WO2012056922A1 - Method and apparatus for manufacturing ceramic electronic component - Google Patents

Method and apparatus for manufacturing ceramic electronic component Download PDF

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Publication number
WO2012056922A1
WO2012056922A1 PCT/JP2011/073793 JP2011073793W WO2012056922A1 WO 2012056922 A1 WO2012056922 A1 WO 2012056922A1 JP 2011073793 W JP2011073793 W JP 2011073793W WO 2012056922 A1 WO2012056922 A1 WO 2012056922A1
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electronic component
superheated steam
ceramic electronic
degreasing
manufacturing
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PCT/JP2011/073793
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French (fr)
Japanese (ja)
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中村　和敬
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株式会社村田製作所
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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Definitions

  • the present invention relates to a method for manufacturing a ceramic electronic component.
  • the present invention also relates to an apparatus for manufacturing a ceramic electronic component.
  • a multilayer ceramic capacitor As a ceramic electronic component formed by firing a molded body containing ceramic powder and a binder, for example, a multilayer ceramic capacitor can be cited.
  • a method for producing a multilayer ceramic capacitor for example, a green sheet is produced by a doctor blade method using a slurry containing ceramic powder and a binder. An internal electrode is printed on the green sheet, and after stacking a plurality of green sheets, they are pressed and cut into chips to form a molded body. Thereafter, external electrodes are formed after degreasing and firing.
  • Patent Document 1 discloses a ceramic molding in which a binder is decomposed and removed by heat treatment at 1000 ° C. or less in a non-oxidizing gas atmosphere containing 5 to 90% by volume of water vapor A body degreasing method is disclosed.
  • the present invention has been made in view of such a problem, and an object of the present invention is to provide a method of manufacturing a ceramic electronic component and a manufacturing apparatus thereof that can be degreased in a short time without causing peeling or cracking.
  • the method for manufacturing a ceramic electronic component according to the present invention includes mixing ceramic powder and a binder to produce a mixture, forming the mixture to form a formed body, and supplying superheated steam to the formed body.
  • the method comprises a step of degreasing the molded body to form a degreased body and a step of firing the degreased body.
  • the superheated steam is supplied in a state of being mixed with air in the step of forming the degreased body.
  • the temperature of the superheated steam is equal to or higher than the thermal decomposition temperature of the binder.
  • the temperature of the superheated steam is preferably 250 to 600 ° C.
  • the molded body has an internal electrode.
  • the present invention is also directed to a ceramic electronic component manufacturing apparatus.
  • An apparatus for manufacturing a ceramic electronic component according to the present invention includes a degreasing chamber in which a molded body containing ceramic powder and a binder is disposed, steam generating means for generating steam, and heating the steam to superheated steam. And a superheated steam supply means for supplying the superheated steam to the molded body.
  • the ceramic electronic component manufacturing apparatus preferably further comprises a degreasing chamber heating means for heating the outer wall of the degreasing chamber.
  • the ceramic electronic component manufacturing apparatus may further include a connection path that connects the water vapor generation means and the superheated steam generation means, and an air introduction path that introduces air into the connection path. preferable.
  • the drainage path is disposed below the degreasing chamber so as to be connected to the degreasing chamber, and the drainage path for discharging the condensed water in the degreasing chamber; It is preferable to further include a drainage tank for storing water.
  • the superheated steam directly permeates the inside of the molded body, the temperature difference between the inside and the outside of the molded body is small, and the inside of the molded body can be heated quickly. Therefore, degreasing is possible in a short time without peeling or cracking.
  • the method for manufacturing a ceramic electronic component according to the present invention is manufactured as follows as an example.
  • make ceramic powder Specifically, it is produced by a solid-phase synthesis method in which compound powders such as oxides, carbonates, chlorides, and metal organic compounds containing the main constituent elements are mixed at a predetermined ratio and calcined.
  • a hydrothermal synthesis method, a hydrolysis method, or the like may be applied.
  • the obtained ceramic powder and a binder are mixed to prepare a slurry as a mixture.
  • the binder include acrylic resin, polyvinyl butyral, polyvinyl alcohol, and vinyl acetate.
  • a plasticizer and a dispersant may be mixed.
  • the obtained mixture is molded to form a molded body.
  • a ceramic green sheet is produced by a sheet forming method or the like.
  • a conductive paste is applied to a predetermined ceramic green sheet by printing or the like. And after laminating
  • the method in which an internal electrode is not formed such as a press molding method, may be used.
  • the molded body is degreased to form a degreased body.
  • superheated steam penetrates directly into the molded body because there are many holes and gaps through which the superheated steam passes. Therefore, the temperature difference between the inside and outside of the molded body is small, and the inside of the molded body can be heated quickly. Therefore, degreasing is possible in a short time while suppressing peeling and cracks that occur during conventional degreasing.
  • heating is performed using water having a higher thermal conductivity than air, so heat efficiency during degreasing is good.
  • the step of forming the degreased body it is preferable to supply superheated steam mixed with air.
  • oxygen is supplied at the same time, so that the thermal decomposition reaction of the binder is facilitated and degreasing is further promoted.
  • the temperature of the superheated steam is equal to or higher than the thermal decomposition temperature of the binder.
  • the thermal decomposition temperature of the binder refers to a temperature at which the thermal decomposition reaction of the binder is started. In this case, the thermal decomposition reaction of the binder is further promoted.
  • the temperature of the superheated steam is 250 to 600 ° C. In this case, the thermal decomposition reaction of the organic component, particularly the carbon component is promoted.
  • the internal electrode is hardly oxidized when degreasing using superheated steam.
  • the material of the internal electrode include those containing Ni, Ag / Pd, Pt, and Cu as main components.
  • the degreased body is fired to obtain a fired body.
  • external electrodes are formed on the end face of the fired body.
  • the external electrode is formed by applying and baking a conductive paste, for example.
