JPH01102808A - Dielectric porcelain compound for temperature compensation - Google Patents
Dielectric porcelain compound for temperature compensationInfo
- Publication number
- JPH01102808A JPH01102808A JP62259269A JP25926987A JPH01102808A JP H01102808 A JPH01102808 A JP H01102808A JP 62259269 A JP62259269 A JP 62259269A JP 25926987 A JP25926987 A JP 25926987A JP H01102808 A JPH01102808 A JP H01102808A
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- parts
- weight
- composition
- temperature
- 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
- 229910052573 porcelain Inorganic materials 0.000 title abstract description 12
- 150000001875 compounds Chemical class 0.000 title 1
- 239000000203 mixture Substances 0.000 claims abstract description 41
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims abstract description 16
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000292 calcium oxide Substances 0.000 claims abstract description 7
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 6
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 4
- 239000000919 ceramic Substances 0.000 claims description 18
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 238000005245 sintering Methods 0.000 abstract description 7
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract description 6
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 4
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000003990 capacitor Substances 0.000 description 7
- 239000003985 ceramic capacitor Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000010953 base metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000807 Ga alloy Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Insulating Materials (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
この発明は温度補償用誘電体磁器組成物に関し、特にた
とえば積層コンデンサの誘電体磁器として用いられる温
度補償用誘電体磁器組成物に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a temperature-compensating dielectric ceramic composition, and particularly to a temperature-compensating dielectric ceramic composition used as dielectric ceramic for a multilayer capacitor, for example.
（従来技術）
従来、この種の温度補償用誘電体磁器組成物としては、
ＭｇＴｉ０ｓ−ＣａＴｉＯｓ系の磁器が用いられていた
。(Prior Art) Conventionally, as this type of dielectric ceramic composition for temperature compensation,
MgTiOs-CaTiOs-based porcelain was used.
（発明が解決しようとする問題点）
しかしながら、ＭｇＴｉ０．、−ＣａＴｉＯ，系の磁器
では、その焼結温度が１３００℃以上と高く、さらに、
非酸化性雰囲気中で焼成した場合に磁器が還元されて絶
縁抵抗値が著しく低下するという問題点を有していた。(Problems to be solved by the invention) However, MgTi0. , -CaTiO, type porcelain has a high sintering temperature of 1300°C or higher, and furthermore,
The problem is that when fired in a non-oxidizing atmosphere, the porcelain is reduced and the insulation resistance value is significantly reduced.
また、積層セラミックコンデンサの一般的な製法におい
ては、ドクタブレード法などの方法によって得られたグ
リーンシートと呼ばれる焼成前のセラミックシート上に
内部電極となる導体金属粉末ペーストを印刷塗布し、こ
れを複数枚交互に積層し圧着したものを焼成する工程が
とられている。In addition, in the general manufacturing method of multilayer ceramic capacitors, a conductive metal powder paste, which will become the internal electrodes, is printed and coated on an unfired ceramic sheet called a green sheet obtained by a method such as the doctor blade method, and multiple layers of this are applied. A process is used in which the sheets are alternately laminated and pressed together and then fired.
そのため、従来の材料では焼成コストが高くつくばかり
でなく、誘電体セラミックと同時に焼成される積層コン
デンサの内部電極の材料として、誘電体セラミックが焼
結する温度で熔融せず、かつ、セラミックが半導体化し
ない高い酸素分圧下で焼成されても酸化されない金属を
用いなければならない、゛このため、従来の材料を積層
コンデンサの誘電体磁器として用いる際には、内部電極
の材料として高融点かつ高温で酸化しにくい高価なパラ
ジウムや白金を使用しなければならず、積層コンデンサ
のコスト低減の障害となっていた。Therefore, not only are conventional materials expensive to sinter, but they are also used as internal electrode materials for multilayer capacitors that are fired at the same time as dielectric ceramics because they do not melt at the temperature at which dielectric ceramics sinter, and ceramics do not melt at the sintering temperature of semiconductors. It is necessary to use metals that do not oxidize even when fired under high oxygen partial pressures that do not oxidize. Therefore, when using conventional materials as dielectric porcelain in multilayer capacitors, it is necessary to use metals that have high melting points and high temperatures as internal electrode materials. This requires the use of expensive palladium or platinum, which is difficult to oxidize, which has been an obstacle to reducing the cost of multilayer capacitors.
