the height of the object to be fired. (4) The height of the frame-shaped body is not less than the height of the object to be fired,
The method for producing a lead-based ceramic electronic component according to (3) above, which has a range of 50 mm or less. (5) An upper lid is arranged on the frame-shaped body via a spacer to form a wasp, and between the frame-shaped body and the spacer,
The method for producing a lead-based ceramic electronic component according to any one of the above (1) to (4), wherein a gap that communicates between the inside and outside of the wasp is formed. (6) The method for manufacturing a lead-based ceramic electronic component according to (5), wherein the spacer is formed integrally with the frame-shaped body. (7) A method of manufacturing a lead-based ceramic electronic component, which comprises stacking the above-mentioned wasps above and performing a firing step. (8) The open rate of one wasp is per total surface area,
The method for producing a lead-based ceramic electronic component according to any one of (1) to (7) above, which is 2% or more. (9) The method for producing a lead-based ceramic electronic component according to any one of the above (1) to (8), wherein the entire upper surface of the wasp is open. (10) The occupancy ratio of the volume of the material to be fired in a single wasp before firing to the inner volume of the wasp is 60 to 10.
The method for producing a lead-based ceramic electronic component according to any one of (1) to (9) above, which is in the range of 0%. (11) The method for manufacturing a lead-based ceramic electronic component according to any one of the above (1) to (10), wherein firing is performed while introducing a reducing atmosphere into the wasp. (12) The introduction rate of the reducing atmosphere into the wasp is 1 to 120 cm / min in terms of linear velocity.
1) A method for manufacturing a lead-based ceramic electronic component.
【００１６】[0016]
【作用および効果】本発明では、少なくとも一部が開放
したコウバチを用い、該コウバチ内に還元性雰囲気を導
入しつつ焼成を行なうようにしたので、ＰｂＯの蒸気圧
が過度に高くなることがなく、しかも残留バインダのバ
ーンアウトの際に生ずる還元性雰囲気をコウバチ外へ効
果的に排出することができるので、電気的特性の良い鉛
系セラミック電子部品を製造することができる。FUNCTION AND EFFECT In the present invention, since at least a part of the mackerel was used and firing was performed while introducing a reducing atmosphere into the mackerel, the vapor pressure of PbO did not become excessively high. Moreover, since the reducing atmosphere generated during burnout of the residual binder can be effectively discharged to the outside of the wasp, it is possible to manufacture a lead-based ceramic electronic component having good electrical characteristics.
【００１７】[0017]
【具体的構成】以下、本発明の具体的構成について詳細
に説明する。Specific Structure The specific structure of the present invention will be described in detail below.
【００１８】本発明の鉛系セラミックは、ＰｂＯ系ペロ
ブスカイト化合物および／またはＰｂＯ系パイロクロア
化合物を主成分とするセラミックである。The lead-based ceramic of the present invention is a ceramic containing a PbO-based perovskite compound and / or a PbO-based pyrochlore compound as a main component.
【００１９】ＰｂＯ系ペロブスカイト化合物としては、
Ｐｂ（Ｍｇ1/3 Ｎｂ2/3 ）Ｏ3 、ＰｂＴｉＯ3 、ＰｂＺ
ｒＯ3 、Ｐｂ（Ｍｇ1/2 Ｗ1/2 ）Ｏ3 、Ｐｂ（Ｎｉ1/3
Ｎｂ2/3 ）Ｏ3 、Ｐｂ（Ｚｎ1/3 Ｎｂ2/3 ）Ｏ3 、Ｐｂ
（Ｎｉ1/2 Ｗｂ1/2 ）Ｏ3 等が挙げられ、上記ペロブス
カイト化合物２種以上からなる複合ペロブスカイト化合
物であってもよい。As the PbO-based perovskite compound,
Pb (Mg 1/3 Nb 2/3 ) O 3 , PbTiO 3 , PbZ
rO 3 , Pb (Mg 1/2 W 1/2 ) O 3 , Pb (Ni 1/3
Nb 2/3 ) O 3 , Pb (Zn 1/3 Nb 2/3 ) O 3 , Pb
(Ni 1/2 Wb 1/2 ) O 3 and the like may be mentioned, and a composite perovskite compound composed of two or more of the above perovskite compounds may be used.
