JPS6386314A - Dielectric ceramic composition - Google Patents
Dielectric ceramic compositionInfo
- Publication number
- JPS6386314A JPS6386314A JP61232820A JP23282086A JPS6386314A JP S6386314 A JPS6386314 A JP S6386314A JP 61232820 A JP61232820 A JP 61232820A JP 23282086 A JP23282086 A JP 23282086A JP S6386314 A JPS6386314 A JP S6386314A
- Authority
- JP
- Japan
- Prior art keywords
- mol
- sample
- point
- composition
- value
- 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
- 239000000203 mixture Substances 0.000 title claims description 42
- 239000000919 ceramic Substances 0.000 title description 20
- 239000000654 additive Substances 0.000 claims description 19
- 230000000996 additive effect Effects 0.000 claims description 19
- 238000010586 diagram Methods 0.000 claims description 7
- 229910052573 porcelain Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000003985 ceramic capacitor Substances 0.000 description 14
- 239000011701 zinc Substances 0.000 description 11
- 239000011572 manganese Substances 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 238000010304 firing Methods 0.000 description 8
- 230000001590 oxidative effect Effects 0.000 description 7
- 238000005245 sintering Methods 0.000 description 6
- 239000003990 capacitor Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000010953 base metal Substances 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000134884 Ericales Species 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920006222 acrylic ester polymer Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- KSCFJBIXMNOVSH-UHFFFAOYSA-N dyphylline Chemical compound O=C1N(C)C(=O)N(C)C2=C1N(CC(O)CO)C=N2 KSCFJBIXMNOVSH-UHFFFAOYSA-N 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 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) [Abstract] 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、ニッケル等の卑金属を内部電極とする温度補
償用積層磁器コンデンサの誘電体として好適な誘電体磁
器組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a dielectric ceramic composition suitable as a dielectric for a temperature-compensating multilayer ceramic capacitor whose internal electrodes are made of a base metal such as nickel.
［従来の技術］
特開昭５９−２２７７６９号公報に、（（Ｓｒ Ｃ
ａ ）１−ｘ ｘ
Ｏ）、ＴｉＯ２から成ル基本成分と、Ｌ ｉ ２０ ト
５ｉ０２とＭＯ（但し、ＭＯはＢａＯ１ＣａＯ及びＳｒ
Ｏの内の少なくとも１種の金属酸化物）から成る添加成
分とを含む誘電体磁器組成物が開示されている。この磁
器組成物は非酸化性雰囲気中で焼結可能であるので、こ
れを使用してニッケル等の卑金属を内部電極とする温度
補償用８を層磁器コンデンサを提供することが出来る。[Prior art] Japanese Patent Application Laid-Open No. 59-227769 describes ((Sr C
a) 1-x x O), a basic component consisting of TiO2, Li 20
A dielectric ceramic composition containing an additive component consisting of at least one metal oxide of O is disclosed. Since this ceramic composition can be sintered in a non-oxidizing atmosphere, it can be used to provide a layered ceramic capacitor for temperature compensation 8 in which internal electrodes are made of a base metal such as nickel.
ところで、温度補償用磁器コンデンサを高性能化及び小
型化するために、高いＱ及び高い抵抗率ρを有する誘電
体磁器組成物が要求されるが、上記公開公報に開示され
ている誘電体磁器組成物では、誘電率の温度係数（ＴＣ
）が＋３５０〜−１０００（ｐＨ１１／”Ｃ）の範囲に
於いて、Ｑが４４００以下であり、必ずしも十分なＱが
得られない、そこで本件出願人は、特願昭６０−２９８
００４号明細書において、（（Ｓｒ ｃａ Ｍ
）０１ｋ （Ｔｉ１゜１−ｘ−ｙ ｘ ｙ
Ｂ２０３とＳｉＯ２とＭＯ（Ｂａ ＯｌＭ（Ｉ ０１Ｚ
ｎＯ１ＳｒＯ及びＣａＯの少なくとも１種）とから成る
添加成分とから成る新しい誘電体磁器組成物を開示した
。この新しい誘電体磁器組成物によれば、温度係数（Ｔ
Ｃ）が＋３５０〜−１ｏｏｏ （ｐｐ１１／℃）の範囲
内及び外において、４５００以上のＱと２０゛Ｃで１．
０ Ｘ１０７Ｍｎ・０１以上の抵抗率ρとを得ることが
できる。By the way, in order to improve the performance and reduce the size of temperature-compensating ceramic capacitors, a dielectric ceramic composition having a high Q and a high resistivity ρ is required, and the dielectric ceramic composition disclosed in the above-mentioned publication is required. For materials, the temperature coefficient of dielectric constant (TC
) in the range of +350 to -1000 (pH 11/''C), Q is less than 4400, and sufficient Q cannot necessarily be obtained.
In the specification of No. 004, ((Sr ca M
)01k (Ti1゜1-x-y x y B203 and SiO2 and MO(Ba OlM(I 01Z
A new dielectric ceramic composition comprising an additive component consisting of at least one of nO1SrO and CaO is disclosed. According to this new dielectric ceramic composition, the temperature coefficient (T
C) within and outside the range of +350 to -1ooo (pp11/℃), Q of 4500 or more and 1.
A resistivity ρ of 0×107Mn·01 or more can be obtained.