以上のことから、積層セラミックコンデンサの低価格化
および小型大容量化のために内部電極の材料を高価な貴
金属から安価な卑金属にすることが望まれていたが、卑
金属たとえば銅を内部電極として用いるためには、銅が
酸化あるいは溶融しない酸素分圧の低い中性または還元
雰囲気中で１０００℃以下で半導体化することなく焼結
し、コンデンサ用誘電体として十分に高い比抵抗と優れ
た誘電特性を有する誘電体磁器組成物が必要とされてい
た。Based on the above, it has been desired to change the material of the internal electrodes from expensive noble metals to cheap base metals in order to reduce the price and make the multilayer ceramic capacitors smaller and larger in capacity. In order to achieve this, copper is sintered at 1000°C or below in a neutral or reducing atmosphere with low oxygen partial pressure where it does not oxidize or melt, without becoming a semiconductor, and has sufficiently high resistivity and excellent dielectric properties as a dielectric for capacitors. There was a need for a dielectric ceramic composition having the following characteristics.
それゆえに、この発明の主たる目的は、１０００℃以下
の低温で焼結し、かつ、非酸化性雰囲気中で焼成しても
磁器の比抵抗値が１０１２Ωｃｍ以上と高い温度補償用
誘電体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 dielectric porcelain composition for temperature compensation which has a high specific resistance value of 1012 Ωcm or more even when sintered at a low temperature of 1000°C or less and in a non-oxidizing atmosphere. The goal is to provide the following.
（問題点を解決するための手段） この発明は、酸化バリウム、酸化カルシウム。(Means for solving problems) This invention uses barium oxide and calcium oxide.
酸化ストロンチウム、酸化珪素および酸化ジルコニウム
を主成分として含み、酸化バリウム、酸化カルシウムお
よび酸化ストロンチウムの含有量の合計を（Ｂａｔ−ａ
−ｂ Ｃａ−ｂＣａａＳｒｂ ”）Ｏ（ただし、０＜ａ
、０＜ｂ、Ｏ＜ａ＋ｂ≦０．９）に換算してＸ重量部と
し、酸化珪素の含有量をＳ ｉ Ｏ，に換算して７重量
部とし、酸化ジルコニウムの含有量をＺｒ０１に換算し
て２重量部としたとき（ただし、Ｘ＋Ｙ＋Ｚ−１００）
、次の各点Ａ、Ｂ。Contains strontium oxide, silicon oxide and zirconium oxide as main components, and the total content of barium oxide, calcium oxide and strontium oxide is (Bat-a)
−b Ca−bCaaSrb ”)O (where 0<a
, 0<b, O<a+b≦0.9), the content of silicon oxide is converted to 7 parts by weight, and the content of zirconium oxide is converted to Zr01. When it is made into 2 parts by weight (X+Y+Z-100)
, the following points A and B.
ＣおよびＤ （Ｘ、 Ｙ、 Ｚ’）
Ａ （５０，４９，１）
Ｂ （５０，２０，３０）
Ｃ（１５，２０，６５）
Ｄ （１５，８４，１）
を頂点とした多角形で囲まれる範囲にある組成のうち、
ｚｒｏｔの一部をＴ ｉ Ｏ，およびＳｎＯ。C and D (X, Y, Z') A (50,49,1) B (50,20,30) C (15,20,65) D (15,84,1) A polygon with vertices Of the compositions within the enclosed range,
A part of zrot is T i O, and SnO.
のうちの１′種以上で１〜３０重量部置換した、温度補
償用誘電体磁器組成物である。This is a dielectric ceramic composition for temperature compensation in which 1 to 30 parts by weight of one or more of the above are substituted.
（発明゛の効果）
この発明によれば、１０００℃以下の低温で焼結し、か
つ、非酸化性雰囲気中で焼成しても比抵抗値がｌ□鳳ｔ
Ω１以上と高い温度補償用誘電体磁器組成物が得られる
。そのため、この温度補償用誘電体磁器組成物を積層コ
ンデンサの誘電体磁器として用いれば、焼成コストを安
価にすることができ、かつ、抵抗値が低くて安価な銅、
銅系合金あるいはその他の卑金属を内部電極として用い
ることができるので、従来に比べて、積層コンデンサの
大幅なコストダウンを図ることができる。(Effects of the invention) According to the invention, even when sintered at a low temperature of 1000°C or less and in a non-oxidizing atmosphere, the specific resistance value remains l
A dielectric ceramic composition for temperature compensation with a high resistance of Ω1 or more can be obtained. Therefore, if this temperature-compensating dielectric ceramic composition is used as the dielectric ceramic of a multilayer capacitor, the firing cost can be reduced, and copper, which is low in resistance and inexpensive, can be used.