  • FIG. 1 is a schematic diagram of an apparatus for manufacturing a ceramic electronic component.
  • a manufacturing apparatus 1 includes a degreasing chamber 52 that houses a molded body containing ceramic powder and a binder, a water vapor generating means 10 for generating water vapor, and heating water vapor into superheated water vapor. Heating steam generating means 30 and superheated steam supply means 40 for supplying superheated steam to the compact.
  • the water vapor generating means 10 has a water vapor generating chamber 12, a water supply means 14, a water tank 18, and a heating means 19.
  • the water 16 supplied from the water supply means 14 is stored in a water tank 18 in the steam generation chamber 12. Then, it is heated by the heating means 19 and evaporated to become water vapor.
  • connection path 24 is provided so as to connect the steam generating means 10 and the superheated steam generating means 30.
  • the superheated steam generating means 30 is provided to heat the steam to form heated steam.
  • the steam flowing in from the connection path 24 is heated by the superheated steam generating means 30 to become heated steam.
  • the air introduction path 22 is provided so as to introduce air into the connection path 26.
  • the superheated steam generated by the superheated steam generation means 30 is mixed with the superheated steam and air in the connection path 26. Then, the superheated steam whose temperature is lowered by mixing with air is reheated by the temperature holding heat source 35 and adjusted to an arbitrary temperature. Thereafter, the superheated steam enters the superheated steam supply means 40.
  • the superheated steam supply means 40 includes a supply path 42 and a nozzle 44.
  • the leading end of the supply path 42 reaches the inside of the degreasing chamber 52.
  • the superheated steam is supplied to the molded body placed on the table 56 in the degreasing chamber 52 through the superheated steam supply means 40.
  • the nozzle 44 is arranged so that superheated steam is ejected toward the surface of the molded body.
  • a degreasing chamber heating means 54 for heating the outer wall of the degreasing chamber 52 is provided around the outer wall of the degreasing chamber 52.
  • the degreasing chamber heating means 54 can prevent dew condensation that occurs in the degreasing chamber 52.
  • a drainage path 72 is arranged so as to be connected to the degreasing chamber 52.
  • the water generated when the molded body is heated is condensed in the degreasing chamber 52 and is discharged out of the degreasing chamber 52 through the drainage path 72.
  • the discharged water is stored as drainage 74 in a drainage tank 76 disposed below the degreasing chamber 52.
  • Gases such as carbon monoxide and methane generated at the time of degreasing are adsorbed with water molecules as described above, and are discharged together with the wastewater into the drainage tank. Therefore, compared with the conventional degreasing, there is an advantage that unnecessary gas is hardly generated.
  • this invention is not limited to said embodiment, A various deformation
  • a ceramic electronic component was produced as follows.
  • a ceramic powder was prepared. Specifically, BaTiO 3 powder, Dy 2 O 3 powder, and SiO 2 powder were prepared as the starting material compound powder. Then, with respect to BaTiO 3 100 mol, 0.02 mol of Dy 2 O 3, a SiO 2 was 0.5mol formulated. Then, pure water was added thereto, and the mixture was pulverized with a ball mill using PSZ beads as a medium. Then, the slurry after the mixing and pulverizing treatment was dehydrated and dried, granulated to have a particle size of about 50 ⁇ m, and then calcined at a temperature of 1200 ° C. for 2 hours.
  • a mixture was prepared. Specifically, with respect to 100 parts by weight of the dried product, 0.8 parts by weight of a polycarboxylic acid ammonium salt-based dispersant, 0.7 parts by weight of a dibutyl phthalate plasticizer, an acrylic resin 15 parts by weight of a system binder and a predetermined amount of pure water were weighed and added. Then, PSZ beads were mixed as media with a ball mill to obtain a sheet forming slurry.
  • a molded body was produced. Specifically, a green sheet having a thickness of 4 ⁇ m was prepared by a doctor blade method using a slurry for sheet forming. And the electrically conductive paste which contains Ni as a main component was printed on the green sheet, and was dried at 60 degreeC for 1 hour. Next, 100 green sheets on which conductive paste was not printed, 51 green sheets on which conductive paste was printed, and 100 green sheets on which conductive paste was not printed were sequentially stacked. These were pressure-bonded at a pressure of 20 MPa and then cut into a size of 2.0 mm ⁇ 1.2 mm. Then, together with the 3 mm ⁇ alumina beads, the cut molded body was put in a pot and subjected to barrel polishing using a planetary mill.
  • the obtained molded body was degreased as follows to prepare samples of Experimental Examples 1 and 2 and Comparative Examples 1 to 4.
  • Experimental Examples 1 and 2 are samples in which superheated steam was directly blown with a blower for 30 minutes to degrease the molded body.
  • Experimental Example 1 is a sample degreased with superheated steam at 250 ° C.
  • Experimental Example 2 is a sample degreased with 600 ° C. superheated steam.
  • Comparative Examples 1 to 4 are samples in which the molded body was heated to 300 ° C. and kept at 300 ° C. for 2 hours by a conventional degreasing method. Comparative Examples 1 to 4 are samples in which the heating rate was changed from 0.2 to 3.0 ° C./min.
  • the degreasing time of Comparative Examples 1 to 4 is the total time of the temperature rising time up to 300 ° C. and 2 hours that is the keeping time at 300 ° C.
  • a conductive paste containing Cu as a main component was applied to the end of the fired body and baked at a predetermined temperature and atmosphere to form external electrodes. Thereafter, electrolytic plating was performed in the order of Ni and Sn to form a plating film on the external electrode.

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Abstract

Provided are: a method for manufacturing a ceramic electronic component, wherein degreasing can be carried out in a short time; and an apparatus for manufacturing a ceramic electronic component. This method for manufacturing a ceramic electronic component is characterized by comprising: a step wherein a mixture is prepared by mixing a ceramic powder and a binder and a molded body is formed by molding the mixture; a step wherein superheated steam is supplied to the molded body so that the molded body is degreased, thereby forming a degreased body; and a step wherein the degreased body is fired.