【００２０】ＰｂＯ系パイロクロア化合物としては、Ｐ
ｂ2 Ｎｂ2 Ｏ7 、Ｐｂ3 Ｎｂ2 Ｏ8、Ｐｂ3 Ｎｂ
4 Ｏ13、Ｐｂ5 Ｎｂ4 Ｏ15等が挙げられ、上記パイロク
ロア化合物２種以上からなる複合パイロクロア化合物で
あってもよい。PbO-based pyrochlore compounds include P
b 2 Nb 2 O 7 , Pb 3 Nb 2 O 8 , Pb 3 Nb
4 O 13 , Pb 5 Nb 4 O 15, etc. may be mentioned, and a composite pyrochlore compound composed of two or more of the above pyrochlore compounds may be used.
【００２１】本発明のセラミック体の組成物には、比誘
電率の温度特性等の電気的特性等の向上を図るためＭｇ
Ｏ、ＭｎＯ、Ｖ2 Ｏ5 、ＮｉＯ、ＣｏＯ等の副成分が含
有されていることが望ましい。上記副成分は、上記主成
分に対し、好ましくは、０．０１〜１０ｍｏｌ％、より
好ましくは０．０５〜２．０ｍｏｌ％含有される。The composition of the ceramic body of the present invention contains Mg in order to improve electric characteristics such as temperature characteristics of relative permittivity.
It is desirable to contain subcomponents such as O, MnO, V 2 O 5 , NiO, and CoO. The sub-component is contained in the main component in an amount of preferably 0.01 to 10 mol%, more preferably 0.05 to 2.0 mol%.
【００２２】本発明のセラミック体の組成物には、更に
焼結助剤が含有されることが望ましい。焼結助剤は、セ
ラミック体の組成によって異なるが、ＰｂＳｉＯ3 、Ｃ
ａＯ、ＳｉＯ2 等を用いることができる。It is desirable that the composition of the ceramic body of the present invention further contains a sintering aid. The sintering aid varies depending on the composition of the ceramic body, but PbSiO 3 , C
aO, SiO 2 or the like can be used.
【００２３】焼結助剤の含有量は、好ましくはセラミッ
ク体材料全体の１０wt％以下である。The content of the sintering aid is preferably 10 wt% or less of the whole ceramic body material.
【００２４】本発明で用いることのできるコウバチ１
は、図１に示したように被焼成物を載置支持するための
支持板２、および枠状体３を備えている。このコウバチ
１は、更に上記枠状体３上に被せられる上蓋４を備えて
いてもよい。このように上蓋４を備える場合には、通
常、図２に示したように、枠状体３の壁の上面と上蓋４
との間にスペーサ５を設け、コウバチ内外を連通する所
定の間隙を形成することが望ましい。上記スペーサ５
は、上記枠状体３、上蓋４と別体であっても、一体であ
ってもよい。Wasp 1 that can be used in the present invention
As shown in FIG. 1, is provided with a support plate 2 for mounting and supporting the object to be fired, and a frame-shaped body 3. The wasp 1 may further include an upper lid 4 that covers the frame-shaped body 3. When the upper lid 4 is thus provided, as shown in FIG. 2, the upper surface of the wall of the frame 3 and the upper lid 4 are usually used.
It is desirable that a spacer 5 be provided between and to form a predetermined gap for communicating the inside and outside of the wasp. The spacer 5
May be a separate body from the frame-shaped body 3 or the upper lid 4, or may be integrated.
【００２５】上記コウバチは、通常、上面全開放や一部
開放、あるいは上記スペーサを用いての側部開放によっ
て使用される。コウバチの開放率は、２〜８０％、好ま
しくは、３〜５０％、より好ましくは４〜４５％であ
る。この開放率は、コウバチを構成する全ての面、例え
ばコウバチが直方体等の６面体である場合には上面、下
面および４つの側面の全ての面に対する開放部分面積率
とする。なお、上記上面の一部開放の場合には、上記上
蓋４を枠状体３に対してずらせて配置し、そのずらせる
度合いで、上記開放率を調整するようにしてもよい。The above-mentioned wasp is usually used by opening the upper surface completely or partially, or by opening the side by using the spacer. The open rate of the wasp is 2 to 80%, preferably 3 to 50%, more preferably 4 to 45%. The open area ratio is defined as an open area ratio with respect to all the surfaces forming the wasp, for example, the upper surface, the lower surface and all the four side surfaces when the wasp is a hexahedron such as a rectangular parallelepiped. When the upper surface is partially opened, the upper lid 4 may be arranged so as to be displaced with respect to the frame body 3, and the opening rate may be adjusted by the degree of the displacement.