［発明が解決しようとする問題点］
上記明細書に開示されている誘電体磁器組成物は、通常
の環境条件（例えば−２５°Ｃ〜＋８５℃）で使用され
るコンデンサの誘電体基体として十分に使用可能である
が、過酷な環境条件（例えば１２５０Ｃ）で使用される
可能性のあるコンデンサの誘電体基体としては十分でな
いことが分かった。即ち、上記明細書に開示されている
誘電体磁器組成物ではＱを５０００以上に保つようにし
て高温（例えば１２５°Ｃ）での抵抗率ρを１．ＯＸ１
０５Ｍｎ・ｃｍ以上にすることは不可能又は困難である
。従って、本発明の目的は非酸化性雰囲気、１２００°
Ｃ以下の焼成で得ることができるものであり、Ｑが５０
００以上、１２５℃における抵抗率ρが１．Ｏｘｌｏ”
ＭＯ・ｃｍ以上である誘電体磁器組成物を提供するこ
とにあ［問題点を解決するための手段］
上記問題点を解決し、上記目的を達成するなめの本発明
は、１００重量部の基本成分と、０．２〜１５．０重量
部の添加成分とから成り、前記基本成分が、（（Ｍａ
Ｍｂ Ｍｎ ）ｏ）ｋ （Ｔｉ１−ｗｌ−ｙ−Ｚ
Ｖ Ｚ
Ｚｒ ）０２ （但し、ＭａはＳｒ （ストロンチウ
ム）とＣａ （カルシウム）との内の少なくとも１種
の金属、ＭｂはＭ（１（マグネシウム）とＺｎ（亜鉛）
との内の少なくとも１種の金属、ｙ、ｚ、ｋ、ｗは、０
．００５≦ｙ≦ｏ、ｉｏｏ 、ｏ、ｏｏｉ≦２≦０゜１
００．１．００≦に≦１．２００ 、０．００５≦Ｗ≦
０．１００の範囲の数値）であり、前記添加成分が、Ｂ
２Ｏ３と８１０２とＭＯ（但し、ＭＯはＢａ Ｏ，Ｍ（
Ｉ ０１Ｚｎ Ｏ，Ｓｒ Ｏｌ及びＣａＯの内の少なく
とも１種の金属酸化物）との組成を示す三角図における
、前記Ｂ２Ｏ３が１モル％、前記５ｉｎ２が８０モル％
、前記ＭＯが１９モル％の点（Ａ）と、前記Ｂ２Ｏ３が
１モル％、前記！３ ｉ ０２が３９モル％、前記ＭＯ
が６０モル％の点（Ｂ）と、前記Ｂ２Ｏ３が３０モル％
、前記５ｉｎ２が０モル％、前記ＭＯが７０モル％の点
（Ｃ）と、前記Ｂ２ｏ３が９０モル％、前記Ｓ ｉ Ｏ
２が０モル％、前記ＭＯが１０モル％の点（Ｄ）と、前
記Ｂ２Ｏ３が９゜モル％、前記５ｉ０２が１０モル％、
前記ＭＯが０モル％の点（Ｅ）と、前記Ｂ２Ｏ３が２０
モル％、前記５１０２が８０モル％、前記ＭＯが０モル
％の点（Ｆ）とを順に桔ぶ６本の直線で囲まれた領域内
のものである誘電体磁器組成物に係わるものである。[Problems to be Solved by the Invention] The dielectric ceramic composition disclosed in the above specification is sufficient as a dielectric substrate for a capacitor used under normal environmental conditions (for example, -25°C to +85°C). However, it has been found that it is not sufficient as a dielectric substrate for capacitors that may be used in harsh environmental conditions (eg 1250C). That is, in the dielectric ceramic composition disclosed in the above specification, the resistivity ρ at high temperature (for example, 125°C) is set to 1.0 by keeping Q at 5000 or more. OX1
It is impossible or difficult to increase the thickness to 0.05 Mn·cm or more. Therefore, the object of the present invention is to use a non-oxidizing atmosphere, 1200°
It can be obtained by firing below C, and Q is 50
00 or higher, and the resistivity ρ at 125°C is 1. “Oxlo”
[Means for solving the problems] The present invention solves the above-mentioned problems and achieves the above-mentioned objects. component and 0.2 to 15.0 parts by weight of additional components, and the basic component is ((Ma
Mb Mn )o)k (Ti1-wl-y-Z
V Z Zr ) 02 (However, Ma is at least one metal of Sr (strontium) and Ca (calcium), Mb is M (1 (magnesium) and Zn (zinc)
At least one metal among, y, z, k, w are 0
．． 005≦y≦o, ioo, o,ooi≦2≦0゜1
00.1.00≦≦1.200, 0.005≦W≦
0.100), and the additive component is B
2O3, 8102 and MO (however, MO is Ba O, M (
In the triangular diagram showing the composition with at least one metal oxide of I01ZnO, SrOl, and CaO, the B2O3 is 1 mol% and the 5in2 is 80 mol%.
, the point (A) where the MO is 19 mol%, and the point (A) where the B2O3 is 1 mol%, the above! 3 i 02 is 39 mol %, the MO
point (B) where B2O3 is 60 mol%, and the point (B) where B2O3 is 30 mol%
, the point (C) where the 5in2 is 0 mol% and the MO is 70 mol%, and the point (C) where the B2o3 is 90 mol% and the S i O
Point (D) where 2 is 0 mol% and the MO is 10 mol%, the B2O3 is 9 mol%, the 5i02 is 10 mol%,
The point (E) where the MO is 0 mol% and the point (E) where the B2O3 is 20
This relates to a dielectric ceramic composition that is within a region surrounded by six straight lines that sequentially surround point (F) where 5102 is 80 mol% and MO is 0 mol%. .
［発明の作用効果］
上記発明の誘電体磁器組成物は、非酸化性雰囲気、１２
００°Ｃ以下の焼成で得られるので、ニッケル等の卑金
属を内部電極とする温度補償用積層磁器コンデンサの誘
電体として好適なものである。この誘電体磁器組成物に
よれば、比誘電率ε が１５１〜３２３ 、Ｑが５００
０以上、誘電率の温度係数ＴＣが−６００〜−３４００
１１１１１／’Ｃ１抵抗率ρが２０°Ｃで１×１０ Ｍ
Ｏ−０１以上、１２５’Ｃで１．Ｏｘｌｏ” ＭＯ・０
１以上の温度補償用磁器コンデンサを得ることができる
。Ｗ′ｉ７述の特願昭６０−２９８００４号明細書に開
示されている誘電体磁器組成物と本願発明の誘電体磁器
組成物との大きな相違点は５０００以上のＱを維持して
１２５℃の抵抗率ρを１．ＯＸ１０５Ｍａ・Ｃ１以上に
することができることである。この様に高いＱを維持し
ながら高温での抵抗率ρの低下を抑制することができる
のは基本成分にＭｎ（マンガン）を含めたためである。[Operations and Effects of the Invention] The dielectric ceramic composition of the invention described above is provided in a non-oxidizing atmosphere, 12
Since it can be obtained by firing at 00°C or lower, it is suitable as a dielectric for temperature-compensating multilayer ceramic capacitors whose internal electrodes are made of base metals such as nickel. According to this dielectric ceramic composition, the relative dielectric constant ε is 151 to 323, and the Q is 500.
0 or more, temperature coefficient of dielectric constant TC is -600 to -3400
11111/'C1 resistivity ρ is 1×10 M at 20°C
O-01 or higher, 1. at 125'C. Oxlo” MO・0
One or more temperature-compensating ceramic capacitors can be obtained. The major difference between the dielectric ceramic composition disclosed in Japanese Patent Application No. 60-298004 mentioned in W'i7 and the dielectric ceramic composition of the present invention is that it maintains a Q of 5000 or more and can be heated at 125°C. The resistivity ρ is 1. It is possible to make it OX105Ma・C1 or higher. The reason why it is possible to suppress the decrease in resistivity ρ at high temperatures while maintaining such a high Q is because Mn (manganese) is included as a basic component.