Description

セラミック電子部品の製造方法及びその製造装置Method for manufacturing ceramic electronic component and apparatus for manufacturing the same
　本発明はセラミック電子部品の製造方法に関するものである。また、セラミック電子部品の製造装置に関するものである。 The present invention relates to a method for manufacturing a ceramic electronic component. The present invention also relates to an apparatus for manufacturing a ceramic electronic component.
　従来、セラミック粉末とバインダとを含んだ成形体を焼成してなるセラミック電子部品として、例えば積層セラミックコンデンサが挙げられる。積層セラミックコンデンサの製造方法としては、例えば、セラミック粉末とバインダとを含むスラリーを用いて、ドクターブレード法でグリーンシートを作製する。そのグリーンシートの上に内部電極を印刷して、グリーンシートを複数枚積み重ねた後に、圧着して、チップ状に切断して、成形体を形成する。その後、脱脂、焼成後に、外部電極を形成する。 Conventionally, as a ceramic electronic component formed by firing a molded body containing ceramic powder and a binder, for example, a multilayer ceramic capacitor can be cited. As a method for producing a multilayer ceramic capacitor, for example, a green sheet is produced by a doctor blade method using a slurry containing ceramic powder and a binder. An internal electrode is printed on the green sheet, and after stacking a plurality of green sheets, they are pressed and cut into chips to form a molded body. Thereafter, external electrodes are formed after degreasing and firing.
　ところで、脱脂時にはバインダが熱分解するため、その熱分解に起因して、成形体の内部構造に欠陥が発生するおそれがある。そのため、内部構造の欠陥を抑えるための方策として、例えば特許文献１では、水蒸気を５～９０体積％含む非酸化性ガス雰囲気中、１０００℃以下で加熱処理してバインダを分解除去する、セラミック成形体の脱脂方法が開示されている。 By the way, since the binder is thermally decomposed during degreasing, there is a possibility that a defect may occur in the internal structure of the molded body due to the thermal decomposition. Therefore, as a measure for suppressing defects in the internal structure, for example, Patent Document 1 discloses a ceramic molding in which a binder is decomposed and removed by heat treatment at 1000 ° C. or less in a non-oxidizing gas atmosphere containing 5 to 90% by volume of water vapor A body degreasing method is disclosed.
特開平７－１０９１７７号公報JP-A-7-109177
　従来の脱脂時の加熱は、ヒーター等の熱源により成形体の周囲の気体を加熱し、その周囲の気体を介して成形体を加熱する。そのため、周囲の気体を加熱する分、熱効率が低く、昇温や降温に時間がかかるという問題がある。また、従来の方法で急激に昇温した場合には、成形体にはがれやクラックが発生するおそれがある。 Conventional heating during degreasing involves heating the gas around the molded body with a heat source such as a heater and heating the molded body through the surrounding gas. Therefore, there is a problem that heat efficiency is low due to heating of the surrounding gas, and it takes time to raise and lower the temperature. Further, when the temperature is rapidly increased by a conventional method, there is a possibility that the molded body may be peeled or cracked.
　本発明はかかる課題に鑑みてなされたものであり、はがれやクラックが発生せずに、短時間で脱脂が可能であるセラミック電子部品の製造方法及びその製造装置を提供することを目的とする。 The present invention has been made in view of such a problem, and an object of the present invention is to provide a method of manufacturing a ceramic electronic component and a manufacturing apparatus thereof that can be degreased in a short time without causing peeling or cracking.
　本発明に係るセラミック電子部品の製造方法は、セラミック粉末とバインダとを混合して混合物を作製し、前記混合物を成形して成形体を形成する工程と、前記成形体に過熱水蒸気を供給することで、前記成形体を脱脂して脱脂体を形成する工程と、前記脱脂体を焼成する工程と、を備えることを特徴としている。 The method for manufacturing a ceramic electronic component according to the present invention includes mixing ceramic powder and a binder to produce a mixture, forming the mixture to form a formed body, and supplying superheated steam to the formed body. Thus, the method comprises a step of degreasing the molded body to form a degreased body and a step of firing the degreased body.
　また、本発明に係るセラミック電子部品の製造方法では、前記脱脂体を形成する工程において、前記過熱水蒸気を空気と混合した状態で供給することが好ましい。 In the method for manufacturing a ceramic electronic component according to the present invention, it is preferable that the superheated steam is supplied in a state of being mixed with air in the step of forming the degreased body.
　また、本発明に係るセラミック電子部品の製造方法では、前記過熱水蒸気の温度が前記バインダの熱分解温度以上であることが好ましい。 In the method for manufacturing a ceramic electronic component according to the present invention, it is preferable that the temperature of the superheated steam is equal to or higher than the thermal decomposition temperature of the binder.
　また、本発明に係るセラミック電子部品の製造方法では、前記過熱水蒸気の温度が２５０～６００℃であることが好ましい。 In the method for manufacturing a ceramic electronic component according to the present invention, the temperature of the superheated steam is preferably 250 to 600 ° C.
　また、本発明に係るセラミック電子部品の製造方法では、前記成形体が内部電極を有することが好ましい。 In the method for manufacturing a ceramic electronic component according to the present invention, it is preferable that the molded body has an internal electrode.
　また、本発明は、セラミック電子部品の製造装置にも向けられる。 The present invention is also directed to a ceramic electronic component manufacturing apparatus.
　本発明に係るセラミック電子部品の製造装置は、セラミック粉末とバインダとを含む成形体を内部に配置する脱脂室と、水蒸気を発生させるための水蒸気発生手段と、前記水蒸気を加熱して過熱水蒸気にするための過熱水蒸気発生手段と、前記成形体に前記過熱水蒸気を供給する過熱水蒸気供給手段と、を備えることを特徴としている。 An apparatus for manufacturing a ceramic electronic component according to the present invention includes a degreasing chamber in which a molded body containing ceramic powder and a binder is disposed, steam generating means for generating steam, and heating the steam to superheated steam. And a superheated steam supply means for supplying the superheated steam to the molded body.