【００２６】上記コウバチは、その全体が同じ材料で形
成されていても、各部品毎に異なる材料で形成されてい
てもよい。その材料としては、アルミナ、ジルコニアお
よびマグネシア等が挙げられる。The above wasp may be made of the same material as a whole, or may be made of a different material for each component. Examples of the material include alumina, zirconia and magnesia.
【００２７】上記コウバチは、通常は、ＰｂＯ蒸気等が
透過できない材料で形成されるが、場合によっては、透
過性材料で形成してもよい。The above-mentioned wasp is usually made of a material that is impermeable to PbO vapor or the like, but may be made of a permeable material in some cases.
【００２８】上記コウバチ内で焼成する被焼成物の、コ
ウバチ内容積の占有率は、コウバチを支持板と枠状体で
構成する場合、焼成前において概ね６０〜１００％の範
囲であることが望ましい。この範囲外であるときには、
コウバチ内のＰｂＯ雰囲気濃度が低すぎるからである。
この場合、コウバチの高さは少なくとも被焼成物（重ね
た場合には、重ねたもの）の高さが必要である。また、
高さの上限は、５０ｍｍ程度とする。これ以上である
と、鉛系セラミック電子部品の焼成中に発生するバイン
ダの分解ガスおよび鉛蒸気の余剰分をコウバチから有効
に排出することが困難となるからである。上記コウバチ
の高さの調節は、通常、所定高さの枠状体を複数用意し
ておき、これを複数積み上げることによって行なわれ
る。例えば、１０ｍｍ高さの枠状体を準備し、３０ｍｍ
の高さのコウバチが必要な場合には上記枠状体を３つ積
み上げるといったようにである。The occupancy rate of the inner volume of the wasp of the material to be fired in the above-mentioned mackerel is preferably in the range of about 60 to 100% before firing when the mackerel is composed of the support plate and the frame. . When it is out of this range,
This is because the PbO atmosphere concentration in the wasp is too low.
In this case, the height of the wasp must be at least the height of the objects to be fired (in the case of overlapping, the overlapping ones). Also,
The upper limit of the height is about 50 mm. This is because if it is more than this, it becomes difficult to effectively discharge the decomposed gas of the binder generated during firing of the lead-based ceramic electronic component and the surplus of lead vapor from the wasp. The height of the wasp is usually adjusted by preparing a plurality of frame-shaped bodies having a predetermined height and stacking the plurality of frame-shaped bodies. For example, prepare a frame body with a height of 10 mm, and
When a big wasp is required, the above three frame-shaped bodies are stacked.
【００２９】また、被焼成物を収納したコウバチを上方
に複数段積み上げて、この状態で焼成を行なってもよ
い。この場合、コウバチの開放部分は、通常、側部とな
る。It is also possible to stack a plurality of wasps containing the objects to be fired upward and fire them in this state. In this case, the open part of the wasp is usually the side part.
【００３０】次に、本発明の誘電体磁器組成物の製造方
法について説明する。Next, a method for producing the dielectric ceramic composition of the present invention will be described.
【００３１】出発原料としては、セラミック組成物を構
成する金属元素の酸化物、例えば酸化鉛、酸化マグネシ
ウム、酸化タングステン、酸化鉄、酸化ニオブ等を用い
ればよい。また、焼成により酸化物となり得る各種化合
物、例えば、炭酸塩や蓚酸塩などを用いてもよい。出発
原料の配合比率は、各金属元素の比率が最終組成と同じ
となるように選択する。As the starting material, oxides of metal elements constituting the ceramic composition, such as lead oxide, magnesium oxide, tungsten oxide, iron oxide and niobium oxide, may be used. Also, various compounds that can be converted into oxides by firing, such as carbonates and oxalates, may be used. The mixing ratio of the starting materials is selected so that the ratio of each metal element is the same as the final composition.