基本成分におけるマンガンの量を増加させるに従って高
温での抵抗率ρが高くなるが、多くなり過ぎるとＱが低
下し、所望の特性を得ることができない。本発明に従う
高温での抵抗率ρの大きい誘電体磁器組成物を使用すれ
ば、コンデサの電極間距離を短くすることができるので
、高温条件下で使用する温度補償用磁器コンデサを小型
化することができる。また、抵抗率ρが大きいのにも拘
らず、高いＱを有する磁器コンデンサを提供することが
できるので、磁器コンデンサを使用する電子回路の高性
能化が可能になる。As the amount of manganese in the basic component increases, the resistivity ρ at high temperatures increases, but if the amount increases too much, Q decreases and desired characteristics cannot be obtained. By using the dielectric ceramic composition having a large resistivity ρ at high temperatures according to the present invention, the distance between the electrodes of the capacitor can be shortened, so that the temperature compensation ceramic capacitor used under high temperature conditions can be miniaturized. Can be done. Further, since it is possible to provide a ceramic capacitor having a high Q despite the large resistivity ρ, it is possible to improve the performance of electronic circuits using the ceramic capacitor.
［実施例コ
次に、本発明の実施例（比較例も含む）について説明す
る。第１表の試料Ｎａ １のに＝１．００、Ｘ＝０．２
８１．ｙ＝０．０１、ｚ＝０．０２、ｗ＝０．０５に従
って決定される組成式
％式％
より具体的には、Ｍａ ＝Ｓｒ ｃａＯ，９７
０，６９０，２８・
Ｍｂ ＝Ｚｎ であるので
ｏ、ｏｉ ｏ、ｏｉ
（Ｓｒ Ｃａ Ｚｎ Ｍｎ ）Ｏ（０
，６９０，２８０，０１０，０２
Ｔｉ Ｚｒ ）０
０．９５ ０．０５ ２
から成る基本成分を得るために、純度９９．０％以上の
５ｒＣ０３（炭酸ストロンチウム）、ＣａＣＯ３（炭酸
カルシウム）、Ｚｎ０（酸化亜鉛）、Ｍｎｏ（酸化マン
ガン）、ＴｉＯ２（酸化チタン）ｎ ｚｒ ｏ□ （酸
化ジルコニウム）を出発原料として用意し、不純物を目
方に入れないで、Ｓｒ Ｃｏ ４７５．６２（１
＜０．６９ モル部相当）ＣａＣ０１３０，７５（＋
（０，２８モル部相当）Ｚｎ Ｏ３，８０ｇ （
０，０１モル部相当〉Ｍｎ Ｏ６，６２（１（０，０２
モル部相当）Ｔｉ ０２３５４．４４ｇ（０，９５モル
部相当）Ｚｒ ０２２８．７７ｇ（０，０５モル部相当
）をそれぞれ秤量し、これ等の原料に水を２，５ｊ加え
て１５時時間式混合した。[Examples] Next, examples (including comparative examples) of the present invention will be described. Sample Na 1 in Table 1 = 1.00, X = 0.2
81. Composition formula % determined according to y=0.01, z=0.02, w=0.05 More specifically, Ma = Sr caO, 97
0,690,28・Mb = Zn, so o, oi o, oi (Sr Ca Zn Mn ) O(0
In order to obtain the basic components consisting of SrCo 475.62 (1
<0.69 molar part equivalent) CaC0130,75 (+
(equivalent to 0.28 mol parts) Zn O3, 80g (
Equivalent to 0,01 mole part> Mn O6,62 (1 (0,02
Weighed 02354.44 g (equivalent to 0.95 mol part) of Ti (equivalent to 0.95 mol part) and 0228.77 g (equivalent to 0.05 mol part) of Zr, added 2.5j of water to these raw materials, and mixed for 15 hours. did.
次に、この原料混合物を１５０’Ｃで４時間乾燥し、し
かる後粉砕した０次に、この粉砕物を、１１００℃で、
２時間大気中で仮焼し、上記組成式の基本成分の粉末を
得た。一方、第２表の試料Ｎ１１ｌの添加成分を得るた
めに、
Ｂ２Ｏ３１，０１（１（１モル％ン
Ｓ ｉ Ｏ７０，０５！ＩＩ （８０モル％）Ｂ ａ
ＣＯ８，４９ｇ（３，８−ｔ−ル％）Ｍ（］ ０
２，２３ｇ （３，８モル％）Ｚｎ Ｏ４，
５１ｇ （３，８モル％）Ｓ ｒ ＣＯ８，１７（
１（３，８モル％）Ｃａ ＣＯ５，５４（１（３，８モ
ル％）を秤量し、これ等にアルコールを３００ｃｃ加え
、ポリエチレンポットにてアルミナボールを用いて１０
時間撹拌した後、大気中１０００℃で２時間仮焼成し、
これを３００ｃｃの水と共にアルミナポットに入れ、ア
ルミナボールで１５時間粉砕し、しかる後、１５０℃で
４時間乾燥させてＢ２Ｏ３が１モル％、５１０２が８０
モル％、ＭＯが１９モル％、（Ｂａ ０３．８モル％＋
Ｍ（ｌ Ｏ３，８モル％＋ＺｎＯ３，８モル％＋５ｒ０
３．８モル％十Ｃａ Ｏ３，８モル％）の組成の添加成
分の粉末を得た。Next, this raw material mixture was dried at 150'C for 4 hours, and then ground.Next, this ground material was dried at 1100'C.
It was calcined in the air for 2 hours to obtain a powder having the basic components of the above composition formula. On the other hand, in order to obtain the additive components of sample N11l in Table 2,
CO8,49g (3,8-t-ru%) M(] 0
2,23g (3,8 mol%) Zn O4,
51g (3,8 mol%) S r CO8,17 (
1 (3.8 mol%) Ca CO5,54 (1 (3.8 mol%)) was weighed, 300 cc of alcohol was added to this, and 100 cc of alcohol was added using an alumina ball in a polyethylene pot.
After stirring for an hour, it was pre-calcined in the air at 1000°C for 2 hours.
This was put in an alumina pot with 300cc of water, crushed with an alumina ball for 15 hours, and then dried at 150°C for 4 hours, so that B2O3 was 1 mol% and 5102 was 80%.
mol%, MO 19 mol%, (Ba 03.8 mol%+
M(l O3, 8 mol% + ZnO3, 8 mol% + 5r0
A powder of additive components having a composition of 3.8 mol% (CaO3, 8 mol%) was obtained.