　また、本発明に係るセラミック電子部品の製造装置では、前記脱脂室の外壁を加熱する脱脂室加熱手段をさらに備えることが好ましい。 Moreover, the ceramic electronic component manufacturing apparatus according to the present invention preferably further comprises a degreasing chamber heating means for heating the outer wall of the degreasing chamber.
　また、本発明に係るセラミック電子部品の製造装置では、前記水蒸気発生手段と前記過熱水蒸気発生手段とを接続する接続経路と、前記接続経路に空気を導入する空気導入経路と、をさらに備えることが好ましい。 The ceramic electronic component manufacturing apparatus according to the present invention may further include a connection path that connects the water vapor generation means and the superheated steam generation means, and an air introduction path that introduces air into the connection path. preferable.
　また、本発明に係るセラミック電子部品の製造方法では、前記脱脂室と接続するように前記脱脂室の下方に配置されており、前記脱脂室内で結露した水を排出する排水経路と、前記排出された水を貯留する排水槽と、をさらに備えることが好ましい。 Further, in the method of manufacturing a ceramic electronic component according to the present invention, the drainage path is disposed below the degreasing chamber so as to be connected to the degreasing chamber, and the drainage path for discharging the condensed water in the degreasing chamber; It is preferable to further include a drainage tank for storing water.
　本発明では、過熱水蒸気が成形体の内部に直接浸透するため、成形体の内部と外部の温度差が小さく、成形体の内部を素早く加熱することができる。したがって、はがれやクラックが発生せずに、短時間で脱脂が可能である。 In the present invention, since the superheated steam directly permeates the inside of the molded body, the temperature difference between the inside and the outside of the molded body is small, and the inside of the molded body can be heated quickly. Therefore, degreasing is possible in a short time without peeling or cracking.
本発明に係るセラミック電子部品の製造装置を示す概略図である。It is the schematic which shows the manufacturing apparatus of the ceramic electronic component which concerns on this invention.
　以下において、本発明を実施するための形態について説明する。 Hereinafter, embodiments for carrying out the present invention will be described.
　本発明に係るセラミック電子部品の製造方法は、一例として、以下のように作製される。 The method for manufacturing a ceramic electronic component according to the present invention is manufactured as follows as an example.
　最初に、セラミック粉末を作製する。具体的には、主成分の構成元素を含む酸化物、炭酸物、塩化物、金属有機化合物等の化合物粉末を所定の割合で混合し、仮焼する固相合成法で作製される。なお、固相合成法の他に、水熱合成法や加水分解法等を適用しても良い。 First, make ceramic powder. Specifically, it is produced by a solid-phase synthesis method in which compound powders such as oxides, carbonates, chlorides, and metal organic compounds containing the main constituent elements are mixed at a predetermined ratio and calcined. In addition to the solid phase synthesis method, a hydrothermal synthesis method, a hydrolysis method, or the like may be applied.
　次に、得られたセラミック粉末とバインダとを混合して、混合物としてのスラリーを作製する。バインダの例としては、アクリル樹脂系、ポリビニルブチラール系、ポリビニルアルコール系、酢酸ビニル系等が挙げられる。なお、バインダの他に、可塑剤や分散剤が混合されていても良い。 Next, the obtained ceramic powder and a binder are mixed to prepare a slurry as a mixture. Examples of the binder include acrylic resin, polyvinyl butyral, polyvinyl alcohol, and vinyl acetate. In addition to the binder, a plasticizer and a dispersant may be mixed.
　次に、得られた混合物を成形して成形体を形成する。まず、上述したスラリーを用いて、シート成形法等によりセラミックグリーンシートを作製する。そして、所定のセラミックグリーンシートに導電性ペーストを印刷等で塗布する。そして、セラミックグリーンシートを複数枚積層した後に圧着して、所定の大きさに切断して、成形体を得る。なお、成形体の形成方法の例としては、プレス成形法等、内部電極が形成されない方法であっても良い。 Next, the obtained mixture is molded to form a molded body. First, using the slurry described above, a ceramic green sheet is produced by a sheet forming method or the like. Then, a conductive paste is applied to a predetermined ceramic green sheet by printing or the like. And after laminating | stacking several ceramic green sheets, it crimps | bonds and cut | disconnects to a predetermined | prescribed magnitude | size and obtains a molded object. In addition, as an example of the formation method of a molded object, the method in which an internal electrode is not formed, such as a press molding method, may be used.
　次に、成形体に過熱水蒸気を供給することで、成形体を脱脂して脱脂体を形成する。本発明のように過熱水蒸気を用いた場合には、成形体の内部には過熱水蒸気が通過する孔や隙間が多いため、過熱水蒸気が成形体の内部に直接浸透する。そのため、成形体の内部と外部の温度差が小さく、成形体の内部を素早く加熱することができる。したがって、従来の脱脂時に生じるはがれやクラックを抑えて、短時間で脱脂が可能である。 Next, by supplying superheated steam to the molded body, the molded body is degreased to form a degreased body. When superheated steam is used as in the present invention, the superheated steam penetrates directly into the molded body because there are many holes and gaps through which the superheated steam passes. Therefore, the temperature difference between the inside and outside of the molded body is small, and the inside of the molded body can be heated quickly. Therefore, degreasing is possible in a short time while suppressing peeling and cracks that occur during conventional degreasing.
　また、水分子はバインダ等の分解時に発生する一酸化炭素やメタンや低級アルコールを吸着するため、脱脂時に一酸化炭素やメタン等の気体が発生しにくい。また、脱脂時にメタン等を原因とする急激な燃焼が生じにくいため、従来の脱脂時に生じるはがれやクラックが発生しにくい。 In addition, since water molecules adsorb carbon monoxide, methane, and lower alcohol generated during decomposition of the binder and the like, gases such as carbon monoxide and methane are hardly generated during degreasing. Further, since rapid combustion due to methane or the like is unlikely to occur during degreasing, peeling and cracks that occur during conventional degreasing are unlikely to occur.
