JPS62226855A - Low temperature sintering ceramic composition for multi-layer substrate - Google Patents
Low temperature sintering ceramic composition for multi-layer substrateInfo
- Publication number
- JPS62226855A JPS62226855A JP61072288A JP7228886A JPS62226855A JP S62226855 A JPS62226855 A JP S62226855A JP 61072288 A JP61072288 A JP 61072288A JP 7228886 A JP7228886 A JP 7228886A JP S62226855 A JPS62226855 A JP S62226855A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- less
- ceramic composition
- low temperature
- multilayer
- 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
- 239000000758 substrate Substances 0.000 title claims description 20
- 239000000203 mixture Substances 0.000 title description 19
- 239000000919 ceramic Substances 0.000 title description 11
- 238000009766 low-temperature sintering Methods 0.000 title 1
- 229910052573 porcelain Inorganic materials 0.000 claims description 14
- 239000004020 conductor Substances 0.000 description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- 230000001590 oxidative effect Effects 0.000 description 9
- 238000005245 sintering Methods 0.000 description 9
- 239000010949 copper Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000010953 base metal Substances 0.000 description 4
- 239000011195 cermet Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- 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 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 description 1
- 229940088601 alpha-terpineol Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000007572 expansion measurement Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 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）
この発明は、多層基板用低温焼結磁器組成物に関し、特
に、複数の磁器層が積層きれ、磁器間に回路が形成され
てなる多層磁器基板に適した、多層基板用低温焼結磁器
組成物に関する。Detailed Description of the Invention (Industrial Application Field) The present invention relates to a low-temperature sintered porcelain composition for a multilayer substrate, and particularly to a multilayer porcelain composition in which a plurality of porcelain layers are laminated and a circuit is formed between the porcelains. The present invention relates to a low-temperature sintered ceramic composition for multilayer substrates, which is suitable for substrates.
（従来技術）
一般に、電子機器の小型化に伴い、電気回路を構成する
各種電子部品を実装するのに磁器基板が汎用され、最近
では、実装密度をさらに高めるため、表面に導電材料で
回路パターンを形成した未焼成の磁器シートをｗ、ｒｌ
ｌ、枚積層し、これを焼成して一体化した多層磁器基板
が開発されている。この種の多層磁器基板の磁器材料に
はアルミナが用いられているが、その焼結温度は１５０
０〜１６００℃と高温であるため、次のような問題があ
った。まず、焼結に多量のエネルギを必要とするため製
造コストが高くなる。また、基板内部に形成される内部
回路などの導電材料が、たとえば、高温の焼結温度に耐
えられるタングステンやモリブデンなどに限定されるた
め、内部回路などの抵抗が大きくなる。そして、アルミ
ナの熱膨張係数がシリコンチップのそれよりも大きいた
め、シリコンチップにサーマルストレスがかかり、クラ
ックの原因になることなどである。そこで、これらの問
題を解決するために、低温で焼結させることができる基
板用磁器組成物として、アルミナに多量の結晶化ガラス
成分を添加したもの、あるいは特開昭５７−１８４２８
９号公報に開示されている組成物のように、ＢａＳｎＯ
３にホウ素を多量に添加したものが用いられている。ま
た、特開昭６ｏ−ｚｚｓ４５４号公報、あるいは特開昭
６０−２２７３１１号公報に開示されているように、ア
ルミナ、シリカ、アルカリ土類金属酸化物、ホウ素、酸
化リチウム、酸化亜鉛などの成分からなるものが用いら
れている。(Prior art) Generally, with the miniaturization of electronic devices, ceramic substrates are commonly used to mount various electronic components that make up electric circuits.Recently, in order to further increase the mounting density, circuit patterns are being patterned using conductive materials on the surface. The unfired porcelain sheet formed with w, rl
A multilayer porcelain substrate has been developed in which the porcelain substrates are laminated and then fired and integrated. Alumina is used as the porcelain material for this type of multilayer porcelain substrate, and its sintering temperature is 150°C.