次に、基本成分の粉末１０００！ＩＩ（１００重量部）
に対して上記添加成分の粉末３０（１（３重量部）を加
え、更に、アクリル酸エステルポリマー、グリセリン、
縮合リン酸塩の水溶液から成る有機バインダを基本成分
と添加成分との合計重量に対して１５重量％添加し、更
に、５０重量％の水を加え、これ等をボールミルに入れ
て粉砕及び混合して磁器原料のスラリーを作製した。Next, the basic ingredient powder is 1000! II (100 parts by weight)
Powder 30 (1 (3 parts by weight)) of the above additive components was added to the solution, and further, acrylic ester polymer, glycerin,
An organic binder consisting of an aqueous solution of condensed phosphate was added in an amount of 15% by weight based on the total weight of the basic components and additive components, and further, 50% by weight of water was added, and these were crushed and mixed in a ball mill. A slurry of porcelain raw materials was prepared.
次に、上記スラリーを真空脱泡機に入れて脱泡し、この
スラリーをリバースロールコータ−に入れ、これをを使
用してポリエステルフィルム上にスラリーに基づく薄膜
を形成し、この薄膜をフィルム上で１００℃に加熱して
乾燥させ、厚さ約２５μｍのグリーンシート（未焼結磁
器シート）を得た。このシートは、長尺なものであるが
、これをＩＱｃＩ角の正方形に打ち抜いて使用する。Next, the above slurry is put into a vacuum defoaming machine to defoam, and this slurry is put into a reverse roll coater, which is used to form a thin film based on the slurry on a polyester film, and this thin film is applied onto the film. The mixture was heated to 100° C. and dried to obtain a green sheet (unsintered porcelain sheet) with a thickness of about 25 μm. This sheet is a long sheet, and is used by punching out a square with an IQcI corner.
一方、内部電極用の導電ペーストは、粒径平均１．５μ
ｌのニッケル粉末１０ｇと、エチルセルローズ０，９ｇ
をブチルカルピトール９．１ｇに溶解させたものとを撹
拌機に入れ、１０時間撹拌することにより得な、この導
電ペーストを長さ１４ ｕ＋ 、幅７１Ｉ１１ のパ
ターンを５０個有するスクリーンを介して上記グリーン
シートの片面に印刷した後、これを乾燥させた。On the other hand, the conductive paste for internal electrodes has an average particle size of 1.5 μm.
10g of nickel powder and 0.9g of ethyl cellulose
was dissolved in 9.1 g of butyl calpitol and placed in a stirrer and stirred for 10 hours. After printing on one side of the green sheet, it was dried.
次に、上記印刷面を上にしてグリーンシートを２枚積層
した。この際、隣接する上下のシートにおいて、その印
刷面がパターンの長手方向に約半分程ずれるように配置
した。更に、この積層物の上下両面にそれぞれ４枚ずつ
厚さ６０μｍのグリーンシートを積層した０次いで、こ
の積層物を約５０℃の温度で厚さ方向に約４０トンの圧
力を加えて圧着させた。しかる後、この積層物を格子状
に裁断し、約く５０個の積層チップを得た。Next, two green sheets were laminated with the printed side facing up. At this time, the adjacent upper and lower sheets were arranged so that their printed surfaces were shifted by about half in the longitudinal direction of the pattern. Furthermore, four 60 μm thick green sheets were laminated on each of the top and bottom surfaces of this laminate.Next, this laminate was crimped by applying approximately 40 tons of pressure in the thickness direction at a temperature of approximately 50°C. . Thereafter, this laminate was cut into a grid shape to obtain approximately 50 laminate chips.
次に、この積層体チップを雰囲気焼成が可能な炉に入れ
、大気雰囲気中で１００°Ｃ／ｈの速度で６００’Ｃま
で昇温して、有機バインダを燃焼させた。Next, this laminate chip was placed in a furnace capable of firing in an atmosphere, and the temperature was raised to 600'C at a rate of 100°C/h in an air atmosphere to burn the organic binder.
しかる後、炉の雰囲気を大気からＨ２２体積％＋Ｎ２９
８体積％の雰囲気に変えた。そして、炉を上述の如き遷
元性雰囲気とした状態を保って、積層体チップの加熱温
度を６００℃から焼結温度の１１９０℃まで１００°Ｃ
／ｈの速度で昇温して１１９０’Ｃ（最高温度）３時間
保持した後、１００℃／ｈの速度で６００°Ｃまで降温
し、雰囲気を大気雰囲気（酸化性雰囲気）におきかえて
、６００℃を３０分間保持して酸化処理を行い、その後
、室温まで冷却して、焼結体チップを得た。After that, the atmosphere of the furnace is changed from the atmosphere to H22 volume % + N29.
The atmosphere was changed to 8% by volume. Then, while maintaining the furnace in a transitional atmosphere as described above, the heating temperature of the stacked chips was increased from 600°C to the sintering temperature of 1190°C by 100°C.
After raising the temperature at a rate of 1190°C/h and holding it at 1190'C (maximum temperature) for 3 hours, the temperature was lowered to 600°C at a rate of 100°C/h, and the atmosphere was changed to air (oxidizing atmosphere). The oxidation treatment was carried out by maintaining the temperature at °C for 30 minutes, and then cooling to room temperature to obtain sintered chips.
次に、電極が露出する焼結体チップの側面に亜鉛とガラ
スフリットとビヒクルとから成る導電性ペーストを塗布
して乾燥し、これを大気中で５５０°Ｃの温度で１５分
間焼付け、亜鉛電極層を形成し、更にこの上に銅を無電
解メッキで被着させて、更にこの上に電気メツキ法でＰ
ｂ−３ｎ半田層を設けて、一対の外部電極を形成した。Next, a conductive paste consisting of zinc, glass frit, and vehicle is applied to the side surface of the sintered chip where the electrodes are exposed, dried, and baked in the air at a temperature of 550°C for 15 minutes to form a zinc electrode. A layer is formed, copper is deposited on top of this by electroless plating, and then P is deposited on top of this by electroplating.
A b-3n solder layer was provided to form a pair of external electrodes.
これにより、第１図に示す如く、誘電体磁器層（１）
、（２） 、（３）と、内部電極（４） 、（５）と、
外部電極（６） 、（７）から成る積層磁器コンデンサ
（１０）が得られた。なお、このコンデンサ（１０）の
誘電体磁器層（２）の厚さは０．０２ ｍｌ、内部電極
（４）（５）の対向面積は、５１ｘ５１１１１−２５１
１１１２テアル。As a result, as shown in Fig. 1, the dielectric ceramic layer (1)
, (2), (3), and internal electrodes (4), (5),
A multilayer ceramic capacitor (10) consisting of external electrodes (6) and (7) was obtained. The thickness of the dielectric ceramic layer (2) of this capacitor (10) is 0.02 ml, and the opposing area of the internal electrodes (4) and (5) is 51 x 51111-251.