　また、従来の脱脂と異なり、空気より熱伝導率の高い水を用いて加熱するため、脱脂時の熱効率が良い。 Also, unlike conventional degreasing, heating is performed using water having a higher thermal conductivity than air, so heat efficiency during degreasing is good.
　脱脂体を形成する工程においては、過熱水蒸気を空気と混合した状態で供給することが好ましい。この場合には、過熱水蒸気のみを成形体に供給する場合に比べて、酸素が同時に供給されることにより、バインダの熱分解反応がされやすく、脱脂がより促進される。 In the step of forming the degreased body, it is preferable to supply superheated steam mixed with air. In this case, compared with the case where only superheated steam is supplied to the molded body, oxygen is supplied at the same time, so that the thermal decomposition reaction of the binder is facilitated and degreasing is further promoted.
　また、過熱水蒸気の温度がバインダの熱分解温度以上であることが好ましい。バインダの熱分解温度とは、バインダの熱分解反応が開始される温度を指す。この場合には、バインダの熱分解反応がより促進されるためである。 Further, it is preferable that the temperature of the superheated steam is equal to or higher than the thermal decomposition temperature of the binder. The thermal decomposition temperature of the binder refers to a temperature at which the thermal decomposition reaction of the binder is started. In this case, the thermal decomposition reaction of the binder is further promoted.
　また、過熱水蒸気の温度が２５０～６００℃であることが好ましい。この場合には、有機成分、特に炭素成分の熱分解反応が促進されるためである。 Further, it is preferable that the temperature of the superheated steam is 250 to 600 ° C. In this case, the thermal decomposition reaction of the organic component, particularly the carbon component is promoted.
　また、成形体が内部電極を有する場合には、過熱水蒸気を用いて脱脂をすると、内部電極が酸化しにくいという利点を有する。内部電極の材質の例としては、Ｎｉ、Ａｇ／Ｐｄ、Ｐｔ、Ｃｕを主成分として含むものが挙げられる。 In addition, when the molded body has an internal electrode, there is an advantage that the internal electrode is hardly oxidized when degreasing using superheated steam. Examples of the material of the internal electrode include those containing Ni, Ag / Pd, Pt, and Cu as main components.
　最後に、脱脂体を焼成して焼成体にする。必要に応じて、焼成体の端面に外部電極を形成する。外部電極は、例えば、導電性ペーストを塗布して、焼き付けることにより形成される。 Finally, the degreased body is fired to obtain a fired body. If necessary, external electrodes are formed on the end face of the fired body. The external electrode is formed by applying and baking a conductive paste, for example.
　次に、本発明に係るセラミック電子部品の製造装置の一例について説明する。図１は、セラミック電子部品の製造装置の概略図である。図１において、製造装置１は、セラミック粉末とバインダとを含む成形体を内部に収納する脱脂室５２と、水蒸気を発生するための水蒸気発生手段１０と、水蒸気を加熱して過熱水蒸気にするための加熱水蒸気発生手段３０と、成形体に過熱水蒸気を供給する過熱水蒸気供給手段４０と、を備えている。 Next, an example of a ceramic electronic component manufacturing apparatus according to the present invention will be described. FIG. 1 is a schematic diagram of an apparatus for manufacturing a ceramic electronic component. In FIG. 1, a manufacturing apparatus 1 includes a degreasing chamber 52 that houses a molded body containing ceramic powder and a binder, a water vapor generating means 10 for generating water vapor, and heating water vapor into superheated water vapor. Heating steam generating means 30 and superheated steam supply means 40 for supplying superheated steam to the compact.
　水蒸気発生手段１０は、水蒸気発生室１２と、水供給手段１４と、水槽１８と、加熱手段１９と、を有している。水供給手段１４から供給された水１６は、水蒸気発生室１２内の水槽１８に貯留される。そして、加熱手段１９により加熱され、蒸発して水蒸気となる。 The water vapor generating means 10 has a water vapor generating chamber 12, a water supply means 14, a water tank 18, and a heating means 19. The water 16 supplied from the water supply means 14 is stored in a water tank 18 in the steam generation chamber 12. Then, it is heated by the heating means 19 and evaporated to become water vapor.
　接続経路２４は、水蒸気発生手段１０と過熱水蒸気発生手段３０とを接続するように設けられている。過熱水蒸気発生手段３０は、水蒸気を加熱して加熱水蒸気にするために設けられている。接続経路２４から流入した水蒸気は、過熱水蒸気発生手段３０で加熱されて加熱水蒸気となる。 The connection path 24 is provided so as to connect the steam generating means 10 and the superheated steam generating means 30. The superheated steam generating means 30 is provided to heat the steam to form heated steam. The steam flowing in from the connection path 24 is heated by the superheated steam generating means 30 to become heated steam.
　空気導入経路２２は、接続経路２６に空気を導入するように設けられている。過熱水蒸気発生手段３０で発生した過熱水蒸気は、接続経路２６で過熱水蒸気と空気の混合状態になる。そして、空気との混合により温度の低下した過熱水蒸気は温度保持用熱源３５で再加熱されて任意の温度に調節される。その後、過熱水蒸気は過熱水蒸気供給手段４０に入る。 The air introduction path 22 is provided so as to introduce air into the connection path 26. The superheated steam generated by the superheated steam generation means 30 is mixed with the superheated steam and air in the connection path 26. Then, the superheated steam whose temperature is lowered by mixing with air is reheated by the temperature holding heat source 35 and adjusted to an arbitrary temperature. Thereafter, the superheated steam enters the superheated steam supply means 40.
