JPH11228236A - Adhesion-preventing material for sintering ceramic and production of ceramic sintered product - Google Patents
Adhesion-preventing material for sintering ceramic and production of ceramic sintered productInfo
- Publication number
- JPH11228236A JPH11228236A JP10051508A JP5150898A JPH11228236A JP H11228236 A JPH11228236 A JP H11228236A JP 10051508 A JP10051508 A JP 10051508A JP 5150898 A JP5150898 A JP 5150898A JP H11228236 A JPH11228236 A JP H11228236A
- Authority
- JP
- Japan
- Prior art keywords
- ceramic
- firing
- adhesion
- zirconia powder
- ceramic green
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 133
- 239000000463 material Substances 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 238000005245 sintering Methods 0.000 title abstract description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 140
- 239000000843 powder Substances 0.000 claims abstract description 74
- 239000002245 particle Substances 0.000 claims abstract description 37
- 238000010304 firing Methods 0.000 claims description 79
- 238000000034 method Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 abstract description 14
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 description 22
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 8
- 230000002950 deficient Effects 0.000 description 8
- 229910008651 TiZr Inorganic materials 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、セラミック焼成用
付着防止材並びにセラミック焼結体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 an adhesion preventing material for ceramic firing and a method for producing a ceramic sintered body.
【０００２】[0002]
【従来の技術】一般に、積層チップコンデンサ，圧電積
層体，圧電フィルタ，複合チップ部品等のチップ部品を
構成するセラミック焼結体を製造するには、ＰｂＴｉＯ
3 またはＰｂ（ＴｉＺｒ）Ｏ3 等のセラミック粉末を主
成分とするセラミックグリーンペーストからセラミック
グリーンシートを押出し成形し、そのセラミックグリー
ンシートより所定形状のセラミックグリーン成形体をプ
レス成形し、このセラミックグリーン成形体を焼成用治
具に複数積層させて焼成炉に送り込むことにより焼成処
理を施すことが行なわれている。2. Description of the Related Art Generally, in order to manufacture a ceramic sintered body constituting a chip component such as a multilayer chip capacitor, a piezoelectric laminate, a piezoelectric filter, a composite chip component, etc., it is necessary to use PbTiO.
A ceramic green sheet is extruded from a ceramic green paste containing a ceramic powder such as 3 or Pb (TiZr) O 3 as a main component, and a ceramic green molded body having a predetermined shape is press-molded from the ceramic green sheet. A firing process is performed by stacking a plurality of bodies on a firing jig and sending the stacked bodies to a firing furnace.
【０００３】その焼成処理にあたっては、焼成用治具と
セラミックグリーン成形体との間並びにセラミックグリ
ーン成形体相互が付着するのを防止するべく、セラミッ
ク焼成用の付着防止材を塗布することが行なわれてい
る。In the firing treatment, an adhesion preventing material for ceramic firing is applied in order to prevent the firing jig and the ceramic green compact and the ceramic green compact from adhering to each other. ing.
【０００４】従来、そのセラミック焼成用付着防止材と
しては融点の高いジルコニア粉末が用いられている（特
開昭６０ー２２１３７８号）。また、このジルコニア粉
末にはＣａＯ，ＭｇＯ，Ｙ2 Ｏ3 等の安定化剤を混入し
たものが用いられている。然し、その安定化ジルコニア
粉末では不純物がセラミックグリーン成形体に著しく拡
散することにより、セラミック焼結体の化学的，機械的
及び電気的特性に影響を来すところから好ましくない。Hitherto, zirconia powder having a high melting point has been used as an adhesion preventing material for ceramic firing (Japanese Patent Application Laid-Open No. 60-221378). The zirconia powder is mixed with a stabilizer such as CaO, MgO, and Y 2 O 3 . However, the stabilized zirconia powder is not preferable because impurities significantly diffuse into the ceramic green compact and affect the chemical, mechanical and electrical properties of the ceramic sintered compact.
【０００５】その安定化ジルコニア粉末に代えて、高純
度のジルコニア粉末を用いても付着防止を図れることは
知られている。また、このジルコニア粉末を用いるとき
にはセラミックグリーン成形体に均一に塗布する必要か
ら、平均粒径が４０μｍ以下のものでなければならない
ことも知られている。It is known that the use of high-purity zirconia powder in place of the stabilized zirconia powder can prevent adhesion. It is also known that when this zirconia powder is used, the average particle size must be 40 μm or less because it is necessary to apply the zirconia powder uniformly to the ceramic green compact.
【０００６】然し、その平均粒径が４０μｍ以下で高純
度のジルコニア粉末を用いたとしても、依然としてジル
コニア粉末の拡散が生じ、また、セラミック焼結体の収
縮率がバラ付くことにより変形やクラックが発生し、更
には、ジルコニア粉末自体の変質も生じて付着防止材と
しての役割を果たさない事態が生ずる。However, even if high-purity zirconia powder having an average particle size of 40 μm or less is used, diffusion of the zirconia powder still occurs, and deformation and cracks occur due to variation in shrinkage of the ceramic sintered body. Occurs, and further, the zirconia powder itself is deteriorated, and does not serve as an adhesion preventing material.
【０００７】茲において、本発明者らは種々条件の異な
るジルコニア粉末を製造し、それを用いて各種のセラミ
ック焼結体を試料として作成し、この試料の中からチッ
プ部品を構成するのに適する化学的，機械的及び電気的
特性を有するものを選別し、その試料に用いたジルコニ
ア粉末の条件を調査，研究した結果、ジルコニア粉末の
純度，平均粒径と共に、比表面積がセラミック焼結体の
特性に影響することを見出した。これと同時に、ジルコ
ニア粉末の純度はどの程度のものであればよいか、ま
た、平均粒径，比表面積は小さ過ぎても不適で上限値と
共に、下限値があることを見出した。[0007] Here, the present inventors produce zirconia powders having different conditions, prepare various ceramic sintered bodies as samples using the zirconia powders, and are suitable for forming chip parts from the samples. As a result of screening and studying the conditions of the zirconia powder used for the sample, the specific surface area of the ceramic sintered body together with the purity and the average particle size of the zirconia powder were determined. It was found to affect the properties. At the same time, it was found that the purity of the zirconia powder should be high, and that the average particle diameter and the specific surface area were too small to be suitable and had a lower limit as well as an upper limit.