【００３２】出発原料の混合は、ボールミルなどを用い
て湿式で行なうことが好ましい。混合後、仮焼を行な
う。上記仮焼は、８００〜９００℃程度の温度で、１〜
４時間程度行なうことが好ましい。仮焼後、それぞれボ
ールミル等により粉砕する。The mixing of the starting materials is preferably carried out wet using a ball mill or the like. After mixing, calcination is performed. The calcination is performed at a temperature of about 800 to 900 ° C. for 1 to
It is preferably carried out for about 4 hours. After calcination, each is crushed by a ball mill or the like.
【００３３】次に、仮焼体粉末にポリビニルアルコール
等のバインダを加えて所定形状に成形する。焼結助剤
は、通常、成形前に仮焼体粉末と混合されるが、出発原
料と混合して用いてもよく、該出発原料と混合して仮焼
してもよい。Next, a binder such as polyvinyl alcohol is added to the calcined powder to form it into a predetermined shape. The sintering aid is usually mixed with the calcined powder before molding, but it may be mixed with the starting material, or may be mixed with the starting material and calcined.
【００３４】成形後、上記コウバチ１の支持板２上に配
置し、焼成する。焼成温度は９００℃〜１２００℃程度
とする。焼結助剤を用いた場合には、焼成温度を低下す
ることができる。なお、焼成時の温度保持時間は、１〜
９時間程度とすればよい。After molding, the mold is placed on the support plate 2 of the wasp 1 and fired. The firing temperature is about 900 ° C to 1200 ° C. When a sintering aid is used, the firing temperature can be lowered. The temperature holding time during firing is 1 to
It may be about 9 hours.
【００３５】本発明では、上記焼成を、コウバチ内に還
元性ガスを供給しつつ行なう。このとき使用することの
できる還元性ガスは、Ｎ2 −ＣＯ、Ｎ2 −ＣＯ−Ｈ
2 Ｏ、ＣＯ−ＣＯ2 、Ｎ2 −Ｈ2 、Ｎ2 −Ｈ2 −Ｈ
2 Ｏ、Ｎ2 −ＮＨ3 、Ｎ2 −ＮＨ3 −Ｈ2 Ｏ等を用いる
ことができる。In the present invention, the above firing is carried out while supplying the reducing gas into the wasp. Reducing gas can be used at this time, N 2 -CO, N 2 -CO -H
2 O, CO-CO 2, N 2 -H 2, N 2 -H 2 -H
2 O, can be used N 2 -NH 3, N 2 -NH 3 -H 2 O or the like.
【００３６】また、還元性ガスのコウバチへの供給量
は、コウバチの形状等によって異なるが、雰囲気ガスの
線速度で、１ｃｍ／ｍｉｎ〜１００ｃｍ／ｍｉｎ程度の
範囲とすれば、コウバチの形状いかんにかかわらず良好
な結果が得られる。The amount of reducing gas supplied to the wasp varies depending on the shape of the wasp, but if the linear velocity of the atmosphere gas is in the range of about 1 cm / min to 100 cm / min, the shape of the wasp will not be affected. Regardless, good results are obtained.
【００３７】本発明のセラミック体は、鉛含有のペロブ
スカイトおよびパイロクロア、または鉛含有化合物の
他、蒸気圧の高い酸化物などにも適用可能である。The ceramic body of the present invention can be applied to lead-containing perovskites and pyrochlores, or lead-containing compounds as well as oxides having a high vapor pressure.
【００３８】本発明の方法によれば、Ｃｕ等の卑金属で
電極を構成することができ、この電極は、セラミック体
と同時焼成することができる。According to the method of the present invention, the electrode can be made of a base metal such as Cu, and this electrode can be co-fired with the ceramic body.
【００３９】[0039]
【実施例】以下、本発明の具体的実施例を示し、本発明
をさらに詳細に説明する。EXAMPLES The present invention will be described in more detail below by showing specific examples of the present invention.