Since copper-based alloys or other base metals can be used for the internal electrodes, the cost of the multilayer capacitor can be significantly reduced compared to conventional ones.
この発明の上述の目的、その他の目的、特徴および利点
は、図・面を参照して行う以下の実施例の詳細な説明か
ら一層明らかとなろう。The above objects, other objects, features and advantages of the present invention will become more apparent from the following detailed description of embodiments with reference to the drawings and drawings.
（実施例） まず、原料として、Ｂ ａ ＣＯ２、Ｃａ ＣＯ＋ 。(Example) First, the raw materials are B a CO2 and Ca CO+.
５ｒＣＯ，、、Ｓ ｆｏｘ 、Ｚｒ０ｔ 、Ｔｉ０ｚ
、Ｓｎｏ、およびＡｌｚＯｚを別表１に示す組成となる
ように秤量し、それらをボールミルで１６時時間式混合
した後、蒸発乾燥して混合粉末を得た。5rCO, , S fox , Zr0t , Ti0z
, Sno, and AlzOz were weighed to have the composition shown in Attached Table 1, mixed in a ball mill for 16 hours, and then evaporated to dryness to obtain a mixed powder.
次に、この混合粉末を８５０℃で２時間仮焼し、これに
結合材として酢酸ビニルを５重量部加え、再びボールミ
ルで１６時時間式混合、粉砕して粉砕物を得た。Next, this mixed powder was calcined at 850° C. for 2 hours, 5 parts by weight of vinyl acetate was added as a binder, and the mixture was again mixed in a ball mill for 16 hours and pulverized to obtain a pulverized product.
そして、この粉砕物を蒸発乾燥して整粒し、果粒状の粉
末を得た。Then, this pulverized product was evaporated to dryness and sized to obtain a granular powder.
それから、こうして得た果粒状の粉末を乾式プレス機で
２ｔＯｎ／ｃ１１の圧力で加圧し、直径２２鶴、厚さ１
．０龍の円板状に成形して成形物を得た。Then, the granular powder thus obtained was pressed with a dry press at a pressure of 2tOn/c11, and the diameter was 22mm and the thickness was 1mm.
．． A molded product was obtained by molding it into a disk shape of zero dragon.
次に、この成形物をＮｚ Ｈｚガス雰囲気中で別表２
に示した各温度条件で２時間焼成を行って、焼成物を得
た。Next, this molded product was heated in a Nz Hz gas atmosphere in Attached Table 2.
Firing was performed for 2 hours under each temperature condition shown in , to obtain a fired product.
さらに、これらの焼成物の両主面に、電極を形成する際
に磁器が特性の変化を受けることを避けるために、Ｉｎ
−Ｇａ合金を塗布して電極を形成し試料１〜１８とした
。Furthermore, in order to avoid changes in the characteristics of the porcelain when forming electrodes on both main surfaces of these fired products, In
Samples 1 to 18 were formed by applying -Ga alloy to form electrodes.
そして、これらの試料について、次に示す各特性をそれ
ぞれの条件や測定方法で測定し、その結果を別表２に示
した。The following properties of these samples were measured using the respective conditions and measurement methods, and the results are shown in Attached Table 2.
（１）比・誘電率；周波数ＩＭＨｚ、温度２５℃の条件
下で測定した。(1) Specific dielectric constant: Measured under the conditions of a frequency of IMHz and a temperature of 25°C.
（２）Ｑ値（品質係数）二周波数ＩＭＨｚ、温度２５℃
の条件下で測定した。(2) Q value (quality factor) dual frequency IMHz, temperature 25℃
Measured under the following conditions.
（３）低温側の静電容量の温度係数（ｐｐｍ／ｌ）
：２５℃での静電容量ＣＩを基準として、これと−５５
℃での静電容Ｉ Ｃ！とから次式（１）によって算出し
た。(3) Temperature coefficient of capacitance on the low temperature side (ppm/l)
: Based on the capacitance CI at 25℃, this and -55
Capacitance I C at °C! It was calculated from the following equation (1).