【０００８】[0008]
【発明が解決しようとする課題】本発明は、化学的，機
械的及び電気的特性に優れたチップ部品を構成可能なセ
ラミック焼結体を製造するべく、その焼成にあたって使
用可能な条件設定したジルコニア粉末をセラミック焼成
用付着防止材として提供することを目的とする。SUMMARY OF THE INVENTION The present invention relates to a zirconia in which the conditions usable for firing are set in order to produce a ceramic sintered body capable of forming a chip component having excellent chemical, mechanical and electrical properties. An object of the present invention is to provide a powder as an adhesion preventing material for ceramic firing.
【０００９】また、本発明はジルコニア粉末をセラミッ
ク焼成用付着防止材として用い、化学的，機械的及び電
気的特性に優れたチップ部品を構成可能なセラミック焼
結体を製造可能なセラミック焼結体の製造方法を提供す
ることを目的とする。Further, the present invention provides a ceramic sintered body capable of producing a ceramic sintered body capable of forming a chip part having excellent chemical, mechanical and electrical properties by using zirconia powder as an adhesion preventing material for ceramic firing. It is an object of the present invention to provide a method for producing the same.
【００１０】[0010]
【課題を解決するための手段】本発明の請求項１に係る
セラミック焼成用付着防止材においては純度が９８．０
％以上で、平均粒径が４０．０μｍ未満，１．５μｍ以
上で、比表面積が３．０ｍ2 ／ｇ％以下，０．５ｍ2 ／
ｇ％以上とジルコニア粉末の使用可能な条件設定をして
なる。According to the first aspect of the present invention, the adhesion preventing material for firing ceramics has a purity of 98.0.
% Or more, average particle diameter is less than 40.0, at 1.5μm or more, a specific surface area of 3.0 m 2 / g% or less, 0.5 m 2 /
g% or more and zirconia powder usable conditions are set.
【００１１】本発明の請求項２に係るセラミック焼結体
の製造方法においては純度が９８．０％以上で、平均粒
径が４０．０μｍ未満，１．５μｍ以上で、比表面積が
３．０ｍ2 ／ｇ％以下，０．５ｍ2 ／ｇ％以上のジルコ
ニア粉末をセラミック焼成用付着防止材として焼成用治
具並びにセラミックグリーン成形体に塗布し、そのセラ
ミックグリーン成形体を焼成用治具に複数積載させて焼
成処理を行うようにされている。According to a second aspect of the present invention, there is provided a method for producing a ceramic sintered body having a purity of 98.0% or more, an average particle diameter of less than 40.0 μm, 1.5 μm or more, and a specific surface area of 3.0 m. 2 / g% or less was applied to the firing jig and the ceramic green body 0.5 m 2 / g% or more of zirconia powder as ceramic firing adhesion preventing material, a plurality of the ceramic green body in the firing jig The sintering process is performed by loading.
【００１２】[0012]
【発明の実施の形態】本発明は、積層チップコンデン
サ，圧電積層体，圧電フィルタ，複合チップ部品等のチ
ップ部品を構成するセラミック焼結体を製造するのに適
用される。そのセラミック焼結体は、ＰｂＴｉＯ3 また
はＰｂ（ＴｉＺｒ）Ｏ3 等のセラミック粉末を主成分と
するセラミックグリーンペーストから押出し成形したセ
ラミックグリーンシートを所定形状のセラミックグリー
ン成形体としてプレス成形した後焼成処理を施すことに
より製造される。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention is applied to manufacturing a ceramic sintered body constituting a chip component such as a multilayer chip capacitor, a piezoelectric laminate, a piezoelectric filter, and a composite chip component. The ceramic sintered body is formed by pressing a ceramic green sheet extruded from a ceramic green paste containing a ceramic powder such as PbTiO 3 or Pb (TiZr) O 3 as a main component as a ceramic green molded body having a predetermined shape and then firing. It is manufactured by applying
【００１３】そのセラミックグリーン成形体は、焼成炉
に送り込む際には複数個を焼成用治具に積層させて送り
込む。この焼成用治具としては、マグネシア，アルミ
ナ，ムライト，ジルコニア製等の材質的に高耐熱性を有
し、構造的にはパレット状或いは棚状に組み立てられた
ものを用いることができる。When the ceramic green compact is fed into a firing furnace, a plurality of ceramic green compacts are stacked on a firing jig and fed. As the firing jig, a material made of magnesia, alumina, mullite, zirconia, or the like having high heat resistance in terms of material and assembled in a pallet-like or shelf-like structure can be used.
【００１４】その積載に先立って、セラミック焼成用の
付着防止材を焼成用治具とセラミックグリーン成形体と
に塗布する。このセラミック焼成用付着防止材としては
高純度のジルコニア（ＺｒＯ2 ）粉末を用い、そのジル
コニア粉末は、１２００℃程度の高温で熱処理した後に
高速気流を利用した乾式粉砕機を用いて粉砕，熱処理す
ることにより得られる。また、塗布は篩い掛け等で焼成
用治具並びにセラミックグリーン成形体に個別に処理す
ることができる。Prior to the loading, an adhesion preventing material for ceramic firing is applied to the firing jig and the ceramic green compact. A high-purity zirconia (ZrO 2 ) powder is used as the adhesion preventing material for ceramic firing, and the zirconia powder is heat-treated at a high temperature of about 1200 ° C. and then pulverized and heat-treated using a dry pulverizer using a high-speed air flow. It can be obtained by: The coating can be individually applied to the firing jig and the ceramic green compact by sieving or the like.
