JPS63254714A - Manufacture of laminated capacitor element - Google Patents
Manufacture of laminated capacitor elementInfo
- Publication number
- JPS63254714A JPS63254714A JP8940387A JP8940387A JPS63254714A JP S63254714 A JPS63254714 A JP S63254714A JP 8940387 A JP8940387 A JP 8940387A JP 8940387 A JP8940387 A JP 8940387A JP S63254714 A JPS63254714 A JP S63254714A
- Authority
- JP
- Japan
- Prior art keywords
- logpo
- temperature
- dielectric
- capacitor element
- partial pressure
- 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.)
- Granted
Links
- 239000003990 capacitor Substances 0.000 title claims description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 40
- 239000001301 oxygen Substances 0.000 claims description 40
- 229910052760 oxygen Inorganic materials 0.000 claims description 40
- 238000010304 firing Methods 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 13
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 10
- 230000008859 change Effects 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 239000007858 starting material Substances 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000005751 Copper oxide Substances 0.000 claims description 5
- 229910000431 copper oxide Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000005749 Copper compound Substances 0.000 claims description 2
- 150000001880 copper compounds Chemical class 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 229910052758 niobium Inorganic materials 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 229910052721 tungsten Inorganic materials 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 20
- 239000007789 gas Substances 0.000 description 18
- 229910052573 porcelain Inorganic materials 0.000 description 15
- 239000000843 powder Substances 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 230000007423 decrease Effects 0.000 description 11
- 229910000831 Steel Inorganic materials 0.000 description 10
- 239000000395 magnesium oxide Substances 0.000 description 10
- 239000010959 steel Substances 0.000 description 10
- 239000003989 dielectric material Substances 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 239000002003 electrode paste Substances 0.000 description 7
- 230000009467 reduction Effects 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 5
- 239000003985 ceramic capacitor Substances 0.000 description 5
- 210000003127 knee Anatomy 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000001465 metallisation Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 239000001856 Ethyl cellulose Substances 0.000 description 3
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 229920001249 ethyl cellulose Polymers 0.000 description 3
- 235000019325 ethyl cellulose Nutrition 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
産業上の利用分野
本発明は積層コンデンサ素子の製造方法に関し、特に鉛
ペロブスカイト酸化物を誘電体に用い鋼または銅を主成
分とする合金を内部電極とする積層コンデンサ素子の製
造方法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for manufacturing a multilayer capacitor element, and in particular to a multilayer capacitor element using lead perovskite oxide as a dielectric material and steel or copper-based alloy as an internal electrode. Relating to a manufacturing method.
従来の技術
近年セラミックコンデンサは素子の小型化、大容量化へ
の要求から積層型セラミックコンデンサが急速に普及し
つつある。また回路の高周波化により従来電界コンデン
サが用いられていた領域に積層型セラミックコンデンサ
素子を用いる必要が発生している。積層型セラミックコ
ンデンサは内部電極とセラミックを一体焼成する工程に
よって通常製造される。従来より高誘電率系のセラミッ
クコンデンサ材料にはチタン酸バリウム系の材料が用い
られてきたが、焼成温度が１３００℃程度と高いため、
内部電極材料としてはＰｉ、Ｐｄなとの高価な金属を用
いる必要があった。このため安価な卑金属を内部電極に
用いようとする試みが成されている。BACKGROUND OF THE INVENTION In recent years, multilayer ceramic capacitors have been rapidly becoming popular due to the demand for smaller ceramic capacitor elements and larger capacitance. Furthermore, as the frequency of circuits increases, it has become necessary to use multilayer ceramic capacitor elements in areas where electrolytic capacitors were conventionally used. Multilayer ceramic capacitors are typically manufactured by a process of integrally firing internal electrodes and ceramics. Barium titanate-based materials have traditionally been used as high-permittivity ceramic capacitor materials, but because the firing temperature is as high as 1300°C,
It was necessary to use expensive metals such as Pi and Pd as internal electrode materials. For this reason, attempts have been made to use inexpensive base metals for the internal electrodes.
これに対し発明者らは鉛ペロブスカイト酸化物を誘電体
に用い銅酸化物によって電極パターンを構成し、焼成温
度より低い温度で電極を金属化した後焼成する積層コン
デンサ素子の製造方法を提案してきた。In response, the inventors have proposed a method for manufacturing a multilayer capacitor element in which lead perovskite oxide is used as the dielectric material, the electrode pattern is composed of copper oxide, the electrodes are metallized at a temperature lower than the firing temperature, and then fired. .
また、金属鋼ペーストより電極パターンを形成し、でき
るだけ金属鋼が酸化しないような雰囲気でパーツアウト
した後焼成する製造方法については特開昭６１−６７２
１４号公報に記載の方法などが知られている。In addition, Japanese Patent Laid-Open No. 61-672 describes a manufacturing method in which an electrode pattern is formed from a metal steel paste, and the parts are removed and fired in an atmosphere that prevents oxidation of the metal steel as much as possible.
The method described in Japanese Patent No. 14 is known.
さらに発明者らは、Ｐｂ （Ｍｇｘ／３Ｎｂｇ／ｓ）
０３゜Ｐｂ （ＮｉＩ／５Ｎｂｚ／ｓ ） Ｏｓを主成
分とした誘電体磁器を用い鋼を内部電極とした積層コン
デンサ素子の焼成時の雰囲気酸素分圧条件について提案
して方法においては、内部電極の出発原料に金属粉末を
用いた場合、誘電体グリーンシート、内部電極ペースト
のバインダ成分のパーツアウト時に内部電極の酸化が発
生しやすい。このためこれらのバインダにはアクリル等
の不活性ガス雰囲気中で分解蒸発飛散する樹脂をもちい
る。しかしこれらのバインダはポリヴイニルブチラール
樹脂等の通常空気中でパーツアウトして用いる樹脂に（
らべ、誘電体グリーンシートの強度が弱（積層工法上の
問題点となっていた。Furthermore, the inventors discovered that Pb (Mgx/3Nbg/s)
03°Pb (NiI/5Nbz/s) We proposed atmospheric oxygen partial pressure conditions during firing of a multilayer capacitor element using dielectric porcelain mainly composed of Os and steel as internal electrodes. When metal powder is used as the starting material, oxidation of the internal electrodes is likely to occur when the binder component of the dielectric green sheet and internal electrode paste is removed. For this reason, these binders use resins such as acrylic which decompose, evaporate and scatter in an inert gas atmosphere. However, these binders are not compatible with resins such as polyvinyl butyral resin, which are normally used as parts in air.