【００４０】出発原料としてＰｂＯ、Ｎｂ2 Ｏ5 、Ｍｇ
ＯおよびＴｉＯ2 を用い、主成分組成Ｐｂ（Ｍｇ1/3 Ｎ
ｂ2/3 ）Ｏ3 ９５ｍｏｌ％、ＰｂＴｉＯ3 ５ｍｏｌ％と
なるように秤量配合した。次いで、これらをボールミル
で湿式混合し、８５０℃で２時間仮焼した。得られた仮
焼体をボールミルで粉砕し、平均粒子径０．９μm （レ
ーザー回折式粒度分布計による測定）の仮焼体粉末とし
た。PbO, Nb 2 O 5 and Mg as starting materials
Using O and TiO 2 , the main component composition Pb (Mg 1/3 N
b 2/3 ) O 3 95 mol% and PbTiO 3 5 mol% were weighed and blended. Then, these were wet mixed with a ball mill and calcined at 850 ° C. for 2 hours. The obtained calcined body was pulverized with a ball mill to obtain a calcined body powder having an average particle diameter of 0.9 μm (measured by a laser diffraction type particle size distribution meter).
【００４１】さらに、ＰｂＯおよびＳｉＯ2 を１：１
（モル比）の割合で秤量配合し、これらをボールミルで
湿式混合し、８００℃で２時間仮焼した後、さらにボー
ルミルで粉砕を行ない、平均粒子径２μm のＰｂＳｉＯ
3 粉末を得た。Further, PbO and SiO 2 are mixed in a ratio of 1: 1.
(Mole ratio) Weighed and blended, wet mixed in a ball mill, calcined at 800 ° C. for 2 hours, and further pulverized in a ball mill to obtain PbSiO having an average particle diameter of 2 μm.
3 powders were obtained.
【００４２】次いで、このＰｂＳｉＯ3 粉末および上記
仮焼体粉末と、副成分となるＭｇＯ粉末（平均粒子径
０．１μm ）とを、ＭｇＯを１ｍｏｌ％、ＰｂＳｉＯ3
を０．１ｍｏｌ％となるように秤量配合し、ボールミル
で湿式混合した。ただし、ＭｇＯおよびＰｂＳｉＯ3 の
比率は主成分を１００モル％としたときの比率である。Next, the PbSiO 3 powder, the calcined powder and the MgO powder (average particle diameter 0.1 μm) as an auxiliary component were mixed with 1 mol% of MgO and PbSiO 3
Was weighed and blended so as to be 0.1 mol%, and wet-mixed with a ball mill. However, the ratio of MgO and PbSiO 3 is the ratio when the main component is 100 mol%.
【００４３】次いで、得られた粉末に有機バインダを加
え、シート化し、このシートに市販の銅ペーストを印刷
法により印刷し、これらを積層、スタック後、切断し
て、チップコンデンサの生成形体とした。Next, an organic binder was added to the obtained powder to form a sheet, and a commercially available copper paste was printed on the sheet by a printing method. These were laminated, stacked and cut to obtain a chip capacitor production form. .
【００４４】銅を内部電極に使用した上記チップコンデ
ンサ成形体の複数の試料を縦８０ｍｍ、横８０ｍｍ、高
さ１５ｍｍの底部密閉型マグネシア製コウバチ中に１段
積みで全面に敷き詰め、天井部は全面解放とした。A plurality of samples of the above chip capacitor molded body using copper as an internal electrode were laid one by one in a bottom-closed magnesia wasp having a length of 80 mm, a width of 80 mm, and a height of 15 mm, and the ceiling was entirely covered. It was released.
【００４５】上記コウバチを内径９５ｍｍ、長さ１ｍの
円筒形アルミナチューブ中央に設置し、コウバチの両側
に断熱材を配し、更にアルミナチューブの両端をシリコ
ン栓で密閉化し、雰囲気制御可能の構造とした。The aforesaid wasp is installed in the center of a cylindrical alumina tube having an inner diameter of 95 mm and a length of 1 m, heat insulating materials are arranged on both sides of the amber, and both ends of the alumina tube are sealed with silicone stoppers to make the atmosphere controllable. did.
【００４６】上記チップ入りコウバチを、６００℃、５
０ｐｐｍＨ2 −Ｎ2 −Ｈ2 Ｏ（露点３０℃）組成の雰囲
気ガス１０００ｍｌ／ｍｉｎを通じる条件でバーンアウ
トした。バーンアウトした後の試料の残留炭素量は、何
れも８０ｐｐｍ以下であった。The above wasps containing chips were heated at 600 ° C. for 5
Burnout was carried out under the condition that an atmospheric gas having a composition of 0 ppm H 2 —N 2 —H 2 O (dew point 30 ° C.) was passed at 1000 ml / min. The residual carbon contents of the samples after burnout were all 80 ppm or less.