【００１５】その焼成用治具に積載されたセラミックグ
リーン成形体には焼成炉に送り込んで、１０００〜１３
００℃程度の高温で０．５〜１０時間程度焼成処理を施
す。この焼成処理後、焼成炉から取り出して一枚毎に仕
分けし、水洗い処理することによりチップ部品を構成す
るセラミック焼結体として得られる。The ceramic green compact loaded on the firing jig is sent to a firing furnace,
A baking treatment is performed at a high temperature of about 00 ° C. for about 0.5 to 10 hours. After this firing treatment, it is taken out of the firing furnace, sorted one by one, and washed with water to obtain a ceramic sintered body constituting a chip component.
【００１６】そのセラミック焼成用の付着防止材として
適するジルコニア粉末の条件を見出すべく、次表で示す
ように種々条件の異なるジルコニア粉末を製造し、各ジ
ルコニア粉末の純度，比表面積並びに平均粒径を測定，
記録した。また、この条件の異なるジルコニア粉末をＰ
ｂＴｉＯ3 のセラミックグリーン成形体並びにジルコニ
ア製の焼成用治具に塗布し、上述した工程を適用するこ
とにより複数個のセラミック焼結体を試料１〜１７とし
て作成した。In order to find conditions of zirconia powder suitable as an adhesion preventing material for firing the ceramic, zirconia powders having various conditions are produced as shown in the following table, and the purity, specific surface area and average particle size of each zirconia powder are determined. Measurement,
Recorded. In addition, zirconia powders having different conditions are referred to as P
A plurality of ceramic sintered bodies were prepared as samples 1 to 17 by applying the ceramic green compact of bTiO 3 and a firing jig made of zirconia and applying the above-described steps.
【００１７】その試料１〜１７の中から、ジルコニア粉
末の拡散量，セラミック焼結体の変形量，ジルコニア粉
末の付着不良率（以下、単に「拡散量」「変形量」「付
着不良率」という。）に基づいてチップ部品を構成する
のに適する化学的，機械的及び電気的特性を有するもの
を選別した。この選別条件は、上述したセラミック焼結
体を用いて構成したチップ部品の化学的，機械的及び電
気的特性を検査することにより特定でき、ジルコニア粉
末の拡散量が０．０６ｗｔ％以下、セラミック焼結体の
変形量が０．０２％以下、ジルコニア粉末の付着不良率
が３％以下のものとした。From among the samples 1 to 17, the diffusion amount of the zirconia powder, the deformation amount of the ceramic sintered body, and the defective adhesion rate of the zirconia powder (hereinafter, simply referred to as “diffusion amount”, “deformation amount”, and “adhesion defective rate”). )), Those having chemical, mechanical and electrical properties suitable for constituting chip components were selected. The selection conditions can be specified by inspecting the chemical, mechanical and electrical characteristics of the chip component formed using the above-mentioned ceramic sintered body. The diffusion amount of the zirconia powder is 0.06% by weight or less, and the ceramic firing is performed. The amount of deformation of the binder was 0.02% or less, and the rate of defective adhesion of zirconia powder was 3% or less.
【００１８】[0018]
【００１９】上記表中で、試料No. の左側に付した＊印
はセラミック焼結体の特性からチップ部品を構成するの
に不適なものを示す。この表から、ジルコニア粉末の純
度については試料１〜５で示すように少なくとも９５．
６％以下では不適で、試料６のように９８．０％以上の
ものでなければならないことが判る。また、試料１５〜
１７のように９８．５〜９９．９％と極めて高純度のも
のであっても、その純度だけでは不適で、他の比表面積
並びに平均粒径の条件を共に満たさければならないこと
も判る。In the above table, an asterisk (*) attached to the left side of the sample No. indicates an unsuitable one for constituting a chip part due to the characteristics of the ceramic sintered body. From this table, the purity of the zirconia powder is at least 95.
It is found that if it is less than 6%, it is unsuitable, and it must be 98.0% or more as in sample 6. In addition, samples 15 to
It can also be seen that even a substance having an extremely high purity of 98.5 to 99.9% as in No. 17 is not suitable for its purity alone and must satisfy other conditions of specific surface area and average particle size.
【００２０】平均粒径からすると、試料１５で示すよう
に平均粒径が４０．０μｍのものは純度が９８．５％
で、比表面積が０．９ｍ2 ／ｇ％であっても、拡散量は
０．０４ｗｔ％、付着不良率は０％であるが、変形量が
０．７％と高いところから不適である。これから、平均
粒径は少なくとも４０．０μｍ未満のものでなけらばな
らないことが判る。In terms of the average particle size, as shown in Sample 15, the sample having an average particle size of 40.0 μm has a purity of 98.5%
Even if the specific surface area is 0.9 m 2 / g%, the diffusion amount is 0.04 wt% and the adhesion failure rate is 0%, but the deformation amount is as high as 0.7%, which is not suitable. This shows that the average particle size must be at least less than 40.0 μm.
【００２１】一方、試料４で示すように平均粒径が１．
３μｍと極めた小さくしかも純度が９３．０％と低けれ
ば、比表面積が２．６ｍ2 ／ｇ％であっても、拡散量が
０．３４ｗｔ％、変形量が０．７％、付着不良率が４％
と不適である。また、試料１６で示すように平均粒径が
１．４μｍ程度のものでは純度が９９．９％、比表面積
が２．８ｍ2 ／ｇ％でも、拡散量が０．２１ｗｔ％で、
変形量が０．６％並びに付着不良率が４％と高いところ
から不適である。このため、平均粒径は試料７で示すよ
うに下限でも１．５μｍ以上が必要であることが判る。On the other hand, as shown in Sample 4, the average particle size was 1.