However, the strength of the dielectric green sheet was weak (a problem with the lamination method).
また内部電極の酸化が発生しないような低酸素分圧雰囲
気下でパーツアウトを実施した場合バインダ成分のカー
ボナイズ現象が発生しやす（、焼成時に誘電体が残留し
ているカーボンにより還元され素子の絶縁抵抗の低下、
焼結密度の低下が発生しやすい問題点を有していた。In addition, if parts are removed in a low oxygen partial pressure atmosphere where internal electrode oxidation does not occur, carbonization of the binder component is likely to occur (during firing, the dielectric is reduced by the remaining carbon, resulting in insulation of the element). decrease in resistance,
This had the problem that the sintered density was likely to decrease.
また内部電極の出発原料に用いるためには、粒径の小さ
い金属粉末が必要で、製造時の粉砕に要するコスト、お
よび金属粉末の防錆処理に要するコストなどのため地金
では安価な銅金属の利点を充分に生かせない問題点があ
った。In addition, in order to use it as a starting material for internal electrodes, metal powder with a small particle size is required, and due to the costs required for pulverization during manufacturing and the cost required for rust prevention treatment of metal powder, copper metal, which is inexpensive as raw metal, is required. There was a problem in that the advantages could not be fully utilized.
これに対し、銅酸化物で電極パターンを構成し積層後夜
気中でバインダーをパーツアウトし焼成温度よりも低い
温度で電極を金属化した後焼成する工法では上記の問題
点を解決しているが、すでに発明者らによって開示され
た実施例における焼成方法では焼成の課程で雰囲気酸素
分圧を１×１０−８に保持しながら焼成する工法をとっ
ており、雰囲気制御上の難点を有しており、焼成炉に投
入する試料量による特性の変化、焼成時の試料をいれる
サヤ中の試料の配置による特性の変動等の難点を有して
いた。On the other hand, the above-mentioned problem is solved by a method in which the electrode pattern is made of copper oxide, the binder is removed in the night air after lamination, the electrode is metallized at a temperature lower than the firing temperature, and then fired. However, the firing method in the embodiments already disclosed by the inventors involves firing while maintaining the atmospheric oxygen partial pressure at 1 x 10-8 during the firing process, which has the disadvantage of controlling the atmosphere. However, this method has disadvantages such as variations in properties depending on the amount of sample put into the firing furnace and variations in properties depending on the placement of the sample in the pod during firing.
問題点を解決するための手段
銅内部電極の出発原料にＣｕ ２０ ＋ Ｃｕ Ｏ＊そ
れらの混合物、もしくは６５０℃以下の空気中で分解し
銅酸化物となる銅化合物のいずれかをを主成分とする原
料を用い、内部電極パターンを誘電体グリーンシートに
印刷し積層したのち、空気中でバインダ成分のパーツア
ウトを行い、その後焼成温度より低い温度で内部電極を
還元して金属化しその後焼成する積層コンデンサの製造
方法において、焼成時の昇温時、最高温度付近での保持
時の雰囲気酸素分圧Ｐｏ２をｌ ｏｇ （Ｐｏ２）（Ｐ
ｏ２）（Ｐｏ２）（Ｐｏ２は気圧）で表したとき、その
温度変化が６５０℃から１０８０℃の範囲で、６５０℃
ニー８．６０≧ＩｏｇＰｏ ２≧−１６，２５７５０℃
ニー７．５６≧ｌｏｇＰｏ ２≧−１３，６０８５０℃
Ｆ−６．８２≧ｌｏｇＰｏ ２≧−１１，３０９５０℃
ニー６．２０≧ｌｏｇＰｏ ２≧−９，４５１０５０℃
ニー５．６５≧ｌｏｇＰｏ ２≧−７，８５１０８０℃
ニー５．３５≧ｌｏｇＰｏ ｚ≧−７，４０の条件を満
たすよう制御しながら処理を行う。Means to solve the problem The starting material for the copper internal electrode is either a mixture of Cu 20 + Cu O* or a copper compound that decomposes in air at 650°C or below to become copper oxide. After printing internal electrode patterns on dielectric green sheets and laminating them using raw materials, the binder component is removed in the air, the internal electrodes are reduced to metallization at a temperature lower than the firing temperature, and then fired. In the manufacturing method of capacitors, the atmospheric oxygen partial pressure Po2 when raising the temperature during firing and holding near the maximum temperature is log (Po2) (P
o2) (Po2) (Po2 is atmospheric pressure), if the temperature change is in the range of 650℃ to 1080℃, 650℃
Knee 8.60≧IogPo 2≧-16,25750℃
Knee 7.56≧logPo 2≧-13,60850℃
F-6.82≧logPo2≧-11,30950℃
Knee 6.20≧logPo 2≧-9,451050℃
Knee 5.65≧logPo 2≧-7,851080℃
Processing is performed while controlling to satisfy the condition of knee 5.35≧logPoz≧−7,40.
作用
上記の様にして製造した積層コンデンサ素子は、焼成時
に電極が酸化せず、かつ誘電体が還元しないので、絶縁
抵抗値が大きく、高周波の誘電損失の小さい積層コンデ
ンサ素子が得られ、また銅金属粉末より安価な鋼酸化物
粉末を内部電極の出発原料に利用できる。Function In the multilayer capacitor element manufactured as described above, the electrodes are not oxidized and the dielectric material is not reduced during firing, so a multilayer capacitor element with high insulation resistance and low dielectric loss at high frequencies can be obtained. Steel oxide powder, which is cheaper than metal powder, can be used as a starting material for internal electrodes.