1112 Theal.
また、焼結後の磁器層（１）（２）（３）の組成は、焼
結前の基本成分と添加成分との混合組成と実質的に同じ
であり、複合プロブスカイト（ｐｅｒｏｖｓｋｉｔｅ）
型構造の基本成分
０．６９ ０．２８ ０．０１ ０．０２）０（
（Ｓｒ Ｃａ Ｚｎ ＭｎＴｉ Ｚｒ
）０
０．９５ ０．０５ ２
の結晶粒子間に８０１モル％と５ｉｎ２８０モル％とＢ
ａＯ３，８モル％とＭ（１０３，８モル％とＺｎＯ３，
８モル％と５ｒ０３．８モル％とＣａＯ３゜８モル％と
から成る添加成分が均一に分布したちのが得られる。Furthermore, the composition of the porcelain layers (1), (2), and (3) after sintering is substantially the same as the mixed composition of the basic components and additive components before sintering, and is a composite perovskite.
Basic components of type structure 0.69 0.28 0.01 0.02) 0(
(Sr Ca Zn MnTi Zr
)0 0.95 0.05 2 between the crystal grains of 801 mol% and 5in280 mol% and B
aO3,8 mol% and M (103,8 mol% and ZnO3,
A uniform distribution of the additive components consisting of 8 mol %, 3.8 mol % 5r0 and 8 mol % CaO3 is obtained.
次に、完成した積層磁器コンデンサの比誘電率ε 、温
度係数ＴＣ，Ｑ、抵抗率ρを測定したとこる第３表の試
料魔１に示す如く、ε、は２７９、ＴＣは−１４２０ａ
ｐｌ／”Ｃ１Ｑは９６００、 ρは２０℃で３．３ Ｘ
１０７Ｍｎ・ＣＩ、１２５℃で１．８ Ｘ１０５Ｍｎ・
ＣＩであった。なお、上記電気的特性は次の９領で測定
した。Next, we measured the dielectric constant ε, temperature coefficient TC, Q, and resistivity ρ of the completed multilayer ceramic capacitor. As shown in Sample 1 of Table 3, ε is 279 and TC is -1420a.
pl/”C1Q is 9600, ρ is 3.3X at 20℃
107Mn・CI, 1.8×105Mn・at 125℃
It was a CI. The above electrical characteristics were measured in the following 9 areas.
（Ａ） 比誘電率ε、は、温度２０℃、周波数ＩＭＨ
ｚ 、交流電圧（実効値）０．５Ｖの条件で￥ｐ電容量
を測定し、この測定値と磁器Ｎ（２）の厚さ０．０５１
１から計算で求めた。(A) The relative permittivity ε is at a temperature of 20°C and a frequency of IMH.
z, measure the capacitance under the condition of AC voltage (effective value) 0.5V, and compare this measured value with the thickness of porcelain N (2) 0.051
Calculated from 1.
（Ｂ） 温度係数（ＴＣ）は、８５°Ｃの静電容量（
Ｃ）と２０゛Ｃの静電容量（ｃ２ｏ）とを測定し、（Ｃ
） Ｑは温度２０℃において、周波数ＩＨＩＩＺ、電
圧［実行値］ ０．５ Ｖの交流でＱメータにより測定
した。(B) The temperature coefficient (TC) is the capacitance at 85°C (
C) and the capacitance (c2o) at 20°C, and (C
) Q was measured using a Q meter at a temperature of 20° C., a frequency IHIIZ, and an AC voltage [actual value] of 0.5 V.
＜Ｄ） 抵抗率ρ（Ｍｎ・ｃｎ）は、温度２０°Ｃ及
び１２５℃においてそれぞれＤＣ５０Ｖを１分間印加し
た後に一対の外部電極（６）（７１間の抵抗値を測定し
、この測定値と寸法とに基づいて計算でもとめた。<D) Resistivity ρ (Mn・cn) is determined by measuring the resistance value between the pair of external electrodes (6) (71) after applying DC 50V for 1 minute at temperatures of 20°C and 125°C, respectively. It was calculated based on the dimensions.
以上、試料Ｎα１の作製方法及びその特性について述べ
たが、その他の試料Ｎｏ、２〜９３についても、基本成
分及び添加成分の組成、これ等の割合、及び還元性雰囲
気（非酸化性雰囲気）での焼成温度を第１表、第２表及
び第３表に示すように変えた他は、試料Ｎα１と全く同
一の方法で積層磁器コンデンサを作製し、同一方法で電
気的特性を測定した。第１表は、それぞれの試料の基本
成分の組成式
％式％
を決定するための各数値に、ｘ、ｙ、ｚ、ｗ、即ち各元
素の原子数の割合を示す数値と、Ｍｂの内容とを示す。The preparation method of sample Nα1 and its characteristics have been described above, but the compositions of the basic components and additive components, their ratios, and the reducing atmosphere (non-oxidizing atmosphere) A multilayer ceramic capacitor was manufactured in exactly the same manner as Sample Nα1, except that the firing temperature was changed as shown in Tables 1, 2, and 3, and the electrical characteristics were measured in the same manner. Table 1 shows the values for determining the compositional formula % formula % of the basic components of each sample, x, y, z, w, that is, the numerical value indicating the ratio of the number of atoms of each element, and the content of Mb. and
第２表は各試料の１００重量部の基本成分に対する添加
成分の添加量（重量部）と、添加成分の組成を示す。こ
の第２表のＭＯの内容の詞には、ＢａＯｌＭｇＯ，Ｚｎ
Ｏ，Ｓｒ Ｏ，ＣａＯの割合がモル％で示されている
。第３表はそれぞれの試料の還元性雰囲気における焼結
のための焼成温度（最高温度）、及び電気的特性を示す
。Table 2 shows the amount (parts by weight) of the additive components relative to 100 parts by weight of the basic components of each sample and the composition of the additive components. The contents of MO in Table 2 include BaOlMgO, Zn
The proportions of O, Sr O, and CaO are shown in mol%. Table 3 shows the firing temperature (maximum temperature) for sintering in a reducing atmosphere and the electrical properties of each sample.
第１表〜第３表から明らかな如く、本発明に従う試料で
は、非酸化性雰囲気、１２００℃以下の焼成で、比誘電
率ε、が１５１〜３２３ 、Ｑが５０００以上、誘電率
の温度係数ＴＣが−６００から−３４００ｐｐｎ／゛Ｃ
の範囲となる。また抵抗率ρは２０℃で１．０×１０
Ｍｎ・Ｃ１１以上、１２５°Ｃで１．ＯＸ１０５Ｍａ
・６１以上となる。As is clear from Tables 1 to 3, in the samples according to the present invention, when fired in a non-oxidizing atmosphere at 1200°C or lower, the relative dielectric constant ε is 151 to 323, the Q is 5000 or more, and the temperature coefficient of the dielectric constant TC is -600 to -3400ppn/゛C
The range is . Also, the resistivity ρ is 1.0×10 at 20℃
Mn・C11 or more, 1. at 125°C. OX105Ma
・It becomes 61 or more.