【００４７】次に、雰囲気ガス組成を２０ｐｐｍＨ2 −
Ｎ2 −Ｈ2 Ｏ（露点３０℃）に切り替えるとともに、コ
ウバチの解放率、および雰囲気ガスの線速度を表１のよ
うに変化させた条件で、連続して昇温し、９５０℃、２
時間保持の条件で焼成した。Next, the atmosphere gas composition is set to 20 ppm H 2 −.
While switching to N 2 —H 2 O (dew point 30 ° C.), the temperature was continuously raised to 950 ° C. under the conditions that the release rate of the wasp and the linear velocity of the atmospheric gas were changed as shown in Table 1.
Firing was performed under the condition of holding time.
【００４８】[0048]
【表１】 [Table 1]
【００４９】得られた焼結チップの両端子に銅電極を塗
布し、窒素雰囲気中で焼付けた後、ニッケル、錫メッキ
処理し、９種類の積層型セラミックチップコンデンサの
サンプルを作製した。積層型セラミックチップコンデン
サのサイズは、３．２ｍｍ×１．６ｍｍ×１．０ｍｍ
で、誘電体層数が４０層であった。Copper electrodes were applied to both terminals of the obtained sintered chip, baked in a nitrogen atmosphere, and plated with nickel and tin to prepare samples of 9 types of multilayer ceramic chip capacitors. The size of the multilayer ceramic chip capacitor is 3.2mm x 1.6mm x 1.0mm
The number of dielectric layers was 40.
【００５０】このようにして得られた積層型セラミック
チップコンデンサのサンプルの全てについて、絶縁抵
抗、絶縁抵抗の加速寿命、およびサンプル１および２に
ついては、耐湿負荷寿命を測定した。その結果を表１に
示した。なお、絶縁抵抗の加速寿命の測定は、温度２０
０℃、印加電圧１Ｖ／μｍの条件で空気中で行なった。
また、耐湿負荷寿命は、温度８５℃、相対湿度８５％、
印加電圧２５Ｖの条件下で行なった。Insulation resistance, accelerated life of insulation resistance, and moisture resistance load life of Samples 1 and 2 were measured for all the samples of the multilayer ceramic chip capacitors thus obtained. The results are shown in Table 1. In addition, the accelerated life of the insulation resistance is measured at a temperature of 20.
It was carried out in air under the conditions of 0 ° C. and an applied voltage of 1 V / μm.
Also, the humidity resistance load life is 85 ° C temperature, 85% relative humidity,
It was performed under the condition of an applied voltage of 25V.
【００５１】表１に示される結果から本発明の効果が明
らかである。すなわち、本発明の積層型セラミックチッ
プコンデンサにおいては、焼成の際、特にコウバチを開
放状態にしてやると、絶縁抵抗の加速寿命、耐湿負荷寿
命が大幅に改善される。From the results shown in Table 1, the effect of the present invention is clear. That is, in the multilayer ceramic chip capacitor of the present invention, the accelerated life of the insulation resistance and the moisture-proof load life are significantly improved when firing, especially when the wasps are opened.
【図面の簡単な説明】[Brief description of drawings]
【図１】本発明で使用されるコウバチの一例を示す斜視
図である。FIG. 1 is a perspective view showing an example of a wasp used in the present invention.
【図２】本発明で使用されるコウバチの他の例を示す斜
視図である。FIG. 2 is a perspective view showing another example of a wasp used in the present invention.