実施例
本発明の積層コンデンサ素子は、誘電体に鉛ペロブスカ
イト系酸化物を用い、鋼または鋼を主成分とする合金を
内部電極とするため、焼成時に電極が酸化せず、かつ誘
電体が還元しないことが求められる。と（に本発明の積
層コンデンサ素子の製造方法においては、一旦電極がパ
ーツアウトを経たのち銅酸化物となり、これを焼成温度
より低い温度で還元して金属化してから焼成するため、
電極の鋼金属は焼成前には微細な粉末で表面活性が高く
特に焼成時の昇温時や最高温度付近での保持時に酸化し
やすい。このため、この課程では雰囲気酸素分圧は銅の
平衡酸素分圧をあまり大きく越える酸素過剰雰囲気では
いけない。いっぽう本発明で用いる鉛ペロブスカイト系
誘電体は、その構成成分により若干の相違はあるが、高
温時においである酸素分圧を境にそれ以下の酸素分圧で
は、誘電体の還元が始まり電気伝導度が増大する。第３
図に本発明で用いる典型的な誘電体組成物である、
（Ｐｂ ＋−ｏ＋ｏ Ｃａ Ｏ８Ｏ’３０）（Ｍ
ｇ＋／５Ｎｂ２／３）Ｏ，フ０Ｔｉｅ−２５（ＮｉＩ／
ｚＷ ＋７ｚ）ＯＯ５０３−０２５の高温下で雰囲気酸
素分圧が変化した際の電気伝導度の変化を示す。第３図
より明らかなように、誘電体磁器の還元が始まる酸素分
圧は低温になるほど低酸素分圧側に変化している。すな
わち本発明の積層コンデンサ素子を焼成するには、この
温度による酸素分圧変化より高酸素分圧側で焼成すれば
、素子がより高抵抗となる。勿論これらの焼成雰囲気の
制御範囲は室温付近より継続するのが望ま−しいが特に
、６５０℃以上の温度で、電極の酸化、誘電体の還元の
反応速度が大きくなるためこの温度以上での制御が素子
の特性を制御するうえで重要となる。Example: The multilayer capacitor element of the present invention uses lead perovskite oxide as the dielectric material and steel or steel-based alloy as the internal electrode, so that the electrodes are not oxidized during firing and the dielectric material is reduced. required not to do so. (In the method for manufacturing a multilayer capacitor element of the present invention, once the electrode has gone through part-out, it becomes a copper oxide, which is reduced to metallization at a temperature lower than the firing temperature, and then fired.
The steel metal of the electrode is a fine powder with high surface activity before firing, and is particularly susceptible to oxidation when the temperature is raised during firing or when it is held near the maximum temperature. For this reason, in this process, the oxygen partial pressure of the atmosphere must not exceed the equilibrium oxygen partial pressure of copper by too much. On the other hand, the lead perovskite dielectric used in the present invention differs slightly depending on its constituent components, but at high temperatures, the oxygen partial pressure reaches a certain level, and at lower oxygen partial pressures, the dielectric begins to reduce and its electrical conductivity decreases. increases. Third
The figure shows a typical dielectric composition used in the present invention, (Pb+-o+oCaO8O'30)(M
g+/5Nb2/3)O, F0Tie-25(NiI/
zW +7z) It shows the change in electrical conductivity when the atmospheric oxygen partial pressure changes under high temperature of OO503-025. As is clear from FIG. 3, the oxygen partial pressure at which reduction of the dielectric ceramic begins changes to a lower oxygen partial pressure side as the temperature becomes lower. That is, in order to fire the multilayer capacitor element of the present invention, if the element is fired at a higher oxygen partial pressure than the change in oxygen partial pressure due to temperature, the element will have a higher resistance. Of course, it is desirable to continue controlling the firing atmosphere from around room temperature, but in particular, the reaction rate of electrode oxidation and dielectric reduction increases at temperatures above 650°C, so control above this temperature is particularly important. is important in controlling the characteristics of the device.
実施例１ 誘電体として次に示す組成式で表される材料を用いた。Example 1 A material represented by the following compositional formula was used as the dielectric.
（Ｐ ｂ＋ 、ｏｏ Ｃａｏ、ｏｇｓ）（Ｍｇｓ／ｓ
Ｎｂｇ／ｓ）ｏ、７ｏ Ｔ ｉｏ、２ｓ（Ｎｉ＋／ｇＷ
１／２）０．０５０！、Ｏ＋！６誘電体粉末は通常の
セラミック製造方法に従い製造した。仮焼条件は８００
℃２時間とした。粉砕した仮焼粉末は仮焼粉末に対し５
ｗ ｔ ’Ｘのポリビニルブチラール樹脂、５０ｗｔ
＊の溶剤と共にボールミルで混合しドクターブレードを
用い厚さ３５μｍにシート化した。内部電極としては平
均粒径０、８ｓｍのＣｕ２０（ＣｕｚＯとして純度９９
％）を出発原料に用いＣｕ２Ｏに対し０．５ｗｔ＊のエ
チルセルロース、２５ｗｔ＄の溶剤とともに三本ロール
で混練し電極ペーストとしスクリーン印刷法を用い誘電
体グリーンシート上に内部電極パターンを印刷した。こ
れを電極が左右交互に引き出されるように積層し切断し
た。(P b+ , oo Cao, ogs) (Mgs/s
Nbg/s) o, 7o T io, 2s(Ni+/gW
1/2) 0.050! , O+! 6 dielectric powder was manufactured according to a conventional ceramic manufacturing method. Calcination conditions are 800
℃ for 2 hours. The pulverized calcined powder is 5% compared to the calcined powder.
wt'X polyvinyl butyral resin, 50wt
The mixture was mixed with the solvent marked * in a ball mill and formed into a sheet with a thickness of 35 μm using a doctor blade. As the internal electrode, Cu20 (purity 99 as CuzO) with an average particle size of 0.8 sm was used.
%) was used as a starting material, and Cu2O was kneaded with 0.5 wt* of ethyl cellulose and 25 wt of solvent using a triple roll to form an electrode paste, and an internal electrode pattern was printed on a dielectric green sheet using a screen printing method. This was laminated so that the electrodes were drawn out alternately on the left and right sides, and then cut.