一方、試料ＮＯ，７，８，９，１０，２９，３３，３４
，３８，４３，４８，４９，５３，５４，５８，６３，
６４，６９，７０，７６，７７，８３では本発明の目的
を達成することができない。従って、これ等は本発明の
範囲外のものである。On the other hand, sample NO, 7, 8, 9, 10, 29, 33, 34
,38,43,48,49,53,54,58,63,
64, 69, 70, 76, 77, and 83 cannot achieve the object of the present invention. Therefore, these are outside the scope of the present invention.
次に、組成の限定理由について述べる。Next, the reasons for limiting the composition will be described.
添加成分の添加量が零の場合には試料間、７７から明ら
かな如く焼成温度が１３００°Ｃであっても緻密な焼結
体が得られないが、試料Ｎａ７８に示す如く添加量が１
００重量部の基本成分に対して０．２重量部の場合には
１１９０°Ｃの焼成で所望の電気的特性を有する焼結体
が得られる。従って、添加成分の下限は０．２重量部で
ある。一方、試料Ｎα８３に示す如く添加量が１８重量
部の場合にはＱが５０００未満となり、所望特性よりも
悪くなるが、試料Ｎ０．８２に示す如く添加量が１５重
量部の場合には、所望の特性を得ることができる。従っ
て、添加量の上限は１５重量部である。When the amount of additive components added is zero, a dense sintered body cannot be obtained even if the firing temperature is 1300°C, as is clear from sample Na77, but as shown in sample Na78, when the amount added is 1.
If the amount is 0.2 parts by weight relative to 00 parts by weight of the basic component, a sintered body having desired electrical properties can be obtained by firing at 1190°C. Therefore, the lower limit of the additive component is 0.2 parts by weight. On the other hand, when the amount added is 18 parts by weight as shown in sample Nα83, Q becomes less than 5,000, which is worse than the desired property. characteristics can be obtained. Therefore, the upper limit of the amount added is 15 parts by weight.
Ｘの値は、例えば試料Ｎａ２４．２５．２６．２７に示
す如く、０から０．９９４までのいずれの値であっても
、所望の電気的特性を得ることができる。従ってＸの値
はＯから０．９９４までの全ての値を含む、なお試料間
、２８に示す如くＸが０．９９４の場合には、Ｘ＋ｙ＋
ｚ＝１となり、結局Ｓｒが零である。従って、本発明に
従う一般式のＭａの内容は、ｓｒ 、ｃａ、Ｓｒ ＋Ｃ
ａのいずれか１つである。Desired electrical characteristics can be obtained by setting the value of X to any value from 0 to 0.994, as shown in sample Na24.25.26.27, for example. Therefore, the value of X includes all values from O to 0.994, and between samples, if
z=1, and Sr is zero after all. Therefore, the content of Ma in the general formula according to the present invention is sr, ca, Sr +C
Any one of a.
ｙの値が試料Ｎα２９．３４に示す如（０，００２の場
合は、Ｍｂ（Ｍｂ及び／又はＺｎ）を添加した効果が見
られないが試料Ｎｏ、３（１，３５に示す如くｙの値が
０．００５の場合には、所望の電気的特性が得られる。When the value of y is 0,002 as shown in sample No. 29.34, no effect of adding Mb (Mb and/or Zn) is seen, but when the value of y is When is 0.005, desired electrical characteristics can be obtained.
従ってｙの値の下限は、０．００５である。一方ｙの値
が試料！１１１３３．３８．４３に示す如＜０．１２の
場合には緻密な焼結体が得られないが、試料Ｎα３２．
３７．４２に示す如く、ｙの値が０．１０の場合には所
望の電気的特性が得られる。従ってｙの値の上限は０．
１０である。Therefore, the lower limit of the value of y is 0.005. On the other hand, the value of y is the sample! As shown in sample Nα32.11133.38.43, a dense sintered body cannot be obtained when <0.12.
As shown in 37.42, when the value of y is 0.10, desired electrical characteristics can be obtained. Therefore, the upper limit of the value of y is 0.
It is 10.
２の値が試料間、４９．５４に示す如＜ ０．０００５
の場合は１２５℃でのρが１．ＯＸｌ０５Ｍｎ・Ｃ１ｌ
を下回ってしまいＭｎＯを添加した効果が見られないが
、試料に５０．５５に示す如く、２の値が０．００１の
場合には所望の電気的特性が得られる。従って２の下限
はｏ、ｏｏｉである。一方、２の値が ０．１２の場合
には試料Ｎｏ、４８．５３．５８．６３に示す如くなと
えρが満足な値であってもＱが５０００未満となってし
まうが、試料Ｎｏ、４７．５２．５７．６２に示す如く
ｚの値が０，１０の場合には所望の電気的特性が得られ
る。従って２の位の上限は０．１０である。なお、例え
ば、試料〜０５４．５５．５６．５７．５８に示す如く
、２の値を、徐々に大きくすると、１２５°Ｃにおける
ρも徐々大きくなり、Ｍｎが葛湯における抵抗率ρの増
大寄与していることが分かる。The value of 2 is between samples, as shown in 49.54 < 0.0005
In the case of , ρ at 125°C is 1. OXl05Mn・C1l
However, when the value of 2 is 0.001, desired electrical characteristics can be obtained as shown in 50.55 in the sample. Therefore, the lower limit of 2 is o, ooi. On the other hand, if the value of 2 is 0.12, as shown in sample No. 48.53.58.63, Q will be less than 5000 even if ρ is a satisfactory value. , 47.52.57.62, when the value of z is 0 or 10, desired electrical characteristics can be obtained. Therefore, the upper limit of the 2's digit is 0.10. For example, as shown in sample ~054.55.56.57.58, when the value of 2 is gradually increased, ρ at 125°C also gradually increases, indicating that Mn contributes to increasing the resistivity ρ in Kuzuto. I can see that
Ｗの値が試料Ｎα６４に示す如＜ ０．００２の場合に
は１２５’Ｃでのρが１．Ｏｘ１０５を下回ってしまい
ＺｒＯ２を添加した効果が見られないが、試料Ｎｏ、６
５に示す如くＷの値が０．００５の場合には所望の電気
的特性が得られる。従ってＷの便の下限は０．００５で
ある。一方、試料Ｎ（１６９に示す如くｗの値が０．１
２の場合には緻密な焼結体が得られないが、試料Ｎｏ、
６８に示す如くｗの値が０．１０の場合には所望の電気
的特性が得られる。従ってＷの値の上限は０．１０であ
る。When the value of W is < 0.002 as shown in sample Nα64, ρ at 125'C is 1. Although the effect of adding ZrO2 cannot be seen as it is lower than Ox105, sample No. 6
As shown in FIG. 5, when the value of W is 0.005, desired electrical characteristics can be obtained. Therefore, the lower limit of W's stool is 0.005. On the other hand, sample N (as shown in 169, the value of w is 0.1
In the case of sample No. 2, a dense sintered body cannot be obtained, but in the case of sample No.