Due to the high temperature of 0 to 1600°C, there were the following problems. First, sintering requires a large amount of energy, which increases manufacturing costs. Further, since the conductive material for the internal circuits formed inside the substrate is limited to, for example, tungsten or molybdenum, which can withstand high sintering temperatures, the resistance of the internal circuits becomes large. Furthermore, since the coefficient of thermal expansion of alumina is larger than that of the silicon chip, thermal stress is applied to the silicon chip, causing cracks. Therefore, in order to solve these problems, as a ceramic composition for a substrate that can be sintered at a low temperature, a ceramic composition in which a large amount of crystallized glass component is added to alumina, or JP-A-57-18428
As in the composition disclosed in Publication No. 9, BaSnO
3 with a large amount of boron added. In addition, as disclosed in JP-A No. 6O-ZZS454 or JP-A No. 60-227311, it is possible to use materials such as alumina, silica, alkaline earth metal oxides, boron, lithium oxide, zinc oxide, etc. Something is being used.
（発明が解決しようとする問題点）
しかしながら、アルミナに多量の結晶化ガラス成分を添
加した組成物では、得られた磁器に空孔が多数存在し、
空孔を介して導体路間にマイグレーションが発生すると
いう問題が生じる。また、特開昭５７−１８４２８９号
公報に開示された組成物では、仮焼物がガラス状となる
ので、その粉砕が困難となるばかりでなく、焼成の際に
ホウ素が激しく蒸発し、導電材料と反応したり、炉の材
料に損傷を与えたりするという問題が生じる。また、特
開昭６０−２２６４５４号公報、特開昭６０−２２７３
１１号公報に開示された組成物についても、多量のホウ
素を用いるため、同様の問題を生じる。また、多量のホ
ウ素の存在はサーメット抵抗体をその表面に形成した場
合に抵抗体を劣化させるという問題を生じる。さらに、
表面に導体を形成すると、多量のホウ素の存在で導体の
特性を劣化させる。その他、酸化リチウムの添加は絶縁
抵抗の信頼性の低下を招くという問題を有している。(Problems to be Solved by the Invention) However, in a composition in which a large amount of crystallized glass component is added to alumina, a large number of pores are present in the resulting porcelain.
A problem arises in that migration occurs between the conductor paths via the holes. Furthermore, in the composition disclosed in JP-A-57-184289, the calcined material becomes glassy, which not only makes it difficult to crush, but also causes the boron to evaporate violently during firing, resulting in a conductive material. Problems arise with reactions and damage to the materials in the furnace. Also, JP-A No. 60-226454, JP-A No. 60-2273
The composition disclosed in Japanese Patent No. 11 also uses a large amount of boron, so similar problems occur. Further, the presence of a large amount of boron causes a problem of deterioration of the resistor when a cermet resistor is formed on the surface thereof. moreover,
When a conductor is formed on the surface, the presence of a large amount of boron deteriorates the characteristics of the conductor. Another problem is that the addition of lithium oxide causes a decrease in the reliability of insulation resistance.
それゆえに、この発明の主たる目的は、低い温度で焼成
でき、特性的には比抵抗が高く、かつ誘電率が低く、ざ
らに誘電体損失が小さく、しかも熱膨張係数がアルミナ
以下である多層基板用低温焼結磁器組成物を提供するこ
とである。Therefore, the main object of the present invention is to provide a multilayer substrate that can be fired at a low temperature, has high specific resistance, low dielectric constant, roughly low dielectric loss, and has a thermal expansion coefficient of less than alumina. An object of the present invention is to provide a low-temperature sintered porcelain composition for use in the present invention.