電極が交互に引き出された端面に上述の電極ペーストを
塗布し外部電極とした。The above-mentioned electrode paste was applied to the end faces from which the electrodes were alternately drawn out to form external electrodes.
このようにして作成した積層体は磁器ボート内に粗粒マ
グネシアを敷きその上に載せ空気中で４５０℃でバイン
ダーをパーツアウトした。The thus-prepared laminate was placed on a porcelain boat with coarse-grained magnesia spread thereon, and the binder was removed in air at 450°C.
第４図に示すように、パーツアウトした積層体試料１４
を載せた磁器ボート１２を管状炉中の内径５０ｍｍの炉
心管１１の内部に入れ、２０℃、３−を零アンモニア水
１５をバブリングした窒素ガスを毎分１リットル流し４
５０℃で８時間保持し、内部電極を還元した。As shown in FIG. 4, the part-out laminate sample 14
The porcelain boat 12 carrying the porcelain boat 12 was placed inside the core tube 11 with an inner diameter of 50 mm in a tube furnace, and 1 liter of nitrogen gas bubbled with zero ammonia water 15 was flowed per minute at 20°C.
The internal electrode was reduced by holding at 50°C for 8 hours.
第５図に焼成時の積層体を入れるマグネシア磁器容器の
断面を、第６図に焼成炉炉心管の断面とガス配管を示す
。マグネシア磁器容器２１内には上述の仮焼粉２２を体
積の１／３程度敷きつめた上に粗粒マグネシア粉２３を
約１−敷き、そのうえにパーツアウトした積層体２５を
置いた。マグネシア磁器の蓋２４をし、管状電気炉の炉
心管２６内に挿入し第１表実験条件Ａ−Ｇの各種成分比
のＮ ２− Ｈ２−Ｈ２０−０２混合ガスを流しながら
１０５０℃まで２００℃／ ｈ ｒで昇温し２時間保持
後４００℃／ｈｒで降温した。雰囲気ガス中の水蒸気量
は絶対湿度センサー２８で測定し、蒸留水をバブリング
するガス量の調節により、制御した。水素ガスは１％Ｈ
２−Ｎ２ガスとして、酸素ガスは、キャリアーガスとし
て流す窒素ガス中に含まれる酸素分を考慮して、さらに
必要な場合は１％０２−Ｎ２ガスとして加えた。各種ガ
スの混合比とそのガスを流した際の１０８０℃までの酸
素分圧の温度変化を第１表に、本発明請求の範囲第１項
記載の酸素分圧範囲を第１図に示す。なお、Ｎ２ガスに
ついては、１．０Ｘ１０−６（ａ ｔｍ）の酸素を不純
物として含んでいるものを用いた。FIG. 5 shows a cross section of a magnesia porcelain container into which a laminate is placed during firing, and FIG. 6 shows a cross section of a firing furnace core tube and gas piping. In the magnesia porcelain container 21, the above-mentioned calcined powder 22 was spread about 1/3 of its volume, and then about 1 - of coarse magnesia powder 23 was spread, and the laminate 25, which had been cut out, was placed thereon. The lid 24 of magnesia porcelain was put on and inserted into the core tube 26 of a tubular electric furnace, and heated at 200°C to 1050°C while flowing N2-H2-H20-02 mixed gas with various component ratios as shown in Table 1 Experimental Conditions A-G. The temperature was raised at a rate of 400° C./hr, held for 2 hours, and then lowered at a rate of 400° C./hr. The amount of water vapor in the atmospheric gas was measured with an absolute humidity sensor 28, and was controlled by adjusting the amount of gas bubbled through the distilled water. Hydrogen gas is 1%H
As the 2-N2 gas, oxygen gas was added as a 1% 02-N2 gas if necessary, taking into consideration the oxygen content contained in the nitrogen gas flowing as a carrier gas. Table 1 shows the mixing ratio of various gases and temperature changes in oxygen partial pressure up to 1080° C. when the gases are flowed, and FIG. 1 shows the oxygen partial pressure range described in claim 1 of the present invention. Note that the N2 gas used contained 1.0 x 10-6 (atm) of oxygen as an impurity.
また炉心管内のＰｏ２は挿入した安定化ジルコニア酸素
センサー２７の大気側と炉内部側に構成した白金電極か
ら引き出した電極間の電圧Ｅ（Ｖ）より次式より求めた
。Further, Po2 in the reactor core tube was determined from the following equation based on the voltage E (V) between the electrodes drawn from the platinum electrodes configured on the atmospheric side of the inserted stabilized zirconia oxygen sensor 27 and the inner side of the reactor.
Ｐｏ ２ ＝０．２・ｅｘｐ（４Ｆ Ｅ ／ ＲＴ ）
ここでＦはファラデ一定数９６４８９クーロン、Ｒはガ
ス定数８．３１４４Ｊ／ｄｅｇ−ｍｏｌ、 Ｔは絶対温
度である。Po 2 =0.2・exp(4FE/RT)
Here, F is the Faraday constant of 96489 coulombs, R is the gas constant of 8.3144 J/deg-mol, and T is the absolute temperature.
（以下余白）
積層コンデンサ素子の外形は２．８Ｘ１．４Ｘ０．９＋
１１１１で有効電極面積は一層当たり１．３１２５ｗａ
２（１，７５ｘＯ，７５ｗａ ） 、電極層の厚みは２
．０μ鴎、誘電体層は一層当たり２５．０μ曽で有効層
は３０層、上下に無効層を２層ずつ設けた。積層コンデ
ンサ素子は容量、ｔａｎδを１ｖの交流電圧を印加し１
００Ｈｚ〜２ ＭＨｚの周波数で測定した。また抵抗率
は５０ｖ／Ｗｌｌの電圧を印加後１分値から求めた。測
定は各条件５０試料について行い、容量（２０℃）が１
００ｎＦ以下、抵抗値がｌ×１０−９Ω、以下、もしく
は抵抗容量積が５０ＯＦΩ以下を不良とし、良品のみの
特性を平均した。(Left below) The outer dimensions of the multilayer capacitor element are 2.8X1.4X0.9+
1111, the effective electrode area is 1.3125 wa per layer.