As shown in 68, when the value of w is 0.10, desired electrical characteristics can be obtained. Therefore, the upper limit of the value of W is 0.10.
ｋの値が試料Ｎα７０に示す如＜０．９９の場合には、
ρが２０℃、１２５°Ｃでそれぞれ４．１ ｘ１０’
、１．Ｏｘ１０１ＭΩ・ｃｎ＋となり更にＱも４００と
大幅に低くなるが、試料Ｎα７１に示す如くｋの値が１
．００の場合には所望の電気的特性が得られる。従って
ｋの値の下限は１．００である。一方、ｋの値が試ｆｌ
Ｎ０７６に示す如＜ １．２５の場合には緻密な焼結体
が得られないが、試料間７５に示す如くｋの値が１．２
０の場合には所望の電気的特性が得られる。従ってｋの
値の上限は１．２０である。If the value of k is <0.99 as shown in sample Nα70,
ρ is 4.1 x 10' at 20°C and 125°C, respectively.
, 1. Ox101MΩ・cn+, and Q is also significantly lower at 400, but as shown in sample Nα71, the value of k is 1.
．． In the case of 00, desired electrical characteristics can be obtained. Therefore, the lower limit of the value of k is 1.00. On the other hand, the value of k is
As shown in No. 76, a dense sintered body cannot be obtained when the value of k is < 1.25, but as shown in No. 75, a dense sintered body cannot be obtained.
In the case of 0, desired electrical characteristics can be obtained. Therefore, the upper limit of the value of k is 1.20.
添加成分の好ましい組成は第２図のＢ２Ｏ２−３ｉＯ７
−ＭＯの組成比を示す三角図に基づいて決定することが
できる。三角図の点（Ａ）は試料ｋｌｌ）Ｂ Ｏ１モ
ル％、Ｓ ＋ ０２８０ モル％、ＭＯ１９モル％の組
成を示し、点（Ｂ）は、試料■２ノＢ Ｏ１モル％、
Ｓ ｉ Ｏ２３９モル％、ＭＯ６０モル％の組成を示し
、点（Ｃ）は試′ｆ４Ｎα３のＢＯ３０モル％、Ｓ ｉ
０２０モル％、Ｍ Ｏ７０モル％の組成を示し、点＜
Ｄ）は試料Ｎ０２４のＢ２０９０モル％、Ｓ ｉ ０２
０モル％、ＭＯ１０モル％の組成を示し、点（Ｅ）は試
料Ｎα・５のＢ２０３９０モル％、Ｓ ｉ ０２１０モ
ル％、ＭＯＩＯモル％の組成を示し、点（Ｆ）は試料Ｎ
α６のＢ２０３２０モル％、５ｉ０８０モル％、ＭＯＯ
モル％の組成を示す。The preferred composition of the additive components is B2O2-3iO7 in Figure 2.
- It can be determined based on a triangular diagram showing the composition ratio of MO. Point (A) in the triangular diagram shows the composition of sample kll) B O 1 mol %, S + 0280 mol %, MO 19 mol %, and point (B) shows the composition of sample II) B O 1 mol %,
It shows the composition of S i O2 39 mol % and MO 60 mol %, and point (C) shows the composition of sample 'f4Nα3 BO 30 mol %, Si
020 mol%, M O 70 mol%, and the point <
D) is B2090 mol% of sample N024, S i 02
Point (E) shows the composition of B20390 mol%, Si 0210 mol%, MOIO mol% of sample Nα・5, and point (F) shows the composition of sample Nα・5.
α6 B20320 mol%, 5i080 mol%, MOO
The composition is shown in mol%.
本発明の範囲に属する試料の添加成分の組成は、三角図
の第１〜第６の点（Ａ）〜（Ｆ）を順に結ぶ６本の直線
で囲まれた領域内の組成になっている。この領域内の組
成とすれば、所望の電気的特性を得ることができる。な
お三角図で試料Ｎｏ、８７〜９３等から明らかな如く、
ＳｉＯとＭＯとのいずれか一方を省いても本発明で目標
としている特性が得られる。The composition of the additive component of the sample that falls within the scope of the present invention is within the area surrounded by six straight lines connecting the first to sixth points (A) to (F) in the triangular diagram in order. . If the composition is within this range, desired electrical characteristics can be obtained. In addition, as is clear from sample Nos. 87 to 93 in the triangular diagram,
Even if either SiO or MO is omitted, the characteristics targeted by the present invention can be obtained.
一方、試料Ｎｏ、 ７．８．９．１０のように、添加成
分の組成が本発明で特定した範囲外となれば、緻密な焼
結体を得ることができない、なお、ＭＯ酸成分、例えば
試料Ｎα１１．１２．１３．１４．１５に示す如くＢａ
Ｏ，Ｍ！］ ０１Ｚｎ Ｏ，Ｓｒ ０１ＣａＯのいず
れか−であってもよいし、又は他の試料に示すように適
当な比率としてもよい。On the other hand, as in Sample No. 7.8.9.10, if the composition of the additive component is outside the range specified in the present invention, a dense sintered body cannot be obtained. As shown in sample Nα11.12.13.14.15, Ba
O, M! ]01ZnO, Sr01CaO, or an appropriate ratio as shown in other samples.
［変形例］
以上本発明の実施例について述べたが、本発明はこれに
限定されるものではなく、例えば次の変形例が可能なも
のである。[Modifications] Although the embodiments of the present invention have been described above, the present invention is not limited thereto, and, for example, the following modifications are possible.
（ａ）基本成分を得るための出発原料であるＭｎＯを本
発明の目的を阻害しない範囲一、でその一部をＭｎＯあ
るいはＭｎ３Ｏ４等のもので置き換えることもできる、
また基本成分及び添加成分にその他の物質を必要に応じ
て適量添加してもよい。(a) MnO, which is the starting material for obtaining the basic component, can be partially replaced with MnO or Mn3O4, etc., within a range that does not impede the purpose of the present invention.
Further, appropriate amounts of other substances may be added to the basic components and additional components as necessary.