また、この発明の目的は、非酸化性雰囲気でしかも１０
００℃以下の低温で焼結可能であり、導体として１１（
Ｃｕ）、ニッケル（Ｎｉ）などの卑金属を用いることが
できる多層基板用低温焼結磁器組成物を提供することで
ある。Further, the object of this invention is to provide a non-oxidizing atmosphere with 10
It can be sintered at low temperatures below 00°C, and can be used as a conductor.
An object of the present invention is to provide a low-temperature sintered ceramic composition for a multilayer substrate in which base metals such as Cu) and nickel (Ni) can be used.
（問題点を解決するための手段）
この発明は、Ｓｉ成分が５ｉＯｚに換τｙして２５〜７
０重景％、重量成分がＢａＯに換算して１５〜７０重蛋
％、Ｂ成分がＢ２Ｏ３に換話して１．５重量％以上で３
重量％未満、ＡＩ酸成分Ａｌ２Ｏ３に換算して１重量％
以上で２０重量％未満、Ｃａ成分がＣａＯに換算してＯ
重量％を超え３０重置部以下含まれる、多ｌ基板用低温
焼結磁器組成物である。(Means for Solving the Problems) This invention provides that the Si component is 25 to 7 τy in terms of 5 iOz.
0 weight%, weight component is 15-70 weight% in terms of BaO, B component is 1.5% by weight or more in terms of B2O3, 3
Less than 1% by weight, calculated as AI acid component Al2O3
or more, less than 20% by weight, Ca component is O in terms of CaO
This is a low-temperature sintered porcelain composition for multi-liter substrates containing more than 30 overlapping parts by weight%.
なお、微量添加物として、Ｌ ｉ ２０、Ｎ２０、Ｎ
ａ ２０などのアルカリ金ＪＫｉ４化物の少なくとも１
種を１．０重ｆｆ１％以下添加するようにしてもよい。In addition, as trace additives, L i 20, N20, N
At least one of alkali gold JKi tetrahydride such as a 20
Seeds may be added in an amount of 1.0 weight ff1% or less.
この発明の多層基板用低温焼結磁器組成物を用いて多層
回路基板を製造する場合、たとえば、５ｉ１Ｂａ、Ｂ、
ＡＩおよびＣａの酸化物もしくは焼成時に分解して酸化
物となる化合物の粉末を秤量、調合し、その原料混合物
を８５０〜９５０℃で仮焼した後、粉砕し、その粉末を
バインダと混練してからシート状に成形し、次いで、得
られたグリーンシートを酸化性雰囲気あるいは非酸化性
もしくは還元雰囲気中、８５０〜１０００℃で焼成すれ
ばよい。また、多層回路基板を製造する場合、グリーン
シート上にＡｇ、Ａｇ−Ｐｄ、Ｃｕ、Ｎｉなどの導電材
料を含有する導電性ペーストで回路パターンを印刷し、
それらを複数枚積層してから、導電性ペーストを構成す
る導電材料に応じた雰囲気で焼成すればよい。内部導電
材料どしてＣｕやＮｉなとの卑金属を使用する場合、そ
れらの酸化を防止するため、非酸化性もしくは二元性の
雰囲気で焼成するのが好ましい。たとえば、窒素をキャ
リアガスとして水蒸気（７０℃）中を通過ぎせ、酸素お
よび水素の含有量を微量含有きせた窒素−水蒸気雰囲気
（通常、Ｎ２９９゜７〜９９．８％）中、８５０〜１０
００℃で焼成するのが好ましい。なお、酸素を微量含有
させるのは、グリーンシートの形成に使用するバインダ
を仮焼段階で、炭素として残存させないために、完全に
燃焼させて除去するためである。When manufacturing a multilayer circuit board using the low-temperature sintered ceramic composition for multilayer boards of the present invention, for example, 5i1Ba, B,
Powders of AI and Ca oxides or compounds that decompose to become oxides during firing are weighed and prepared, and the raw material mixture is calcined at 850 to 950°C, then crushed, and the powder is kneaded with a binder. The green sheet may be formed into a sheet shape, and then the obtained green sheet may be fired at 850 to 1000°C in an oxidizing atmosphere, a non-oxidizing atmosphere, or a reducing atmosphere. In addition, when manufacturing a multilayer circuit board, a circuit pattern is printed on a green sheet using a conductive paste containing a conductive material such as Ag, Ag-Pd, Cu, or Ni.