１ コウバチ ２ 支持板 ３ 枠状体 ４ 上蓋 ５ スペーサ 1 Wasp 2 Support plate 3 Frame 4 Top lid 5 Spacer
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成５年５月２４日[Submission date] May 24, 1993
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】図面[Document name to be corrected] Drawing
【補正対象項目名】全図[Correction target item name] All drawings
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【図１】 [Figure 1]
【図２】 [Fig. 2]
フロントページの続き (72)発明者 高橋 徹 東京都中央区日本橋一丁目13番１号 ティ ーディーケイ株式会社内 (72)発明者 澤村 建太郎 東京都中央区日本橋一丁目13番１号 ティ ーディーケイ株式会社内Front page continuation (72) Toru Takahashi 1-13-1 Nihonbashi, Chuo-ku, Tokyo TDC Corporation (72) Kentaro Sawamura 1-13-1 Nihonbashi, Chuo-ku, Tokyo TDC Corporation Within
Claims (12)
物を原料に用いる電子部品の製造方法において、その焼
成工程を、少なくとも一部が開放したコウバチを用い、
還元性ガスを該コウバチ内に供給しつつ行い、焼成中に
発生するバインダの分解ガスおよび鉛蒸気の余剰分をコ
ウバチから排出するようにしたことを特徴とする鉛系セ
ラミック電子部品の製造方法。1. A method of manufacturing an electronic component using, as a raw material, a ceramic composition containing a lead compound as a main component, the firing step of which is performed using at least a part of an wasp,
A method for producing a lead-based ceramic electronic component, characterized in that a reducing gas is supplied while being supplied to the wasp, and a decomposition gas of a binder generated during firing and an excess of lead vapor are discharged from the bee.
持板と、上部が開放した状態で、前記セラミック電子部
品を取り囲む枠状体とを備えている請求項１の鉛系セラ
ミック電子部品の製造方法。2. The lead-based ceramic electronic component according to claim 1, wherein the wasp comprises a support plate for supporting the object to be fired and a frame-shaped body surrounding the ceramic electronic component in a state where an upper portion thereof is open. Production method.
さ以上である請求項２の鉛系セラミック電子部品の製造
方法。3. The method for manufacturing a lead-based ceramic electronic component according to claim 2, wherein the height of the frame-shaped body is not less than the height of the object to be fired.
さ以上、５０ｍｍ以下の範囲である請求項３の鉛系セラ
ミック電子部品の製造方法。4. The method for producing a lead-based ceramic electronic component according to claim 3, wherein the height of the frame-shaped body is in the range of not less than the height of the object to be fired and not more than 50 mm.
蓋を配置してコウバチを構成し、前記枠状体とスペーサ
の間に、コウバチ内外を連通する間隙を形成するように
した請求項１ないし４のいずれかの鉛系セラミック電子
部品の製造方法。5. An upper lid is arranged on the frame-shaped body via a spacer to form a wasp, and a gap is formed between the frame-shaped body and the spacer to communicate the inside and outside of the wasp. Item 5. A method for manufacturing a lead-based ceramic electronic component according to any one of Items 1 to 4.
されている請求項５の鉛系セラミック電子部品の製造方
法。6. The method for manufacturing a lead-based ceramic electronic component according to claim 5, wherein the spacer is formed integrally with the frame-shaped body.
焼成工程を行なう鉛系セラミック電子部品の製造方法。7. A method of manufacturing a lead-based ceramic electronic component, comprising stacking the wasps according to claim 5 on top and performing a firing step.
たりで、２％以上である請求項１ないし７のいずれかの
鉛系セラミック電子部品の製造方法。8. The method for producing a lead-based ceramic electronic component according to claim 1, wherein the open rate of one wasp is 2% or more per the total surface area.
１ないし８のいずれかの鉛系セラミック電子部品の製造
方法。9. The method for producing a lead-based ceramic electronic component according to claim 1, wherein the entire upper surface of the wasp is open.
る被焼成物の体積のコウバチ内容積に対する占有率が６
０〜１００％の範囲である請求項１ないし９のいずれか
の鉛系セラミック電子部品の製造方法。10. The occupancy rate of the volume of the material to be fired in one wasp before firing is 6 with respect to the inner volume of the wasp.
The method for producing a lead-based ceramic electronic component according to any one of claims 1 to 9, wherein the content is in the range of 0 to 100%.
しつつ焼成を行なう請求項１ないし１０のいずれかの鉛
系セラミック電子部品の製造方法。11. The method for producing a lead-based ceramic electronic component according to claim 1, wherein the firing is performed while introducing a reducing atmosphere into the wasp.