（ｂ）基本成分を得るための出発原料を、実施例で示し
たちの以外の例えば、Ｓｒ Ｏ，Ｃａ Ｏ等の酸化物又
は水酸化物又はその他の化合物としてもよい、また、添
加成分の出発原料を酸化物、水酸化物等の他の化合物と
してもよい。(b) The starting materials for obtaining the basic components may be oxides or hydroxides other than those shown in the examples, such as Sr O, Ca O, etc., or other compounds. Other compounds such as oxides and hydroxides may be used as the raw materials.
（ｃ）酸化温度を６００℃以外の焼結温度よりも低い温
度（好ましくは１０００℃以下）としてもよい。(c) The oxidation temperature may be set to a temperature other than 600°C lower than the sintering temperature (preferably 1000°C or less).
即ち、ニッケル等の電極と磁器の酸化とを考慮して種々
変更することが可能である。That is, various changes can be made in consideration of the electrode made of nickel or the like and the oxidation of the ceramic.
（ｄ）非酸化性雰囲気中の焼成温度を、電極材料を考慮
して程々変えることが出来る。(d) The firing temperature in a non-oxidizing atmosphere can be changed moderately in consideration of the electrode material.
（ｅ）焼結を中性雰囲気で行ってもよい。(e) Sintering may be performed in a neutral atmosphere.
（ｆ）積層磁器コンデンサ以外の一般的な磁器コンデン
サにも勿ｋｌｉ用可能である。(f) Of course, general ceramic capacitors other than multilayer ceramic capacitors can also be used.
１図は第は本発明の実施例に係わる積層型磁器コンデン
サを示す断面図である。第２図は添加成分の組成範囲を
示す三角図である。
（１）（２）（３）・・・誘電体磁器層、（４）（５）
・・・内部電極、（６）（７）・・・外部電極。FIG. 1 is a sectional view showing a multilayer ceramic capacitor according to an embodiment of the present invention. FIG. 2 is a triangular diagram showing the composition range of additive components. (1)(2)(3)...Dielectric ceramic layer, (4)(5)
...Internal electrode, (6) (7)...External electrode.
Claims (1)
量部の添加成分とから成り、前記基本成分が、｛（Ｍａ
＿１＿−＿ｙ＿−＿ｚＭｂ＿ｙＭｎ＿ｚ）＿Ｏ｝＿ｋ（
Ｔｉ＿１＿−＿ｗＺｒ＿ｗ）Ｏ＿２ （但し、ＭａはＳｒとＣａとの内の少なくとも１種の金
属、ＭｂはＭｇとＺｎとの内の少なくとも１種の金属、
ｙ、ｚ、ｋ、ｗは、０．００５≦ｙ≦０．１００、０．
００１≦ｚ≦０．１００、１．００≦ｋ≦１．２０、０
．００５≦ｗ≦０．１００の範囲の数値）であり、前記
添加成分が、Ｂ＿２Ｏ＿３とＳｉＯ＿２とＭＯ（但し、
ＭＯはＢａＯ、Ｍｇｏ、ＺｎＯ、ＳｒＯ、及びＣａＯの
内の少なくとも１種の金属酸化物）との組成を示す三角
図における、 前記Ｂ＿２Ｏ＿３が１モル％、前記ＳｉＯ＿２が８０モ
ル％、前記ＭＯが１９モル％の点（Ａ）と、前記Ｂ＿２
Ｏ＿３が１モル％、前記ＳｉＯ＿２が３９モル％、前記
ＭＯが６０モル％の点（Ｂ）と、前記Ｂ＿２Ｏ＿３が３
０モル％、前記ＳｉＯ＿２が０モル％、前記ＭＯが７０
モル％の点（Ｃ）と、前記Ｂ＿２Ｏ＿３が９０モル％、
前記ＳｉＯ＿２が０モル％、前記ＭＯが１０モル％の点
（Ｄ）と、前記Ｂ＿２Ｏ＿３が９０モル％、前記ＳｉＯ
＿２が１０モル％、前記ＭＯが０モル％の点（Ｅ）と、
前記Ｂ＿２Ｏ＿３が２０モル％、前記ＳｉＯ＿２が８０
モル％、前記ＭＯが０モル％の点（Ｆ）とを順に結ぶ６
本の直線で囲まれた領域内のものである誘電体磁器組成
物。(1) Consists of 100 parts by weight of a basic component and 0.2 to 15.0 parts by weight of additional components, and the basic component is {(Ma
_1_-_y_-_zMb_yMn_z)_O}_k(
Ti_1_-_wZr_w)O_2 (However, Ma is at least one metal among Sr and Ca, Mb is at least one metal among Mg and Zn,
y, z, k, w are 0.005≦y≦0.100, 0.
001≦z≦0.100, 1.00≦k≦1.20, 0
．． 005≦w≦0.100), and the additive components are B_2O_3, SiO_2, and MO (however,
In the triangular diagram showing the composition of MO (at least one metal oxide of BaO, Mgo, ZnO, SrO, and CaO), B_2O_3 is 1 mol%, SiO_2 is 80 mol%, and MO is 19 Point (A) of mol% and the above B_2
The point (B) where O_3 is 1 mol%, the SiO_2 is 39 mol%, and the MO is 60 mol%, and the B_2O_3 is 3
0 mol%, the SiO_2 is 0 mol%, the MO is 70
Point (C) of mol% and the above B_2O_3 is 90 mol%,
Point (D) where the SiO_2 is 0 mol% and the MO is 10 mol%, and the point (D) where the B_2O_3 is 90 mol% and the SiO
A point (E) where _2 is 10 mol% and the MO is 0 mol%,
The B_2O_3 is 20 mol%, and the SiO_2 is 80 mol%.
mol%, connect the point (F) where the MO is 0 mol% in order 6
Dielectric porcelain compositions that are within the area enclosed by straight lines in the book.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61232820A JPS6386314A (en) | 1986-09-30 | 1986-09-30 | Dielectric ceramic composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61232820A JPS6386314A (en) | 1986-09-30 | 1986-09-30 | Dielectric ceramic composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6386314A true JPS6386314A (en) | 1988-04-16 |
| JPH0551122B2 JPH0551122B2 (en) | 1993-07-30 |
Family
ID=16945290
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61232820A Granted JPS6386314A (en) | 1986-09-30 | 1986-09-30 | Dielectric ceramic composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6386314A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000018701A1 (en) | 1998-09-30 | 2000-04-06 | Tdk Corporation | Unreduced dielectric ceramic material, process for producing the same, and layer-built ceramic capacitor |
-
1986
- 1986-09-30 JP JP61232820A patent/JPS6386314A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0551122B2 (en) | 1993-07-30 |
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