If it is as small as 3 μm and the purity is as low as 93.0%, even if the specific surface area is 2.6 m 2 / g%, the diffusion amount is 0.34 wt%, the deformation amount is 0.7%, and the adhesion failure rate is low. Is 4%
And unsuitable. Further, as shown in Sample 16, even if the average particle size is about 1.4 μm, the purity is 99.9%, and even if the specific surface area is 2.8 m 2 / g%, the diffusion amount is 0.21 wt%.
It is unsuitable because the deformation amount is as high as 0.6% and the defective adhesion rate is as high as 4%. Therefore, it is understood that the average particle size needs to be 1.5 μm or more even at the lower limit as shown in Sample 7.
【００２２】比表面積からすると、試料１２で示すよう
に比表面積が６．８ｍ2 ／ｇ％のものでは純度９９．９
％、平均粒径１６．７μｍでも、拡散量が０．２１ｗｔ
％、変形量が０．６％、付着不良率が４％と不適であ
る。また、試料１７で示すように比表面積が０．３ｍ2
／ｇ％のものでは純度が９８．５％、平均粒径が３８．
０μｍでも、変形量が０．８％と高いところから不適で
ある。In terms of the specific surface area, as shown in Sample 12, the sample having a specific surface area of 6.8 m 2 / g% has a purity of 99.9.
%, Even with an average particle size of 16.7 μm, the diffusion amount is 0.21 wt.
%, The deformation amount is 0.6%, and the adhesion failure rate is 4%, which is inappropriate. Further, as shown in Sample 17, the specific surface area was 0.3 m 2.
/ G%, the purity is 98.5% and the average particle size is 38.
Even at 0 μm, it is not suitable because the deformation amount is as high as 0.8%.
【００２３】これに対し、試料１３で示すように比表面
積が３．０ｍ2 ／ｇ％以下のものでは、拡散量が０．０
４ｗｔ％、変形量が０．０２％、付着不良率が０％と適
する。また、試料６で示すように比表面積が０．５ｍ2
／ｇ％以上のものでも、拡散量が０．０４ｗｔ％、変形
量が０．０２％、付着不良率が０％と適することが判
る。On the other hand, when the specific surface area is 3.0 m 2 / g% or less as shown in Sample 13, the diffusion amount is 0.0
4 wt%, the deformation amount is 0.02%, and the adhesion failure rate is 0%. Further, as shown in Sample 6, the specific surface area was 0.5 m 2.
/ G% or more, the diffusion amount is 0.04 wt%, the deformation amount is 0.02%, and the adhesion failure rate is 0%.
【００２４】以上総合すると、ジルコニア粉末はセラミ
ック焼成用付着防止材として純度が９８．０％以上で、
平均粒径が４０．０μｍ未満，１．５μｍ以上で、比表
面積が３．０ｍ2 ／ｇ％以下，０．５ｍ2 ／ｇ％以上の
ものが好ましい。また、そのジルコニア粉末をセラミッ
ク焼成用付着防止材として焼成用治具並びにセラミック
グリーン成形体に塗布し、そのセラミックグリーン成形
体を焼成用治具に複数積載させて焼成処理を行うことに
より、拡散量が００４〜００６ｗｔ％、変形量が０．０
２％程度に抑えられて付着不良率が０％となるセラミッ
ク焼結体を得ることができる。In summary, the zirconia powder has a purity of 98.0% or more as an adhesion preventing material for ceramic firing.
Those having an average particle size of less than 40.0 μm, 1.5 μm or more, and a specific surface area of 3.0 m 2 / g% or less and 0.5 m 2 / g% or more are preferred. In addition, the zirconia powder is applied to a firing jig and a ceramic green compact as an anti-adhesion material for ceramic firing, and a plurality of the ceramic green compacts are stacked on a firing jig and subjected to a firing treatment, whereby the diffusion amount is reduced. Is 004 to 006 wt% and the deformation amount is 0.0
It is possible to obtain a ceramic sintered body that is suppressed to about 2% and has an adhesion failure rate of 0%.
【００２５】[0025]
【発明の効果】本発明の請求項１に係るセラミック焼成
用付着防止材に依れば、ジルコニア粉末をセラミック焼
成用の付着防止材として有用なものとすることができ
る。According to the anti-adhesion material for ceramic firing according to claim 1 of the present invention, zirconia powder can be used as an anti-adhesion material for ceramic firing.
【００２６】本発明の請求項２に係るセラミック焼結体
の製造方法に依れば、チップ部品を構成するのに好適な
化学的，機械的及び電気的特性を有するセラミック焼結
体を得ることができる。According to the method for manufacturing a ceramic sintered body according to the second aspect of the present invention, a ceramic sintered body having suitable chemical, mechanical and electrical properties for forming a chip component is obtained. Can be.
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成１０年５月６日[Submission date] May 6, 1998
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】全文[Correction target item name] Full text
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【書類名】 明細書[Document Name] Statement
【発明の名称】 セラミック焼成用付着防止材並び
にセラミック焼結体の製造方法Patent application title: Adhesion preventing material for ceramic firing and method for producing ceramic sintered body
【特許請求の範囲】[Claims]
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【発明の属する技術分野】本発明は、セラミック焼成用
付着防止材並びにセラミック焼結体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 an adhesion preventing material for ceramic firing and a method for producing a ceramic sintered body.