　過熱水蒸気供給手段４０は、供給経路４２とノズル４４とを備えている。そして、供給経路４２の先端は脱脂室５２の内部に到達している。過熱水蒸気は過熱水蒸気供給手段４０を経て、脱脂室内５２の台５６に載置されている成形体に供給される。ノズル４４は、過熱水蒸気が成形体の表面に向かって噴出するように配置されている。 The superheated steam supply means 40 includes a supply path 42 and a nozzle 44. The leading end of the supply path 42 reaches the inside of the degreasing chamber 52. The superheated steam is supplied to the molded body placed on the table 56 in the degreasing chamber 52 through the superheated steam supply means 40. The nozzle 44 is arranged so that superheated steam is ejected toward the surface of the molded body.
　従来の脱脂の場合には、脱脂室内の空気を加熱する必要があるため、熱源を脱脂室内に配置する。そのため、水蒸気が多い場合には、熱源に水蒸気が結露して、漏電するおそれがある。一方、本発明では、過熱水蒸気発生手段３０の熱源は脱脂室５２の室外に配置され脱脂室５２から分離されているため、熱源での漏電を防ぐことができる。 In the case of conventional degreasing, since it is necessary to heat the air in the degreasing chamber, a heat source is arranged in the degreasing chamber. Therefore, when there is much water vapor | steam, there exists a possibility that water vapor | steam may condense to a heat source and an electric leakage may occur. On the other hand, in the present invention, since the heat source of the superheated steam generating means 30 is arranged outside the degreasing chamber 52 and separated from the degreasing chamber 52, leakage of the heat source can be prevented.
　脱脂室５２の外壁の周囲には、脱脂室５２の外壁を加熱する脱脂室加熱手段５４が設けられている。脱脂室加熱手段５４により、脱脂室５２内に生じる結露を防ぐことが可能である。 A degreasing chamber heating means 54 for heating the outer wall of the degreasing chamber 52 is provided around the outer wall of the degreasing chamber 52. The degreasing chamber heating means 54 can prevent dew condensation that occurs in the degreasing chamber 52.
　脱脂室５２の下方には、排水経路７２が脱脂室５２と接続されるように配置されている。成形体を加熱する際に発生した水は脱脂室５２内で結露し、排水経路７２を通って脱脂室５２の外へ排出される。排出された水は、脱脂室５２の下方に配置されている排水槽７６に排水７４として貯留される。脱脂時に発生する一酸化炭素やメタン等の気体は、前述したように水分子と吸着して、排水と一緒に排水槽に排出される。そのため、従来の脱脂と比較すると、不要な気体が発生しにくい利点を有する。 Below the degreasing chamber 52, a drainage path 72 is arranged so as to be connected to the degreasing chamber 52. The water generated when the molded body is heated is condensed in the degreasing chamber 52 and is discharged out of the degreasing chamber 52 through the drainage path 72. The discharged water is stored as drainage 74 in a drainage tank 76 disposed below the degreasing chamber 52. Gases such as carbon monoxide and methane generated at the time of degreasing are adsorbed with water molecules as described above, and are discharged together with the wastewater into the drainage tank. Therefore, compared with the conventional degreasing, there is an advantage that unnecessary gas is hardly generated.
　なお、本発明は上記の実施形態に限定されるものではなく、要旨を逸脱しない範囲において種々の変形が可能である。 In addition, this invention is not limited to said embodiment, A various deformation | transformation is possible in the range which does not deviate from a summary.
　［実験例］
　以下のようにしてセラミック電子部品を作製した。 [Experimental example]
A ceramic electronic component was produced as follows.
　最初に、セラミック粉末を作製した。具体的には、出発原料の化合物粉末として、ＢａＴｉＯ3粉末、Ｄｙ2Ｏ3粉末、及びＳｉＯ2粉末を準備した。そして、ＢａＴｉＯ3１００ｍｏｌに対して、Ｄｙ2Ｏ3を０．０２ｍｏｌ、ＳｉＯ2を０．５ｍｏｌ調合した。そして、これに純水を加えて、ＰＳＺビーズをメディアとしてボールミルで混合粉砕処理を行った。そして、混合粉砕処理後のスラリーを脱水乾燥して、５０μｍ程度の粒径となるように造粒した後、１２００℃の温度で２時間仮焼した。そして、仮焼後に純水を加え、ＰＳＺビーズをメディアとしてボールミルで平均粒径が０．５μｍになるまで混合粉砕処理を行った。その後、スラリーを脱水乾燥してセラミック粉末を作製した。 First, a ceramic powder was prepared. Specifically, BaTiO 3 powder, Dy 2 O 3 powder, and SiO 2 powder were prepared as the starting material compound powder. Then, with respect to BaTiO 3 100 mol, 0.02 mol of Dy 2 O 3, a SiO 2 was 0.5mol formulated. Then, pure water was added thereto, and the mixture was pulverized with a ball mill using PSZ beads as a medium. Then, the slurry after the mixing and pulverizing treatment was dehydrated and dried, granulated to have a particle size of about 50 μm, and then calcined at a temperature of 1200 ° C. for 2 hours. Then, pure water was added after calcination, and the mixture was pulverized with PSZ beads as a medium until the average particle size became 0.5 μm with a ball mill. Thereafter, the slurry was dehydrated and dried to produce a ceramic powder.
　次に、混合物を作製した。具体的には、上記の乾燥物１００重量部に対して、ポリカルボン酸アンモニウム塩系の分散剤を０．８重量部と、フタル酸ジブチル系の可塑剤を０．７重量部と、アクリル樹脂系のバインダを１５重量部と、所定量の純水とを秤量して加えた。そして、ＰＳＺビーズをメディアとしてボールミルで混合して、シート成形用のスラリーとした。 Next, a mixture was prepared. Specifically, with respect to 100 parts by weight of the dried product, 0.8 parts by weight of a polycarboxylic acid ammonium salt-based dispersant, 0.7 parts by weight of a dibutyl phthalate plasticizer, an acrylic resin 15 parts by weight of a system binder and a predetermined amount of pure water were weighed and added. Then, PSZ beads were mixed as media with a ball mill to obtain a sheet forming slurry.
