JPH0664933B2 - Dielectric porcelain composition - Google Patents
Dielectric porcelain compositionInfo
- Publication number
- JPH0664933B2 JPH0664933B2 JP61098973A JP9897386A JPH0664933B2 JP H0664933 B2 JPH0664933 B2 JP H0664933B2 JP 61098973 A JP61098973 A JP 61098973A JP 9897386 A JP9897386 A JP 9897386A JP H0664933 B2 JPH0664933 B2 JP H0664933B2
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Description
【発明の詳細な説明】 ＜産業上の利用分野＞ この発明は誘電率が6000以上と高く、焼結温度が950〜1
000℃と低く、比抵抗が１×1011Ω・cm以上と高く、さ
らに温度に対する静電容量の変化率の小さい誘電体磁器
組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention has a high dielectric constant of 6000 or more and a sintering temperature of 950 to 1
The present invention relates to a dielectric ceramic composition having a low resistivity of 000 ° C., a high specific resistance of 1 × 10 11 Ω · cm or more, and a small rate of change of capacitance with temperature.
＜従来の技術とその問題点＞ 従来、高誘電率系磁器コンデンサ材料としてBaTiO3を主
体としたものが知られている。<Conventional Technology and Its Problems> Conventionally, a material mainly composed of BaTiO 3 is known as a high dielectric constant type ceramic capacitor material.
しかし、これらは温度に対する静電容量の変化率がＪＩ
Ｓ規格のＤ特性（−25℃〜＋85℃において△Ｃ／Ｃ２０
＝＋20〜−30％）に入るものは室温での誘電率が5000程
度と低い。However, these have a change rate of capacitance with temperature of JI
S standard D characteristics (△ C / C 20 at -25 ℃ to + 85 ℃)
= + 20 to -30%) has a low dielectric constant of about 5000 at room temperature.
さらに、これらの組成系はその焼結温度が何れも1300〜
1400℃と高い欠点を有している。Furthermore, these composition systems all have sintering temperatures of 1300-
It has a high defect of 1400 ℃.
このため焼成コストが高くつくほか、積層磁器コンデン
サにおいては、生の磁器シートの上に電極を予め形成し
たものを複数枚積み重ねてから焼成されるので、この電
極材料としては、1300℃以上の高温においても溶融した
り、酸化したり、誘電体と反応したりすることのない高
融点の貴金属類例えば白金やパラジウムなどを用いなけ
ればならなかった。For this reason, the firing cost is high, and in a laminated porcelain capacitor, multiple pre-formed electrodes are stacked on a raw porcelain sheet and then fired. In this case, it has been necessary to use a noble metal having a high melting point, such as platinum or palladium, which does not melt, oxidize, or react with the dielectric.
鉛複合ペロブスカイト誘電体磁器組成物において、比誘
電率10,000以上、焼結温度1050℃以下という組成系は既
に知られている。In the lead composite perovskite dielectric ceramic composition, a composition system having a relative dielectric constant of 10,000 or more and a sintering temperature of 1050 ° C. or less is already known.
しかし、これらは温度に対する静電容量の変化率が大き
い。そこで温度に対する静電容量の変化率が小さく、ま
た高誘電率で、さらにPbOの蒸発を少なくするために低
温での焼成が可能な組成物が望まれていた。However, these have a large rate of change in capacitance with temperature. Therefore, there has been a demand for a composition that has a small rate of change in capacitance with respect to temperature, has a high dielectric constant, and can be fired at low temperature in order to reduce evaporation of PbO.
＜問題点を解決するための手段＞ 本発明者らは上記の問題点を解決するために、誘電率が
6000以上と高く、焼結温度が950〜1000℃と低く、比抵
抗が１×1011Ω・cm以上と高く、さらに温度に対する静
電容量の変化率がＪＩＳ規格のＤ特性（△Ｃ／Ｃ２０＝
＋20〜−30％）を満足する誘電体磁器組成物を見出した
ものである。<Means for Solving Problems> In order to solve the above problems, the present inventors
High as 6000 or higher, sintering temperature as low as 950-1000 ℃, high specific resistance as high as 1 × 10 11 Ωcm or more, and the rate of change of capacitance with temperature is JIS standard D characteristic (△ C / C 20 =
The inventors have found a dielectric ceramic composition satisfying +20 to -30%).