の導入量が、線速度で１〜１２０ｃｍ／ｍｉｎである請
求項１１の鉛系セラミック電子部品の製造方法。12. The method for producing a lead-based ceramic electronic component according to claim 11, wherein the introduction amount of the reducing atmosphere into the wasp is 1 to 120 cm / min in linear velocity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5095245A JPH06283378A (en) | 1993-03-29 | 1993-03-29 | Manufacture of lead series ceramic electronic component |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5095245A JPH06283378A (en) | 1993-03-29 | 1993-03-29 | Manufacture of lead series ceramic electronic component |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06283378A true JPH06283378A (en) | 1994-10-07 |
Family
ID=14132374
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5095245A Withdrawn JPH06283378A (en) | 1993-03-29 | 1993-03-29 | Manufacture of lead series ceramic electronic component |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06283378A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021516204A (en) * | 2018-03-13 | 2021-07-01 | ティーディーケイ・エレクトロニクス・アクチェンゲゼルシャフトＴｄｋ Ｅｌｅｃｔｒｏｎｉｃｓ Ａｇ | Polycrystalline ceramic solid and method for producing polycrystalline ceramic solid |
| CN115947598A (en) * | 2022-10-21 | 2023-04-11 | 西安交通大学 | Antiferroelectric material capable of being co-fired with base metal inner electrode and preparation method thereof |
-
1993
- 1993-03-29 JP JP5095245A patent/JPH06283378A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021516204A (en) * | 2018-03-13 | 2021-07-01 | ティーディーケイ・エレクトロニクス・アクチェンゲゼルシャフトＴｄｋ Ｅｌｅｃｔｒｏｎｉｃｓ Ａｇ | Polycrystalline ceramic solid and method for producing polycrystalline ceramic solid |
| US11680021B2 (en) | 2018-03-13 | 2023-06-20 | Tdk Electronics Ag | Polycrystalline ceramic solid and method for producing a polycrystalline ceramic solid |
| CN115947598A (en) * | 2022-10-21 | 2023-04-11 | 西安交通大学 | Antiferroelectric material capable of being co-fired with base metal inner electrode and preparation method thereof |
| CN115947598B (en) * | 2022-10-21 | 2024-03-22 | 西安交通大学 | Antiferroelectric material capable of being co-fired with base metal inner electrode and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0423738B1 (en) | Ceramic multilayer chip capacitor and method for making | |
| US6310761B1 (en) | Dielectric ceramic composition and monolithic ceramic capacitor | |
| US9748041B2 (en) | Multilayer ceramic capacitor including main phase grains and a secondary phase | |
| EP0534378A1 (en) | Non-reducible dielectric ceramic composition | |
| EP0137565A2 (en) | Multilayer ceramic capacitor | |
| JP2019140199A (en) | Multilayer ceramic capacitor and manufacturing method thereof | |
| US9082553B2 (en) | Laminated ceramic capacitor and manufacturing method therefor | |
| EP0368619B1 (en) | Dielectric ceramic composition | |
| EP1547989B1 (en) | Piezoelectric porcelain composition, piezoelectric element, and method for production thereof | |
| US6743518B2 (en) | Ceramic capacitor and method for the manufacture thereof | |
| JPH06283378A (en) | Manufacture of lead series ceramic electronic component | |
| US5093757A (en) | Dielectric ceramic composition | |
| US7149073B2 (en) | Electroceramic component | |
| KR100237294B1 (en) | Multi-layer ceramic capacitor manufacturing method | |
| JP6539589B2 (en) | Dielectric ceramic composition, dielectric device and method for manufacturing them | |
| JP3000781B2 (en) | Method of firing ceramic compact containing high vapor pressure oxide | |
| US20030104917A1 (en) | Dielectric ceramic composition and laminated ceramic parts using the same | |
| JPH07183155A (en) | Laminated ceramic electronic component and its manufacture | |
| JP2872454B2 (en) | Manufacturing method of grain boundary insulated semiconductor laminated ceramic capacitor | |
| JP2523834B2 (en) | High dielectric constant dielectric ceramic composition | |
| KR100372687B1 (en) | A method for manufacturing multilayer ceramic capacitor having low deviation in dielectric properties | |
| JP2984115B2 (en) | Manufacturing method of grain boundary insulated semiconductor porcelain capacitor | |
| JPH05262556A (en) | Production of dielectric porcelain | |
| JP3652164B2 (en) | Dielectric porcelain plate, manufacturing method thereof, and electronic component | |
| JPH1154359A (en) | Laminated ceramic capacitor, dielectric ceramics and manufacture of dielectric ceramics |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Application deemed to be withdrawn because no request for examination was validly filed |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20000530 |