【０００２】[0002]
【従来の技術】一般に、積層チップコンデンサ，圧電積
層体，圧電フィルタ，複合チップ部品等のチップ部品を
構成するセラミック焼結体を製造するには、ＰｂＴｉＯ
３またはＰｂ（ＴｉＺｒ）Ｏ３等のセラミック粉末を主
成分とするセラミックグリーンペーストからセラミック
グリーンシートを押出し成形し、そのセラミックグリー
ンシートより所定形状のセラミックグリーン成形体をプ
レス成形し、このセラミックグリーン成形体を焼成用治
具に複数積層させて焼成炉に送り込むことにより焼成処
理を施すことが行なわれている。2. Description of the Related Art Generally, in order to manufacture a ceramic sintered body constituting a chip component such as a multilayer chip capacitor, a piezoelectric laminate, a piezoelectric filter, a composite chip component, etc., it is necessary to use PbTiO.
A ceramic green sheet is extruded from a ceramic green paste containing a ceramic powder such as Pb (TiZr) O 3 or Pb (TiZr) O 3 as a main component, and a ceramic green molded body having a predetermined shape is press-molded from the ceramic green sheet. A firing process is performed by stacking a plurality of bodies on a firing jig and sending the stacked bodies to a firing furnace.
【０００３】その焼成処理にあたっては、焼成用治具と
セラミックグリーン成形体との間並びにセラミックグリ
ーン成形体相互が付着するのを防止するべく、セラミッ
ク焼成用の付着防止材を塗布することが行なわれてい
る。In the firing treatment, an adhesion preventing material for ceramic firing is applied in order to prevent the firing jig and the ceramic green compact and the ceramic green compact from adhering to each other. ing.
【０００４】従来、そのセラミック焼成用付着防止材と
しては融点の高いジルコニア粉末が用いられている（特
開昭６０−２２１３７８号）。また、このジルコニア粉
末にはＣａＯ，ＭｇＯ，Ｙ２Ｏ３等の安定化剤を混入し
たものが用いられている。然し、その安定化ジルコニア
粉末では不純物がセラミックグリーン成形体に著しく拡
散することにより、セラミック焼結体の化学的，機械的
及び電気的特性に影響を来すところから好ましくない。Hitherto, a zirconia powder having a high melting point has been used as an adhesion preventing material for ceramic firing (Japanese Patent Application Laid-Open No. 60-221378). The zirconia powder is mixed with a stabilizer such as CaO, MgO, and Y 2 O 3 . However, the stabilized zirconia powder is not preferable because impurities significantly diffuse into the ceramic green compact and affect the chemical, mechanical and electrical properties of the ceramic sintered compact.
【０００５】その安定化ジルコニア粉末に代えて、高純
度のジルコニア粉末を用いても付着防止を図れることは
知られている。また、このジルコニア粉末を用いるとき
にはセラミックグリーン成形体に均一に塗布する必要か
ら、平均粒径が４０μｍ以下のものでなければならない
ことも知られている。It is known that the use of high-purity zirconia powder in place of the stabilized zirconia powder can prevent adhesion. It is also known that when this zirconia powder is used, the average particle size must be 40 μm or less because it is necessary to apply the zirconia powder uniformly to the ceramic green compact.
【０００６】然し、その平均粒径が４０μｍ以下で高純
度のジルコニア粉末を用いたとしても、依然としてジル
コニア粉末の拡散が生じ、また、セラミック焼結体の収
縮率がバラ付くことにより変形やクラックが発生し、更
には、ジルコニア粉末自体の変質も生じて付着防止材と
しての役割を果たさない事態が生ずる。However, even if high-purity zirconia powder having an average particle size of 40 μm or less is used, diffusion of the zirconia powder still occurs, and deformation and cracks occur due to variation in shrinkage of the ceramic sintered body. Occurs, and further, the zirconia powder itself is deteriorated, and does not serve as an adhesion preventing material.
【０００７】茲において、本発明者らは種々条件の異な
るジルコニア粉末を製造し、それを用いて各種のセラミ
ック焼結体を試料として作成し、この試料の中からチッ
プ部品を構成するのに適する化学的，機械的及び電気的
特性を有するものを選別し、その試料に用いたジルコニ
ア粉末の条件を調査，研究した結果、ジルコニア粉末の
純度，平均粒径と共に、比表面積がセラミック焼結体の
特性に影響することを見出した。これと同時に、ジルコ
ニア粉末の純度はどの程度のものであればよいか、ま
た、平均粒径，比表面積は小さ過ぎても不適で上限値と
共に、下限値があることを見出した。[0007] Here, the present inventors produce zirconia powders having different conditions, prepare various ceramic sintered bodies as samples using the zirconia powders, and are suitable for forming chip parts from the samples. As a result of screening and studying the conditions of the zirconia powder used for the sample, the specific surface area of the ceramic sintered body together with the purity and the average particle size of the zirconia powder were determined. It was found to affect the properties. At the same time, it was found that the purity of the zirconia powder should be high, and that the average particle diameter and the specific surface area were too small to be suitable and had a lower limit as well as an upper limit.
【０００８】[0008]
【発明が解決しようとする課題】本発明は、化学的，機
械的及び電気的特性に優れたチップ部品を構成可能なセ
ラミック焼結体を製造するべく、その焼成にあたって使
用可能な条件設定したジルコニア粉末をセラミック焼成
用付着防止材として提供することを目的とする。SUMMARY OF THE INVENTION The present invention relates to a zirconia in which the conditions usable for firing are set in order to produce a ceramic sintered body capable of forming a chip component having excellent chemical, mechanical and electrical properties. An object of the present invention is to provide a powder as an adhesion preventing material for ceramic firing.
【０００９】また、本発明はジルコニア粉末をセラミッ
ク焼成用付着防止材として用い、化学的，機械的及び電
気的特性に優れたチップ部品を構成可能なセラミック焼
結体を製造可能なセラミック焼結体の製造方法を提供す
ることを目的とする。Further, the present invention provides a ceramic sintered body capable of producing a ceramic sintered body capable of forming a chip part having excellent chemical, mechanical and electrical properties by using zirconia powder as an adhesion preventing material for ceramic firing. It is an object of the present invention to provide a method for producing the same.