After laminating a plurality of them, they may be fired in an atmosphere depending on the conductive material constituting the conductive paste. When using a base metal such as Cu or Ni as the internal conductive material, it is preferable to sinter in a non-oxidizing or binary atmosphere to prevent oxidation of the base metal. For example, nitrogen is passed through water vapor (70°C) as a carrier gas, and 850 to 10
It is preferable to bake at 00°C. The reason why a small amount of oxygen is included is to completely burn off and remove the binder used for forming the green sheet during the calcination stage so that it does not remain as carbon.
この発明の上述の目的、その他の目的、特徴および利点
は、以下の実施例の詳細な説明から一層明らかになろう
。The above objects, other objects, features and advantages of the present invention will become more apparent from the detailed description of the following embodiments.
（実施例１）
原料として、ＢａＯ，ＳｉＯＡＩ Ｏ２−２３’
ＢＯもしくはＢＮまたはＢ ４Ｃ１Ｃａ ＯまたはＣａ
ＣＯ３を、別表１の組成になるように秤量して混合し
た。この混合物を８５０〜９５０℃で仮焼し、粉砕した
後、有機バインダを加えて混練し、ドクターブレード法
によって厚き１ｍｍのシート状に成形した。このグリー
ンシートをＰＪ１３０ｍｍ１横１０ｍｍにカットし、こ
れを空気中、８５０〜１０００℃で１時間焼成して磁器
を得た。また、このグリーンシートを樅３１１１ｆｆ＋
、横２０ｍｍの角板状にカットして、これを３枚積層し
、２００Ｋｇ／ｃｍ２で加圧し角柱状にした。そして、
これを上述の方法で焼成し、熱膨張測定用の試料とした
。(Example 1) As raw materials, BaO, SiOAI O2-23' BO or BN or B 4C1Ca O or Ca
CO3 was weighed and mixed to have the composition shown in Attached Table 1. This mixture was calcined at 850 to 950°C, pulverized, then kneaded with an organic binder and formed into a 1 mm thick sheet by a doctor blade method. This green sheet was cut into pieces with a PJ of 130 mm and a width of 10 mm, and this was fired in air at 850 to 1000° C. for 1 hour to obtain porcelain. Also, use this green sheet as a fir 3111ff+
It was cut into a rectangular plate shape with a width of 20 mm, and three of these plates were laminated and pressed at 200 kg/cm2 to form a rectangular column shape. and,
This was fired by the method described above and used as a sample for thermal expansion measurement.
これらの試料について、次のとおり各特性をそれぞれの
条件や測定方法で測定し、別表１に示す結果を得た。Regarding these samples, each characteristic was measured using the respective conditions and measurement methods as follows, and the results shown in Attached Table 1 were obtained.