低温側の静電容量の温度係数（ρｐｍ／’ｔ’）（Ｃｇ
−Ｃ＋） ＸＩＯ’
（４）高温側の静電容量の温度係数（ｐｐｍ／ ”ｃ
） ：２５℃での静電容量Ｃ，を基準として、これと
１２５℃での静電容ｔＣ８とから次式（２）によって算
出した。Temperature coefficient of capacitance on the low temperature side (ρpm/'t') (Cg
-C+) XIO' (4) Temperature coefficient of capacitance on high temperature side (ppm/"c
): Calculated using the following equation (2) from the capacitance C at 25° C. and the capacitance tC8 at 125° C.
高温側の静電容量の温度係数（ｐｐｍ／ ’Ｃ）（ｃ、
−ｃ、） ｘｌＯ’
（５）比抵抗：２５℃でｓ、 ｏ ｏ ｖ直流電圧を印
加して電流値を測定し、それらから算出した。Temperature coefficient of capacitance on high temperature side (ppm/'C) (c,
-c,) xlO' (5) Specific resistance: A DC voltage of s, o v was applied at 25°C, the current value was measured, and it was calculated from them.
なお、別表１および別表２中で＊印を付したものはこの
発明の範囲外のものであり、それ以外はこの発明の範囲
内のものである。In addition, those marked with * in Attached Tables 1 and 2 are outside the scope of this invention, and the others are within the scope of this invention.
また、別表１および別表２に示した各試料の主成分の組
成を図中に３成分組成図で示した。この図面においてＯ
印を付した数字は各試料番号を示す。In addition, the composition of the main components of each sample shown in Attached Table 1 and Attached Table 2 is shown in a three-component composition diagram in the figure. In this drawing O
The marked numbers indicate each sample number.
さらに、この図中には、この発明の組成物の主成分の組
成比を示す領域を、−成魚Ａ、Ｂ、ＣおよびＤを頂点と
した４角形で示した。すなわち、酸化バリウム、酸化カ
ルシウムおよび酸化ストロンチウムの含有量の合計を（
Ｂ ａ Ｉ−ｍ−ｈＣａ ＠ ５ｒｂ）０に換算してＸ
重量部とし、酸化珪素の含有量をＳ ｉ Ｏ，に換算し
て７重量部とし、酸化ジルコニウムの含有量をＺｒ０ｚ
に換算して２重量部としたとき（ただし、Ｘ＋Ｙ＋Ｚ＝
１００）、この発明の組成物の主成分の組成比（Ｘ、Ｙ
、Ｚ〉は、組成点Ａ （５０，４９，１）、Ｂ （５０
゜２０．３０）、Ｃ（１５，２０，６５）およびＤ（１
５，８４，１）を頂点とした多角形で囲まれる領域内ア
組成比に相当するのである。Further, in this figure, regions showing the composition ratios of the main components of the composition of the present invention are shown as rectangles with -adult fish A, B, C, and D as vertices. In other words, the total content of barium oxide, calcium oxide and strontium oxide is (
B a I-m-hCa @ 5rb) converted to 0
parts by weight, the content of silicon oxide is 7 parts by weight converted to SiO, and the content of zirconium oxide is Zr0z.
When converted to 2 parts by weight (X+Y+Z=
100), the composition ratio of the main components of the composition of this invention (X, Y
, Z〉 are composition points A (50,49,1), B (50
゜20.30), C(15,20,65) and D(1
This corresponds to the a composition ratio within the area surrounded by the polygon with vertices 5, 84, 1).
そして、この発明にかかる組成物は、上述の主成分中の
ＺｒＯ，の一部がＴｉｅ、およびＳｎＯ２のうちの１種
以上で１〜３０重量部置換され、さらに、必要に応じて
、主成分１００重量部に対して酸化アルミニウムがＡｔ
’ｇＯｓに換算して２０３１量部以下（０重量部を含ま
ず）添加含有される。Further, in the composition according to the present invention, a part of ZrO in the above-mentioned main component is replaced with 1 to 30 parts by weight of one or more of Tie and SnO2, and further, if necessary, ZrO in the main component Aluminum oxide is At per 100 parts by weight
It is added and contained at most 2031 parts by weight (excluding 0 parts by weight) in terms of 'gOs.
なお、この図中には、０＜ａ、Ｏｒｂかつ０くａ＋ｂ≦
０．９の関係が成り立つことは表されていない。In addition, in this figure, 0<a, Orb and 0ku a+b≦
It is not shown that the relationship of 0.9 holds true.