【００１０】[0010]
【課題を解決するための手段】本発明の請求項１に係る
セラミック焼成用付着防止材においては純度が９８．０
％以上で、平均粒径が４０．０μｍ未満，１．５μｍ以
上で、比表面積が３．０ｍ２／ｇ以下，０．５ｍ２／ｇ
以上とジルコニア粉末の使用可能な条件設定をしてな
る。According to the first aspect of the present invention, the adhesion preventing material for firing ceramics has a purity of 98.0.
% Or more, an average particle diameter of less than 40.0 μm, 1.5 μm or more, and a specific surface area of 3.0 m 2 / g or less, 0.5 m 2 / g.
The conditions for use of the zirconia powder are set as described above.
【００１１】本発明の請求項２に係るセラミック焼結体
の製造方法においては純度が９８．０％以上で、平均粒
径が４０．０μｍ未満，１．５μｍ以上で、比表面積が
３．０ｍ２／ｇ以下，０．５ｍ２／ｇ以上のジルコニア
粉末をセラミック焼成用付着防止材として焼成用治具並
びにセラミックグリーン成形体に塗布し、そのセラミッ
クグリーン成形体を焼成用治具に複数積載させて焼成処
理を行うようにされている。According to a second aspect of the present invention, there is provided a method for producing a ceramic sintered body having a purity of 98.0% or more, an average particle diameter of less than 40.0 μm, 1.5 μm or more, and a specific surface area of 3.0 m. 2 / g or less, 0.5 m 2 / g or more zirconia powder is applied to a firing jig and a ceramic green compact as an adhesion preventing material for ceramic firing, and a plurality of the ceramic green compacts are stacked on the firing jig. The baking process is performed.
【００１２】[0012]
【発明の実施の形態】本発明は、積層チップコンデン
サ，圧電積層体，圧電フィルタ，複合チップ部品等のチ
ップ部品を構成するセラミック焼結体を製造するのに適
用される。そのセラミック焼結体は、ＰｂＴｉＯ３また
はＰｂ（ＴｉＺｒ）Ｏ３等のセラミック粉末を主成分と
するセラミックグリーンペーストから押出し成形したセ
ラミックグリーンシートを所定形状のセラミックグリー
ン成形体としてプレス成形した後焼成処理を施すことに
より製造される。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention is applied to manufacturing a ceramic sintered body constituting a chip component such as a multilayer chip capacitor, a piezoelectric laminate, a piezoelectric filter, and a composite chip component. The ceramic sintered body is formed by pressing a ceramic green sheet extruded from a ceramic green paste containing a ceramic powder such as PbTiO 3 or Pb (TiZr) O 3 as a main component into a ceramic green molded body having a predetermined shape and then firing. It is manufactured by applying
【００１３】そのセラミックグリーン成形体は、焼成炉
に送り込む際には複数個を焼成用治具に積層させて送り
込む。この焼成用治具としては、マグネシア，アルミ
ナ，ムライト，ジルコニア製等の材質的に高耐熱性を有
し、構造的にはパレット状或いは棚状に組み立てられた
ものを用いることができる。When the ceramic green compact is fed into a firing furnace, a plurality of ceramic green compacts are stacked on a firing jig and fed. As the firing jig, a material made of magnesia, alumina, mullite, zirconia, or the like having high heat resistance in terms of material and assembled in a pallet-like or shelf-like structure can be used.
【００１４】その積載に先立って、セラミック焼成用の
付着防止材を焼成用治具とセラミックグリーン成形体と
に塗布する。このセラミック焼成用付着防止材としては
高純度のジルコニア（ＺｒＯ２）粉末を用い、そのジル
コニア粉末は、１２００℃程度の高温で熱処理した後に
高速気流を利用した乾式粉砕機を用いて粉砕，熱処理す
ることにより得られる。また、塗布は篩い掛け等で焼成
用治具並びにセラミックグリーン成形体に個別に処理す
ることができる。Prior to the loading, an adhesion preventing material for ceramic firing is applied to the firing jig and the ceramic green compact. High-purity zirconia (ZrO 2 ) powder is used as the adhesion preventing material for ceramic firing, and the zirconia powder is heat-treated at a high temperature of about 1200 ° C., and then pulverized and heat-treated using a dry pulverizer using a high-speed air flow. It can be obtained by: The coating can be individually applied to the firing jig and the ceramic green compact by sieving or the like.
【００１５】その焼成用治具に積載されたセラミックグ
リーン成形体には焼成炉に送り込んで、１０００〜１３
００℃程度の高温で０．５〜１０時間程度焼成処理を施
す。この焼成処理後、焼成炉から取り出して一枚毎に仕
分けし、水洗い処理することによりチップ部品を構成す
るセラミック焼結体として得られる。The ceramic green compact loaded on the firing jig is sent to a firing furnace,
A baking treatment is performed at a high temperature of about 00 ° C. for about 0.5 to 10 hours. After this firing treatment, it is taken out of the firing furnace, sorted one by one, and washed with water to obtain a ceramic sintered body constituting a chip component.
【００１６】そのセラミック焼成用の付着防止材として
適するジルコニア粉末の条件を見出すべく、次表で示す
ように種々条件の異なるジルコニア粉末を製造し、各ジ
ルコニア粉末の純度，比表面積並びに平均粒径を測定，
記録した。また、この条件の異なるジルコニア粉末をＰ
ｂＴｉＯ３のセラミックグリーン成形体並びにジルコニ
ア製の焼成用治具に塗布し、上述した工程を適用するこ
とにより複数個のセラミック焼結体を試料１〜１７とし
て作成した。In order to find conditions of zirconia powder suitable as an adhesion preventing material for firing the ceramic, zirconia powders having various conditions are produced as shown in the following table, and the purity, specific surface area and average particle size of each zirconia powder are determined. Measurement,
Recorded. In addition, zirconia powders having different conditions are referred to as P
A plurality of ceramic sintered bodies were prepared as samples 1 to 17 by applying to a ceramic green compact of bTiO 3 and a firing jig made of zirconia and applying the above-described steps.