誘電率：ＩＭＨｚの条件
誘電体損失：ＩＭＨｚの条件
比抵抗二直流１００■の条件
抗折強度：次の（１）式より算出
式中、Ｔｒ：抗折強度、
Ｐ ：試料が切断したときの荷重（Ｋｇ）ｌ ：支点間
距離（ｃｍ）
ｂ ：試料の輻（ｃｍ）
ｄ ：試料の厚さくａｍ）
熱膨張係数：次の（２）式より算出
式中、α ：熱膨張係数
ΔＬ：加熱による試料の見掛けの伸び
（ＩｎＩｌｌ）
Ｌ ：室温での試料の長き（ｍｍ）
Ｔ１：室温
”ｒ：５００℃
αＳ ｉ Ｏ２：石英ガラスの熱膨張係数また、これと
は別に同じ方法で厚さ０．３〜０．４ｍｍのグリーンシ
ートを作成する一方、粒径５μｍ以下のＡｇまたばＡｇ
−Ｐ ｄの導電材料粉末と有機質ビヒクルとを重量比８
０ ： ２０の割合で混合して導電ペーストを調整して
、前述のグリーンシートの表面に各導電性ペーストを全
面に印刷し、これを３枚積層して熱圧着し、空気中８５
０〜１０００’Ｃで焼成した。なお、有機質ビヒクルは
、エチルセルロースをα−テレピネオールで１０倍に希
釈したものを使用した。Dielectric constant: IMHz condition Dielectric loss: IMHz condition Specific resistance 2 DC 100cm condition Transverse strength: Calculated from the following formula (1) In the formula, Tr: Transverse strength, P: When the sample is cut Load (Kg) l: Distance between fulcrums (cm) b: Convergence of sample (cm) d: Thickness of sample (am) Coefficient of thermal expansion: Calculated from the following formula (2), α: Coefficient of thermal expansion ΔL: Apparent elongation of the sample due to heating (InIll) L: Length of the sample at room temperature (mm) T1: Room temperature"r: 500°C αS i O2: Coefficient of thermal expansion of silica glass Also, separately from this, the thickness can be measured using the same method. While creating a green sheet of 0.3 to 0.4 mm, Ag or Ag with a particle size of 5 μm or less
- Pd conductive material powder and organic vehicle at a weight ratio of 8
The conductive pastes were adjusted by mixing them in a ratio of 0:20, each conductive paste was printed on the entire surface of the green sheet, three sheets were stacked, thermo-compressed, and heated at 85% in the air.
It was fired at 0-1000'C. The organic vehicle used was ethyl cellulose diluted 10 times with α-terpineol.
こうして得られた多層磁器基板について、磁器とＡｇま
たはＡｇ−Ｐｄとの反応を分析したところ、両者間での
反応は見られず、ＡｇおよびＡｇ−Ｐｄはいずれも良好
な導電性を示し、Ａｇの面積抵抗は２ｍΩ／口で、Ａｇ
−Ｐｄの面積抵抗は２０ｍΩ／口であった。When the reaction between the porcelain and Ag or Ag-Pd was analyzed for the thus obtained multilayer ceramic substrate, no reaction was observed between the two, and both Ag and Ag-Pd showed good conductivity. The areal resistance of Ag
-Pd had a sheet resistance of 20 mΩ/hole.
（実施例２）
実施例１で作成した厚さ１ｍｍのグリーンシートを用い
、樅３０ ｍｍ ％横１０ｍｍの角板状にカットしたグ
リーンシートを、水蒸気（７０℃）中に通過させた窒素
をキャリアガスとする窒素−水蒸気の還元性もしくは非
酸化性雰囲気中９００℃の温度で完全燃焼させ、９５０
〜１０００℃で１時間焼成して試料とした。また、実施
例１と同様にして、加圧成形しｔ：角柱状の試料につい
ても、上述と同じ焼成を行ない、熱膨張係数測定用の試
料とした。そして、これらの試料を用いて、実施例１中
で測定した各特性について測定し、別表２の結果を得た
。(Example 2) Using the green sheet with a thickness of 1 mm prepared in Example 1, the green sheet was cut into a rectangular plate shape of 30 mm thick fir and 10 mm in width. Complete combustion at a temperature of 900°C in a reducing or non-oxidizing atmosphere of nitrogen-steam as a gas,
A sample was prepared by firing at ~1000°C for 1 hour. Further, in the same manner as in Example 1, a pressure-formed prismatic sample was also fired in the same manner as described above, and was used as a sample for measuring the coefficient of thermal expansion. Using these samples, each characteristic measured in Example 1 was measured, and the results shown in Appendix 2 were obtained.