また、各試料の主成分中のＺｒＯ，の一部をＴｉＱｌお
よびＳｎｕｇで置換した割合は、別表１に示され図中に
は示されていない。Further, the ratio of ZrO in the main component of each sample being partially replaced by TiQl and Snug is shown in Attached Table 1 and is not shown in the figure.
次に、この発明にかかる温度補償用誘電体磁器組成物を
上述の範囲に限定した理由について説明する。Next, the reason why the temperature compensating dielectric ceramic composition according to the present invention is limited to the above range will be explained.
（１）３成分組成図に示す組成点ＡおよびＢを結ぶ線分
の外側の組成領域では、Ｑ値が１０００以下となりかつ
静電容量の温度係数が＋１１００ｐｐ ／ ’Ｃ以上と
なり、しかも、焼結磁器素体の表面上にガラス質が浮く
ので好ましくない（試料番号６参照）。(1) In the composition region outside the line segment connecting composition points A and B shown in the ternary composition diagram, the Q value is 1000 or less, the temperature coefficient of capacitance is +1100pp/'C or more, and sintering This is undesirable because vitreous material floats on the surface of the porcelain body (see sample number 6).
（２）３成分組成図に示す組成点ＡおよびＤを結ぶ線分
の外側の組成領域でも、Ｑ値が１０００以下となりかつ
静電容量の温度係数が＋１１００ｐｐ ／ ’Ｃ以上と
なり、しかも、焼結磁器素体の表面上にガラス質が浮く
ので好ましくない（試料番号５参照）。(2) Even in the composition region outside the line segment connecting composition points A and D shown in the ternary composition diagram, the Q value is 1000 or less, the temperature coefficient of capacitance is +1100pp/'C or more, and sintering This is undesirable because vitreous material floats on the surface of the porcelain body (see sample number 5).
（３）３成分組成図に示す組成点ＢおよびＣを結ぶ線分
の外側の組成領域では、１１５０°Ｃの温度で焼成して
も緻密な焼結体が得られないので好ましくない（試料番
号７参照）。(3) In the composition region outside the line segment connecting composition points B and C shown in the ternary composition diagram, a dense sintered body cannot be obtained even if fired at a temperature of 1150°C, which is undesirable (sample no. (see 7).
（４）３成分組成図に示す組成点ＣおよびＤを結ぶ線分
の外側の組成領域でも、１１５０℃の温度で焼成しても
緻密な焼結体が得られないので好ましくない（試料番号
８参照）。(4) Even in the composition region outside the line segment connecting composition points C and D shown in the ternary composition diagram, a dense sintered body cannot be obtained even if fired at a temperature of 1150°C, which is not preferable (sample number 8). reference).
（５）主成分に酸化バリウムが全く含まれない場合、す
なわちａ＋ｂ”１の場合、１１５０℃の温度で焼成して
も緻密な焼結体が得られないので好ましくない（試料番
号１４および１５参照）。(5) If the main component does not contain barium oxide at all, that is, in the case of a+b''1, it is not preferable because a dense sintered body cannot be obtained even if fired at a temperature of 1150°C (see sample numbers 14 and 15). ).
（６）ＺｒＯ，の一部をＴ ｓ Ｏｚ ＋ Ｓ ｎ Ｏ
ｔで置換することによって、高温側と低温側とにおける
静電容量の温度係数の差が小さくなる。これは、ＺｒＯ
２のうちの１重量部以上をＴｉＯ□あるいはＳｎＯ，で
置換することによって効果を確認することができる（試
料番号１２および１６参照）。(6) Part of ZrO is T s Oz + S n O
By replacing it with t, the difference in temperature coefficient of capacitance between the high temperature side and the low temperature side becomes smaller. This is ZrO
The effect can be confirmed by replacing 1 part by weight or more of 2 with TiO□ or SnO (see sample numbers 12 and 16).
しかし、ＺｒＯ＋＋のうちの３０重量部より多くＴｉＯ
２あるいはＳｎＯ□で置換すると磁器の焼結性が低下し
焼結温度が１１５０℃以上と高くなるため好ましくない
（試料番号１７参照）。However, more than 30 parts by weight of ZrO++
2 or SnO□ is not preferable because it lowers the sinterability of the porcelain and increases the sintering temperature to 1150° C. or higher (see sample number 17).