即ち、この発明はPb(Ni1/3Nb2/3)O3-Pb(Zn1/3Nb2/3)O3-
PbTiO3の３成分系の固溶体よりなる磁器組成物におい
て、該組成物を構成する個々の酸化物組成比率（重量
％）が Pb3O4 66.69〜69.18、 NiO 4.00〜7.14 Nb2O5 17.43〜25.67、 ZnO 0.08〜3.48 TiO2 0.23〜8.47 であり、かつPb(Ni1/3Nb2/3)O3-Pb(Zn1/3Nb2/3)O3-PbTi
O3と表わしたときのモル比率（％）が Pb(Ni1/3Nb2/3)O3 55.0〜98.0 Pb(Zn1/3Nb2/3)O3 1.0〜44.0 PbTiO3 1.0〜35.0 と表わされ、主成分を 〔Pb(Ni1/3Nb2/3)O3〕ｘ〔Pb(Zn1/3Nb2/3)O3〕y〔PbTiO
3〕ｚ（但し、ｘ＋ｙ＋ｚ＝1.00）と表わしたときに図
面に示す３成分組成図において、下記 Ａ （0.64、0.01、0.35） Ｂ （0.55、0.10、0.35） Ｃ （0.55、0.44、0.01） Ｄ （0.98、0.01、0.01） の組成点を結ぶ線上、およびこの４点にて囲まれる組成
範囲で表わされ、かつ主成分を100重量部としたとき、
副成分としてＡ(Mn1/2Nb1/2)Ｏ３ （但し、ＡはPb、Ba、Sr、Caより選ばれた１種以上の元
素）で表わされる組成物を0.5〜5.0重量部、さらにＢ(C
u1/2W1/2)Ｏ３（但し、ＢはPb、Ba、Sr、Caより選ばれ
た１種以上の元素）で表わされる組成物を0.5〜5.0重量
部含有したことを特徴とする誘電体磁器組成物を提供す
るものである。That is, this invention is Pb (Ni 1/3 Nb 2/3 ) O 3 -Pb (Zn 1/3 Nb 2/3 ) O 3-
In a porcelain composition consisting of a ternary solid solution of PbTiO 3 , the individual oxide composition ratio (wt%) constituting the composition is Pb 3 O 4 66.69 to 69.18, NiO 4.00 to 7.14 Nb 2 O 5 17.43 to 25.67, ZnO 0.08 to 3.48 TiO 2 0.23 to 8.47, and Pb (Ni 1/3 Nb 2/3 ) O 3 -Pb (Zn 1/3 Nb 2/3 ) O 3 -PbTi
The molar ratio (%) when expressed as O 3 is Pb (Ni 1/3 Nb 2/3 ) O 3 55.0 to 98.0 Pb (Zn 1/3 Nb 2/3 ) O 3 1.0 to 44.0 PbTiO 3 1.0 to 35.0 The main component is [Pb (Ni 1/3 Nb 2/3 ) O 3 ] x [Pb (Zn 1/3 Nb 2/3 ) O 3 ] y [PbTiO
3 ] z (however, x + y + z = 1.00), in the three-component composition diagram shown in the drawing, the following A (0.64, 0.01, 0.35) B (0.55, 0.10, 0.35) C (0.55, 0.44, 0.01) D It is expressed on the line connecting the composition points of (0.98, 0.01, 0.01) and the composition range surrounded by these four points, and when the main component is 100 parts by weight,
0.5 to 5.0 parts by weight of a composition represented by A (Mn 1/2 Nb 1/2 ) O 3 (where A is one or more elements selected from Pb, Ba, Sr, and Ca) as an accessory component, Furthermore, B (C
u 1/2 W 1/2 ) O 3 (wherein B is one or more elements selected from Pb, Ba, Sr and Ca) is contained in an amount of 0.5 to 5.0 parts by weight. The present invention provides a dielectric ceramic composition.
＜作用＞ この発明において主成分および副成分の範囲を上記のよ
うに限定する理由は次の通りである。<Operation> In the present invention, the reason for limiting the ranges of the main component and the sub-components as described above is as follows.