また、実施例１の後半で述べた厚さ０．３〜０．４ｍｍ
のグリーンシートを用い、その表面上に粒径５μｍ以下
の銅粉末と有機質ビヒクルとを重量比８０ ： ２０の
割合で混合した銅ペーストを印刷し、これを３枚積層し
て熱圧着し、窒素−水蒸気の還元性もしくは非酸化性雰
囲気中９５０〜１０００℃で１時間焼成した。こうして
得た多層磁器基板のＣｕ導体は酸化されておらず、良好
な導電性を示し、その面積抵抗は２ｍΩ／口であった。In addition, the thickness 0.3 to 0.4 mm described in the latter half of Example 1
A copper paste made by mixing copper powder with a particle size of 5 μm or less and an organic vehicle at a weight ratio of 80:20 was printed on the surface of the green sheet, and three sheets of this were stacked and bonded by thermocompression. - Calcined at 950-1000°C for 1 hour in a reducing or non-oxidizing atmosphere of water vapor. The Cu conductor of the multilayer ceramic substrate thus obtained was not oxidized and exhibited good conductivity, and its sheet resistance was 2 mΩ/hole.
別表１、別表２の結果は次の基準に従うて判定きれた。The results in Attached Tables 1 and 2 were determined according to the following criteria.
焼結温度：１０００℃以下（Ｃｕ導体およびＡｇ−Ｐｄ
導体の使用可能な温度、た
だしＡｇ−Ｐｄ導体はＡｇ ： Ｐｄ＝８０ ： ２０
のもの）
誘電率（ε）：ＩＭＨｚの条件ドで１０以下（アルミナ
の誘電率の値以下）
誘電体損失（ｔａｎδ）：ＩＭＨｚの条件下で０゜２％
以下
抗折強度： １５００Ｋｇ／ｃｍ２以上熱膨張係数：
７． ＯＸ １０’／ｌ：以下（アルミナの熱膨張係数
の値以下）
非酸化性雰囲気で使用できるサーメット抵抗を表面に形
成した場合、この発明にかかる多層磁器基板上のサーメ
ット抵抗はアルミナ基板と同等の特性が得られた。また
Ｂ２Ｏ３Ｍｋを３重量％にすると半田付は性が悪くなる
ことが確認された。Sintering temperature: 1000℃ or less (Cu conductor and Ag-Pd
Usable temperature of conductor, except for Ag-Pd conductor: Ag: Pd = 80: 20
) Dielectric constant (ε): 10 or less under IMHz conditions (less than the dielectric constant of alumina) Dielectric loss (tan δ): 0°2% under IMHz conditions
Breaking strength below: 1500Kg/cm2 or more Coefficient of thermal expansion:
7. OX 10'/l: Below (below the value of the thermal expansion coefficient of alumina) When a cermet resistor that can be used in a non-oxidizing atmosphere is formed on the surface, the cermet resistor on the multilayer ceramic substrate according to the present invention is equivalent to the alumina substrate. characteristics were obtained. It was also confirmed that when B2O3Mk was increased to 3% by weight, the soldering properties deteriorated.
なお、別表１および別表２において、＊印を付したもの
はこの発明範囲外のものであり、それ以外はこの発明範
囲内のものである。In addition, in Attached Table 1 and Attached Table 2, those marked with * are outside the scope of this invention, and the others are within the scope of this invention.
別表１および別表２から明らかなように、この発明の多
層基板用低温焼結磁器組成物における組成範囲を前記し
た範囲に限定した理由は次の通りである。As is clear from Attached Tables 1 and 2, the reason why the composition range of the low temperature sintered ceramic composition for multilayer substrates of the present invention is limited to the above range is as follows.