2 (1,75xO,75wa), the thickness of the electrode layer is 2
．． The dielectric layer had a thickness of 0μ, 25.0μ per layer, 30 effective layers, and 2 invalid layers above and below. The multilayer capacitor element has a capacitance, tan δ, of 1 V by applying an AC voltage of 1 V.
Measurements were made at frequencies from 00 Hz to 2 MHz. Further, the resistivity was determined from the value 1 minute after applying a voltage of 50 V/Wll. Measurements were carried out on 50 samples under each condition, with a capacity (20°C) of 1
00 nF or less, a resistance value of 1×10 −9 Ω or less, or a resistance-capacitance product of 50 OF Ω or less were considered defective, and the characteristics of only non-defective products were averaged.
第２表に容量、ｔａｎδ、抵抗値不良数を示した。Table 2 shows the capacitance, tan δ, and number of defective resistance values.
（以下余白）
第１表、第２表より明らかなように、焼成時の昇温時、
最高温度付近での保持時の雰囲気酸素分圧Ｐｏ２（気圧
）が特許請求の範囲内で焼成した素子は、いずれも高い
抵抗値を有しており、容量も設計値程度まで達しており
、ｔａｎδも小さい値を示している。いっぽうＰｏ２が
すべての温度範囲で限定範囲より大きい実験条件Ａ、お
よび低温時に限定範囲より大きくなる実験条件Ｇでは、
電極の酸化が発生し、容量の低下、または抵抗値の低下
が発生し、不良数が増大する。またＰｏ２がすべての温
度範囲で限定範囲より小さい実験条件Ｆでは、誘電体の
還元が発生し誘電体中より金属鉛が析出し、これが電極
金属と固溶して融点を下げるため、焼成時に電極の熔融
が発生し電極が板状に形成されず、局在化する現象が現
れ、容量の大幅な低下が発生し不良数が増大する
なお、本実施例では焼成工程中冷却時も同じガスを流し
続けたので、降温時の酸素分圧変化も昇温時と同様の変
化を示す。(Left below) As is clear from Tables 1 and 2, when the temperature is raised during firing,
All elements fired with atmospheric oxygen partial pressure Po2 (atmospheric pressure) within the claimed range when held near the maximum temperature have a high resistance value, the capacity has reached the design value, and the tan δ also shows a small value. On the other hand, in experimental condition A where Po2 is larger than the limited range in all temperature ranges and experimental condition G where Po2 is larger than the limited range at low temperatures,
Oxidation of the electrode occurs, resulting in a decrease in capacitance or resistance, and an increase in the number of defects. In addition, under experimental condition F where Po2 is smaller than the limited range in all temperature ranges, reduction of the dielectric occurs and metallic lead precipitates from within the dielectric, which dissolves in solid solution with the electrode metal and lowers the melting point. As a result, the electrode is not formed into a plate shape and is localized, resulting in a significant decrease in capacity and an increase in the number of defects.In this example, the same gas was used during cooling during the firing process. Since the flow continued, the change in oxygen partial pressure when the temperature was lowered also showed the same change as when the temperature was raised.
実施例２
誘電体材料、およびそのシート化については実施例１と
同様の方法を用いた。Example 2 The same method as in Example 1 was used for the dielectric material and its sheet formation.
内部電極としては平均粒径１．２μｍのＣｕ０（ＣｕＯ
として純度９７％）を出発原料に用い、これに誘電体の
仮焼粉を１０ｗｔ２；加え混合したものに０．５ｗｔ零
のエチルセルロース、２５ｗｔ零の溶剤とともに三本ロ
ールで混練し電極ペーストとしスクリーン印刷法を用い
誘電体グリーンシート上に内部電極パターンを印刷した
。これを電極が左右交互に引き出されるように積層し切
断した。The internal electrode was made of Cu0 (CuO) with an average particle size of 1.2 μm.
(purity 97%) was used as the starting material, 10wt2 of calcined dielectric powder was added to this, and the mixture was kneaded with three rolls with 0.5wt zero ethyl cellulose and 25wt zero solvent to form an electrode paste and screen printing. An internal electrode pattern was printed on a dielectric green sheet using the method. This was laminated so that the electrodes were drawn out alternately on the left and right sides, and then cut.
電極が交互に引き出された端面に上述の電極ペーストを
塗布し外部電極とした。The above-mentioned electrode paste was applied to the end faces from which the electrodes were alternately drawn out to form external electrodes.
このようにして作成した積層体は磁器ボート内に粗粒ジ
ルコニアを敷きその上に載せ空気中で５００℃でバイン
ダーをパーツアウトした。The thus-prepared laminate was placed on a porcelain boat with coarse zirconia spread thereon, and the binder was removed in air at 500°C.
パーツアウトした積層体を載せた磁器ボートを管状炉中
の内径５０＋ｅｍの炉心管内部に入れ、１．５体積％の
水蒸気ガス、０．０５体積％の水素ガスを含む窒素ガス
（不純物として酸素を０゜００１体積％含む）を毎分１
リットル流し６００℃で４時間保持した。The porcelain boat carrying the parts-out laminate was placed inside a core tube with an inner diameter of 50+em in a tube furnace, and nitrogen gas containing 1.5% by volume of steam gas and 0.05% by volume of hydrogen gas (with oxygen as an impurity) 0°001% by volume) per minute
A liter flow was maintained at 600° C. for 4 hours.
焼成時の容器、炉心管の内部の構成は実施例１同様の方
法をとった。焼成温度は１０８０℃とし、焼成時に流す
雰囲気ガスは実施例１と同様のＮ２−Ｈ！−８２０−０
２混合ガスとし、昇温時、最高温度付近での保持時に流
すガスは実施例１の実験条件Ｃと同一の条件とし、冷却
開始時よりガスの混合条件を酸素センサーにより酸素分
圧を測定しながら調節し冷却した。第３表に各条件の酸
素分圧の温度変化を示す。第２図に各条件の酸素分圧の
温度変化と特許請求の範囲第２項で限定した酸素分圧範
囲を示す。The internal structure of the container and furnace tube during firing was the same as in Example 1. The firing temperature was 1080°C, and the atmospheric gas flowed during firing was the same as in Example 1, N2-H! -820-0
The gas flowed during heating up and holding near the maximum temperature was the same as experimental condition C in Example 1, and from the start of cooling, the oxygen partial pressure was measured using an oxygen sensor under the gas mixing conditions. The mixture was adjusted and cooled. Table 3 shows temperature changes in oxygen partial pressure under each condition. FIG. 2 shows temperature changes in oxygen partial pressure under various conditions and the oxygen partial pressure range defined in claim 2.