【００１７】その試料１〜１７の中から、ジルコニア粉
末の拡散量，セラミック焼結体の変形量，ジルコニア粉
末の付着不良率（以下、単に「拡散量」「変形量」「付
着不良率」という。）に基づいてチップ部品を構成する
のに適する化学的，機械的及び電気的特性を有するもの
を選別した。この選別条件は、上述したセラミック焼結
体を用いて構成したチップ部品の化学的，機械的及び電
気的特性を検査することにより特定でき、ジルコニア粉
末の拡散量が０．０６ｗｔ％以下、セラミック焼結体の
変形量が０．０２％以下、ジルコニア粉末の付着不良率
が３％以下のものとした。From among the samples 1 to 17, the diffusion amount of the zirconia powder, the deformation amount of the ceramic sintered body, and the defective adhesion rate of the zirconia powder (hereinafter, simply referred to as “diffusion amount”, “deformation amount”, and “adhesion defective rate”). )), Those having chemical, mechanical and electrical properties suitable for constituting chip components were selected. The selection conditions can be specified by inspecting the chemical, mechanical and electrical characteristics of the chip component formed using the above-mentioned ceramic sintered body. The diffusion amount of the zirconia powder is 0.06% by weight or less, and the ceramic firing is performed. The amount of deformation of the binder was 0.02% or less, and the rate of defective adhesion of zirconia powder was 3% or less.
【００１８】[0018]
【表】 【table】
【００１９】上記表中で、試料Ｎｏ．の左側に付した＊
印はセラミック焼結体の特性からチップ部品を構成する
のに不適なものを示す。この表から、ジルコニア粉末の
純度については試料１〜５で示すように少なくとも９
５．６％以下では不適で、試料６のように９８．０％以
上のものでなければならないことが判る。また、試料１
５〜１７のように９８．５〜９９．９％と極めて高純度
のものであっても、その純度だけでは不適で、他の比表
面積並びに平均粒径の条件を共に満たさければならない
ことも判る。In the above table, sample No. * Attached to the left of
The marks indicate those that are unsuitable for constituting chip components due to the characteristics of the ceramic sintered body. From this table, it is found that the purity of the zirconia powder is at least 9 as shown in samples 1 to 5.
It is found that when the content is 5.6% or less, it is unsuitable, and it must be 98.0% or more as in Sample 6. Sample 1
Even if the purity is as high as 98.5 to 99.9% as in 5 to 17, it is not suitable only by its purity, and it is necessary to satisfy the conditions of other specific surface area and average particle size together. I understand.
【００２０】平均粒径からすると、試料１５で示すよう
に平均粒径が４０．０μｍのものは純度が９８．５％
で、比表面積が０．９ｍ２／ｇであっても、拡散量は
０．０４ｗｔ％、付着不良率は０％であるが、変形量が
０．７％と高いところから不適である。これから、平均
粒径は少なくとも４０．０μｍ未満のものでなけらばな
らないことが判る。In terms of the average particle size, as shown in Sample 15, the sample having an average particle size of 40.0 μm has a purity of 98.5%
Even if the specific surface area is 0.9 m 2 / g, the diffusion amount is 0.04 wt% and the adhesion failure rate is 0%, but the deformation amount is as high as 0.7%, which is inappropriate. This shows that the average particle size must be at least less than 40.0 μm.
【００２１】一方、試料４で示すように平均粒径が１．
３μｍと極めて小さくしかも純度が９３．０％と低けれ
ば、比表面積が２．６ｍ２／ｇであっても、拡散量が
０．３４ｗｔ％、変形量が０．７％、付着不良率が４％
と不適である。また、試料１６で示すように平均粒径が
１．４μｍ程度のものでは純度が９９．９％、比表面積
が２．８ｍ２／ｇでも、拡散量が０．２１ｗｔ％で、変
形量が０．６％並びに付着不良率が４％と高いところか
ら不適である。このため、平均粒径は試料７で示すよう
に下限でも１．５μｍ以上が必要であることが判る。On the other hand, as shown in Sample 4, the average particle size was 1.
If it is as small as 3 μm and the purity is as low as 93.0%, even if the specific surface area is 2.6 m 2 / g, the diffusion amount is 0.34 wt%, the deformation amount is 0.7%, and the adhesion failure rate is 4 %
And unsuitable. Further, as shown in Sample 16, when the average particle diameter is about 1.4 μm, the purity is 99.9%, and even if the specific surface area is 2.8 m 2 / g, the diffusion amount is 0.21 wt% and the deformation amount is 0. It is unsuitable because it has a high adhesion failure rate of 0.6% and a defective adhesion rate of 4%. Therefore, it is understood that the average particle size needs to be 1.5 μm or more even at the lower limit as shown in Sample 7.
【００２２】比表面積からすると、試料１２で示すよう
に比表面積が６．８ｍ２／ｇのものでは純度９９．９
％、平均粒径１６．７μｍでも、拡散量が０．２１ｗｔ
％、変形量が０．６％、付着不良率が４％と不適であ
る。また、試料１７で示すように比表面積が０．３ｍ２
／ｇのものでは純度が９８．５％、平均粒径が３８．０
μｍでも、変形量が０．８％と高いところから不適であ
る。In terms of the specific surface area, as shown in sample 12, the sample having a specific surface area of 6.8 m 2 / g has a purity of 99.9.
%, Even with an average particle size of 16.7 μm, the diffusion amount is 0.21 wt.
%, The deformation amount is 0.6%, and the adhesion failure rate is 4%, which is inappropriate. Further, as shown in Sample 17, the specific surface area was 0.3 m 2.