（１）Ｓ１０２が７０重畳％を超えると、抗折強度が１
５００Ｋｇ／ａｍ２未満になり、かつ焼結温度が１００
０℃より高くなるので好ましくない（試料番号１参照）
。一方、Ｓ ｉ ０２が２５ｆｔ景％未満では、誘電率
が１０より大きくなるので好ましくない（試料番号４参
照）。(1) When S102 exceeds 70% overlap, the bending strength is 1
less than 500Kg/am2, and the sintering temperature is 100Kg/am2
It is not preferable because it becomes higher than 0℃ (see sample number 1)
. On the other hand, if S i 02 is less than 25 ft.%, the dielectric constant becomes greater than 10, which is not preferable (see sample number 4).
（２）ＢａＯがＴｏｉ量％を超えると、誘電率が１０よ
り大きくなるので好ましくない（試料番号５参照）。一
方、ＢａＯが１５重量％未満では、焼結温度が１０００
℃より高くなり好ましくない（試料番号１２参照）。(2) If BaO exceeds the amount of Toi%, the dielectric constant becomes greater than 10, which is not preferable (see sample number 5). On the other hand, when BaO is less than 15% by weight, the sintering temperature is 1000% by weight.
℃, which is not preferable (see sample number 12).
（３）ＣａＯが３０重置部を超えると、焼結温度が１０
００℃より高くなり好ましくない（試料番号１１）。一
方、ＣａＯが含有されていないときは、熱膨張係数が７
．０Ｘ１０−６／’Ｃより大きくなり好ましくない（試
料番号８参照）。(3) When the CaO content exceeds 30, the sintering temperature increases to 10
It becomes higher than 00°C, which is not preferable (sample number 11). On the other hand, when CaO is not contained, the thermal expansion coefficient is 7.
．． It becomes larger than 0X10-6/'C, which is not preferable (see sample number 8).
（４） Ａ ｌ ２０３が２０Ｍ量％以上になると、誘
電体損失が０．２％より大きくなり好ましくない（試料
番号１４参照）。一方、ＡＪ２２ｏ３が１重量％以下の
ときは、焼結温度が１ｏｏｏ℃より高くなり好ましくな
い（試料番号１５参照）。(4) When Al 203 exceeds 20 M%, the dielectric loss becomes greater than 0.2%, which is not preferable (see sample number 14). On the other hand, when AJ22o3 is 1% by weight or less, the sintering temperature becomes higher than 100° C., which is not preferable (see sample number 15).
（５）Ｂ２０３が３重量％以上であると、抗折強度が１
５００Ｋｇ／ｃｍ２より小さくなり好ましくない（試料
番号１２参照）。一方、ＢａＯ３が１．５！ｉ％未満で
は、焼結温度が１０００℃より高くなるので好ましくな
い（試料番号１９参照）。(5) When B203 is 3% by weight or more, the bending strength is 1
It is less than 500 Kg/cm2, which is not preferable (see sample number 12). On the other hand, BaO3 is 1.5! If it is less than i%, the sintering temperature will become higher than 1000°C, which is not preferable (see sample number 19).
（発明の効果）
この発明によれば、高比抵抗かつ低誘電率で誘電体損失
が少なく、しかも熱膨張例数がアルミナよりも小きくな
る。また、製造過程においても仮焼後の粉砕などの処理
がしゃす＜、シかも、１０００℃以下で焼成でき、酸化
性雰囲気中あるいは非酸化性雰囲気中で焼成しても、電
気的特性、物理的特性ざらには熱的特性の変化がな（、
内部導体との反応も見られないので、内部導体材料とし
て、たとえば、Ａｇ、Ａｇ−Ｐｄペースト、Ｃｕおよび
Ｎｉなとの卑金属を使用することができ、多層基板のコ
ストダウンを図ることができる。(Effects of the Invention) According to the present invention, the material has high resistivity and low dielectric constant, has low dielectric loss, and has a smaller number of thermal expansion cases than alumina. In addition, even in the manufacturing process, processing such as pulverization after calcination is difficult, and it can be fired at temperatures below 1000°C, and even when fired in an oxidizing or non-oxidizing atmosphere, the electrical properties and physical properties There is no change in thermal properties (,
Since there is no reaction with the internal conductor, base metals such as Ag, Ag-Pd paste, Cu, and Ni can be used as the internal conductor material, and the cost of the multilayer board can be reduced.