　次に、成形体を作製した。具体的には、シート成形用のスラリーを用いて、ドクターブレード法により厚み４μｍのグリーンシートを作製した。そして、Ｎｉを主成分として含む導電性ペーストをグリーンシート上に印刷して、６０℃で１時間乾燥させた。次に、導電性ペーストが印刷されていないグリーンシートを１００枚、導電性ペーストが印刷されたグリーンシートを５１枚、導電性ペーストが印刷されていないグリーンシートを１００枚、順次積層した。そして、これらを２０ＭＰａの圧力で圧着した後、２．０ｍｍ×１．２ｍｍの寸法に切断した。そして、３ｍｍφのアルミナビーズとともに、切断した成形体をポットに入れて、遊星ミルを用いてバレル研磨を施した。 Next, a molded body was produced. Specifically, a green sheet having a thickness of 4 μm was prepared by a doctor blade method using a slurry for sheet forming. And the electrically conductive paste which contains Ni as a main component was printed on the green sheet, and was dried at 60 degreeC for 1 hour. Next, 100 green sheets on which conductive paste was not printed, 51 green sheets on which conductive paste was printed, and 100 green sheets on which conductive paste was not printed were sequentially stacked. These were pressure-bonded at a pressure of 20 MPa and then cut into a size of 2.0 mm × 1.2 mm. Then, together with the 3 mmφ alumina beads, the cut molded body was put in a pot and subjected to barrel polishing using a planetary mill.
　得られた成形体に対して、以下のように脱脂を行い、実験例１、２と比較例１～４の試料を作製した。 The obtained molded body was degreased as follows to prepare samples of Experimental Examples 1 and 2 and Comparative Examples 1 to 4.
　（実験例１、２）
　実験例１、２は、過熱水蒸気をブロアで３０分間直接吹きかけて、成形体を脱脂した試料である。実験例１は２５０℃の過熱水蒸気で脱脂した試料である。また、実験例２は６００℃の過熱水蒸気で脱脂した試料である。 (Experimental Examples 1 and 2)
Experimental Examples 1 and 2 are samples in which superheated steam was directly blown with a blower for 30 minutes to degrease the molded body. Experimental Example 1 is a sample degreased with superheated steam at 250 ° C. Experimental Example 2 is a sample degreased with 600 ° C. superheated steam.
　（比較例１～４）
　比較例１～４は、従来の脱脂方法で、成形体を３００℃まで昇温させて、３００℃で２時間キープした試料である。比較例１～４は昇温速度を０．２～３．０℃／分まで変えた試料である。比較例１～４の脱脂時間は、３００℃までの昇温時間と、３００℃でのキープ時間である２時間を合計した時間である。 (Comparative Examples 1 to 4)
Comparative Examples 1 to 4 are samples in which the molded body was heated to 300 ° C. and kept at 300 ° C. for 2 hours by a conventional degreasing method. Comparative Examples 1 to 4 are samples in which the heating rate was changed from 0.2 to 3.0 ° C./min. The degreasing time of Comparative Examples 1 to 4 is the total time of the temperature rising time up to 300 ° C. and 2 hours that is the keeping time at 300 ° C.
　得られた実験例１、２と比較例１～４の試料を、Ｈ2２％、Ｎ2９８体積％の雰囲気で１２５０℃の温度で５時間焼成した。 The obtained sample of Comparative Example 1-4 and Experimental Examples 1 and 2, H 2 2%, and calcined 5 hours at a temperature of 1250 ° C. in an atmosphere of N 2 98 vol%.
　次に、焼成体の端部に、Ｃｕを主成分とする導電性ペーストを塗布して、所定の温度、雰囲気で焼き付けて、外部電極を形成した。その後、Ｎｉ、Ｓｎの順に電解めっきを施して、外部電極上にめっき膜を形成した。 Next, a conductive paste containing Cu as a main component was applied to the end of the fired body and baked at a predetermined temperature and atmosphere to form external electrodes. Thereafter, electrolytic plating was performed in the order of Ni and Sn to form a plating film on the external electrode.
　以上のように得られたセラミック電子部品の外観と電気特性を評価した。外観は、クラックとはがれの項目について、１００個目視で確認した。また、εｒおよびＱは、ＬＣＲメータで１ｋＨｚ，０．１Ｖｒｍｓの条件で測定を行った。また、耐圧は、直流電圧を印加し、徐々に昇圧して、試料が破壊した電圧より求めた。εｒ、Ｑおよび耐圧は、２０個測定してその平均を求めた。表１にその結果を示す。比較例３と比較例４では、セラミックと内部電極との間ではがれが生じたため電気特性の評価を行うことができなかった。 The appearance and electrical characteristics of the ceramic electronic parts obtained as described above were evaluated. Appearance was confirmed by visually checking 100 items for cracking and peeling. Εr and Q were measured with an LCR meter under the conditions of 1 kHz and 0.1 Vrms. The withstand voltage was obtained from the voltage at which the sample was destroyed by applying a DC voltage and gradually increasing the voltage. εr, Q, and breakdown voltage were measured and 20 averages were obtained. Table 1 shows the results. In Comparative Example 3 and Comparative Example 4, the electrical characteristics could not be evaluated because peeling occurred between the ceramic and the internal electrode.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　従来の方法で脱脂時間を短縮する場合には、昇温速度を上げる必要がある。そして、比較例３、４のように昇温速度を上げた場合には、はがれが生じ、電気特性の評価を行うことができなかった。 In order to shorten the degreasing time by the conventional method, it is necessary to increase the heating rate. When the temperature raising rate was increased as in Comparative Examples 3 and 4, peeling occurred, and the electrical characteristics could not be evaluated.