（７）さらに、ＡｌｔＣｈを主成分１００重量部に対し
て２０重量部以下添加含有すると、磁器の特性にばらつ
きが少なくなりかつ特性が一定の水準でそろう。しかし
、ＡｌｚＯｉの添加量が２０重量部を超えると焼結温度
が１１５０℃以上と高くなるため好ましくない（試料番
号１１参照）。(7) Furthermore, when 20 parts by weight or less of AltCh is added to 100 parts by weight of the main component, variations in the characteristics of the porcelain will be reduced and the characteristics will be uniform at a certain level. However, if the amount of AlzOi added exceeds 20 parts by weight, the sintering temperature will increase to 1150° C. or higher, which is not preferable (see sample number 11).
それに対して、この発明の範囲内の試料では、還元雰囲
気中で１０００℃以下で焼結し、温度に対する静電容量
の温度係数の絶対値が１１００ｐｐ ／ ’Ｃ以下と小
さく、品質係数（Ｑ値）が１０００以上と高く、２５℃
における比抵抗が１０１２Ω口以上の特性が得られる。On the other hand, samples within the scope of the present invention are sintered at 1000°C or less in a reducing atmosphere, have a small absolute value of the temperature coefficient of capacitance with respect to temperature of 1100pp/'C or less, and have a quality coefficient (Q value). ) is high at over 1000 and at 25℃
A characteristic with a specific resistance of 1012Ω or more can be obtained.
したがって、この発明にかかる誘電体磁器組成物をセラ
ミックコンデンサの誘電体として用いれば、焼成コスト
の低減が可能となる。また、この発明にかかる誘電体磁
器組成物を積層セラミックコンデンサの誘電体として用
いれば、従来の高価な貴金属に比べて安価な銅、ニッケ
ル、鉄、クロムなどの卑金属あるいはこれらからなる合
金を内部電極とすることが可能になり、積層セラミック
コンデンサの大容量化にともなう電極コストの増大を解
消することができ、低価格な積層セラミックコンデンサ
を得ることができる。Therefore, if the dielectric ceramic composition according to the present invention is used as a dielectric of a ceramic capacitor, it is possible to reduce the firing cost. Furthermore, if the dielectric ceramic composition according to the present invention is used as a dielectric of a multilayer ceramic capacitor, base metals such as copper, nickel, iron, and chromium, or alloys made of these metals, which are cheaper than conventional expensive precious metals, can be used for internal electrodes. This makes it possible to eliminate the increase in electrode cost that accompanies an increase in the capacity of a multilayer ceramic capacitor, and to obtain a low-cost multilayer ceramic capacitor.
なお、上述の実施例において焼成雰囲気としてＮｚ
Ｈｚからなる還元性雰囲気を用いたが、この発明では、
Ａｒ、Ｇｏ、ＣＯｚ ＋ Ｈｚ 、Ｎｚおよびこれら
の混合雰囲気ガスを用いてもよいことはいうまで゛もな
い。In addition, in the above-mentioned example, the firing atmosphere was Nz
Although a reducing atmosphere consisting of Hz was used, in this invention,
It goes without saying that Ar, Go, COz + Hz, Nz, and mixed atmospheric gases thereof may be used.
図はこの発明の組成物の主成分の配合比を示す３成分組
成図である。
特許出願人 株式会社 村田製作所
代理人 弁理士 岡 １） 全 啓
表−２
Ｓｉ０２ｓｌｌｔｎ：ＹThe figure is a three-component composition diagram showing the blending ratio of the main components of the composition of the present invention. Patent Applicant: Murata Manufacturing Co., Ltd. Representative: Patent Attorney Oka 1) Zenkei Hyo-2 Si02slltn:Y
Claims (1)
ム，酸化珪素および酸化ジルコニウムを主成分として含
み、 前記酸化バリウム，前記酸化カルシウムおよび前記酸化
ストロンチウムの含有量の合計を（Ｂａ＿１＿−＿ａ＿
−＿ｂＣａ＿ａＳｒ＿ｂ）Ｏ（ただし、０＜ａ，０＜ｂ
，０＜ａ＋ｂ≦０．９）に換算してＸ重量部とし、前記
酸化珪素の含有量をＳｉＯ＿２に換算してＹ重量部とし
、前記酸化ジルコニウムの含有量をＺｒＯ＿２に換算し
てＺ重量部としたとき（ただし、Ｘ＋Ｙ＋Ｚ＝１００）
、次の各点Ａ，Ｂ，ＣおよびＤ（Ｘ，Ｙ，Ｚ） Ａ（５０，４９，１） Ｂ（５０，２０，３０） Ｃ（１５，２０，６５） Ｄ（１５，８４，１） を頂点とした多角形で囲まれる範囲にある組成のうち、
ＺｒＯ＿２の一部をＴｉＯ＿２およびＳｎＯ＿２のうち
の１種以上で１〜３０重量部置換した、温度補償用誘電
体磁器組成物。 ２ 前記主成分１００重量部に対して、さらに酸化アル
ミニウムをＡｌ＿２Ｏ＿３に換算して２０重量部以下（
０重量部を含まず）添加含有した、特許請求の範囲第１
項記載の温度補償用誘電体磁器組成物。[Scope of Claims] 1 Contains barium oxide, calcium oxide, strontium oxide, silicon oxide and zirconium oxide as main components, and the total content of the barium oxide, the calcium oxide and the strontium oxide is (Ba_1_-_a_