（以下余白）
第３表
積層コンデンサ素子の外形は２．８ｘ１．４ｘＯ，９閣
で有効電極面積は一層当たり１．３１２５園１’（１，
７５ｘＯ，７Ｓ園）、電極層の厚みは２．０μｍ、誘電
体層は一層当たり２５．０μ讃で有効層は３０層、上下
に無効層を２ｐＩＪずつ設けた。積層コンデンサ素子は
容量、ｔａｎδをＩ■の交流電圧を印加し１００Ｈｚ〜
２ ＭＨｚの周波数で測定した。また抵抗率は５０Ｖ／
＋ｎ＋＋＋の電圧を印加後１分値から求めた。試料の測
定数、不良条件は実施例１と同様の条件とした。(Left below) The outer dimensions of the third layer multilayer capacitor element are 2.8x1.4xO, 9 layers, and the effective electrode area is 1.3125mm 1' (1
75xO, 7S), the thickness of the electrode layer was 2.0 μm, the dielectric layer was 25.0 μm thick per layer, there were 30 effective layers, and 2 pIJ of invalid layers above and below. The multilayer capacitor element has a capacitance, tan δ, of 100 Hz ~ by applying an AC voltage of I■.
Measurements were made at a frequency of 2 MHz. Also, the resistivity is 50V/
The voltage of +n+++ was determined from the value 1 minute after application. The number of samples measured and the failure conditions were the same as in Example 1.
第４表に容量とその温度変化率、ｔａｎδ、抵抗値、不
良数を示した。Table 4 shows the capacity, its temperature change rate, tan δ, resistance value, and number of defects.
（以下余白）
第４表より明らかなように、冷却時の酸素分圧変化条件
は昇温時の酸素分圧変化に比べ、高酸素分圧側の条件が
広がり、広い範囲で特性条件を満足する試料かえられた
。しかし実験条件Ｉより高酸素分圧条件である実験条件
Ｈでは銅が酸化し誘電体中に拡散するため、素子の抵抗
値が低下し、実験条件Ｌ（昇温時Ｅと同じ）より低酸素
分圧条件である実験条件Ｍ（昇温時Ｆと同じ）では素子
の還元による抵抗値低下が発生した。(Left below) As is clear from Table 4, the conditions for oxygen partial pressure change during cooling are wider than those for oxygen partial pressure changes during temperature rise, and the characteristic conditions are satisfied over a wide range. The sample was changed. However, under experimental condition H, which is a higher oxygen partial pressure condition than experimental condition I, copper oxidizes and diffuses into the dielectric, resulting in a decrease in the resistance value of the element, and lower oxygen concentration than experimental condition L (same as E at elevated temperature). Under experimental condition M, which is a partial pressure condition (same as temperature increase F), a decrease in resistance value occurred due to reduction of the element.
実施例３
誘電体材料としては第５表に示す組成物を用いた。誘電
体の合成方法は通常のセラミック製造方法によった。そ
のシート化については実施例１と同様の方法を用いた。Example 3 The compositions shown in Table 5 were used as dielectric materials. The dielectric was synthesized using a conventional ceramic manufacturing method. The same method as in Example 1 was used to form the sheet into a sheet.
内部電極としては実施例１に用いた平均粒径０．８μｍ
のＣｕ ２０９０ｗ ｔ ｇ 。As for the internal electrode, the average particle size used in Example 1 was 0.8 μm.
Cu 2090wtg.
平均粒径１．５ｕｍのＣｕ ＯＨ２１０ｗｔｇの混合物
を出発原料に用いこれに対し０．５ｗｔｔのエチルセル
ロース、２５ｗｔｇの溶剤とともに三本ロールで混練し
電極ペーストとしスクリーン印刷法を用い誘電体グリー
ンシート上に内部電極パターンを印刷した。これを電極
が左右交互に引き出されるように積層し切断した。A mixture of 210 wtg of Cu OH with an average particle size of 1.5 um was used as a starting material, and the mixture was kneaded with 0.5 wtt of ethyl cellulose and 25 wtg of solvent using a triple roll to form an electrode paste, which was printed internally on a dielectric green sheet using a screen printing method. An electrode pattern was printed. This was laminated so that the electrodes were drawn out alternately on the left and right sides, and then cut.
電極が交互に引き出された端面に上述の電極ペーストを
塗布し外部電極とした。The above-mentioned electrode paste was applied to the end faces from which the electrodes were alternately drawn out to form external electrodes.
このようにして作成した積層体は磁器ボート内に粗粒ジ
ルコニアを敷きその上に載せ空気中で５００℃でバイン
ダーをパーツアウトした。The thus-prepared laminate was placed on a porcelain boat with coarse zirconia spread thereon, and the binder was removed in air at 500°C.
パーツアウトした積層体を載せた磁器ボートを図１に示
す管状炉中の内径５０ＩＩｌｌｌの炉心管内部に入れ、
３ ｗ ｔ ’Ｘアンモニア水をバブリングした窒素ガ
スを毎分１リットル流し６５０℃で１時間保持した。The porcelain boat carrying the part-out laminate was placed inside the tube furnace tube with an inner diameter of 50IIll in the tube furnace shown in Fig. 1.
Nitrogen gas bubbled with 3wt'X ammonia water was flowed at 1 liter per minute and maintained at 650°C for 1 hour.
これを実施例１の実験条件Ａ−Ｇの各成分ガスを流して
同様の方法で焼成した。焼成温度は１０５０℃とした。This was fired in the same manner as in Example 1 by flowing each component gas under experimental conditions A to G. The firing temperature was 1050°C.