まず、主成分の組成限定理由について述べると、図にお
ける組成点Ａ、Ｂを結ぶ線の外側、および組成点Ｂ、Ｃ
を結ぶ線の外側では温度に対する静電容量の変化率がＪ
ＩＳ規格のＤ特性（即ち−25℃〜＋85℃において△Ｃ／
Ｃ２０＝＋20〜−30％）よりも大きくなって好ましくな
い。First, the reason for limiting the composition of the main component will be described. Outside the line connecting the composition points A and B in the figure and the composition points B and C.
The rate of change of capacitance with temperature is J outside the line connecting
IS standard D characteristics (that is, ΔC / at -25 ° C to + 85 ° C)
C 20 = + 20 to −30%), which is not preferable.
組成点Ｃ、Ｄを結ぶ線の外側では誘電率が6000より低く
なり、温度に対する静電容量の変化率が前述したＪＩＳ
規格のＤ特性よりも大きくなり好ましくない。Outside the line connecting the composition points C and D, the permittivity becomes lower than 6000, and the rate of change of the capacitance with respect to temperature is as described in JIS.
It is not preferable because it is larger than the standard D characteristic.
さらに組成点Ｄ、Ａを結ぶ線の外側では焼成温度が1000
℃を越え、誘電体損失も２％より大きくなり、また温度
に対する静電容量の変化率がＪＩＳ規格のＤ特性よりも
大きくなり好ましくない。Furthermore, the firing temperature is 1000 outside the line connecting the composition points D and A.
When the temperature exceeds ℃, the dielectric loss becomes larger than 2%, and the rate of change of the capacitance with respect to temperature becomes larger than the D characteristic of JIS standard, which is not preferable.
次に副成分の含有効果および範囲限定理由について述べ
ると、Ａ(Mn1/2Nb1/2)Ｏ３を含有させることにより、比
抵抗を向上させることができるが、Ａ(Mn1/2Nb1/2)Ｏ３
が主成分に対して0.5重量部未満では、誘電体損失が２
％を越えるとともに、比抵抗が１×1011Ω・cmより低く
なり、一方５重量部を越えると、誘電率が5000より低く
なり、誘電体損失も２％を越え、また温度に対する静電
容量の変化率がＪＩＳ規格のＤ特性よりも大きくなり好
ましくない。Then the described content effects and scope reasons of limiting subcomponents, by incorporating A (Mn 1/2 Nb 1/2) O 3, it is possible to improve the specific resistance, A (Mn 1/2 Nb 1/2 ) O 3
Is less than 0.5 parts by weight relative to the main component, the dielectric loss is 2
%, The specific resistance will be lower than 1 × 10 11 Ω · cm, while if it exceeds 5 parts by weight, the dielectric constant will be lower than 5000, the dielectric loss will also exceed 2%, and the capacitance with temperature will increase. Change rate is larger than the D characteristic of JIS standard, which is not preferable.
さらにまた、Ｂ(Cu1/2W1/2)Ｏ３を含有させると焼結温
度を下げることができ、PbOの蒸発を抑えることができ
るが、Ｂ(Cu1/2W1/2)Ｏ３が主成分に対して0.5重量部未
満では焼成温度が1000℃を越え、５重量部を越えると温
度に対する静電容量の変化率がＪＩＳ規格のＤ特性より
大きくなって好ましくない。Furthermore, when B (Cu 1/2 W 1/2 ) O 3 is contained, the sintering temperature can be lowered and the evaporation of PbO can be suppressed, but B (Cu 1/2 W 1/2 ) If O 3 is less than 0.5 parts by weight with respect to the main component, the firing temperature exceeds 1000 ° C., and if it exceeds 5 parts by weight, the rate of change in electrostatic capacity with respect to temperature becomes larger than the D characteristic of JIS standard, which is not preferable.
＜実施例＞ 以下、実施例によりこの発明を詳細に説明する。<Examples> Hereinafter, the present invention will be described in detail with reference to Examples.