−_bCa_aSr_b)O (where 0<a, 0<b
. When (X+Y+Z=100)
, each of the following points A, B, C and D (X, Y, Z) A (50, 49, 1) B (50, 20, 30) C (15, 20, 65) D (15, 84, 1 ) among the compositions within the range surrounded by the polygon with vertices,
A dielectric ceramic composition for temperature compensation, in which a part of ZrO_2 is replaced with 1 to 30 parts by weight of one or more of TiO_2 and SnO_2. 2 With respect to 100 parts by weight of the main component, 20 parts by weight or less of aluminum oxide converted to Al_2O_3 (
Claim 1, which contains (excluding 0 parts by weight)
A dielectric ceramic composition for temperature compensation as described in 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62259269A JPH01102808A (en) | 1987-10-14 | 1987-10-14 | Dielectric porcelain compound for temperature compensation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62259269A JPH01102808A (en) | 1987-10-14 | 1987-10-14 | Dielectric porcelain compound for temperature compensation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01102808A true JPH01102808A (en) | 1989-04-20 |
| JPH0528448B2 JPH0528448B2 (en) | 1993-04-26 |
Family
ID=17331752
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62259269A Granted JPH01102808A (en) | 1987-10-14 | 1987-10-14 | Dielectric porcelain compound for temperature compensation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01102808A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05190021A (en) * | 1992-01-16 | 1993-07-30 | Taiyo Yuden Co Ltd | Dielectric porcelain composition and manufacture thereof |
| JPH05190017A (en) * | 1992-01-16 | 1993-07-30 | Taiyo Yuden Co Ltd | Dielectric porcelain composition and manufacture thereof |
| JPH05190016A (en) * | 1992-01-16 | 1993-07-30 | Taiyo Yuden Co Ltd | Dielectric porcelain composition and manufacture thereof |
| JPH05190019A (en) * | 1992-01-16 | 1993-07-30 | Taiyo Yuden Co Ltd | Dielectric porcelain composition and manufacture thereof |
| JPH05190020A (en) * | 1992-01-16 | 1993-07-30 | Taiyo Yuden Co Ltd | Dielectric porcelain composition and manufacture thereof |
| JPH05190018A (en) * | 1992-01-16 | 1993-07-30 | Taiyo Yuden Co Ltd | Dielectric porcelain composition and manufacture thereof |
-
1987
- 1987-10-14 JP JP62259269A patent/JPH01102808A/en active Granted
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05190021A (en) * | 1992-01-16 | 1993-07-30 | Taiyo Yuden Co Ltd | Dielectric porcelain composition and manufacture thereof |
| JPH05190017A (en) * | 1992-01-16 | 1993-07-30 | Taiyo Yuden Co Ltd | Dielectric porcelain composition and manufacture thereof |
| JPH05190016A (en) * | 1992-01-16 | 1993-07-30 | Taiyo Yuden Co Ltd | Dielectric porcelain composition and manufacture thereof |
| JPH05190019A (en) * | 1992-01-16 | 1993-07-30 | Taiyo Yuden Co Ltd | Dielectric porcelain composition and manufacture thereof |
| JPH05190020A (en) * | 1992-01-16 | 1993-07-30 | Taiyo Yuden Co Ltd | Dielectric porcelain composition and manufacture thereof |
| JPH05190018A (en) * | 1992-01-16 | 1993-07-30 | Taiyo Yuden Co Ltd | Dielectric porcelain composition and manufacture thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0528448B2 (en) | 1993-04-26 |
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