積層コンデンサ素子の外形、有効電極面積、電極層の厚
み、誘電体層は一層当たり厚み、有効層数、等は実施例
１と同様とした。また特性測定条件も実施例１と同様と
した。試料の測定数、不良条件は実施例１と同様とした
が容量不良については試料組成の誘電率より計算した容
量の５０％以下となるものとした。The outer shape of the multilayer capacitor element, the effective electrode area, the thickness of the electrode layer, the thickness of each dielectric layer, the number of effective layers, etc. were the same as in Example 1. Further, the characteristics measurement conditions were also the same as in Example 1. The number of samples measured and the failure conditions were the same as in Example 1, but the capacity failure was 50% or less of the capacity calculated from the dielectric constant of the sample composition.
第６表に各組成各焼成条件での不良数を示した。Table 6 shows the number of defects for each composition and under each firing condition.
（以下余白）
第６表より明らかなように、誘電体が特許請求の範囲第
１項記載の鉛ペロブスカイトからなる組成物をもちいた
セラミック積層コンデンサはいずれの組成物を用いた場
合も、特許請求の範囲第一項記載の酸素分圧の温度変化
範囲で焼成した場合高い抵抗値を示し、請求の範囲より
高酸素分圧雰囲気で焼成した場合は電極の酸化により発
生した酸化鋼の誘電体中への拡散による素子抵抗値の減
少、および容量の低下が発生し、低酸素分圧雰囲気で焼
成した場合は、誘電体の還元により発生した金属鉛の電
極への固溶による電極の局在化の原因による容量の低下
、誘電体の還元による素子抵抗値の減少が現れる。(Leaving space below) As is clear from Table 6, the ceramic multilayer capacitor whose dielectric uses the composition of lead perovskite described in claim 1 does not claim When fired in the temperature change range of oxygen partial pressure described in the first item, a high resistance value is exhibited, and when fired in an atmosphere with a higher oxygen partial pressure than the claimed range, oxidation occurs in the dielectric of the steel due to oxidation of the electrode. When fired in a low oxygen partial pressure atmosphere, the element resistance value decreases due to diffusion into the electrode, and the capacitance decreases.If fired in a low oxygen partial pressure atmosphere, the electrode becomes localized due to the solid solution of metallic lead generated by the reduction of the dielectric material into the electrode. There is a decrease in capacitance due to this cause, and a decrease in element resistance due to reduction of the dielectric.
発明の効果
本発明の積層コンデンサ素子の製造方法によると、鉛へ
ロブスカイトを誘電体に用い銅を内部電極とする積層コ
ンデンサ素子において、絶縁抵抗値が大きく、高周波の
誘電損失の小さい積層コンデンサ素子かえられ、かつま
た鋼金属粉末より安価な銅酸化物粉末を内部電極の出発
原料に利用でき電極コストを削減できる。Effects of the Invention According to the method of manufacturing a multilayer capacitor element of the present invention, it is possible to replace a multilayer capacitor element with a large insulation resistance value and low dielectric loss at high frequencies in a multilayer capacitor element using lead helobskite as a dielectric and copper as an internal electrode. Furthermore, copper oxide powder, which is cheaper than steel metal powder, can be used as the starting material for the internal electrodes, reducing electrode costs.
第１図および第２図は、本発明の実施例における焼成時
の酸素分圧の温度変化を示すグラフ、第３図は、本発明
の一実施例における誘電体組成物の、高温度下で雰囲気
酸素分圧が変化した際の電気伝導度の変化を示すグラフ
、第４図は、本発明の一実施例における電極金属化処理
の際の炉心管内部の配置とガス配管の状態を示す断面図
、第５図は、焼成時の積層体を入れるマグネシア磁器容
器の断面図、第６図は、焼成時の炉心管内部の配置を示
す断面図、第７図は、本発明の他の実施例における電極
金属化処理の際の炉心管内部の配置とガス配管の状態を
示す断面図である。
１１・・・・炉心管、１２・・・・磁器ボート、１３・
・・・粗粒マグネシア、１４・・・・積層体試料、１５
・・・・アンモニア水、２１・・・・マグネシア磁器容
器、２２・・・・仮焼粉、２３・・・・粗粒マグネシア
粉、２４・・・・マグネシア磁器蓋、２５・・・・電極
を金属化処理した積層体、２６・・・・炉心管、２７・
・・・安定化ジルコニア酸素センサー、２８・・・・絶
対湿度センサー。
代理人の氏名 弁理士 中尾敏男 ほか１名第１図
温度（’Ｃ）
第２図
温度（℃）
第３図
一１ｏｇ Ｐｏ２（ａｔｅ）
第４図
第５図
第６図
第７図FIGS. 1 and 2 are graphs showing temperature changes in oxygen partial pressure during firing in an example of the present invention, and FIG. 3 is a graph showing changes in oxygen partial pressure under high temperature in an example of the present invention. A graph showing changes in electrical conductivity when atmospheric oxygen partial pressure changes, and FIG. 4 is a cross section showing the arrangement inside the furnace tube and the state of gas piping during electrode metallization treatment in one embodiment of the present invention. 5 is a cross-sectional view of a magnesia porcelain container containing a laminate during firing, FIG. 6 is a cross-sectional view showing the arrangement inside the furnace tube during firing, and FIG. 7 is another embodiment of the present invention. FIG. 3 is a cross-sectional view showing the arrangement inside the furnace tube and the state of gas piping during electrode metallization treatment in an example. 11... Furnace tube, 12... Porcelain boat, 13...
... Coarse grain magnesia, 14 ... Laminate sample, 15
... Ammonia water, 21 ... Magnesia porcelain container, 22 ... Calcined powder, 23 ... Coarse grain magnesia powder, 24 ... Magnesia porcelain lid, 25 ... Electrode 26. Furnace core tube, 27.