また、熱膨張係数がアルミナ以下であるため、サーマル
ストレスによるクラックが生じにくくなる。Furthermore, since the coefficient of thermal expansion is less than or equal to alumina, cracks due to thermal stress are less likely to occur.
ざらに、サーメット抵抗材料などを印刷して、抵抗体も
形成することができる。Alternatively, a resistor can also be formed by printing a cermet resistive material or the like.
Claims (1)
重量％未満、 Ａｌ成分がＡｌ＿２Ｏ＿３に換算して１重量％以上で２
０重量％未満、 Ｃａ成分がＣａＯに換算して０重量％を超え３０重量％
以下含まれる、 多層基板用低温焼結磁器基板。[Claims] The Si component is 25 to 70% by weight in terms of SiO_2, the Ba component is 15 to 70% by weight in terms of BaO, and the B component is 1.5% by weight or more in terms of B_2O_3.
Less than 2% by weight, when the Al content is 1% by weight or more calculated as Al_2O_3
Less than 0% by weight, Ca component exceeds 0% by weight and 30% by weight in terms of CaO
Included below are low temperature sintered porcelain substrates for multilayer substrates.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61072288A JPS62226855A (en) | 1986-03-28 | 1986-03-28 | Low temperature sintering ceramic composition for multi-layer substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61072288A JPS62226855A (en) | 1986-03-28 | 1986-03-28 | Low temperature sintering ceramic composition for multi-layer substrate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62226855A true JPS62226855A (en) | 1987-10-05 |
Family
ID=13484940
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61072288A Pending JPS62226855A (en) | 1986-03-28 | 1986-03-28 | Low temperature sintering ceramic composition for multi-layer substrate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62226855A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016185921A1 (en) * | 2015-05-15 | 2016-11-24 | 株式会社村田製作所 | Low-temperature-sintering ceramic material, ceramic sintered body, and ceramic electronic component |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62187159A (en) * | 1986-02-10 | 1987-08-15 | 株式会社村田製作所 | Low temperature sinterable ceramic composition for multi-layer substrate |
-
1986
- 1986-03-28 JP JP61072288A patent/JPS62226855A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62187159A (en) * | 1986-02-10 | 1987-08-15 | 株式会社村田製作所 | Low temperature sinterable ceramic composition for multi-layer substrate |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016185921A1 (en) * | 2015-05-15 | 2016-11-24 | 株式会社村田製作所 | Low-temperature-sintering ceramic material, ceramic sintered body, and ceramic electronic component |
| CN107531577A (en) * | 2015-05-15 | 2018-01-02 | 株式会社村田制作所 | Low-temperature sintered ceramics material, ceramic sintered bodies and ceramic electronic components |
| JPWO2016185921A1 (en) * | 2015-05-15 | 2018-01-18 | 株式会社村田製作所 | Low temperature sintered ceramic materials, ceramic sintered bodies and ceramic electronic components |
| US20180044244A1 (en) * | 2015-05-15 | 2018-02-15 | Murata Manufacturing Co., Ltd. | Low temperature cofired ceramic material, ceramic sintered body, and ceramic electronic component |
| US10906839B2 (en) | 2015-05-15 | 2021-02-02 | Murata Manufacturing Co., Ltd. | Low temperature cofired ceramic material, ceramic sintered body, and ceramic electronic component |
| DE112016001804B4 (en) | 2015-05-15 | 2021-12-16 | Murata Manufacturing Co., Ltd. | Low-temperature single-fused ceramic, ceramic sintered body and electronic ceramic component |
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