　一方、本発明の過熱水蒸気で脱脂した実験例１、２では、比較例１、２と同様の電気特性が得られている。また、従来の方法では１２時間以上かかっていた脱脂時間が３０分となり、短時間での脱脂が可能であった。 On the other hand, in Experimental Examples 1 and 2 degreased with superheated steam of the present invention, the same electrical characteristics as Comparative Examples 1 and 2 were obtained. Moreover, the degreasing time, which took 12 hours or more in the conventional method, was 30 minutes, and degreasing was possible in a short time.
　また、実験例１と２の脱脂中に発生した気体に着火しようと試みたが、着火することができなかった。したがって、実験例１と２では、燃焼する不要な気体が発生していないことが分かった。 In addition, although an attempt was made to ignite the gas generated during the degreasing in Experimental Examples 1 and 2, the gas could not be ignited. Therefore, in Experimental Examples 1 and 2, it was found that no unnecessary gas for burning was generated.
　１　製造装置
　１０　水蒸気発生手段
　１２　水蒸気発生室
　１４　水供給手段
　１６　水
　１８　水槽
　１９　加熱手段
　２２　空気導入経路
　２４、２６　接続経路
　３０　過熱水蒸気発生手段
　３５　温度保持用熱源
　４０　過熱水蒸気供給手段
　４２　供給経路
　４４　ノズル
　５２　脱脂室
　５４　脱脂室加熱手段
　５６　台
　７２　排水経路
　７４　排水
　７６　排水槽 DESCRIPTION OF SYMBOLS 1 Manufacturing apparatus 10 Water vapor generation means 12 Water vapor generation chamber 14 Water supply means 16 Water 18 Water tank 19 Heating means 22 Air introduction path 24, 26 Connection path 30 Superheated steam generation means 35 Heat source for temperature maintenance 40 Superheated steam supply means 42 Supply path 44 Nozzle 52 Degreasing chamber 54 Degreasing chamber heating means 56 units 72 Drainage path 74 Drainage 76 Drainage tank

Claims (9)

  1. 　セラミック粉末とバインダとを混合して混合物を作製し、前記混合物を成形して成形体を形成する工程と、
    　前記成形体に過熱水蒸気を供給することで、前記成形体を脱脂して脱脂体を形成する工程と、
    　前記脱脂体を焼成する工程と、
    を備える、セラミック電子部品の製造方法。     Mixing ceramic powder and a binder to produce a mixture, and forming the mixture to form a molded body; and
    Supplying superheated steam to the molded body to degrease the molded body to form a degreased body;
    Firing the degreased body;
    A method for manufacturing a ceramic electronic component.
  2. 　前記脱脂体を形成する工程において、前記過熱水蒸気を空気と混合した状態で供給する、請求項１に記載のセラミック電子部品の製造方法。 The method for producing a ceramic electronic component according to claim 1, wherein in the step of forming the degreased body, the superheated steam is supplied in a state of being mixed with air.
  3. 　前記過熱水蒸気の温度が前記バインダの熱分解温度以上である、請求項１または２に記載のセラミック電子部品の製造方法。 The method for producing a ceramic electronic component according to claim 1 or 2, wherein a temperature of the superheated steam is equal to or higher than a thermal decomposition temperature of the binder.
  4. 　前記過熱水蒸気の温度が２５０～６００℃である、請求項１～３のいずれか１項に記載のセラミック電子部品の製造方法。 The method for manufacturing a ceramic electronic component according to any one of claims 1 to 3, wherein the temperature of the superheated steam is 250 to 600 ° C.
  5. 　前記成形体が内部電極を有する、請求項１～４のいずれか１項に記載のセラミック電子部品の製造方法。 The method for manufacturing a ceramic electronic component according to any one of claims 1 to 4, wherein the formed body has an internal electrode.
  6. 　セラミック粉末とバインダとを含む成形体を内部に収納する脱脂室と、
    　水蒸気を発生させるための水蒸気発生手段と、
    　前記水蒸気を加熱して過熱水蒸気にするための過熱水蒸気発生手段と、
    　前記成形体に前記過熱水蒸気を供給する過熱水蒸気供給手段と、
    を備える、セラミック電子部品の製造装置。     A degreasing chamber for accommodating therein a molded body containing ceramic powder and a binder;
    Water vapor generating means for generating water vapor;
    Superheated steam generating means for heating the steam to superheated steam;
    Superheated steam supply means for supplying the superheated steam to the molded body;
    A ceramic electronic component manufacturing apparatus comprising:
  7. 　前記脱脂室の外壁を加熱する脱脂室加熱手段をさらに備える、請求項６に記載のセラミック電子部品の製造装置。 The apparatus for manufacturing a ceramic electronic component according to claim 6, further comprising a degreasing chamber heating means for heating an outer wall of the degreasing chamber.
  8. 　前記水蒸気発生手段と前記過熱水蒸気発生手段とを接続する接続経路と、前記接続経路に空気を導入する空気導入経路と、をさらに備える、請求項６または７に記載のセラミック電子部品の製造装置。 The apparatus for manufacturing a ceramic electronic component according to claim 6 or 7, further comprising: a connection path that connects the water vapor generation means and the superheated steam generation means; and an air introduction path that introduces air into the connection path.
  9. 　前記脱脂室と接続するように前記脱脂室の下方に配置されており、前記脱脂室内で結露した水を排出する排水経路と、前記排出された水を貯留する排水槽と、をさらに備える、請求項６～８のいずれか１項に記載のセラミック電子部品の製造装置。 The drainage path which is arrange | positioned under the said degreasing | defatting chamber so that it may connect with the said degreasing | defatting chamber, drains the condensed water in the said degreasing | defatting chamber, and the drainage tank which stores the discharged | emitted water is further provided. Item 9. The apparatus for manufacturing a ceramic electronic component according to any one of Items 6 to 8.
PCT/JP2011/073793 2010-10-26 2011-10-17 Method and apparatus for manufacturing ceramic electronic component WO2012056922A1 (en)

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