...Stabilized zirconia oxygen sensor, 28...Absolute humidity sensor. Name of agent: Patent attorney Toshio Nakao and one other person Figure 1 Temperature ('C) Figure 2 Temperature (℃) Figure 3 -11og Po2 (ate) Figure 4 Figure 5 Figure 6 Figure 7
Claims (3)
たは銅を主成分とする合金を内部電極とする積層コンデ
ンサ素子を製造する際、銅内部電極の出発原料にＣｕ＿
２Ｏ、ＣｕＯ、それらの混合物、もしくは６５０℃以下
の空気中で分解し銅酸化物となる銅化合物のいずれかを
を主成分とする原料を用い、内部電極パターンを誘電体
グリーンシートに印刷し積層したのち、空気中でバイン
ダ成分のパーツアウトを行い、その後焼成温度より低い
温度で内部電極を還元して金属化し、その後焼成する積
層コンデンサの製造方法において、焼成時の昇温時、最
高温度付近での保持時の雰囲気酸素分圧Ｐｏ＿２をｌｏ
ｇ（Ｐｏ＿２）（Ｐｏ＿２は気圧）で表したとき、その
温度変化が６５０℃から１０８０℃の範囲で、 ６５０℃：−８．６０≧ｌｏｇｐｏ＿２≧−１６．２５
７５０℃：−７．５６≧ｌｏｇｐｏ＿２≧−１３．６０
８５０℃：−６．８２≧ｌｏｇｐｏ＿２≧−１１．３０
９５０℃：−６．２０≧ｌｏｇｐｏ＿２≧−９．４５１
０５０℃：−５．６５≧ｌｏｇｐｏ＿２≧−７．８５１
０８０℃：−５．３５≧ｌｏｇｐｏ＿２≧−７．４０の
条件を満たすことを特徴とする、積層コンデンサ素子の
製造方法。(1) When producing a multilayer capacitor element that uses lead perovskite oxide as a dielectric and conductive or copper-based alloy as an internal electrode, the starting material for the copper internal electrode is Cu_
An internal electrode pattern is printed on a dielectric green sheet and laminated using a raw material whose main component is 2O, CuO, a mixture thereof, or a copper compound that decomposes in air below 650°C to form copper oxide. In the manufacturing method for multilayer capacitors, in which the binder component is then removed in the air, the internal electrodes are reduced and metallized at a temperature lower than the firing temperature, and then fired, the temperature is near the maximum temperature when the temperature is raised during firing. The atmospheric oxygen partial pressure Po_2 when held at lo
When expressed in g(Po_2) (Po_2 is atmospheric pressure), when the temperature change is in the range of 650°C to 1080°C, 650°C: -8.60≧logpo_2≧-16.25
750℃: -7.56≧logpo_2≧-13.60
850℃: -6.82≧logpo_2≧-11.30
950℃: -6.20≧logpo_2≧-9.451
050℃: -5.65≧logpo_2≧-7.851
080°C: A method for manufacturing a multilayer capacitor element, characterized by satisfying the following condition: -5.35≧logpo_2≧-7.40.
ｇ（Ｐｏ＿２）（Ｐｏ＿２は気圧）で表したとき、その
温度変化が６５０℃から１０８０℃の範囲で、 ６５０℃：−５．００≧ｌｏｇｐｏ＿２≧−１６．２５
７５０℃：−５．００≧ｌｏｇｐｏ＿２≧−１３．６０
８５０℃：−５．００≧ｌｏｇｐｏ＿２≧−１１．３０
９５０℃：−５．５０≧ｌｏｇｐｏ＿２≧−９．４５１
０５０℃：−５．６５≧ｌｏｇｐｏ＿２≧−７．８５１
０８０℃：−５．３５≧ｌｏｇｐｏ＿２≧−７．４０の
条件を満たすことを特徴とする特許請求の範囲第１項記
載の積層コンデンサ素子の製造方法。(2) Atmospheric oxygen partial pressure Po_2 when lowering the temperature during firing is lo
When expressed in g(Po_2) (Po_2 is atmospheric pressure), when the temperature change is in the range of 650°C to 1080°C, 650°C: -5.00≧logpo_2≧-16.25
750℃: -5.00≧logpo_2≧-13.60
850℃: -5.00≧logpo_2≧-11.30
950℃: -5.50≧logpo_2≧-9.451
050℃: -5.65≧logpo_2≧-7.851
The method for manufacturing a multilayer capacitor element according to claim 1, characterized in that the following condition is satisfied: 080°C: -5.35≧logpo_2≧-7.40.
から選ばれた成分Ａと、Ｍｇ、Ｎｉ、Ｚｎ、Ｔｉ、Ｎｂ
、およびＷからなる群Ｂより選ばれた成分Ｂの両者の成
分を含み、ＡはＰｂとそれ以外の成分の少なくとも一つ
を含み、Ｂは群Ｂの成分の少なくとも二つを含み、かつ
Ａの成分のモル数の合計をａ、Ｂの成分の合計をｂとし
た時、ａ／ｂ＞１．００であるような組成物である鉛ペ
ロブスカイト系酸化物からなることを特徴とする特許請
求の範囲第１項記載の積層コンデンサ素子の製造方法。(3) Group A in which the dielectric consists of Pb, Ca, Sr, and Ba
Component A selected from Mg, Ni, Zn, Ti, Nb
, and component B selected from group B consisting of W, A contains at least one of Pb and other components, B contains at least two of the components of group B, and A A patent claim characterized in that the lead perovskite oxide has a composition such that a/b>1.00, where a is the sum of the moles of the components B and b is the sum of the moles of the components B. A method for manufacturing a multilayer capacitor element according to item 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8940387A JPH0734417B2 (en) | 1987-04-10 | 1987-04-10 | Method for manufacturing multilayer capacitor element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8940387A JPH0734417B2 (en) | 1987-04-10 | 1987-04-10 | Method for manufacturing multilayer capacitor element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63254714A true JPS63254714A (en) | 1988-10-21 |
| JPH0734417B2 JPH0734417B2 (en) | 1995-04-12 |
Family
ID=13969673
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8940387A Expired - Lifetime JPH0734417B2 (en) | 1987-04-10 | 1987-04-10 | Method for manufacturing multilayer capacitor element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0734417B2 (en) |
-
1987
- 1987-04-10 JP JP8940387A patent/JPH0734417B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0734417B2 (en) | 1995-04-12 |
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