出発原料として工業用のPb3O4、NiO、Nb2O5、ZnO、Ti
O2、MnO2、CuO、WO3、BaCO3、SrCO3、CaCO3などを用
い、これらを秤量して予めPb(Ni1/3Nb2/3)O3、Pb(Zn1/3N
b2/3)O3、PbTiO3、Pb(Mn1/2Nb1/2)O3、Ba(Mn1/2Nb1/2)
O3、Sr(Mn1/2Nb1/2)O3、Ca(Mn1/2Nb1/2)O3、Pb(Cu1/2W
1/2)O3、Ba(Cu 1/2W1/2)O3、Sr(Cu1/2W1/2)O 3、Ca(Cu
1/2W1/2)O3となるように各々配合した。Industrial Pb 3 O 4 , NiO, Nb 2 O 5 , ZnO, Ti as starting materials
O 2, MnO 2, CuO, WO 3, BaCO 3, SrCO 3, CaCO 3 using a previously weighed these Pb (Ni 1/3 Nb 2/3) O 3, Pb (Zn 1/3 N
b 2/3 ) O 3 , PbTiO 3 , Pb (Mn 1/2 Nb 1/2 ) O 3 , Ba (Mn 1/2 Nb 1/2 ).
O 3 , Sr (Mn 1/2 Nb 1/2 ) O 3 , Ca (Mn 1/2 Nb 1/2 ) O 3 , Pb (Cu 1/2 W
1/2 ) O 3 , Ba (Cu 1/2 W 1/2 ) O 3 , Sr (Cu 1/2 W 1/2 ) O 3 , Ca (Cu
Each was blended so that it would be 1/2 W 1/2 ) O 3 .
次にPbTiO3は950℃、その他の組成物は850℃で夫々２時
間仮焼し、所定の化合物粉体を得た。Next, PbTiO 3 was calcined at 950 ° C. and the other compositions were calcined at 850 ° C. for 2 hours, respectively, to obtain a predetermined compound powder.
次いで、このようにして得られた化合物を第１表に示す
各所望の配合比となるように配合し、結合剤としての酢
酸ビニル系バインダを５重量部加え、ボールミルによっ
て湿式混合した。その後蒸発乾燥し、整粒により粉末状
にしてこれを１ton/cm2の圧力で直径12mm、厚さ1.5mmの
円板に成形した。次いで、この円板をPb雰囲気の電気炉
を用い、第２表に示す各焼成温度で１時間焼成した。そ
の後電極としてAgベーストを800℃で焼きつけ測定試料
とした。Then, the compounds thus obtained were blended so as to have the respective desired blending ratios shown in Table 1, 5 parts by weight of a vinyl acetate binder as a binder was added, and the mixture was wet mixed by a ball mill. Then, it was evaporated to dryness, sized to a powder, and shaped into a disk having a diameter of 12 mm and a thickness of 1.5 mm at a pressure of 1 ton / cm 2 . Then, the disc was fired for 1 hour at each firing temperature shown in Table 2 using an electric furnace in a Pb atmosphere. Thereafter, an Ag base as an electrode was baked at 800 ° C. to obtain a measurement sample.
各試料については誘電率（ε）および誘電率正接（tan
δ）を１ＫＨｚ、１Ｖrms、20℃の条件で測定した。ま
た比抵抗を500ＶＤ、Ｃの条件で測定した。For each sample, the permittivity (ε) and the permittivity tangent (tan
δ) was measured under the conditions of 1 KHz, 1 Vrms, and 20 ° C. The specific resistance was measured under the conditions of 500 VD and C.
なお、静電容量の温度特性は20℃の値を基準とし、−25
℃、＋85℃の温度での変化率で表わした。これらの測定
結果は第２表に示した。なお＊印の試料番号のものはこ
の発明の請求範囲外である。Note that the temperature characteristic of capacitance is based on the value of 20 ℃,
Expressed as the rate of change at temperatures of ℃ and + 85 ℃. The results of these measurements are shown in Table 2. Samples marked with * are outside the scope of the claims of the present invention.
＜発明の効果＞ 上表から、この発明の誘電体磁器組成物は、誘電率が60
00以上、誘電体損失が２％以下、比抵抗が１×1011Ω・
cm以上、焼成温度が950〜1000℃であり、かつ温度に対
する静電容量の変化率がＪＩＳ規格のＤ特性（−25℃〜
＋85℃において△Ｃ／Ｃ２０＝＋20〜−30％）を満足す
るものを得た。 <Effects of the Invention> From the above table, the dielectric ceramic composition of the present invention has a dielectric constant of 60.
00 or more, dielectric loss 2% or less, specific resistance 1 × 10 11 Ω ・
cm or more, the firing temperature is 950 to 1000 ° C, and the rate of change in capacitance with temperature is the D characteristic of JIS standard (-25 ° C to
A product satisfying ΔC / C 20 = + 20 to −30% at + 85 ° C. was obtained.