/ G, the purity is 98.5% and the average particle size is 38.0.
Even with μm, it is not suitable because the deformation amount is as high as 0.8%.
【００２３】これに対し、試料１３で示すように比表面
積が３．０ｍ２／ｇ以下のものでは、拡散量が０．０４
ｗｔ％、変形量が０．０２％、付着不良率が０％と適す
る。また、試料６で示すように比表面積が０．５ｍ２／
ｇ以上のものでも、拡散量が０．０４ｗｔ％、変形量が
０．０２％、付着不良率が０％と適することが判る。On the other hand, when the specific surface area is 3.0 m 2 / g or less as shown in Sample 13, the diffusion amount is 0.04
It is suitable that the wt%, the deformation amount is 0.02%, and the adhesion failure rate is 0%. Further, as shown in Sample 6, the specific surface area was 0.5 m 2 /
It can be seen that, even with g or more, the diffusion amount is suitable at 0.04 wt%, the deformation amount is 0.02%, and the adhesion failure rate is 0%.
【００２４】以上総合すると、ジルコニア粉末はセラミ
ック焼成用付着防止材として純度が９８．０％以上で、
平均粒径が４０．０μｍ未満，１．５μｍ以上で、比表
面積が３．０ｍ２／ｇ以下，０．５ｍ２／ｇ以上のもの
が好ましい。また、そのジルコニア粉末をセラミック焼
成用付着防止材として焼成用治具並びにセラミックグリ
ーン成形体に塗布し、そのセラミックグリーン成形体を
焼成用治具に複数積載させて焼成処理を行うことによ
り、拡散量が００４〜００６ｗｔ％、変形量が０．０２
％程度に抑えられて付着不良率が０％となるセラミック
焼結体を得ることができる。In summary, the zirconia powder has a purity of 98.0% or more as an adhesion preventing material for ceramic firing.
Those having an average particle size of less than 40.0 μm, 1.5 μm or more, and a specific surface area of 3.0 m 2 / g or less and 0.5 m 2 / g or more are preferable. Also, the zirconia powder is applied to a firing jig and a ceramic green compact as an anti-adhesion material for ceramic firing, and a plurality of the ceramic green compacts are stacked on a firing jig and subjected to a firing treatment, whereby the diffusion amount is reduced. Is 004 to 006 wt% and the deformation amount is 0.02
%, And a ceramic sintered body having an adhesion failure rate of 0% can be obtained.
【００２５】[0025]
【発明の効果】本発明の請求項１に係るセラミック焼成
用付着防止材に依れば、ジルコニア粉末をセラミック焼
成用の付着防止材として有用なものとすることができ
る。According to the anti-adhesion material for ceramic firing according to claim 1 of the present invention, zirconia powder can be used as an anti-adhesion material for ceramic firing.
【００２６】本発明の請求項２に係るセラミック焼結体
の製造方法に依れば、チップ部品を構成するのに好適な
化学的，機械的及び電気的特性を有するセラミック焼結
体を得ることができる。According to the method for manufacturing a ceramic sintered body according to the second aspect of the present invention, a ceramic sintered body having suitable chemical, mechanical and electrical properties for forming a chip component is obtained. Can be.
Claims (2)
０．０μｍ未満，１．５μｍ以上で、比表面積が３．０
ｍ2 ／ｇ％以下，０．５ｍ2 ／ｇ％以上のジルコニア粉
末でなることを特徴とするセラミック焼成用付着防止
材。(1) a purity of 98.0% or more and an average particle size of 4
Less than 0.0 μm, 1.5 μm or more, specific surface area of 3.0
An anti-adhesion material for ceramic firing, comprising zirconia powder of m 2 / g% or less and 0.5 m 2 / g% or more.
０．０μｍ未満，１．５μｍ以上で、比表面積が３．０
ｍ2 ／ｇ％以下，０．５ｍ2 ／ｇ％以上のジルコニア粉
末をセラミック焼成用付着防止材として焼成用治具並び
にセラミックグリーン成形体に塗布し、そのセラミック
グリーン成形体を焼成用治具に複数積載させて焼成処理
を行うようにしたことを特徴とするセラミック焼結体の
製造方法。2. Purity is 98.0% or more and average particle size is 4%.
Less than 0.0 μm, 1.5 μm or more, specific surface area of 3.0
A zirconia powder of m 2 / g% or less and 0.5 m 2 / g% or more is applied to a firing jig and a ceramic green compact as an adhesion preventing material for ceramic firing, and the ceramic green compact is applied to the firing jig. A method for manufacturing a ceramic sintered body, wherein a plurality of stacked ceramic bodies are fired.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10051508A JPH11228236A (en) | 1998-02-17 | 1998-02-17 | Adhesion-preventing material for sintering ceramic and production of ceramic sintered product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10051508A JPH11228236A (en) | 1998-02-17 | 1998-02-17 | Adhesion-preventing material for sintering ceramic and production of ceramic sintered product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11228236A true JPH11228236A (en) | 1999-08-24 |
Family
ID=12888950
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10051508A Pending JPH11228236A (en) | 1998-02-17 | 1998-02-17 | Adhesion-preventing material for sintering ceramic and production of ceramic sintered product |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11228236A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003192454A (en) * | 2001-09-10 | 2003-07-09 | Noritake Co Ltd | Production method of sheet member |
| JP2016135724A (en) * | 2015-01-23 | 2016-07-28 | Ｊｆｅケミカル株式会社 | Method for producing MnZn ferrite core |
-
1998
- 1998-02-17 JP JP10051508A patent/JPH11228236A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003192454A (en) * | 2001-09-10 | 2003-07-09 | Noritake Co Ltd | Production method of sheet member |
| JP2016135724A (en) * | 2015-01-23 | 2016-07-28 | Ｊｆｅケミカル株式会社 | Method for producing MnZn ferrite core |
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