また、出発原料を夫々所定の化合物の比になるように秤
量し、一度に混合して850℃で仮焼した場合、（試料番
号18）も前述した方法、即ち、各々の組成物の化合物粉
末を混合した時と同程度の特性を得ることができた。When the starting materials are weighed so that the ratios of the respective compounds are predetermined, mixed at one time and calcined at 850 ° C., (Sample No. 18) is also the method described above, that is, the compound powder of each composition. It was possible to obtain the same characteristics as those obtained by mixing.
図面はこの発明の磁器組成物における組成のうちｘ、
ｙ、ｚの範囲を示す説明図である。The drawing shows x among the compositions in the porcelain composition of the present invention,
It is explanatory drawing which shows the range of y and z.
Claims (1)
O3の３成分系の固溶体よりなる磁器組成物において、該
組成物を構成する個々の酸化物組成比率（重量％）が Pb3O4 66.69〜69.18、 NiO 4.00〜7.14、 Nb2O5 17.43〜25.67、 ZnO 0.08〜3.48 TiO2 0.23〜8.47 であり、かつPb(Ni1/3Nb2/3)O3-Pb(Zn1/3Nb2/3)O3-PbTi
O3と表わしたときのモル比率（％）が Pb(Ni1/3Nb2/3)O3 55.0〜98.0 Pb(Zn1/3Nb2/3)O3 1.0〜44.0 PbTiO3 1.0〜35.0 と表わされ、主成分を100重量部としたとき、副成分と
してＡ(Mn1/2Nb1/2)Ｏ３ （但し、ＡはPb、Ba、Sr、Caより選ばれた１種以上の元
素）で表わされる組成物を0.5〜5.0重量部とＢ(Ca1/2W
1/2)Ｏ３（但し、ＢはPb、Ba、Sr、Caより選ばれた１種
以上の元素）で表わされる組成物を0.5〜5.0重量部含有
することを特徴とする誘電体磁器組成物。1. Pb (Ni 1/3 Nb 2/3 ) O 3 -Pb (Zn 1/3 Nb 2/3 ) O 3 -PbTi
In a porcelain composition composed of a three-component solid solution of O 3 , the individual oxide composition ratio (wt%) constituting the composition is Pb 3 O 4 66.69 to 69.18, NiO 4.00 to 7.14, Nb 2 O 5 17.43. ~ 25.67, ZnO 0.08 to 3.48 TiO 2 0.23 to 8.47, and Pb (Ni 1/3 Nb 2/3 ) O 3 -Pb (Zn 1/3 Nb 2/3 ) O 3 -PbTi
The molar ratio (%) when expressed as O 3 is Pb (Ni 1/3 Nb 2/3 ) O 3 55.0 to 98.0 Pb (Zn 1/3 Nb 2/3 ) O 3 1.0 to 44.0 PbTiO 3 1.0 to 35.0 When the main component is 100 parts by weight, A (Mn 1/2 Nb 1/2 ) O 3 (where A is one or more selected from Pb, Ba, Sr, and Ca) 0.5 to 5.0 parts by weight of B (Ca 1/2 W)
1/2 ) O 3 (wherein B is one or more elements selected from Pb, Ba, Sr, and Ca) in a proportion of 0.5 to 5.0 parts by weight. object.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61098973A JPH0664933B2 (en) | 1986-04-28 | 1986-04-28 | Dielectric porcelain composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61098973A JPH0664933B2 (en) | 1986-04-28 | 1986-04-28 | Dielectric porcelain composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62254309A JPS62254309A (en) | 1987-11-06 |
| JPH0664933B2 true JPH0664933B2 (en) | 1994-08-22 |
Family
ID=14233977
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61098973A Expired - Lifetime JPH0664933B2 (en) | 1986-04-28 | 1986-04-28 | Dielectric porcelain composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0664933B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08104087A (en) * | 1994-10-05 | 1996-04-23 | Focus Syst:Kk | Document |
-
1986
- 1986-04-28 JP JP61098973A patent/JPH0664933B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08104087A (en) * | 1994-10-05 | 1996-04-23 | Focus Syst:Kk | Document |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62254309A (en) | 1987-11-06 |
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